WO2023196330A1 - Procédés de conversion d'oléfines c2+ en oléfines à nombre de carbones plus élevé, utiles pour la production de compositions de distillats isoparaffiniques - Google Patents

Procédés de conversion d'oléfines c2+ en oléfines à nombre de carbones plus élevé, utiles pour la production de compositions de distillats isoparaffiniques Download PDF

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WO2023196330A1
WO2023196330A1 PCT/US2023/017456 US2023017456W WO2023196330A1 WO 2023196330 A1 WO2023196330 A1 WO 2023196330A1 US 2023017456 W US2023017456 W US 2023017456W WO 2023196330 A1 WO2023196330 A1 WO 2023196330A1
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vol
stream
ethylene
wppm
olefins
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PCT/US2023/017456
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English (en)
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Matthew J. Vincent
Keith H. Kuechler
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ExxonMobil Technology and Engineering Company
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Priority claimed from US17/820,159 external-priority patent/US12012562B2/en
Application filed by ExxonMobil Technology and Engineering Company filed Critical ExxonMobil Technology and Engineering Company
Publication of WO2023196330A1 publication Critical patent/WO2023196330A1/fr

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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
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • 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
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • 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

Definitions

  • Olefins are valued feedstocks in chemical manufacturing.
  • light olefins like ethylene and propylene are useful in polymerization reactions.
  • Higher carbon olefins like C6+ olefins and C8+ olefins, which may be produced by oligomerizing light olefins, are useful in producing specialty surfactants, lubricants, jet/aviati on fuel, diesel fuel, fuel additives, and the like.
  • Many oligomerization catalyst systems have been investigated for increasing the yield of preferred higher carbon olefins and with greater yields. However, the steps in upgrading light olefins to higher carbon olefins have remained reasonably unchanged.
  • the present application relates to methods for converting C2+ olefins to higher carbon number olefins.
  • a nonlimiting example method for producing a diesel boiling range composition comprises: oligomerizing an ethylene stream to a C4+ olefin stream in a first olefin oligomerization unit comprising a serial reactor and a lights removal column, wherein the C4+ olefin stream contains no greater than 10 wt% of methane, ethylene, and ethane combined in a first oligomerization; and wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 20 wppm each of carbon monoxide and hydrogen; oligomerizing the C4+ olefin stream and a propyl ene/C4+ olefin stream in a second oligomerization unit to produce an isoolefinic stream; wherein at least a portion of the isool efinic stream is used to create the diesel boiling range
  • a nonlimiting example method for producing a diesel boiling range composition comprises: providing a raw olefin stream comprising ethylene, propylene and C4+ olefins, wherein at least 10 wt% of all olefins in the raw olefin stream are ethylene, and further containing at least 1000 wppm of each methane and ethane, and at least 100 wppm of each carbon monoxide and hydrogen; subjecting the raw olefin stream to a separation operation to remove hydrogen, carbon monoxide, propylene and C4+ olefins from the raw olefin stream, and produce an ethylene stream containing at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 20 wppm each of carbon monoxide and hydrogen, wherein at least 95 wt% of all the ethylene in the raw olefin stream is recovered in the ethylene stream
  • FIG. 1 illustrates a nonlimiting example of a method of the present disclosure.
  • FIG. 2 illustrates a nonlimiting example of a method of the present disclosure.
  • FIG. 3 illustrates a nonlimiting example of a method of the present disclosure.
  • FIG. 4 illustrates a nonlimiting example of a method of the present disclosure.
  • FIG. 5 illustrates a nonlimiting example of a method of the present disclosure.
  • FIG. 6 shows results from the analysis.
  • the present application relates to methods for converting C2+ olefins to higher carbon number olefins.
  • Said olefins and/or said olefins converted to paraffins may be useful for a variety of other applications including fuels and blendstocks for fuels. More specifically, the conversion may include two oligomerization processes that may advantageously improve the overall ethylene conversion while having flexibility and efficiencies that may provide energy and cost savings.
  • methanol obtained by a variety of processes may be referred to as “sustainable” methanol.
  • processes may include, but are not limited to, reforming municipal waste, reforming biomass, fermenting biomass, electrolyzing water to produce hydrogen for reaction with carbon monoxide and/or carbon dioxide, and the like, and any combination thereof.
  • distillation points and boiling points can be determined according to ASTM D2887.
  • ASTM D7169 can be used. It is noted that still other methods of boiling point characterization may be provided in the examples. The values generated by such other methods are believed to be indicative of the values that would be obtained under ASTM D2887 and/or ASTM D7169.
  • distillate boiling range is defined as 140°C to 370°C.
  • a distillate boiling range fraction is defined as a fraction having a T10 distillation point of 170°C or more and a T90 distillation point of 370°C or less.
  • the diesel boiling range is defined as 170°C to 370°C.
  • a diesel boiling range fraction is defined as a fraction having a T10 distillation point of 170°C or more, a final boiling point of 300°C or more, and a T90 distillation point of 370°C or less.
  • An atmospheric resid is defined as a bottoms fraction having a T10 distillation point of 149°C or higher, or 350°C or higher.
  • the vacuum gas oil (VGO) boiling range is defined as 370°C to 565°C.
  • a vacuum gas oil boiling range fraction (also referred to as a heavy distillate) can have a T10 distillation point of 350°C or higher and a T90 distillation point of 538°C or less.
  • a vacuum resid is defined as a bottoms fraction having a T10 distillation point of 500°C or higher, or 538°C or higher, or 565°C or higher. It is noted that the definitions for distillate boiling range fraction, kerosene (or jet fuel) boiling range fraction, diesel boiling range fraction, atmospheric resid, and vacuum resid are based on boiling point only. Thus, a distillate boiling range fraction, diesel fraction, atmospheric resid fraction, vacuum gas oil fraction, and/or vacuum resid fraction can include components that did not pass through a distillation tower or other separation stage based on boiling point.
  • a hydroprocessed fraction refers to a hydrocarbon fraction and/or hydrocarbonaceous fraction that has been exposed to a catalyst having hydroprocessing activity in the presence of 300 kPa-a or more of hydrogen at a temperature of 200°C or more.
  • hydroprocessed fractions include hydroprocessed distillate fractions (i.e., a hydroprocessed fraction having the distillate boiling range), hydroprocessed kerosene fractions (i.e., a hydroprocessed fraction having the kerosene boiling range) and hydroprocessed diesel fractions (i.e., a hydroprocessed fraction having the diesel boiling range).
  • hydroprocessed fraction derived from a biological source can correspond to a hydroprocessed distillate fraction, a hydroprocessed kerosene fraction, and/or a hydroprocessed diesel fraction, depending on the boiling range of the hydroprocessed fraction.
  • Density of a blend at 15°C can be determined according to ASTM D4052.
  • Sulfur (in wppm or wt%) can be determined according to ASTM D2622, while nitrogen (in wppm or wt%) can be determined according to D4629.
  • Pour point can be determined according to ASTM D5950.
  • Cloud point can be determined according to D2500.
  • Freeze point can be determined according to ASTM D5972.
  • Cetane number can be determined according to ASTM D4737, procedure A.
  • Kinematic viscosity can be determined according to ASTM D445.
  • Aromatics content can be determined according to ASTM D1319. Flash point can be determined according to ASTM D56.
  • density in kg/m 3
  • sulfur in wppm
  • kinematic viscosity at 50°C in cSt
  • pour point can be determined according to ISO 3016.
  • sediment can be determined according to ISO 10307-2.
  • CCAI calculated carbon aromaticity index
  • Micro carbon residue content can be determined according to ASTM D4530.
  • the content of n-heptane insolubles can be determined according to ASTM D3279. Flash point can be determined according to ASTM D93.
  • the metals content can be determined according to ASTM D8056. Nitrogen can be determined according to D4629 for lower concentrations and D5762 for higher concentrations, as appropriate.
  • n-paraffins the content of n-paraffins, isoparaffins, cycloparaffins, aromatics, and/or olefins can be determined according to test method UOP 990. It is noted that for some of the paraffin, n-paraffin, and isoparaffin contents described below, the contents were determined using gas chromatography according to the Linear Paraffin method. The n-paraffin peaks from a hydrocarbon sample in gas chromatography are well known. The n-paraffin peaks can be separately integrated to determine the n-paraffin content of a sample using gas chromatography.
  • the peaks in a GC spectrum between the n-paraffin peaks can be assigned as isoparaffins with the same carbon number as the lower peak, so that a total amount of paraffins having a given carbon number can be determined.
  • the isoparaffin content for a given carbon number can be determined by subtracting the n-paraffin content from the total paraffin content. It is believed that the values herein determined by the Linear Paraffin method are representative of the values that would be obtained according to UOP 990.
  • UOP 990 can be used to determine paraffin, naphthene, and aromatics content. It is noted that for some paraffin, naphthene, and/or aromatics contents described herein, supercritical fluid chromatography (SFC) was used. It is believed that the SFC characterization values are representative of what would be obtained according to UOP 990. For SFC characterization, the characterization was performed using a commercial supercritical fluid chromatograph system, and the methodology represents an expansion on the methodology described in ASTM D5186 to allow for separate characterization of paraffins and naphthenes. The expansion on the ASTM D5186 methodology was enabled by using additional separation columns, to allow for resolution of naphthenes and paraffins.
  • SFC supercritical fluid chromatography
  • the system was equipped with the following components: a high pressure pump for delivery of supercritical carbon dioxide mobile phase; temperature controlled column oven; auto-sampler with high pressure liquid injection valve for delivery of sample material into mobile phase; flame ionization detector; mobile phase splitter (low dead volume tee); back pressure regulator to keep the CO2 in supercritical state; and a computer and data system for control of components and recording of data signal.
  • a high pressure pump for delivery of supercritical carbon dioxide mobile phase
  • temperature controlled column oven auto-sampler with high pressure liquid injection valve for delivery of sample material into mobile phase
  • flame ionization detector flame ionization detector
  • mobile phase splitter low dead volume tee
  • back pressure regulator to keep the CO2 in supercritical state
  • a computer and data system for control of components and recording of data signal.
  • approximately 75 milligrams of sample was diluted in 2 milliliters of toluene and loaded in standard septum cap autosampler vials. The sample was introduced based via the high pressure sampling valve.
  • the SFC separation was performed using multiple commercial silica packed columns (5 micron with either 60 or 30 angstrom pores) connected in series (250 mm in length either 2 mm or 4 mm ID). Column temperature was held typically at 35 or 40°C. For analysis, the head pressure of columns was typically 250 bar. Liquid CO2 flow rates were typically 0.3 ml/minute for 2 mm ID columns or 2.0 ml/minute for 4 mm ID columns.
  • the SFC FID signal was integrated into paraffin and naphthenic regions. In addition to characterizing aromatics according to ASTM D5186, a supercritical fluid chromatograph was used to analyze samples for split of total paraffins and total naphthenes. A variety of standards employing typical molecular types can be used to calibrate the paraffin/naphthene split for quantification.
  • paraffin refers to saturated hydrocarbons that may be linear or branched.
  • the paraffin may be straight-chain or branched-chain and is considered to be a non-ring compound.
  • Paraffin is intended to embrace all structural isomeric forms of paraffins.
  • n-paraffin has the expected definition of a straight chain alkane (no branches or rings in the carbon chain).
  • isoparaffin is used herein to refer to any alkane that includes one or more branches in the carbon chain but does not include any ring structures.
  • paraffin encompasses the terms “n-paraffin” and “isoparaffin.”
  • iso-olefin is analogous to “isoparaffin,” but refers to an alkene rather than an alkane.
  • an iso-olefin is defined as an alkene that includes at least one branch in the carbon chain but that does not include a ring structure.
  • naphthene refers to a cycloalkane (also known as a cycloparaffin). Therefore, naphthenes correspond to saturated ring structures.
  • the term naphthene encompasses single-ring naphthenes and multi-ring naphthenes.
  • the multi-ring naphthenes may have two or more rings, e.g., two-rings, three-rings, four-rings, five-rings, six-rings, seven-rings, eight-rings, nine-rings, and ten-rings.
  • the rings may be fused and/or bridged.
  • the naphthene can also include various side chains, such as one or more alkyl side chains of 1-10 carbons.
  • saturates refers to all straight chain, branched, and cyclic paraffins. Thus, saturates correspond to a combination of paraffins and naphthenes.
  • aromatic ring means five or six atoms joined in a ring structure wherein (i) at least four of the atoms joined in the ring structure are carbon atoms and (ii) all of the carbon atoms joined in the ring structure are aromatic carbon atoms. Therefore, aromatic rings correspond to unsaturated ring structures. Aromatic carbons can be identified using, for example, 13 C Nuclear Magnetic Resonance.
  • Aromatic rings having atoms attached to the ring e.g., one or more heteroatoms, one or more carbon atoms, etc.
