Process for converting C2 + olefins to higher carbon number olefins useful for producing isoparaffin kerosene compositions

Abstract

A process for producing a blended jet boiling range composition stream can include: oligomerizing an ethylene stream to a C4 + olefin stream in a first olefin oligomerization unit, wherein the C4 + olefin stream contains no greater than 10 wt% combined methane, ethylene, and ethane; wherein the ethylene stream contains at least 50 wt% of ethylene, at least 2000 wppm of ethane, no more than 1000 wppm of methane, and each no more than 20 wppm of carbon monoxide and hydrogen; oligomerizing the C4 + olefin stream and the propylene / C4 + olefin stream in a second oligomerization unit to produce an isoolefin stream; subjecting at least a portion of the isoolefin stream to a hydrotreating process with hydrogen as a process gas to produce an isoparaffin stream having an olefin content of not greater than 10 wt%; and generating a blended jet boiling range using at least a portion of the isoparaffin stream.

Description

Technical Field

[0001] The present invention relates to a process for converting C2+ olefins into higher carbon number olefins. The higher carbon olefins can be used to produce isoparaffinic kerosene compositions. Background Art

[0002] Olefins are valuable raw materials in chemical manufacturing. For example, light olefins such as ethylene and propylene can be used for polymerization. Higher carbon olefins such as C6+ olefins and C8+ olefins that can be produced by oligomerization of light olefins can be used to produce special surfactants, lubricants, jet / aviation fuels, diesel fuels, fuel additives, etc. Many oligomerization catalyst systems have been studied to increase the productivity of preferred higher carbon olefins and have higher productivity. However, the step of upgrading light olefins to higher carbon olefins remains reasonable unchanged. Summary of the invention

[0003] The present application relates to a process for converting C2+ olefins to higher carbon number olefins.

[0004] A non-limiting exemplary process for producing a blended jet boiling range composition stream comprises: oligomerizing an ethylene stream into a C4+ olefin stream in a first olefin oligomerization unit comprising a series reactor and a lightness removal column, wherein the C4+ olefin stream contains no more than 10 wt% of combined methane, ethylene and ethane; wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more 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 isoolefin stream; subjecting at least a portion of the isoolefin stream to a hydrotreating process using hydrogen as a treat gas to produce an isoolefin stream having an olefin content of no more than 10 wt%. greater than 10 wt % of an isoparaffin stream; and using at least a portion of the isoparaffin stream to produce the blended jet boiling range composition, the blended jet boiling range composition comprising: 30 vol % to 99 vol % of an isoparaffin blend component, the isoparaffin blend component being derived from the isoparaffin stream, the isoparaffin stream containing 80 wt % or more of isoparaffins, 5.0 wt % or less of olefins, and 5.0 wt % or less of C19+ hydrocarbons; 1.0 vol % to 70 vol % of a mineral jet boiling range fraction; and a T10 distillation point of 205° C. or less, a final boiling point of 300° C. or less, a freezing point of -40° C. or less, and 2.0 wt % or more of C17-C18 hydrocarbons.

[0005] A non-limiting exemplary method for producing a blended jet 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 comprising at least 1000 wppm of methane and ethane each, and at least 100 wppm of carbon monoxide and hydrogen each; 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 more than 1000 wppm methane, and no more than 20 wppm of carbon monoxide and hydrogen each, wherein at least 95 wt% of all ethylene in the raw olefin stream is recovered in the ethylene stream; providing at least a portion of the ethylene stream to a first olefin oligomerization unit comprising one or more series reactors and a lightness remover to convert at least 90% of the ethylene contained in the ethylene stream into a combined olefin stream containing no more than 10 wt% of methane and ethane in a single pass through the series reactors; The invention relates to a method for preparing a jet-range blended composition comprising: providing a first olefin oligomerization unit with at least a portion of each of the propylene and the C4+ olefins removed from the first olefin stream and at least a portion of the second C4+ stream to produce an iso-olefin stream; and subjecting at least a portion of the iso-olefin stream to a hydrotreatment process using hydrogen as a treatment gas to produce an iso-paraffin stream having an olefin content of not more than 10 wt %; and using at least a portion of the iso-paraffin stream to produce the blended jet-range composition, the blended jet-range composition The invention comprises: 30 vol% to 99 vol% of an isoparaffin blend component, the isoparaffin blend component is derived from the isoparaffin stream, the isoparaffin stream contains 80 wt% or more of isoparaffins, 5.0 wt% or less of olefins and 5.0 wt% or less of C19+ hydrocarbons; 1.0 vol% to 70 vol% of a mineral jet boiling range fraction; and a T10 distillation point of 205°C or less, a final boiling point of 300°C or less, a freezing point of -40°C or less, and 2.0 wt% or more of C17-C18 hydrocarbons.