  • Aromatic rings having atoms attached to the ring e.g., one or more heteroatoms, one or more carbon atoms, etc.
  • Aromatic rings having atoms attached to the ring are within the scope of the term “aromatic ring.”
  • ring structures that include one or more heteroatoms can correspond to an “aromatic ring” if the ring structure otherwise falls within the definition of an “aromatic ring.”
  • non-aromatic ring means four or more carbon atoms joined in at least one ring structure wherein at least one of the four or more carbon atoms in the ring structure is not an aromatic carbon atom.
  • Non-aromatic rings having atoms attached to the ring e.g., one or more heteroatoms, one or more carbon atoms, etc., but which are not part of the ring structure, are within the scope of the term “non-aromatic ring.”
  • aromatics refers to all compounds that include at least one aromatic ring. Such compounds that include at least one aromatic ring include compounds that have one or more hydrocarbon substituents. It is noted that a compound including at least one aromatic ring and at least one non-aromatic ring falls within the definition of the term “aromatics.” [0031] It is noted that some hydrocarbons present within a feed or product may fall outside of the definitions for paraffins, naphthenes, and aromatics. For example, any alkenes that are not part of an aromatic compound would fall outside of the above definitions. Similarly, non-aromatic compounds that include a heteroatom, such as sulfur, oxygen, or nitrogen, are not included in the definition of paraffins or naphthenes.
  • Cx hydrocarbon indicates hydrocarbon molecules having the number of carbon atoms represented by the number “x ”
  • Cx+ hydrocarbons indicates those molecules noted above having the number of carbon atoms represented by the number “x” or greater.
  • C17+ hydrocarbons would include C17, C18, and higher carbon number hydrocarbons.
  • Cx- hydrocarbons indicates those molecules noted above having the number of carbon atoms represented by the number “x” or fewer.
  • FIG. 1 illustrates a nonlimiting example of a method 100 of the present disclosure.
  • the illustrated method 100 includes a first oligomerization 104 and a second oligomerization 110 and, optionally, hydroprocessing 114.
  • an ethylene stream 102 undergoes the first oligomerization 104, which produces a C4+ olefin stream 106.
  • the C4+ olefin stream 106 and a propylene/C4+ olefin stream 108 then undergo a second oligomerization 110.
  • the second oligomerization 110 produces an isoolefinic stream 112.
  • the isoolefinic stream 112 has many potential uses.
  • the isoolefinic stream 112 undergoes hydroprocessing 114 and produces an isoparaffinic stream 116.
  • the ethylene stream 102 may contain at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 20 wppm each of carbon monoxide and hydrogen (or (i) at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 5 wppm each of carbon monoxide and hydrogen, or (ii) at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 1 wppm each of carbon monoxide and hydrogen).
  • the ethylene may be present in the ethylene stream 102 in an amount of at least 50 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99.9 wt%, or 50 wt% to 99 wt%, or 60 wt% to 95 wt%, or 70 wt% to 90 wt%.
  • the ethane may be present in the ethylene stream 102 in an amount of at least 2000 wppm, or at least 5000 wppm, or at least 1 wt%, or at least 10 wt%, or at least 25 wt%, or at least 45 wt%, or 2000 wppm to 45 wt%, or 2000 wppm to 25 wt%, or 5000 wppm to 10 wt%.
  • Each of carbon monoxide and hydrogen, individually, may be present in the ethylene stream 102 in an amount of no greater than 20 wppm, no greater than 5 wppm, no greater than 1 wppm, or no greater than 0.5 wppm, or no greater than 0.1 wppm, or 0.001 wppm to 20 wppm, or 0.001 wppm to 5 wppm, or 0.001 wppm to 1 wppm, or 0.001 wppm to 0.5 wppm.
  • the two oligomerizations have similar chemical reactions, but are not identical steps. The chemistries of these steps may be accomplished by very different processes.
  • the first oligomerization 104 may be achieved with high efficiency and efficacy in the liquid phase using a homogenous catalyst.
  • the second oligomerization 110 of higher molecular weight olefins, such as propylene and butenes may be more efficiently and effectively carried out with a heterogeneous catalyst under conditions where some or all of the components are supercritical.
  • the resultant olefins may be included as a portion of the feedstock in the second oligomerization 110, thereby increasing the overall yield of the higher molecular weight olefins (e.g., C10+ olefins). That is, the feedstock for the second oligomerization 110 has minimal amounts of ethylene.
  • the process may benefit from separately using (a) a first oligomerization catalyst specific to high yields of ethylene oligomerization and (b) second oligomerization catalysts that have high yields of distillate-range olefins from olefin feedstock that has minimal amounts of ethylene. Because the two oligomerizations are completed as separate processes (although said processes may be performed in different portions of the same vessel), the overall methods and systems may have higher yields of distillate-range olefins that may then be used to produce the isoparaffinic stream and additional fuel products (e.g., distillates, jet fuel, kerosene, and the like).
  • additional fuel products e.g., distillates, jet fuel, kerosene, and the like.
  • the ethylene stream 102 undergoes the first oligomerization 104 at least 95% of the ethylene present in the ethylene stream 102 may be converted to a C4+ olefins (e.g., C4 olefins, C6 olefins, C8 olefins, and CIO olefins).
  • a C4+ olefins e.g., C4 olefins, C6 olefins, C8 olefins, and CIO olefins.
  • the C4+ olefin stream 106 may contain no greater than 10 wt% of methane, ethylene, and ethane combined (or (i) no greater than 5 wt% of methane, ethylene, and ethane combined, or (ii) no greater than 2000 wppm of methane, ethylene, and ethane combined, or (iii) no greater than 1000 wppm of methane, ethylene, and ethane combined, or (iv) at least 10 wppm and no greater than 10 wt% (or 2000 wppm, or 1000 wppm) of methane, ethylene, and ethane combined).
  • Having a low amount of carbon monoxide and hydrogen in the ethylene stream 102 may allow for high conversion of the ethylene to C4+ olefins in the first oligomerization 104.
  • carbon monoxide and hydrogen may be deleterious to the catalyst system in the first oligomerization 104, especially if the first oligomerization 104 utilizes nickel.
  • the first oligomerization 104 may be largely unaffected by saturated hydrocarbons like methane and ethane, which may allow for higher concentrations of saturated hydrocarbons.
  • the ethylene stream 102 may be from any suitable source including, but not limited to, ethylene derived from an ethanol dehydration reaction, a steam cracker, a fluidized catalytic cracker (FCC), a catalytic conversion reaction of methanol typically called “Methanol To Olefins (MTO),” and the like, and any combination of sources.
  • MTO Methanol To Olefins
  • most MTO processes may also satisfactorily convert other alcohols like ethanol or butanol, and/or ethers like dimethyl ether (DME) or diethyl ether (DEE), typically in some proportion with methanol, to useful olefins with the same catalysts and equipment given minor adjustments for rates and/or concentrations of various reaction products and contaminants.
  • DME dimethyl ether
  • DEE diethyl ether
  • oxygen containing molecules such as ketones, aldehydes and esters may also be converted to olefins, but not desirably given that their relative hydrogen deficiency to alcohols also produces more carbonaceous coke on the catalysts. Nonetheless, minor quantities of the aforementioned oxygenates are produced by the MTO reaction as byproducts, recovered in some form and recycled back to the MTO reactor in combination with the main alcohol feed. Hence, a more generic term often used for these types of technologies is “oxygenates to olefins.”
  • the first oligomerization 104 may occur in a first oligomerization unit, which may comprise one more serial reactors, typically fixed bed adiabatic reactor housing (or otherwise containing) the oligomerization catalyst or a continuous stirred tank reactor (CSTR) or pumparound piping system for housing a homogeneous oligomerization catalyst.
  • a first oligomerization unit which may comprise one more serial reactors, typically fixed bed adiabatic reactor housing (or otherwise containing) the oligomerization catalyst or a continuous stirred tank reactor (CSTR) or pumparound piping system for housing a homogeneous oligomerization catalyst.
  • CSTR continuous stirred tank reactor
  • Examples of catalysts used in the first oligomerization 104 may include, but are not limited to, (a) homogenous catalysts including (al) homogenous catalysts containing organic aluminum, nickel, titanium, and/or zirconium or (a2) Ziegler types where (al) or (a2) may optionally include a ligand for activating the metal and may optionally include a solvent such has a hydrocarbon or ionic liquid cyclohexane; (b) heterogeneous catalysts such as (bl) solid phosphoric acid, (b2) microporous materials such as zeolites, for example, ZSM-5 catalyst, ZSM- 57 catalyst, ZSM-22 catalyst, ZSM-48 catalyst, ZSM-12 catalyst, or (b3) silicoaluminophosphate (SAPO) molecular sieves; (c) the like; and (d) any mixture thereof.
  • SAPO silicoaluminophosphate
  • the first oligomerization 104 may utilize a homogeneous organometallic catalyst. This may include, for example, nickel and other metal liganded catalysts as described in “Oligomerization of Monoolefins by Homogeneous Catalysts,” A. Forestiere, et al., Oil & Gas Science and Technology - Rev. IFP, Vol. 64 (2009), No. 6, pp. 649-667. Limiting the concentration of C10+ olefins to minor amounts (e.g. no more than about 15 wt% of the total C4+ oligomer product) may be optimal for feeding the stream to the second oligomerization 110.
  • a homogeneous organometallic catalyst may include, for example, nickel and other metal liganded catalysts as described in “Oligomerization of Monoolefins by Homogeneous Catalysts,” A. Forestiere, et al., Oil & Gas Science and Technology - Rev. I
  • the second oligomerization 110 may function acceptably well with C10+ olefins in the reactor system feed, but may function most efficiently with a relatively low concentration of those components.
  • a C10+ molecule is already in the carbon number range of distillate products such as diesel and jet fuel, so the main benefit of feeding it to the second oligomerization 110 is to provide the molecule with an alkyl branch (through adding a lighter olefin) to decrease its freeze point, at the risk of increased deleterious cracking reactions to which higher carbon number olefins are susceptible.
  • Contact between the ethylene stream 102 and the first oligomerization catalyst may be under conditions suitable for oligomerizing ethylene.
  • the temperature may be about 25°C to about 300°C (or about 50°C to about 200°C).
  • the pressure may be about 100 psia to about 2000 psia (or about 200 psia to about 1200 psia, or about 250 psia to about 1000 psia).
  • the propylene/C4+ olefin stream 108 and the C4+ olefin stream 106 undergo the second oligomerization 110 (e.g., in a second oligomerization unit) to produce the isoolefinic stream 112.
  • the method may include mixing (or otherwise blending) the propyl ene/C4+ olefin stream 108 and the C4+ olefin stream 106 before undergoing the second oligomerization 110.
  • the second oligomerization 110 that produces the isoolefinic stream 112 may optionally utilize the process described in U.S. Patent 7,692,049, which is incorporated by reference in its entirety.
  • the propylene/C4+ olefin stream 108 may contain any single C3 to C9 olefin or any mixture thereof in any proportion.
  • the propylene/C4+ olefin stream 108 may contain at least 50 wt% C3+ olefins.
  • the C3+ olefins may be present in the propyl ene/C4+ olefin stream 108 in an amount of at least 50 wt%, at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 95 wt%, or 50 wt% to 80 wt%, or 60wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 95 wt%.
  • the distribution of carbon numbers for the C3+ olefins may vary based on the source of the propylene/C4+ olefin stream 108.
  • the propylene/C4+ olefin stream 108 may comprise at least 5 wt% propylene, at least 5 wt% C4 olefin, and C5+ olefins such that the C3+ olefin concentration is a at least 50 wt% of the propylene/C4+ olefin stream 108.
  • C3 olefins may be present in the propylene/C4+ olefin stream 108 in an amount of at least 5 wt%, at least 10 wt%, or at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or 5 wt% to 80 wt%, or 5 wt% to 30 wt%, or 10 wt% to 50 wt%, or 25 wt% to 75 wt%, or 40 wt% to 80 wt% of the propylene/C4+ olefin stream 108.
  • C4 olefins may be present in the propylene/C4+ olefin stream 108 in an amount of at least 5 wt%, at least 10 wt%, or at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or 5 wt% to 80 wt%, or 5 wt% to 30 wt%, or 10 wt% to 50 wt%, or 25 wt% to 75 wt%, or 40 wt% to 80 wt% of the propylene/C4+ olefin stream 108.
  • C5 olefins may be present in the propyl ene/C4+ olefin stream 108 in an amount of at least 5 wt%, at least 10 wt%, or at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or 5 wt% to 80 wt%, or 5 wt% to 30 wt%, or 10 wt% to 50 wt%, or 25 wt% to 75 wt%, or 40 wt% to 80 wt% of the propylene/C4+ olefin stream 108.
  • C6 olefins may be present in the propylene/C4+ olefin stream 108 in an amount of at least 5 wt%, at least 10 wt%, or at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or 5 wt% to 80 wt%, or 5 wt% to 30 wt%, or 10 wt% to 50 wt%, or 25 wt% to 75 wt%, or 40 wt% to 80 wt% of the propylene/C4+ olefin stream 108.
  • the propylene/C4+ olefin stream 108 may comprise propylene, at least 5 wt% C4 olefins, at least 40 wt% C5 olefins, and at least 10 wt% C6 olefins.
  • the propyl ene/C4+ olefin stream 108 may comprise propylene, at least 20 wt% C4 olefins, at least 40 wt% C5 olefins, and at least 10 wt% C6 olefins.
  • the propyl ene/C4+ olefin stream 108 may comprise propylene, at least 40 wt% C4 olefins, at least 40 wt% C5 olefins, and at least 10 wt% C6 olefins.
  • the propyl ene/C4+ olefin stream 108 may be from any suitable source including, but not limited to, C4+ byproducts derived from a propane dehydrogenation reactor, a butane dehydrogenation reactor, a steam cracker, a fluidized catalytic cracker (FCC), a catalytic conversion reaction of methanol typically called “Methanol To Olefins” (MTO), the like, and any combinations of sources.
  • the second oligomerization 110 may occur in an oligomerization unit, which may comprise a fixed bed adiabatic reactor housing (or otherwise containing) the oligomerization catalyst or an isothermal tubular reactor housing (or otherwise containing) the oligomerization catalyst.
  • oligomerization catalysts that may be used in the second oligomerization 110 may include, but are not limited to, the zeolite families respectively comprising, MWW family (e.g., MCM-22), *BEA family (e.g., zeolite beta ), FAU catalyst, MTW family (e.g., ZSM-12), TON family (e.g., ZSM-22), MTT family (e.g., ZSM-23), *MRE family (e.g., ZSM-48), MFS family (e.g., ZSM-57), SAPO molecular sieves, the like, and any mixture thereof.
  • MWW family e.g., MCM-22
  • *BEA family e.g., zeolite beta
  • FAU catalyst e.g., zeolite beta
  • MTW family e.g., ZSM-12
  • TON family e.g., ZSM-22
  • MTT family e.g., ZSM-23
  • the second oligomerization unit or a unit between the second oligomerization unit and the hydroprocessing unit may remove at least one light olefin (e.g., C3-C9 olefins, or C3 to C6 olefins, or C3 to C8 olefins) stream from the isoolefinic stream 112. Said light olefins may be recycled back as a portion of the feed to the oligomerization unit along with the propylene/C4+ olefin stream 108 and the C4+ olefin stream 106.
  • at least one light olefin e.g., C3-C9 olefins, or C3 to C6 olefins, or C3 to C8 olefins
  • the isoolefinic stream 112 may contain predominantly C6+ olefins (or C8+ olefins, or C9+ olefins).
  • the isoolefinic stream 112 may contain at least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99 wt%, or 50 wt% to 80 wt%, or 60wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) C6+ olefins (e.g., C6 to C20 olefins) with no greater than 20 wt% C5- olefins (or no greater than 10 wt% C5- olefins, or no greater than 5 wt% C5- o
  • the isoolefinic stream 112 may contain at least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99 wt%, or 50 wt% to 80 wt%, or 60wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) C9+ olefins (e.g., C9 to C20 olefins) with no greater than 20 wt% C8- olefins (or no greater than 10 wt% C8- olefins, or no greater than 5 wt% C8- olefins).
  • C9+ olefins e.g., C9 to C20 olefins
  • At least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99 wt%, or 50 wt% to 80 wt%, or 60wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) of the olefins in the isoolefinic stream 112 may be isoolefinic.
  • 80 wt% or more of the isoolefinic stream 112, or 90 wt% or more, or 94 wt% or more, or 97 wt% or more, may be composed of C9 to C20 isoolefins.
  • 2.0 wt% to 25 wt% of the isoolefinic stream 112 may be composed of C9 olefins (e.g., C9 isoolefins), or 2.0 wt% to 15 wt%, or 5.0 wt% to 25 wt%, or 5.0 wt% to 15 wt%, or 2.0 wt% to 10 wt%.
  • 1.0 wt% to 15 wt% of the isoolefinic stream 112 may be composed of C17+ olefins (e.g., C17+ isoolefins), or 2.5 wt% to 15 wt%.
  • 1.0 wt% to 15 wt% of the isoolefinic stream 112 may be composed of C17 and/or C18 olefins (e.g., C17 and/or C18 isoolefins), or 2.5 wt% to 15 wt%, or 1.0 wt% to 10 wt%, or 2.5 wt% to 10 wt%.
  • the isoolefinic stream 112 may contain 5.0 wt% or less of C19+ olefins (e.g., C19+ isoolefins), or 3.0 wt% or less, or 1.0 wt% or less, such as down to having substantially no content of Cl 9+ hydrocarbons. Further, the isoolefinic stream 112 may include 5.0 wt% or less of C8- olefins, or 3.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less, such as down to 0.1 wt% or possibly still lower (i.e., substantially no C8- olefins).
  • C19+ olefins e.g., C19+ isoolefins
  • 1.0 wt% or less such as down to having substantially no content of Cl 9+ hydrocarbons.
  • the isoolefinic stream 112 may include 5.0 wt% or less of
  • the isoolefinic stream 112 can contain 60 wt% to 90 wt% of Cl 1 to C18 olefins (e.g., Cl l to C18 isoolefins). Additionally or alternately, the isoolefinic stream 112 may contain 50 wt% to 75 wt% of C12 to C16 olefins (e.g., C12 to C16 isoolefins). This is particularly advantageous for being suitable for further processing (e.g., hydroprocessing) where the resultant product is flexible for use as an aviation or diesel fuel.
  • the isoolefinic stream 112 may contain a reduced or minimized amount of aromatics. This can correspond to containing 5.0 wt% or less of aromatics, or 3.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less, or 0.1 wt% or less, such as down to having substantially no aromatics content.
  • the composition of the isoolefinic stream 112, or a portion or fraction thereof, may be a suitable product for use in a variety of applications or suitable for further processing to suitable product for use in a variety of applications.
  • the isoolefinic stream 112 may be suitable for further processing to produce a blend composition (e.g., jet fuel blend stock, diesel fuel blend stock, distillate blend stock, kerosene blend stock, and the like), specialty chemicals (e.g., surfactants, lubricants, solvents, hydraulic and other working fluids, and the like), and the like.
  • a blend composition e.g., jet fuel blend stock, diesel fuel blend stock, distillate blend stock, kerosene blend stock, and the like
  • specialty chemicals e.g., surfactants, lubricants, solvents, hydraulic and other working fluids, and the like
  • a portion or all of the isoolefinic stream 112 may be further subjected to hydroprocessing 114 to create the isoparaffinic stream 116 (preferably having no greater than 10 wt% olefin content).
  • Mild hydroprocessing can generally convert iso-olefins to isoparaffins with a reduced or minimized amount of reduction in the size of the carbon chains in a fraction.
  • hydroprocessing of a kerosene fraction can also be used to remove sulfur, remove nitrogen, saturate olefins, saturate aromatics, and/or for other purposes.
  • a feedstock that is partially or entirely composed of a jet fuel boiling range fraction is treated in a hydrotreatment (or other hydroprocessing) reactor that includes one or more hydrotreatment stages or beds.
  • the reaction conditions in the hydrotreatment stage(s) can be conditions suitable for reducing the sulfur content of the feedstream, such as conditions suitable for reducing the sulfur content of the feedstream to 500 wppm or less, or 100 wppm or less, or 10 wppm or less, such as down to 0.5 wppm or possibly still lower.
  • the reaction conditions can include an LHSV of 0.1 to 20.0 hr' 1 , a hydrogen partial pressure from about 50 psig (0.34 MPag) to about 3000 psig (20.7 MPag), a treat gas containing at least about 50% hydrogen, and a temperature of from about 450°F (232°C) to about 800°F (427°C).
  • the reaction conditions include an LHSV of from about 0.3 to about 5 hr' 1 , a hydrogen partial pressure from about 100 psig (0.69 MPag) to about 1000 psig (6.9 MPag), and a temperature of from about 700°F (371°C) to about 750°F (399°C).
  • a hydrotreatment reactor can be used that operates at a relatively low total pressure values, such as total pressures of about 200 psig (1.4 MPag) to about 800 psig (5.5 MPag).
  • the pressure in a stage in the hydrotreatment reactor can be at least about 200 psig (1.4 MPag), or at least about 300 psig (2.1 MPag), or at least about 400 psig (2.8 MPag), or at least about 450 psig (3.1 MPag).
  • the pressure in a stage in the hydrotreatment reactor can be about 800 psig (5.5 MPag) or less, or about 700 psig (4.8 MPag) or less, or about 600 psig (4.1 MPag) or less.
  • the catalyst in a hydrotreatment stage can be a conventional hydrotreating catalyst, such as a catalyst composed of a Group VIB metal and/or a Group VIII metal on a support.
  • Suitable metals include cobalt, nickel, molybdenum, tungsten, or combinations thereof.
  • Preferred combinations of metals include nickel and molybdenum or nickel, cobalt, and molybdenum.
  • Suitable supports include silica, silica-alumina, alumina, and titania.
  • the isoparaffinic stream 116 resulting from hydroprocessing 114 may be suitable for creating blend compositions (e.g., jet fuel blend stock, diesel fuel blend stock, distillate blend stock, kerosene blend stock, and the like).
  • blend compositions e.g., jet fuel blend stock, diesel fuel blend stock, distillate blend stock, kerosene blend stock, and the like.
  • the isoolefinic stream 112 and the resultant isoparaffinic stream 116 may have a low aromatic content, which may be advantageous for producing low aromatic content fuels (e.g. jet fuels, jet fuel blend stocks).
  • the isoparaffinic stream 116 may have a similar carbon number distribution to the isoolefinic stream 112 but as paraffins rather than olefins. Therefore, the isoparaffinic stream 116 may contain predominantly C6+ isoparaffins (or C8+ isoparaffins, or C9+ isoparaffins).
  • the isoparaffinic stream 116 may contain at least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or 50 wt% to 99 wt%, or 50 wt% to 80 wt%, or 60wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) C6+ paraffins (e.g., C6 to C20 paraffins) with no greater than 20 wt% C5- paraffins (or no greater than 10 wt% C5- paraffins, or no greater than 5 wt% C5- paraffins).
  • C6+ paraffins e.g., C6 to C20 paraffins
  • 80 wt% or more of the isoparaffinic stream 116 may be composed of C9 to C20 isoparaffins.
  • 2.0 wt% to 25 wt% of the isoparaffinic stream 116 may be composed of C9 paraffins (e.g., C9 isoparaffins), or 2.0 wt% to 15 wt%, or 5.0 wt% to 25 wt%, or 5.0 wt% to 15 wt%, or 2.0 wt% to 10 wt%.
  • 1.0 wt% to 15 wt% of the isoparaffinic stream 116 may be composed ofC17+ paraffins (e.g., C17+ isoparaffins), or 2.5 wt% to 15 wt%. In some aspects, 1.0 wt% to 15 wt% of the isoparaffinic stream 116 may be composed of C17 and/or C18 paraffins (e.g., C17 and/or C18 isoparaffins), or 2.5 wt% to 15 wt%, or 1.0 wt% to 10 wt%, or 2.5 wt% to 10 wt%.
  • the isoparaffinic stream 116 may contain 5.0 wt% or less of Cl 9+ paraffins (e.g., Cl 9+ isoparaffins), or 3.0 wt% or less, or 1.0 wt% or less, such as down to having substantially no content of Cl 9+ hydrocarbons. Further, the isoparaffinic stream 116 may include 5.0 wt% or less of C8- paraffins, or 3.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less, such as down to 0.1 wt% or possibly still lower (i.e., substantially no C8- paraffins).
  • Cl 9+ paraffins e.g., Cl 9+ isoparaffins
  • the isoparaffinic stream 116 may include 5.0 wt% or less of C8- paraffins, or 3.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less, such as down to 0.1 w
  • the isoparaffinic stream 116 can contain 60 wt% to 90 wt% of Cl l to C18 paraffins (e.g., Cl l to C18 isoparaffins). Additionally or alternately, the isoparaffinic stream 116 may contain 50 wt% to 75 wt% of C12 to C16 paraffins (e.g., C12 to C16 isoparaffins). This is particularly advantageous for being suitable for further processing (e.g., hydroprocessing) where the resultant product is flexible for use as an aviation or diesel fuel.
  • the isoparaffinic stream 116 may contain a reduced or minimized amount of aromatics. This can correspond to containing 5.0 wt% or less of aromatics, or 3.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less, or 0.1 wt% or less, such as down to having substantially no aromatics content.