[0006] These and other features and properties of the disclosed methods of the present disclosure and their advantageous applications and / or uses will become apparent from the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] To assist persons of ordinary skill in the relevant art in making and using the subject matter herein, reference is made to the accompanying drawings. The following drawings are included to illustrate certain aspects of the present disclosure and should not be construed as an exclusive configuration. As will occur to those skilled in the art having the benefit of this disclosure, the disclosed subject matter is capable of considerable modification, alteration, combination, and equivalence in form and function.

[0008] Figure 1 Non-limiting examples of the methods of the present disclosure are presented.

[0009] Figure 2 Non-limiting examples of the methods of the present disclosure are presented.

[0010] Figure 3 Non-limiting examples of the methods of the present disclosure are presented.

[0011] Figure 4 Non-limiting examples of the methods of the present disclosure are presented.

[0012] Figure 5 Non-limiting examples of the methods of the present disclosure are presented.

[0013] Figure 6 Composition information for blends of isoparaffin blend components with conventional jet fuel is shown.

[0014] Figure 7 Composition information is shown for blends of another isoparaffin blend component with conventional jet fuel.

[0015] Figure 8 The isoolefin and isoparaffin blend components are shown. 1 H NMR characterization results. DETAILED DESCRIPTION

[0016] The application relates to a method for converting C2+ olefins into higher carbon number olefins. The olefins and / or the olefins converted into paraffins can be used for various other applications, including the blend feedstock of fuel and fuel. More specifically, conversion can include two oligomerization processes, which can advantageously improve overall ethylene conversion, while having flexibility and efficiency that can provide energy and cost savings.

[0017] definition

[0018] All numerical values ​​in the detailed description and claims herein are modified by the indicated value of "about" or "approximately", and take into account experimental error and variations that would be expected by a person of ordinary skill in the art.

[0019] In this discussion, a jet fuel or jet fuel blend component that contains at least a portion of synthetic jet boiling range compounds (ie, jet boiling range compounds that are not derived from a processed mineral source) is defined as a synthetic jet fuel or synthetic jet fuel blend component.

[0020] In this discussion, if methanol is used as a feedstock for forming olefins, methanol obtained by various processes may be referred to as "sustainable" methanol. Examples of such 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, etc. and any combination thereof.

[0021] Commercial standards for jet fuels currently generally specify various properties. Examples of property specifications and / or typical properties of commercial jet fuels include a total acidity of 0.1 mg KOH / g or less, or 0.015 mg KOH / g or less, a sulfur content of 3000 wppm or less, a maximum freezing point of -40°C or -47°C, a viscosity of 8.0 cSt or less at -20°C, a flash point of at least 38°C, an initial boiling point of 140°C or more, a T10 distillation point of 205°C or less, and / or a final boiling point of 300°C or less. Another example of a property specification is a specification of a maximum deposit thickness on a heater tube surface and / or a maximum pressure increase during a thermal stability test at 260°C (according to ASTM D3241), such as a maximum deposit thickness of 85 nm and / or a maximum pressure increase of 25 mm Hg. Still another example of a property specification can be a water separation grade, such as a water separation grade of 85 or more, as measured according to ASTM D3948. The water separation grade provides an indication of the amount of surfactant present in a jet fuel boiling range sample. Petroleum fractions having an appropriate boiling range and also meeting the various requirements of commercial standards can be tested (such as according to ASTM D3241) and certified for use as jet fuel. In some aspects, the kerosene boiling range fraction can correspond to a jet fuel fraction that meets the specifications of a jet fuel according to ASTM D1655. This can include a thermal stability breakpoint of 260°C or higher, or 275°C or higher, as defined by ASTM D3241.

[0022] Unless otherwise specified, distillation points and boiling points can be determined according to ASTM D86. Note that still other methods of boiling point characterization can also be provided in the examples. The values ​​produced by such other methods are considered to be indicative of the values ​​obtained according to ASTM D86.