  • FIG. 1 provides nonlimiting examples of sources for the ethylene stream 102 and the propyl ene/C4+ olefin stream 108, FIG. 1 does not illustrate said sources.
  • FIG. 2 illustrates a nonlimiting example that includes a process for converting an oxygenate to olefin then separating of the olefin product to yield potential sources for both the ethylene stream and the propylene/C4+ olefin stream.
  • FIG. 2 illustrates a nonlimiting example method 200 of the present disclosure showing an oxygenate to olefin reaction 220, followed by separation 226 of the product from the oxygenate to olefin process 220, a first oligomerization 204, and a second oligomerization 210.
  • an oxygenate stream 218 e.g., comprising methanol and, optionally, dimethyl ether
  • the raw olefin stream 224 then undergoes separation 226 into an ethylene stream 202 and a propylene/C4+ olefin stream 208.
  • the ethylene stream 202 then undergoes a first oligomerization 204 to yield a C4+ olefin stream 206.
  • the propylene/C4+ olefin stream 208 and C4+ olefin stream 206 may then be used in a variety of applications.
  • the propylene/C4+ olefin stream 208 and C4+ olefin stream 206 are inputs for a second oligomerization 210 to produce an isoolefinic stream 212.
  • the second oligomerization may be excluded, and the propylene/C4+ olefin stream 208 and C4+ olefin stream 206 may be used as feeds for other processes.
  • the oxygenate stream 218 may be from any suitable source.
  • the oxygenate e.g., methanol
  • the oxygenate may be produced from reforming natural gas, reforming coal, reforming municipal waste, reforming biomass, fermenting biomass, electrolyzing water to produce hydrogen for reaction with carbon monoxide and/or carbon dioxide, and the like, and any combination thereof.
  • electrolyzing water produces hydrogen and oxygen.
  • the hydrogen may then be reacted with carbon monoxide and/or carbon dioxide to produce methanol.
  • Examples of methanol conversion catalysts that may be utilized in the oxygenate to olefin reaction 220 may include, but are not limited to, microporous materials, such as zeolites, SAPOs and ALPO materials.
  • Such materials may include, but are not limited to, the zeolite families respectively comprising, MWW family (e.g., MCM-22), *BEA family (e.g., zeolite beta ), ZSM- 11, (MEL) family (e.g., ZSM-12), TON family (e.g., ZSM-22), MTT family (e.g., ZSM-23), *MRE family (e.g., ZSM-48), MFS family (e.g., ZSM-57), ZSM-5 (MFI), ALPO-18 (AEI) and S APO-34 (CHA) or their mixtures (including intergrowths).
  • MCM-22 e.g., MCM-22
  • *BEA family e.g., zeolite beta
  • Contact of the oxygenate stream 218 with the methanol conversion catalyst may be under conditions suitable for producing olefins.
  • the inlet temperature may be about 300°C to about 625°C (or about 400°C to about 600°C, or about 450°C to about 550°C).
  • the pressure may be about 20 psia to about 300 psia (or about 30 psia to about 250 psia, or about 50 psia to about 150 psia).
  • the oxygenate to olefin reaction 220 may occur in a fixed bed adiabatic reactor that houses (or otherwise containing) the methanol conversion catalyst and accepts an input of a oxygenate stream 218.
  • a resulting raw olefin stream 224 may comprise ethylene, propylene, and C4+ olefins, wherein at least 10 wt% of all olefins in the stream may be ethylene.
  • the raw olefin stream 224 may further comprise at least 1000 wppm each of methane and ethane, and at least 100 wppm each of carbon monoxide and hydrogen.
  • the raw olefin stream 224 may include other components within the volatility range from hydrogen to butanes, such as propane or dimethyl ether. The exact composition of the raw olefin stream 224 will depend on the specific method of producing the raw olefin stream 224, and further on the specific means of operating those methods.
  • the raw olefin stream 224 may have been treated (e.g., in a unit in which the oxygenate to olefin reaction 220 occurs or downstream thereof) by various methods to remove some of the byproducts generated by a given method of producing olefins. Such methods and related systems may be employed on the raw olefin stream 224 within the scope of the present disclosure, but are not shown in FIG. 2.
  • Examples of such methods may include, but are not limited to, reactor effluent quenching and bulk water removal, gas compression, washing with a caustic solution to remove carbon dioxide, gas drying to bone dry, separation of C5+ species from C4 species, or selective saturation with hydrogen to remove acetylene and methylacetylene, among others well documented in the art.
  • the present disclosure may be readily adapted by one skilled in the art to use the raw olefin stream 224 derived from a wide range of olefin production processes. It may also be useful to combine olefin streams from different sources or processes.
  • ethylene derived from an ethanol dehydration reaction may be combined with hydrogen, CO, propylene, unreacted propane and C4+ byproducts derived from a propane dehydrogenation reaction to create the raw olefin stream 224.
  • the raw olefin stream 224 then undergoes separation 226 to produce the ethylene stream 202 and the propyl ene/C4+ olefin stream 208.
  • the separation 226 may occur in a separation system. Examples of separation apparatuses that may be included in the separation system may include, but are not limited to, fractionators, membranes, the like, and any combination thereof.
  • the separation 226 may occur in the same unit as the oxygenate to olefin reaction 220 or in a downstream unit.
  • the separation 226 involves differences in component volatility using equipment such as flash drums and distillation columns, which may be configured in a number of ways to create an ethylene stream 202 that exits the separation 226. From the raw olefin stream 224, hydrogen, carbon monoxide, propylene, and C4+ olefins may be separated out to produce the ethylene stream 202.
  • the ethylene stream 202 may contain at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 20 wppm each of carbon monoxide and hydrogen (or (i) at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 5 wppm each of carbon monoxide and hydrogen, or (ii) at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 1 wppm each of carbon monoxide and hydrogen), and at least 95 wt% of all the ethylene in the raw olefin stream 224 may be recovered in the ethylene stream 202.
  • the ethylene stream 202 may also contain at least 90% of the ethane present in the raw olefin stream 224.
  • Separation 226 creates a separate line for the lower volatility components separated from the ethylene and ethane in the ethylene stream 202, such as propylene and C4+ olefins, which exits the separation as propylene/C4+ olefin stream 208.
  • the separation process may also include membrane and absorption systems instead of or in addition to distillation towers.
  • the compositional description of ethylene stream 102 of FIG. 1 applies to the ethylene stream 202 of FIG. 2.
  • FIG. 2 illustrates the propylene/C4+ olefin stream 208 after the separation 226 as a single stream, but the propylene/C4+ olefin stream 208 may be two separate streams (e.g., a first stream comprising relatively pure propylene and a second stream comprising relatively pure C4+ olefin).
  • This additional separation may be performed with additional distillation columns, and may include separation of propylene from propane and components of similar or lower volatility like dimethyl ether.
  • This process is particularly useful if the source of olefins is oxygenate conversion that can make significant amounts of dimethyl ether, or catalytic cracking that can make significant amounts of propane, both of which are not particularly desirable to provide to the optional second oligomerization 210.
  • FIG. 1 The disclosure of FIG. 1 for the ethylene stream 102, the first oligomerization 104, the C4+ olefin stream 106, the propylene/C4+ olefin stream 108, the second oligomerization 110, and isoolefinic stream 112 apply to the ethylene stream 202, the first oligomerization 204, the C4+ olefin stream 206, the propyl ene/C4+ olefin stream 208, the second oligomerization 210, and isoolefinic stream 212 of FIG. 2. Further, embodiments may include further processing isoolefinic stream 212 as discussed relative to the further processing of isoolefinic stream 112 including hydroprocessing to produce an isoparaffinic stream.
  • FIG. 3 illustrates a nonlimiting example of a method 300 of the present disclosure where a nonlimiting example separation 326 is described.
  • the disclosure relating to steps, streams, processes, units, etc. with reference numbers with the final two numbers corresponding to a foregoing reference number in FIG. 1 and/or FIG. 2 e.g., propylene/C4+ olefin stream 108) applies to the corresponding steps, streams, processes, units, etc. having reference numbers with the same final two numbers in FIG. 3 (e.g., propyl ene/C4+ olefin stream 308).
  • the separation 326 illustrated in FIG. 3 is a nonlimiting example of a separation and is one of many possible separations that may be used in separations shown in any of the other FIGS, in the present disclosure.
  • a raw olefin stream 324 undergoes separation 326 to remove hydrogen, carbon monoxide, propylene and C4+ olefins from the ethylene and ethane.
  • the separation 326 creates three separate streams where (1) the higher volatility components (e.g., methane, hydrogen, and carbon monoxide) form a high volatility stream 334, (2) the lower volatility components (e.g., propylene and C4+ olefins) form a propylene/C4+ olefin stream 308, and (3) the intermediate volatility components (e.g., ethylene and ethane) form the ethylene stream 302.
  • the higher volatility components e.g., methane, hydrogen, and carbon monoxide
  • the lower volatility components e.g., propylene and C4+ olefins
  • the intermediate volatility components e.g., ethylene and ethane
  • the raw olefin stream 324 is first introduced to a demethanizer distillation column 328 that separates the lower volatility components (e.g., propylene and C4+ olefins) from the higher and intermediate volatility components (e.g., ethylene, ethane, methane, carbon monoxide, and hydrogen) to yield the propylene/C4+ olefin stream 308 and a first overhead stream 330, respectively.
  • the first overhead stream 330 is then directed to a demethanizer distillation column 332 to separate the higher volatility components from the intermediate volatility components to yield the high volatility stream 334 and the ethylene stream 302.
  • the ethylene stream 302 may contain at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 20 wppm each of carbon monoxide and hydrogen (or (i) at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 5 wppm each of carbon monoxide and hydrogen, or (ii) at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 1 wppm each of carbon monoxide and hydrogen), and at least 95 wt% of all the ethylene in the raw olefin stream 324 may be recovered in the ethylene stream 302.
  • the ethylene stream 302 may also contain at least 90% of the ethane present in the raw olefin stream in line 324, which eliminates the need for a distillation column serving to separate ethylene from ethane (known in the art as a “C2 Splitter”).
  • the ethylene stream 302 then undergoes a first oligomerization 304, which produces a C4+ olefin stream 306.
  • the C4+ olefin stream 306 and the propylene/C4+ olefin stream 308 are then used as feed in the second oligomerization 310.
  • the C4+ olefin stream 306 combines with the propylene/C4+ olefin stream 308 into a feed stream 338, which enters the second oligomerization 310.
  • the second oligomerization 310 generates the desired isoolefinic stream 312.
  • embodiments may include further processing isoolefinic stream 312 as discussed relative to the further processing of isoolefinic stream 112 including hydroprocessing to produce an isoparaffinic stream.
  • FIG. 4 illustrates a nonlimiting example of a method 400 of the present disclosure where a nonlimiting example first oligomerization 404 is described.
  • the disclosure relating to steps, streams, processes, units, etc. with reference numbers with the final two numbers corresponding to a foregoing reference number in FIG. 1, FIG. 2, and/or FIG. 3 (e.g., propyl ene/C4+ olefin stream 108) applies to the corresponding steps, streams, processes, units, etc. having reference numbers with the same final two numbers in FIG. 3 (e.g., propylene/C4+ olefin stream 308).
  • the first oligomerization 404 illustrated in FIG. 4 is a nonlimiting example of a separation and is one of many possible separations that may be used in separations shown in any of the other FIGS, in the present disclosure.
  • the raw olefin stream 424 undergoes a separation 426 to create at least two streams: an ethylene stream 402 and a propylene/C4+ olefin stream 408, and, optionally, a high volatility stream 434 (for example, when the separation 426 occurs according to the separation 326 of FIG. 3).
  • the ethylene stream 402 then undergoes a first oligomerization 404, which may convert at least 95% of the ethylene present in the ethylene stream 402 to a C4+ olefin stream 406.
  • the C4+ olefin stream 406 may contain no greater than 10 wt% of methane, ethylene, and ethane combined (or (i) no greater than 5 wt% of methane, ethylene, and ethane combined, or (ii) no greater than 2000 wppm of methane, ethylene, and ethane combined, or (iii) no greater than 1000 wppm of methane, ethylene, and ethane combined, or (iv) at least 10 wppm and no greater than 10 wt% (or 2000 wppm, or 1000 wppm) of methane, ethylene, and ethane combined).
  • the C4+ olefin stream 406 and the propyl ene/C4+ olefin stream 408 then undergo a second oligomerization 410. While optional, as illustrated, said streams 406 and 408 are combined into feed stream 438 before the second oligomerization 410 to yield an isoolefinic stream 412. Further, embodiments may include further processing isoolefinic stream 412 as discussed relative to the further processing of isoolefinic stream 112 including hydroprocessing to produce an isoparaffinic stream.
  • the process of the first oligomerization 404 may include introducing the ethylene stream 402 into a reactor 442 where an oligomerization reaction of the ethylene stream 402 to an intermediate C4+ olefin stream 444 occurs. Said oligomerization may convert at least 95% of that ethylene in the ethylene stream 402 to C4+ oligomers in one pass through the reactor 442.
  • a first oligomerization unit may include two or more reactors arranged in series, with the hydrocarbon product from one reactor, including some product oligomers and unreacted ethylene, sent as feed to the next reactor in series to convert additional ethylene to the oligomer product.
  • a first oligomerization unit may include two or more reactors arranged in parallel, for example splitting the feed into two streams to two separate reactors, increase the overall capacity of first oligomerization unit.
  • a hybrid of the foregoing with some reactors arranged in parallel and others in series may be included in a first oligomerization unit.
  • the intermediate C4+ olefin stream 444 from the reactor 442 is then introduced to a lights removal column 446 to remove components with volatility higher than butenes, and potentially a minor amount of butenes as well, to generate a light fuel gas stream 436.
  • the higher volatility components in the light fuel gas stream 436 may include mainly methane, ethane, and unreacted ethylene.
  • the separation of saturated hydrocarbons like methane and ethane from the intermediate C4+ olefin stream 444 using the lights removal column 446 may advantageously be less energy intensive and/or require less complicated components than if the saturated hydrocarbons were separated from closer volatility ethylene in the earlier separation 426.
  • the upstream separation may produce only two streams where the higher volatility components remain present in the ethylene stream.
  • said higher volatility components may be removed at the first oligomerization by inclusion of a lights removal column downstream of the oligomerization reactor. Said lights removal column may be within the first oligomerization unit or downstream thereof.
  • Another advantage of including a lights removal column downstream of the reactor 442 is that the first oligomerization reaction and first oligomerization catalyst may be largely unaffected by the saturated hydrocarbons, as the saturated hydrocarbons are essentially inert in the first oligomerization reaction. Therefore, the requirements for separating the saturated hydrocarbons in separation 426 can be relaxed or eliminated, which has significant energy use benefits and cost benefits.
  • FIG. 5 illustrates a nonlimiting example of a method 500 of the present disclosure where a nonlimiting example second oligomerization 510 is described.
  • the disclosure relating to steps, streams, processes, units, etc. with reference numbers with the final two numbers corresponding to a foregoing reference number in FIG. 1, FIG. 2, FIG. 3, and/or FIG. 4 e.g., propylene/C4+ olefin stream 108) applies to the corresponding steps, streams, processes, units, etc. having reference numbers with the same final two numbers in FIG. 3 (e.g., propylene/C4+ olefin stream 308).
  • the second oligomerization 510 illustrated in FIG. 5 is a nonlimiting example of a separation and is one of many possible separations that may be used in separations shown in any of the other FIGS, in the present disclosure.
  • a raw olefin stream 524 enters a separation 526, which produces an ethylene stream 502, and a propylene/C4+ olefin stream 508, and, optionally, a high volatility stream 534 (for example, when the separation 526 occurs according to the separation 326 of FIG. 3).
  • the ethylene stream 502 undergoes a first oligomerization 504 and separation, which produces a C4+ olefin stream 506 and, optionally, a light fuel gas stream 436 (for example, when a lights removal column is used, the first oligomerization 504 may occur according to the first oligomerization 404 of FIG. 4).
  • the C4+ olefin stream 506 and the propylene/C4+ olefin stream 508 then undergo a second oligomerization 510. While optional, as illustrated, said streams 506 and 508 are combined into feed stream 538 before the second oligomerization 510 to yield an isoolefinic stream 512.
  • the second oligomerization 510 is illustrated as being conducted in a second oligomerization unit that comprises a reactor 552, a mogas/di still ate fractionation column 556, and a debutanizer fractionation column 562.
  • the feed stream 538 joins with a top recycle stream 568 and a bottom recycle stream 566 to form a combined second oligomerization reactor feed stream 550 comprising C4-C10+ olefins that may contain no greater than about 10 wt% C10+ olefins.
  • Combined feed stream 550 is provided to reactor 552 that generates a reactor product 554 rich in distillate range C10+ olefins (e.g., C10+ isoolefins), along with unreacted and newly made C4 - C9 olefins of various isomers.
  • the C4- purge stream 540 is removed from second oligomerization unit 510 while the C5+ second mogas stream 564 is split into two streams, typically with the majority becoming the bottom recycle stream 566 and the rest becoming a mogas product purge stream 548 that is also removed from second oligomerization unit 510.
  • the propylene/C4+ olefin stream 508 and the C4+ olefin stream 506 may be separately introduced to the reactor 552. In variations within the scope of the present disclosure, depending on the exact compositions involved, including olefins and potential small concentration contaminants, it may be desirable to provide each of the streams 506 and 508 to separate points within second oligomerization unit.
  • the C4+ olefin stream 508 may contain up to 15 wt% or even greater of C10+ olefins that are already in the distillate range.
  • the propylene/C4+ olefin stream 508 can be a feed gas for reactor 552 and the C4+ olefin stream 506 can be added directly to the mogas/distillate fractionation column 556.
  • the mogas/distillate fractionation column 556 will separate the C10+ molecules in the C4+ olefin stream 506 directly into the isoolefin stream 512, and separate the lower carbon number molecules in the C4+ olefin stream 506 into the mogas range material 558, the great majority of which will become a recycle feed to the reactor 552 to produce additional isoolefin stream 512.
  • embodiments may include further processing isoolefinic stream 512 as discussed relative to the further processing of isoolefinic stream 112 including hydroprocessing to produce an isoparaffinic stream.
  • an isoparaffmic blend component e.g., all or a portion of an isoparaffmic stream discussed in FIGS. 1-5
  • isoolefinic blend component e.g., all or a portion of an isoolefinic stream discussed in FIGS. 1-5
  • a fraction will contain 50 wt% or more of a combined weight of isoparaffins and iso-olefins, or 60 wt% or more, or 70 wt% or more, or 80 wt% or more, such as up to the fraction substantially being composed of isoparaffins and iso-olefins (i.e., less than 5.0 wt% of other types of hydrocarbons / compounds, or less than 3.0 wt%, or less than 1.0 wt%, such as down to zero).
  • an isoparaffmic blend component refers to a fraction containing less than 5.0 wt% iso-olefins and 80 wt% or more of isoparaffins (relative to the weight of the fraction), or 85 wt% or more, or 90 wt% or more, such as up to having substantially all of the fraction correspond to isoparaffins.
  • An isoolefinic blend component refers to a fraction that a) satisfies the requirement for the combined amount of iso-olefins and isoparaffins, and b) contains 5.0 wt% or more of iso-olefins, or 25 wt% or more, or 50 wt% or more, or 70 wt% or more, such as up to having substantially all of the fraction correspond to iso-olefins.
  • an isoparaffinic blend component and/or an isoolefinic blend component can have one or more of the following properties.
  • 80 wt% or more of the blend component, or 90 wt% or more, or 94 wt% or more, or 97 wt% or more is composed of Cg to C20 iso-olefins, isoparaffins, or a combination thereof.
  • 2.0 wt% to 25 wt% of the blend component is composed of C9 hydrocarbons, or 2.0 wt% to 15 wt%, or 5.0 wt% to 25 wt%, or 5.0 wt% to 15 wt%, or 2.0 wt% to 10 wt%.
  • 1.0 wt% to 15 wt% of the blend component is composed of C17+ hydrocarbons, or 2.5 wt% to 15 wt%.
  • 1.0 wt% to 15 wt% of the blend component is composed of C17 and/or Cis hydrocarbons, or 2.5 wt% to 15 wt%, or 1.0 wt% to 10 wt%, or 2.5 wt% to 10 wt%.
  • the blend component can contain 5.0 wt% or less of C19+ hydrocarbons, or 3.0 wt% or less, or 1.0 wt% or less, such as down to having substantially no content of C19+ hydrocarbons.
  • the blend component can include 5.0 wt% or less of Cs- hydrocarbons, or 3.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less, such as down to 0.1 wt% or possibly still lower (i.e., substantially no Cs- content).
  • the blend component has a specific gravity at 15°C of 0.730 g/cm 3 to 0.775 g/cm 3 .
  • the blend component can contain 60 wt% to 90 wt% of Cn to Cis isoparaffins, iso-olefins, or a combination thereof, based on the weight of the blend component. Additionally or alternately, the blend component can contain 50 wt% to 75 wt% of Cn to Ci6 isoparaffins, iso-olefins, or a combination thereof based on the weight of the blend component. Having high amounts of larger isoparaffins can be beneficial for diesel fuel and/or diesel fuel blend component applications. Having higher amounts of larger isoparaffins / iso-olefins can be beneficial for marine fuel or marine fuel blend component applications.
  • the blend component can have a kinematic viscosity at 40°C of 1.9 cSt to 3.0 cSt, or 2.0 cSt to 3.0 cSt, or 2.2 cSt to 3.0 cSt, or 1.9 cSt to 2.8 cSt, or 2.0 cSt to 2.8 cSt, or 2.2 cSt to 2.8 cSt. Still further additionally or alternately, the blend component can have a cloud point of -50°C or less, or -60°C or less, such as down to -100°C or possibly still lower.
  • An isoparaffinic blend component and/or isoolefinic blend component can be blended with one or more other fractions to form a diesel boiling range product.
  • fractions that can be blended with an isoparaffinic blend component and/or isoolefinic blend component include, but are not limited to, conventional diesel fractions, mineral diesel boiling range fractions, and various types of synthetic diesel boiling range fractions, such as hydrotreated vegetable oil, biodiesel (e.g., derived from processing of fatty acid methyl esters), other bio-derived diesel fractions, and/or Fischer-Tropsch fractions.
  • Other challenged fractions where at least a portion of the fraction corresponds to diesel boiling range components can also be blended with an isoparaffinic blend component and/or isoolefinic blend component.
  • a blended product can contain 1.0 vol% or more of an isoparaffinic blend component, or 10 vol% or more, or 20 vol% or more, or 30 vol% or more, or 40 vol% or more, or 60 vol% or more, or 75 vol% or more, such as up to 99 vol% or possibly still higher.
  • such a blended product can include 1.0 vol% to 50 vol% of an isoparaffinic blend component, or 1.0 vol% to 10 vol%, or 1.0 vol% to 30 vol%, or 10 vol% to 50 vol%, or 10 vol% to 30 vol%, or 30 vol% to 50 vol%.
  • such a blended product can include 1.0 vol% to 99 vol% of an isoparaffinic blend component, or 1.0 vol% to 95 vol%, or 1.0 vol% to 70 vol%, or 1.0 vol% to 50 vol%, or 10 vol% to 99 vol%, or 10 vol% to 95 vol%, or 10 vol% to 70 vol%, or 10 vol% to 50 vol%, or 30 vol% to 99 vol%, or 30 vol% to 95 vol%, or 30 vol% to 70 vol%, or 30 vol% to 50 vol%, or 50 vol% to 99 vol%, or 50 vol% to 95 vol%, or 50 vol% to 70 vol%, or 70 vol% to 99 vol%.
  • a blended product can contain 1.0 vol% or more of an isoparaffinic blend component, or 10 vol% or more, or 20 vol% or more, or 30 vol% or more, or 40 vol% or more, or 60 vol% or more, or 75 vol% or more, such as up to 99 vol% or possibly still higher.
  • such a blended product can include 1.0 vol% to 50 vol% of an isoparaffinic blend component, or 1.0 vol% to 10 vol%, or 1.0 vol% to 30 vol%, or 10 vol% to 50 vol%, or 10 vol% to 30 vol%, or 30 vol% to 50 vol%.
  • such a blended product can include 1.0 vol% to 99 vol% of an isoparaffinic blend component, or 1.0 vol% to 95 vol%, or 1.0 vol% to 70 vol%, or 1.0 vol% to 50 vol%, or 10 vol% to 99 vol%, or 10 vol% to 95 vol%, or 10 vol% to 70 vol%, or 10 vol% to 50 vol%, or 30 vol% to 99 vol%, or 30 vol% to 95 vol%, or 30 vol% to 70 vol%, or 30 vol% to 50 vol%, or 50 vol% to 99 vol%, or 50 vol% to 95 vol%, or 50 vol% to 70 vol%, or 70 vol% to 99 vol %.
  • the resulting blended product can include an unexpectedly high content of C12- isoparaffins and/or iso-olefins.
  • the resulting blended product can contain 6.0 wt% or more of C12- isoparaffins and/or iso-olefins, or 10 wt% or more, or 15 wt% or more, 20 wt% or more, such as up to 40 wt% or possibly still higher.
  • the resulting blended product can include an unexpectedly high content of C12 isoparaffins and/or iso-olefins.
  • the resulting blended product can have a density at 15°C of 0.760 g/cm 3 to 0.840 g/cm 3 .