[0023] In this discussion, the jet fuel boiling range or kerosene boiling range is defined as 140° C. to 300° C. A jet fuel boiling range fraction or kerosene boiling range fraction is defined as a fraction having a T10 distillation point of 140° C. to 205° C. or less and a final boiling point of 300° C. or less. Note that jet fuel boiling range fractions may also sometimes have a flash point of 38° C. or greater, although kerosene boiling range fractions do not necessarily have such a requirement.

[0024] In this discussion, a hydrotreated fraction refers to a hydrocarbon fraction and / or hydrocarbon-containing fraction that has been exposed to a catalyst having hydrotreated activity in the presence of 300 kPa-a or more of hydrogen at a temperature of 200° C. or more. Examples of hydrotreated fractions include a hydrotreated distillate fraction (i.e., a hydrotreated fraction having a distillate boiling range), a hydrotreated kerosene fraction (i.e., a hydrotreated fraction having a kerosene boiling range), and a hydrotreated diesel fraction (i.e., a hydrotreated fraction having a diesel boiling range). Note that a hydrotreated fraction derived from a biological source, such as a hydrotreated vegetable oil, may correspond to a hydrotreated distillate fraction, a hydrotreated kerosene fraction, and / or a hydrotreated diesel fraction, depending on the boiling range of the hydrotreated fraction.

[0025] With regard to the properties of kerosene / jet boiling range fractions and / or blends of such fractions with other components to form kerosene / jet boiling range fuels, a variety of methods may be used. Density of the blend at 15°C (kg / m 3 ) may be determined according to ASTM D4052. Sulfur (in wppm or wt %) may be determined according to ASTM D2622, and nitrogen (in wppm or wt %) may be determined according to D4629. Kinematic viscosity at -20°C or -40°C (in cSt) may be determined according to ASTM D445. Pour point may be determined according to ASTM D5949. Cloud point may be determined according to D5773. Freeze point may be determined according to D5972. Flash point may be determined according to ASTM D56. Aromatic content may be determined according to ASTM D1319. Cetane number may be determined according to ASTM D613.

[0026] In this discussion, the content of normal paraffins, isoparaffins, cycloparaffins, aromatic compounds and / or olefins can be determined according to test method UOP 990. Note that for some paraffins, normal paraffins and isoparaffins described below, the content is determined using gas chromatography according to the linear paraffin method. The normal paraffin peak from a hydrocarbon sample in gas chromatography is well known. The normal paraffin peak can be integrated separately to determine the normal paraffin content of a sample using gas chromatography. The peak in the GC spectrum between the normal paraffin peaks can be designated as an isoparaffin with the same carbon number as the lower peak, so that the total amount of paraffins with a given carbon number can be determined. The isoparaffin content of a given carbon number can be determined by subtracting the normal paraffin content from the total paraffin content. It is believed that the values ​​determined herein by the linear paraffin method represent the values ​​obtained according to UOP 990.

[0027] As described above, the UOP 990 can be used to determine the paraffin, cycloalkane, and aromatic content. Note that for some of the paraffin, cycloalkane, and / or aromatic content described herein, supercritical fluid chromatography (SFC) was used. It is believed that the SFC characterization values ​​represent the values ​​obtained according to the UOP 990. For the SFC characterization, a commercial supercritical fluid chromatograph system was used for characterization, and the method represents an extension of the method described in ASTM D5186 to allow for the separate characterization of paraffins and cycloalkanes. The extension of the ASTM D5186 method is achieved by using an additional separation column to allow for the resolution of cycloalkanes and paraffins. The system is equipped with the following components: a high-pressure pump for delivering a supercritical carbon dioxide mobile phase; a temperature-controlled tower oven; an autosampler with a high-pressure liquid injection valve for delivering sample material into the mobile phase; a flame ionization detector; a mobile phase separator (low dead volume tee); a flow separator for maintaining CO 2 a back pressure regulator in a supercritical state; and a computer and data system for controlling the components and recording data signals. For analysis, approximately 75 mg of sample was diluted in 2 ml of toluene and loaded into a standard soundproof plate cap autosampler vial. The sample was introduced through a high pressure sampling valve. SFC separations were performed using multiple commercial silica packing columns (5 microns with 60 or 30 angstrom pores) (250 mm long, 2 mm or 4 mm ID) connected in series. The column temperature was typically maintained at 35 or 40°C. For analysis, the column head pressure was typically 250 bar. Liquid CO 2 The flow rate for a 2 mm ID column is typically 0.3 ml / min or 2.0 ml / min for a 4 mm ID column. The SFC FID signal is integrated into the paraffin and cycloparaffin regions. In addition to characterizing aromatic compounds according to ASTM D5186, supercritical fluid chromatographs are used to analyze the splitting of total paraffins and total cycloparaffins in the sample. Various standards using typical molecular types can be used to calibrate the paraffin / cycloparaffin splitting for quantitative analysis.