  • the density at 15°C can be 0.760 g/cm 3 to 0.825 g/cm 3 , or 0.760 g/cm 3 to 0.810 g/cm 3 , or 0.760 g/cm 3 to 0.800 g/cm 3 , or 0.775 g/cm 3 to 0.825 g/cm 3 , or 0.775 g/cm 3 to 0.810 g/cm 3 , or 0.775 g/cm 3 to 0.800 g/cm 3 , or 0.790 g/cm 3 to 0.825 g/cm 3 .
  • the density at 15°C can be 0.790 g/cm 3 to 0.840 g/cm 3 , or 0.800 g/cm 3 to 0.840 g/cm 3 , or 0.815 g/cm 3 to 0.840 g/cm 3 , or 0.790 g/cm 3 to 0.825 g/cm 3 , or 0.800 g/cm 3 to 0.825 g/cm 3 .
  • the cetane number of the resulting blend when an isoparaffinic blend component and/or an isoolefinic blend component is blended with a conventional diesel boiling range fraction and/or a mineral diesel boiling range fraction, the cetane number of the resulting blend can be lower than the cetane number of the conventional diesel boiling range fraction and/or the mineral diesel boiling range fraction.
  • the cetane number of the resulting blend when an isoparaffinic blend component and/or an isoolefinic blend component is blended with a bio-derived diesel boiling range fraction (e,g Berry biodiesel, hydrotreated vegetable oil, diesel derived from fatty acid methyl ester), the cetane number of the resulting blend can be lower than the cetane number of the bio-derived diesel boiling range fraction.
  • the cetane number of the resulting blend can be 54.0 or less, or 53.0 or less, such as down to 52.0, or down to 50.0.
  • an isoparaffinic blend component and/or isoolefinic blend component can have favorable cold flow properties relative to other types of blend components.
  • at least 20 vol% (or at least 40 vol%, or at least 60 vol%, such as up to 80 vol%) of an isoparaffinic blend component and/or isoolefinic blend component is blended with at least 20 vol% (or at least 40 vol%, or at least 60 vol%, such as up to 80 vol%) of conventional / mineral diesel boiling range component
  • the cloud point of the resulting blend can be lower than the cloud point of the conventional / mineral diesel boiling range fraction by 10°C or more, or 15°C or more, or 20°C or more, such as up to 60°C or possibly still more.
  • the cloud point of the resulting blend can be lower than the cloud point of the synthetic diesel boiling range fraction by 10°C or more, or 15°C or more, or 20°C or more, such as up to 60°C lower or possibly still more.
  • the resulting blended product can contain a reduced or minimized amount of aromatics. This can correspond to containing 15 wt% or less of aromatics, or 10 wt% or less, or 5.0 wt% or less, or 3.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less, or 0.1 wt% or less, such as down to having substantially no aromatics content. Additionally or alternately, the sulfur content can be 500 wppm or less, or 250 wppm or less, or 100 wppm or less, or 10 wppm or less, such as down to 0.5 wppm or possibly still lower.
  • diesel fuel boiling range fraction after blending components together to form a diesel fuel boiling range fraction, it may be desirable to further treat the diesel boiling range fraction for any convenient reason, such as by hydroprocessing the diesel fuel boiling range fraction to reduce or remove heteroatoms such as sulfur, nitrogen and oxygen and/or to improve cold flow properties.
  • an isoparaffinic blend component e.g., all or a portion of an isoparaffinic stream discussed in FIGS. 1-5) and/or isoolefinic blend component (e.g., all or a portion of an isool efinic stream discussed in FIGS. 1-5) can be blended with one or more other fractions to form a marine fuel oil product or marine fuel oil blending component, such as a very low sulfur fuel oil (VLSFO) or an ultra low sulfur fuel oil (ULSFO).
  • VLSFO very low sulfur fuel oil
  • ULSFO ultra low sulfur fuel oil
  • an isoparaffinic blend component and/or isoolefinic blend component can be blended with one or more other fractions to a form a marine gas oil product and/or marine gas oil blending component.
  • fractions that can be blended with an isoparaffinic blend component and/or isoolefinic blend component include, but are not limited to, conventional fuel oil fractions (including low sulfur fuel oil, VLSFO, and/or ULSFO), mineral fuel oil fractions, renewable fractions, hydroprocessed and/or non-hydroprocessed fractions, and cracked fractions.
  • hydroprocessed fractions include hydroprocessed distillate fractions (i.e., a hydroprocessed fraction having the distillate boiling range) and hydroprocessed resid fractions (i.e., a hydroprocessed fraction having the resid boiling range). It is noted that a hydroprocessed fraction derived from a biological source, such as hydrotreated vegetable oil, can correspond to a hydroprocessed distillate fraction and/or a hydroprocessed resid fraction, depending on the boiling range of the hydroprocessed fraction.
  • Renewable blending components can correspond to renewable distillate and/or vacuum gas oil and/or vacuum resid boiling range components that are renewable based on one or more attributes. Some renewable blending components can correspond to components that are renewable based on being of biological origin. Examples of renewable blending components of biological origin can include, but are not limited to, fatty acid methyl esters (FAME), fatty acid alkyl esters, biodiesel, biomethanol, biologically derived dimethyl ether, oxymethylene ether, liquid derived from biomass, pyrolysis products from pyrolysis of biomass, products from gasification of biomass, and hydrotreated vegetable oil.
  • FAME fatty acid methyl esters
  • fatty acid alkyl esters biodiesel
  • biomethanol biologically derived dimethyl ether
  • oxymethylene ether liquid derived from biomass
  • pyrolysis products from pyrolysis of biomass products from gasification of biomass
  • hydrotreated vegetable oil hydrotreated vegetable oil.
  • isoparaffinic blend components and/or isoolefinic blend components as described herein may be blended with any of the following and any combination thereof in order to form a fuel and/or fuel blending component: low sulfur diesel (sulfur content of less than 500 wppm), ultra low sulfur diesel (sulfur content ⁇ 10 or ⁇ 15 ppmw), low sulfur gas oil, ultra low sulfur gasoil, low sulfur kerosene, ultra low sulfur kerosene, hydrotreated straight run diesel, hydrotreated straight run gas oil, hydrotreated straight run kerosene, hydrotreated cycle oil, hydrotreated thermally cracked diesel, hydrotreated thermally cracked gas oil, hydrotreated thermally cracked kerosene, hydrotreated coker diesel, hydrotreated coker gas oil, hydrotreated coker kerosene, hydrocracker diesel, hydrocracker gas oil, hydrocracker kerosene, gas-to-liquid diesel, gas-to-liquid kerosene, gas-to-liquid vacuum gas oil, hydrotreated vegetable oil, fatty acid
  • a blended product can contain 1.0 vol% to 50 vol% of an isoparaffinic blend component and/or isoolefinic blend component, or 10 vol% or more to 50 vol%, or 20 vol% to 50 vol%, or 1.0 vol% to 40 vol%, or 10 vol% to 40 vol%, or 20 vol% to 40 vol%, or 1.0 vol% to 30 vol%, or 10 vol% to 30 vol%, or 1.0 vol% to 20 vol%.
  • a blended product can contain 1.0 vol% to 50 vol% of an isoolefinic blend component, or 10 vol% or more to 50 vol%, or 20 vol% to 50 vol%, or 1.0 vol% to 40 vol%, or 10 vol% to 40 vol%, or 20 vol% to 40 vol%, or 1.0 vol% to 30 vol%, or 10 vol% to 30 vol%, or 1.0 vol% to 20 vol%.
  • a blended product can contain 1.0 vol% or more of an isoparaffinic blend component and/or isoolefinic blend component, or 10 vol% or more, or 20 vol% or more, or 30 vol% or more, or 40 vol% or more, or 60 vol% or more, or 75 vol% or more, such as up to 99 vol% or possibly still higher.
  • such a blended product can include 1.0 vol% to 40 vol% of an isoparaffinic blend component and/or isoolefinic blend component, or 1.0 vol% to 20 vol%, or 10 vol% to 40 vol%, or 10 vol% to 20 vol%, or 20 vol% to 40 vol%.
  • such a blended product can include 20 vol% to 80 vol% of an isoparaffinic blend component and/or isoolefinic blend component, or 20 vol% to 60 vol%, or 20 vol% to 40 vol%, or 40 vol% to 80 vol%, or 40 vol% to 60 vol%, or 60 vol% to 80 vol%.
  • the resulting blended product can include an unexpectedly high content of C12- isoparaffins and/or iso-olefins.
  • the resulting blended product can contain 6.0 wt% or more of C12- isoparaffins and/or iso-olefins, or 10 wt% or more, or 15 wt% or more, 20 wt% or more, such as up to 40 wt% or possibly still higher.
  • the resulting blended product can include an unexpectedly high content of C12 isoparaffins and/or iso-olefins.
  • the resulting blended product can include 6.0 wt% or more of C12 isoparaffins and/or iso-olefins, or 10 wt% or more, such as up to 20 wt% or possibly still higher.
  • the resulting blended product can have an unexpectedly high content of C9 hydrocarbons.
  • the resulting blended product can contain 5.0 wt% or more of C9 hydrocarbons, or 10 wt% or more, or 15 wt% or more, such as up to 25 wt% or possibly still higher.
  • the resulting blended product can have a density at 15°C of 0.850 g/cm 3 to 0.980 g/cm 3 , or 0.850 g/cm 3 to 0.950 g/cm 3 , or 0.850 g/cm 3 to 0.900 g/cm 3 , or 0.875 g/cm 3 to 0.980 g/cm 3 , or 0.875 g/cm 3 to 0.950 g/cm 3 , or 0.900 g/cm 3 to 0.980 g/cm 3 , or 0.900 g/cm 3 to 0.950 g/cm 3 , or 0.925 g/cm 3 to 0.980 g/cm 3 , or 0.925 g/cm 3 to 0.950 g/cm 3 . Additionally or alternately, the resulting blended product can have a flash point of 60°C or higher, or 70°C or higher, or 80°C
  • an isoparaffinic blend component and/or isoolefinic blend component can have favorable cold flow properties relative to other types of blend components.
  • the resulting blended product includes a) 10 vol% or more of an isoparaffinic blend component and/or isoolefinic blend component, and b) 50 vol% or more of a conventional and/or mineral blend component
  • the resulting blended product can have a cloud point that is lower than the cloud point of the conventional and/or mineral blend component by 10°C or more, or 15°C or more, or 20°C or more, such as up to 60°C lower or possibly still more.
  • the resulting blended product includes a) 10 vol% or more of an isoparaffinic blend component and/or isoolefinic blend component, and b) 40 vol% or more of a synthetic component (different from the isoparaffinic blend component and/or isoolefinic blend component)
  • the resulting blended product can have a cloud point that is lower than the cloud point of the bio-derived component by 10°C or more, or 15°C or more, or 20°C or more, such as up to 60°C lower or possibly still more.
  • the resulting blended product can have a cloud point of 6°C or less, or 0°C or less, or -6°C or less, or -12°C or less, such as down to -30°C or possibly still lower.
  • the resulting blended product can have a kinematic viscosity at 50°C of 200 cSt or less, or 100 cSt or less, or 50 cSt or less, or 20 cSt or less, or 10 cSt or less, such as down to 1.0 cSt or possibly still lower.
  • the resulting blended product can have a kinematic viscosity at 50°C of 20 cSt to 100 cSt, or 20 cSt to 50 cSt.
  • the resulting blended product can have a kinematic viscosity at 40°C of 2.0 cSt to 6.0 cSt, or 2.0 cSt to 5.0 cSt, or 3.0 cSt to 6.0 cSt, or 3.0 cSt to 5.0 cSt.
  • the resulting blended product can have a calculated carbon aromaticity index (CCAI) of 780 to 820, or 790 to 810, or 800 to 820.
  • CCAI carbon aromaticity index
  • an isoparaffinic blend component and/or isoolefinic blend component can have a favorable estimated cetane number relative to other types of blend components.
  • the resulting blended product can have an estimated cetane number that is higher than the estimated cetane number for the conventional fuel oil and/or mineral fuel oil.
  • the resulting blended product can have an estimated cetane number that is higher than the estimated cetane number for the bioderived component.
  • an isoparaffinic blend component and/or isoolefinic blend component can have a favorable estimated energy content relative to other types of blend components.
  • 10 vol% or more of an isoparaffinic blend component and/or isoolefinic blend component is blended with 50 vol% or more of a conventional fuel oil and/or mineral fuel oil
  • the resulting blended product can have an energy content that is higher than the energy content for the conventional fuel oil and/or mineral fuel oil.
  • the resulting blended product can have an energy content that is higher than the energy content for the bio-derived component.
  • an isoparaffinic blend component and/or an isoolefinic blend component can assist with reducing the sulfur content of a resulting blend. Because an isoparaffinic blend component and/or isoolefinic blend component typically has less than 100 wppm of sulfur (or less than 50 wppm, such as down to having substantially no sulfur content), such a blend component can offset a higher sulfur content in other components of a blend.