[0028] As used herein, the term "paraffin" refers to a saturated hydrocarbon that can be straight or branched. Paraffins can be straight or branched and are considered to be non-cyclic compounds. "Paraffms" are intended to encompass all structural isomeric forms of paraffins. The term "n-paraffin" has the expected definition of a straight chain alkane (no branches or rings in the carbon chain). The term "isoparaffin" is used herein to refer to any alkane that contains one or more branches in the carbon chain but does not contain any ring structure. The term "paraffin" encompasses the terms "n-paraffin" and "isoparaffin".

[0029] In this discussion, the term "isoolefin" is similar to "isoparaffin", but refers to an olefin rather than an alkane. Thus, an isoolefin is defined as an olefin that contains at least one branch in the carbon chain but does not contain a ring structure.

[0030] In this discussion, the term "naphthene" refers to cycloalkane (also known as cycloparaffin). Thus, cycloalkane corresponds to a saturated ring structure. The term cycloalkane encompasses monocyclic cycloalkanes and polycyclic cycloalkanes. Polycyclic cycloalkanes can have two or more rings, such as bicyclic, tricyclic, tetracyclic, pentacyclic, hexacyclic, heptacyclic, octacyclic, nonacyclic and decacyclic. These rings can be fused and / or bridged. Cycloalkanes can also contain various side chains, such as one or more alkyl side chains of 1-10 carbons.

[0031] In this discussion, the term "saturates" refers to all linear, branched, and cyclic alkanes. Thus, saturates correspond to a combination of alkanes and cycloalkanes.

[0032] In this discussion, the term "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. Thus, an aromatic ring corresponds to an unsaturated ring structure. For example, 13 C NMR is used to identify aromatic carbons. Aromatic rings having atoms attached to the ring (e.g., one or more heteroatoms, one or more carbon atoms, etc.) but not part of the ring structure are within the scope of the term "aromatic ring." Additionally, note that ring structures containing one or more heteroatoms (such as sulfur, nitrogen, or oxygen) can correspond to "aromatic rings" if the ring structure otherwise falls within the definition of "aromatic ring."

[0033] In this discussion, the term "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 (e.g., one or more heteroatoms, one or more carbon atoms, etc.) attached to the ring but not part of the ring structure are within the scope of the term "non-aromatic ring."

[0034] In this discussion, the term "aromatic compound" refers to all compounds containing at least one aromatic ring. Such compounds containing at least one aromatic ring include compounds with one or more hydrocarbon substituents. Note that compounds containing at least one aromatic ring and at least one non-aromatic ring fall within the definition of the term "aromatic compound".

[0035] Note that some hydrocarbons present in the feed or product may fall outside the definitions of paraffins, cycloalkanes, and aromatics. For example, any olefin that is not part of an aromatic compound falls outside the above definitions. Similarly, non-aromatic compounds containing heteroatoms such as sulfur, oxygen, or nitrogen are not included in the definition of paraffins or cycloalkanes.

[0036] As used herein, the term "Cx hydrocarbons" or "Cx" refers to hydrocarbon molecules having a carbon number represented by the number "x". The term "Cx+ hydrocarbons" refers to the above molecules having a carbon number represented by the number "x" or greater. For example, "C17+ hydrocarbons" will include hydrocarbons of C17, C18, and higher carbon numbers. Similarly, "Cx- hydrocarbons" refers to the above molecules having a carbon number represented by the number "x" or less.

[0037] Methods and compositions

[0038] Figure 1 A non-limiting example of a process 100 of the present disclosure is shown. The shown process 100 comprises a first oligomerization 104 and a second oligomerization 110, and optionally a hydroprocessing 114. Briefly, an ethylene stream 102 undergoes a 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 isoolefin stream 112. The isoolefin stream 112 has many potential uses. In a non-limiting example, the isoolefin stream 112 undergoes a hydroprocessing 114 and produces an isoparaffin stream 116.