  • the resulting blended product can have a sulfur content of 5000 wppm or less, or 2500 wppm or less, or 1000 wppm or less, or 500 wppm or less, such as down to 10 wppm or possibly still lower.
  • a blended product includes only an isoparaffinic / isoolefinic blend components mixed with synthetic (e.g., bio-derived, Fischer-Tropsch) blend components
  • low sulfur contents can be achieved, such as sulfur contents of 100 wppm or less, or 10 wppm or less, such as down to having substantially no sulfur content (0.1 wppm or less).
  • the resulting blended product can include at least a portion of one or more conventional VLSFO fractions, ULSFO fractions, and/or marine gas oil (MGO) fractions.
  • a conventional VLSFO, ULSFO, or MGO is defined herein as a fraction that already qualifies as a VLSFO fuel, ULSFO fuel, or MGO fuel under ISO 8217 (either Table 1 or Table 2).
  • the resulting blended product can include 1.0 vol% to 99 vol% of a conventional diesel fuel fraction, or 1.0 vol% to 90 vol%, or 1.0 vol% to 70 vol%, or 1.0 vol% to 50 vol%, or 1.0 vol% to 30 vol%, or 1.0 vol% to 10 vol%, or 10 vol% to 99 vol%, or 10 vol% to 90 vol%, or 10 vol% to 70 vol%, or 10 vol% to 50 vol%, or 10 vol% to 30 vol%, or 30 vol% to 99 vol%, or 30 vol% to 90 vol%, or 30 vol% to 70 vol%, or 50 vol% to 99 vol%, or 50 vol% to 90 vol%, or 70 vol% to 99 vol%, or 70 vol% to 90 vol%.
  • the resulting blended product can include at least a portion of one or more mineral distillate boiling range fractions, vacuum gas oil boiling range fractions, and/or resid boiling range fractions.
  • the resulting blended product can include 1.0 vol% to 99 vol% of one or more mineral fraction(s), or 1.0 vol% to 90 vol%, or 1.0 vol% to 70 vol%, or 1.0 vol% to 50 vol%, or 1.0 vol% to 30 vol%, or 1.0 vol% to 10 vol%, or 10 vol% to 99 vol%, or 10 vol% to 90 vol%, or 10 vol% to 70 vol%, or 10 vol% to 50 vol%, or 10 vol% to 30 vol%, or 30 vol% to 99 vol%, or 30 vol% to 90 vol%, or 30 vol% to 70 vol%, or 50 vol% to 99 vol%, or 50 vol% to 90 vol%, or 70 vol% to 99 vol%, or 70 vol% to 90 vol%.
  • the resulting blended product can include at least a portion of one or more synthetic fractions (different from the isoparaffinic blend component and/or isoolefinic blend component), such as bio-derived fractions and/or Fischer-Trospsch derived fractions.
  • the resulting blended product can include 1.0 vol% to 99 vol% of a fraction, or 1.0 vol% to 90 vol%, or 1.0 vol% to 70 vol%, or 1.0 vol% to 50 vol%, or 1.0 vol% to 30 vol%, or 1.0 vol% to 10 vol%, or 10 vol% to 99 vol%, or 10 vol% to 90 vol%, or 10 vol% to 70 vol%, or 10 vol% to 50 vol%, or 10 vol% to 30 vol%, or 30 vol% to 99 vol%, or 30 vol% to 90 vol%, or 30 vol% to 70 vol%, or 50 vol% to 99 vol%, or 50 vol% to 90 vol%, or 70 vol% to 99 vol%, or 70 vol% to 90 vol%.
  • an isoparaffinic and/or isoolefinic blend component can be blended with a plurality of different types of fractions.
  • a blended product can include two or more (or three or more) of a conventional fraction, a mineral fraction, and a synthetic fraction.
  • 3 H NMR can be used to roughly characterize the amount of hydrogen in a sample that corresponds to CH3 groups (primary or terminal carbons), CH2 groups (secondary carbons) and CH groups (tertiary carbons).
  • CH3 groups primary or terminal carbons
  • CH2 groups secondary carbons
  • CH groups tertiary carbons
  • This impact of aromatic rings is general for all types of 'H NMR, and the change in the detected number of CH3 groups, CH2 groups, and CH groups is minimal for any sample containing less than 60 wt% aromatics.
  • 1 H NMR can be used to characterize in a repeatable manner the content of CH3 groups, CH2 groups, and CH groups in a sample.
  • 1 H NMR can be used to characterize the number of CH3 groups, CH2 groups, and CH groups in a sample in the following manner. Based on peak position, 'H NMR can generally characterize hydrogens in a hydrocarbon (or hydrocarbon-like) sample as falling into one of 6 types of groups: 1) hydrogens attached to an aromatic ring; 2) hydrogens attached to carbons that are part of an olefinic bond; 3) hydrogens attached to a carbon that is alpha to an aromatic ring (i.e., hydrogen is attached to a first carbon, the first carbon is attached to a second carbon that is part of an aromatic ring); 4) hydrogens that are part of a CH3; 5) hydrogens that are part of a CH2 group, and 6) hydrogens that are part of a CH group.
  • the peaks corresponding to these 6 types of hydrogen can then be integrated. This provides relative ratios for the amount of each type of hydrogen that is present. These ratios can then be used to determine the relative percentages of the corresponding types of carbons that are present in a sample.
  • the amount of hydrogens present needs to be divided by 3 or 2, respectively, in order to convert the relative hydrogen amount detected by NMR into a relative number of CH3 groups or CH2 groups.
  • the amount of CH3 groups detected based on 1 H NMR may be slightly lower than the actual content of CH3 groups. However, this is a small error for samples having less than 60 wt% aromatics.
  • references to CH3 groups in a sample are defined as CH3 groups as detected by 1 H NMR, without an attempt to correct the NMR value based on this possible undercounting error due to the presence of aromatics.
  • CH2 groups are defined as paraffinic / aliphatic CH2 groups as determined based on 'H NMR. This is determined by integration of the hydrogen peak corresponding to the peak in the NMR spectrum that corresponds to hydrogens that are part of a CH2 group. It is noted that hydrogens from any CH2 group that is alpha or beta to an aromatic ring are not part of this peak. Additionally, hydrogens from a CH3 group that is beta to an aromatic ring are included in this peak. Therefore, to the degree aromatics are present, the amount of CH2 groups detected based on 1 H NMR may be slightly lower, slightly higher, or the same as the actual content of CH2 groups. However, this is a small error for samples having less than 60 wt% aromatics.
  • references to CH2 groups in a sample are defined as CH2 groups as detected by 'H NMR, without an attempt to correct the NMR value based on possible undercounting and/or overcounting errors due to the presence of aromatics. It is noted that CH2 groups that are part of a naphthene ring are included in the CH2 NMR peak.
  • CH groups are defined as paraffinic / aliphatic CH groups as determined based on 'H NMR. This is determined by integration of the hydrogen peak corresponding to the peak in the NMR spectrum that corresponds to hydrogens that are part of a CH group. As noted above, any hydrogens directly attached to an aromatic ring are not included in this peak. Additionally, it is noted that hydrogens from any CH group that is alpha or beta to an aromatic ring are not part of this peak. Further, hydrogens from a CH2 group that is beta to an aromatic ring are included in this peak. Therefore, to the degree aromatics are present, the amount of CH groups detected based on 1 H NMR may be slightly lower, slightly higher, or the same as the actual content of CH groups.
  • references to CH groups in a sample are defined as paraffinic / aliphatic CH groups as detected by 1 H NMR, without an attempt to correct the NMR value based on possible undercounting and/or overcounting errors due to the presence of aromatics. It is noted that CH groups that are part of a naphthene ring are included in the CH NMR peak.
  • a resulting blend By blending an at least a portion of the isoparaffinic stream (also referred to as an isoparaffinic blend component) with another fraction, a resulting blend can be formed that has a ratio of CH3 groups to CH2 groups (both as determined based on 'H NMR) of 1.01 to 2.30, or 1.01 to 2.00, or 1.01 to 1.80, or 1.01 to 1.50, or 1.01 to 1.15, or 1.36 to 2.30, or 1.36 to 2.00, or 1.36 to 1.80, or 1.70 to 2.30. It is noted that the ratio of CH3 to CH2 groups can vary depending on the type of fraction that is blended with an isoparaffinic blend component.
  • an isoparaffinic blend component with a mineral jet boiling range fraction, a mineral distillate boiling range fraction, or a Fischer-Tropsch fraction and/or fraction with a high n-paraffin content will tend to result in blends having a lower ratio.
  • blending an isoparaffinic blend component with a fraction that has been highly isomerized in a catalytic dewaxing / isomerization process will tend to result in blends having a higher ratio.
  • 13 C NMR was used to characterize the quaternary carbon content of the C12 fraction of various samples.
  • gas chromatography can be used to separate the C12 compounds present in a sample from the remaining hydrocarbons.
  • a straightforward method that can be used for forming a C12 fraction is the normal paraffin (or linear paraffin) gas chromatograph method. That is, for an appropriate gas chromatograph with a separation column of adequate resolution, a normal paraffin of a given carbon number is assumed to delineate a peak, above which, species may be assumed to comprise the carbon number of the next higher carbon number normal paraffin peak. For example, all peaks for material eluting in between the peaks for n-decane and n-undecane are assumed to be C11 species.
  • the resulting C12 fraction can then be characterized using 13 C NMR. It has been discovered that the C12 fraction of an isoparaffinic blend component made according to the methods described herein can have an unexpectedly low content of quaternary carbons relative to a fraction made by catalytic isomerization of n-paraffins. In such aspects, the quaternary carbon content of the C 12 fraction of an isoparaffinic blend component can be 1.5% or less of the total carbons present in the C12 fraction, or 1.4% or less, or 1.3% or less, such as down to 1.0% or possibly still lower.
  • Embodiment 1 A method for producing a diesel boiling range composition comprising: oligomerizing an ethylene stream to a C4+ olefin stream in a first olefin oligomerization unit comprising a serial reactor and a lights removal column, wherein the C4+ olefin stream contains no greater than 10 wt% of methane, ethylene, and ethane combined in a first oligomerization; and wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 20 wppm each of carbon monoxide and hydrogen; oligomerizing the C4+ olefin stream and a propylene/C4+ olefin stream in a second oligomerization unit to produce an isoolefinic stream; wherein at least a portion of the isool efinic stream is used to create the diesel boiling range
  • Embodiment 2 The method of Embodiment 1, wherein the C4+ olefin stream contains no greater than 5 wt% of methane, ethylene, and ethane combined.
  • Embodiment 4 The method of any of Embodiments 1-3, wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 5 wppm each of carbon monoxide and hydrogen.
  • Embodiment 6 The method of any of Embodiments 1-5 further comprising: hydroprocessing the isoolefinic stream with hydrogen as treat gas to produce an isoparaffinic stream having no greater than 10 wt% olefin content.
  • Embodiment 7 The method of any of Embodiments 1-6, wherein the C4+ olefin stream and the propylene/C4+ olefin stream combine before the second oligomerization.
  • Embodiment s The method of any of Embodiments 1-7, wherein the first oligomerization unit utilizes homogeneous catalysis, and wherein the second oligomerization unit utilize a heterogeneous catalyst.
  • Embodiment 9 The method of any of Embodiments 1-9, wherein the second oligomerization recycles a portion of the C4+ olefin stream that is not oligomerized to pass it through the second oligomerization again.
  • Embodiment 10 The method of any of Embodiments 1-9 further comprising: converting a methanol to olefins to produce a raw olefin stream; wherein the raw olefin stream comprises ethylene, propylene and C4+ olefins, wherein at least 10 wt% of all olefins in the raw olefin stream are ethylene, and further containing at least 1000 wppm of each methane and ethane, and at least 100 wppm of each carbon monoxide and hydrogen; and separating the raw olefin stream to remove hydrogen, carbon monoxide, propylene and C4+ olefins from the raw olefin stream, and produce the ethylene stream.
  • Embodiment 11 The method of Embodiment 10, wherein the ethylene stream contains at least 90% of the ethane present in the raw olefin stream.
  • Embodiment 12 The method of Embodiment 10, wherein the methanol is converted to olefins by using a silicoaluminophosphate catalyst, an aluminosilicate catalyst, or steam cracking.
  • Embodiment 13 A method for producing a diesel boiling range composition comprising: providing a raw olefin stream comprising ethylene, propylene and C4+ olefins, wherein at least 10 wt% of all olefins in the raw olefin stream are ethylene, and further containing at least 1000 wppm of each methane and ethane, and at least 100 wppm of each carbon monoxide and hydrogen; subjecting the raw olefin stream to a separation operation to remove hydrogen, carbon monoxide, propylene and C4+ olefins from the raw olefin stream, and produce an ethylene stream containing at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 20 wppm each of carbon monoxide and hydrogen, wherein at least 95 wt% of all the ethylene in the raw olefin stream is recovered in the
  • Embodiment 14 The method of Embodiment 13, wherein the C4+ olefin stream contains no greater than 5 wt% of methane, ethylene, and ethane combined.
  • Embodiment 15 The method of any of Embodiments 13-14, wherein the C4+ olefin stream contains no greater than 2000 wppm of methane, ethylene, and ethane combined.
  • Embodiment 16 The method of any of Embodiments 13-15, wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 5 wppm each of carbon monoxide and hydrogen.
  • Embodiment 17 The method of any of Embodiments 13-16, wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm of methane, and no greater than 1 wppm each of carbon monoxide and hydrogen.
  • Embodiment 18 The method of any of Embodiments 13-17 further comprising subjecting at least a portion of the isool efinic stream to a hydroprocessing process with hydrogen as treat gas to produce an isoparaffinic stream having no greater than 10 wt% olefin content.
  • Embodiment 19 The method of Embodiment 18 further wherein at least a portion of the isoolefinic blend component, an isoparaffinic blend component sourced from the isoparaffinic stream, or a combination thereof is used to create the diesel boiling range composition comprising: 1.0 vol% to 75 vol% of a blend component comprising the isoparaffinic blend component, the isoolefinic blend component, or a combination thereof, containing 80 wt% or more of combined isoparaffins and isoolefins; 20 vol% to 99 vol% of a mineral distillate boiling range fraction; and a cetane number of 40 or more and a cloud point that is at least 5.0°C lower than a cloud point of the mineral distillate boiling range fraction.
  • Embodiment 20 The method of any of Embodiments 13-19, wherein the ethylene stream contains at least 90% of the ethane present in the raw olefin stream.
  • Embodiment 22 The method of Embodiment 21, further comprising: additional distillation columns in the separation operation, wherein the propylene is separated from C4+ olefins and then further separated from propane and components of similar or lower volatility.
  • Embodiment 24 The method of any of Embodiments 13-23, wherein the second oligomerization unit comprises: a serial reactor; a distillate fractionation column that outputs the isoolefinic stream; and a debutanizer fractionation column that purges C4- olefins.
  • Embodiment 25 The method of Embodiment 24, wherein the distillate fractionation column also outputs C9- olefins, of which a first portion is recycled to the serial reactor and a second portion is sent to the debutanizer fractionation column; and wherein the debutanizer fractionation column also outputs C5+ olefins, of which a first portion is recycled to the serial reactor and a second portion is purged.
  • Embodiment 26 The method of Embodiment 24, wherein the second C4+ stream travels first to the distillate fractionation tower when entering the second oligomerization unit, while the propylene and the C4+ olefins removed from the raw olefins stream travel first to the serial reactor.
  • Embodiment 27 The method of any of Embodiments 13-26 further comprising: converting a methanol to olefins to produce the raw olefin stream.
  • Embodiment 28 The method of Embodiment 27, wherein the methanol is converted to olefins by using a silicoaluminophosphate catalyst, an aluminosilicate catalyst, or steam cracking.
  • Table 1A shows the weight percentage of isoparaffins having various hydrocarbon chain lengths in the resulting isoparaffmic blend components.
  • the samples are referred to as IPB-1, IPB-2, and IPB-3 (for Isoparaffmic Blend Component).
  • IPB-1 isoparaffins having various hydrocarbon chain lengths in the resulting isoparaffmic blend components.
  • IPB-2 for Isoparaffmic Blend Component
  • IPB-3 for Isoparaffmic Blend Component
  • isoparaffin carbon chain length distributions in a representative hydroprocessed vegetable oil (HVO) sample represents a vegetable oil that has been exposed to hydrotreating and some type of hydroisomerization.
  • HVO represents a vegetable oil that has been exposed to hydrotreating and some type of hydroisomerization.
  • Tables IB, 1C, ID, and IE show the weight percentage of isoparaffins of various chain lengths that would be incorporated into a blended product that included 70 wt% of an isoparaffinic blend component (Table IB), 50 wt% (Table 1C), 30 wt% (Table ID), or 10 wt% (Table IE). Due to the difference in the peaks for the chain length distributions, even adding 10 wt% of an isoparaffinic (or isool efinic) blend component to a hydrotreated vegetable oil can result in substantial changes in the C12- portion of the isoparaffin chain length distribution of the resulting blended product.
  • the conventional diesel sample contained relatively few C14- isoparaffins.
  • the C13 - C14 isoparaffins corresponded to less than 3 wt% of the diesel sample, while the C12- isoparaffins corresponded to less than 1.1 wt% of the sample.
  • the IPB samples are highly isomerized, so that 95+ wt% or more of the hydrocarbons in the IPB samples correspond to isoparaffins.
  • the IPB samples include 15 wt% or more of C13 - C14 isoparaffins, 22 wt% or more of C12 isoparaffins, and 30 wt% or more of Cn- isoparaffins.
  • Tables 2B, 2C, 2D, and 2E show the weight percentage of isoparaffins of various chain lengths that would be incorporated into a blended product that included 70 vol% of an isoparaffinic blend component (Table 2), 50 vol% (Table 3), or 30 vol% (Table 4), with the balance corresponding to the diesel sample.
  • Table 2 shows the weight percentage of isoparaffins of various chain lengths that would be incorporated into a blended product that included 70 vol% of an isoparaffinic blend component (Table 2), 50 vol% (Table 3), or 30 vol% (Table 4), with the balance corresponding to the diesel sample.
  • Table 2B, 2C, 2D, and 2E show the weight percentage of isoparaffins of various chain lengths that would be incorporated into a blended product that included 70 vol% of an isoparaffinic blend component (Table 2), 50 vol% (Table 3), or 30 vol% (Table 4), with the balance corresponding to the diesel sample.
  • Table 2B, 2C, 2D, and 2E show the
  • IPB-1 and IPB-2 in Example 1 were used, in combination with two conventional European diesel fuels and two bio-derived fractions, to produce model blended fuels based on the various fractions.
  • a series of measurements were made on IPB-1, IPB-2, two different diesel fuels that meet the requirements of EN 590 (the fuels are referred to herein as EPD-1 and EPD-2), the hydrotreated vegetable oil from Example 1, and diesel boiling range fraction based on rapeseed methyl ether (RME).
  • Table 3 shows the measured properties of the various fractions.
  • Table 3 The measured values in Table 3 were used as the basis for preparing a series of model blends to form potential diesel boiling range fuels.
  • Table 4 shows model blend results for blends formed using 25 wt% of either IPB-1 or IPB-2 in combination with 75 wt% of either EPD-1 or EPD-2.
  • Table 5 shows a second series of model blends.
  • the first two blends include higher percentages of IPB-2 mixed with EPD-2.
  • the second two blends include IPB-1, EPD-2, and either one or both bio-derived fractions shown in Table 3.
  • an isoparaffinic blend component can be added to a conventional diesel in quantities of 30 wt% or more, or 40 wt% or more, while still provide a kinematic viscosity at 40°C of greater than 2.0 cSt.
  • bio-derived fractions generally have poor cloud point properties.
  • Table 6 shows additional modeled blends where an isoparaffinic blend component is mixed with one or both of the bio-derived fractions shown in Table 3.
  • the empirical blending model was also used to generate model blends for incorporating isoparaffinic blend components into various types of marine fuels.
  • Table 7 shows blends of IPB-1 and IPB-2 with a commercially available VLSFO. The measured properties of the VLSFO are also provided for comparison, along with portions of the specification for RMG 380 (the type of VLSFO) from ISO 8217 Table 2.
  • Isoparafinnic (and/or isoolefinic) blend components can also be used to make ULSFO fuels or fuel blending components.
  • Table 8 shows modeled examples of blending IPB-1 or IPB-2 with a hydroprocessed vacuum resid fraction. Measured values for the neat hydroprocessed resid (HDP VR) are also shown, along with values for HDME 50, a commercially available ULSFO. Portions of the specification for an RMD80 fuel oil from ISO 8217 Table 2 are also provided.
  • Blends of an isoparaffinic blend component (and/or an isoolefinic blend component) with both renewable fractions and mineral fraction can also be used to form marine fuel oils.
  • Table 9 shows modeled blends of IPB-1 with a higher sulfur content fuel oil (either lightly hydroprocessed or not hydroprocessed).
  • One of the blends corresponds to a 50 wt% / 50 wt% mixture of IPB-1 and the fuel oil (FO).
  • the other blend includes 35 wt% IPB-1, 50 wt% of a fatty acid methyl ester fraction, and 15 wt% of the fuel oil.
  • measured values for the neat fuel oil are provided, along with some of the specification for an RMA fuel oil according to ISO 8217 Table 2.
  • Isoparaffinic blend components can also be used for formation of blended products corresponding to marine gas oils or marine gas oil blending components.
  • Table 10 shows modeled blends of 70 wt% of IPB-1 with either 30 wt% of a commercially available MGO or 30 wt% of a fatty acid methyl ester. Measured values for the neat MGO are provided, along with some of the specifications for a DMA marine gas oil under ISO 8217 Table 1.
  • the isoparaffinic blend component IPB-1 was formed according to the method described herein, where an isoolefinic blend component was formed by olefin oligomerization. A portion of the isoolefinic blend component was then exposed to hydrotreating conditions to saturate the portion, thus forming the IPB-1 sample. In addition to forming the isoparaffinic blend component, two additional portions of the isoolefinic blend component were exposed to conditions for partial saturation of olefins, resulting in components containing roughly 30 wt% olefins / 70 wt% paraffins and 70 wt% olefins / 30 wt% paraffins.
  • the isoolefinic blend component, the isoparaffinic blend component, and the two partially saturated components were characterized using 1 H NMR to characterize the ratio of CH3 groups to CH2 groups, as determined from the 'H NMR results.
  • FIG. 6 shows results from the 'H NMR analysis.
  • the first column of data corresponds to data for the substantially fully saturated isoparaffinic blend component (IPB-1).
  • the second column and third column show the partially saturated products, while the final column corresponds to data for the isoolefinic blend component, as made from the oligomerization process.
  • the isoolefinic blend component (prior to any saturation) had the highest ratio of CPF, groups to CH2 groups. As saturation increased, the ratio of CH3 groups to CH2 groups went decreased, with the isoparffinic blend component (IPB-1) having a ratio of CH3 to CH2 groups (as determined based on X H NMR) of 1.18.
  • liquids with high n-paraffin contents tend to have ratios of CH3 to CH2 that are well below 1.00.
  • Commercial fuel products generally have ratios below 1.00, although a high isoparaffin content / low aromatic content diesel can approach 1.00.
  • Fluids containing high contents of naphthenes have CH3 to CH2 ratios above 2.30.
  • fractions with high isoparaffin content, where the isoparaffin content is formed by catalytic isomerization have CH3 to CH2 ratios above 2.30.
  • a sample of IPB-1 was separated using a gas chromatograph to form a C12 fraction.
  • the resulting C12 fraction was analyzed using 13 C NMR to determine the content of quaternary carbons in the sample.
  • C12 fractions were also formed from two other mineral sources after exposing the sources to deep catalytic isomerization. Table 12 shows the results from analysis of the C12 fractions.
  • the quaternary carbon content of the C12 fraction was substantially lower than the other fractions.
  • the C12 fraction had a quaternary carbon content of greater than 1.60% relative to the total number of carbons in the sample, while the C12 fraction from the isoparaffinic blend component has a quaternary carbon content of 1.60% or less, or 1.50% or less, or 1.40% or less, such as down to 1.20% or possibly still lower.
  • compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values.

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Abstract

Un exemple non limitatif de procédé de production d'une composition à gamme d'ébullition diesel comprend les étapes suivantes : oligomérisation d'un flux d'éthylène en un flux d'oléfines C4+ dans une première unité d'oligomérisation d'oléfines, le flux d'oléfines C4+ contenant au maximum 10 % en poids de méthane, d'éthylène et d'éthane combinés dans une première oligomérisation, et le flux d'éthylène contenant au minimum 50 % en poids d'éthylène, au minimum 2 000 wppm d'éthane, au maximum 1 000 wppm de méthane et au maximum 20 wppm chacun de monoxyde de carbone et d'hydrogène ; oligomérisation du flux d'oléfines C4+ et d'un flux de propylène/oléfines C4+ dans une deuxième unité d'oligomérisation pour produire un flux isooléfinique ; au moins une partie du flux isooléfinique étant utilisée pour créer la composition de gamme d'ébullition diesel.
PCT/US2023/017456 2022-04-06 2023-04-04 Procédés de conversion d'oléfines c2+ en oléfines à nombre de carbones plus élevé, utiles pour la production de compositions de distillats isoparaffiniques WO2023196330A1 (fr)

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