[0039] The ethylene stream 102 may contain at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 20 wppm each of carbon monoxide and hydrogen (or (i) at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 5 wppm each of carbon monoxide and hydrogen, or (ii) at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more 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%. 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%. Methane may be present in the ethylene stream 102 in an amount of no greater than 1000 wppm, or no greater than 500 wppm, or no greater than 250 wppm, or 10 wppm to 1000 wppm, or 10 wppm to 250 wppm, or 100 wppm to 500 wppm, or 250 wppm to 1000 wppm. Each of carbon monoxide and hydrogen can each 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.

[0040] These two kinds of oligomerization have similar chemical reactions, but are not identical steps. The chemical substances of these steps can be realized by very different processes. For example, the first oligomerization 104 can be realized in liquid phase with high efficiency and efficacy using homogeneous catalysts. On the contrary, the second oligomerization 110 of higher molecular weight olefins such as propylene and butene can be carried out more efficiently and effectively with heterogeneous catalysts under the condition that some or all components are supercritical. By oligomerizing ethylene into higher molecular weight olefins (the first oligomerization 104) alone, the obtained olefins can be included as a part of the raw materials in the second oligomerization 110, thereby increasing the total yield of higher molecular weight olefins (for example, C10+ olefins). That is to say, the raw materials of the second oligomerization 110 have the least amount of ethylene. In general, the process may benefit from using (a) the first oligomerization catalyst with specificity for high yield ethylene oligomerization and (b) the second oligomerization catalyst with high yield distillate range olefins obtained from the olefin raw materials with the lowest ethylene content, respectively. Because the two oligomerizations are accomplished as separate processes (although the processes may be conducted in different parts of the same vessel), the overall method and system can have a higher yield of distillate range olefins, which can then be used to produce an isoparaffin stream and additional fuel products (e.g., distillates, jet fuel, kerosene, etc.).

[0041] At least 95% of the ethylene present in the ethylene stream 102 may be converted to C4+ olefins (e.g., C4 olefins, C6 olefins, C8 olefins, and C10 olefins) when the ethylene stream 102 undergoes the first oligomerization 104. The C4+ olefin stream 106 is no greater than 10 wt% of the combined methane, ethylene, and ethane (or (i) no greater than 5 wt% of the combined methane, ethylene, and ethane, or (ii) no greater than 2000 wppm of the combined methane, ethylene, and ethane, or (iii) no greater than 1000 wppm of the combined methane, ethylene, and ethane, or (iv) at least 10 wt% and no greater than 10 wt% (or 2000 wppm or 1000 wppm) of the combined methane, ethylene, and ethane). The C4+ olefins may be present in the C4+ olefin stream 106 in an amount of at least 99 wt%, or at least 99.5 wt%, or at least 99.999 wt%, or between 99 wt% and 99.999 wt%.

[0042] Having small amounts of carbon monoxide and hydrogen in the ethylene stream 102 can allow for high conversion of ethylene to C4+ olefins in the first oligomerization 104. For example, carbon monoxide and hydrogen can be detrimental to the catalyst system in the first oligomerization 104, especially if nickel is used in the first oligomerization 104. However, the first oligomerization 104 can be largely unaffected by saturated hydrocarbons like methane and ethane, which can allow for higher concentrations of saturated hydrocarbons.

[0043] Ethylene stream 102 can come from any suitable source, including but not limited to ethylene derived from ethanol dehydration reaction, steam cracker, fluid catalytic cracker (FCC), ethylene catalytic conversion reaction of methanol commonly referred to as "methanol to olefins (MTO)", etc., and any combination of sources. Note that, with fine-tuning of the rates and / or concentrations of various reaction products and pollutants, most MTO processes can also use the same catalyst and equipment to satisfactorily convert other alcohols such as ethanol or butanol, and / or ethers such as dimethyl ether (DME) or diethyl ether (DEE) into useful olefins, usually in a certain proportion with methanol. Other oxygen-containing molecules such as ketones, aldehydes and esters can also be converted into olefins, but considering their relative hydrogen deficiency to alcohol, more carbonaceous coke will also be produced on the catalyst, which is not ideal. Nevertheless, a small amount of the above oxygen-containing compounds are produced as by-products by the MTO reaction, recovered in some form and recycled back to the MTO reactor with the main alcohol feed. Therefore, the more general term commonly used for these types of technologies is "conversion of oxygen-containing compounds to olefins".

[0044] The first oligomerization 104 may occur in a first oligomerization unit, which may include one or more reactors in series, typically a fixed bed adiabatic reactor housing (or otherwise containing) an oligomerization catalyst, or a continuously stirred tank reactor (CSTR) or a pumped-loop piping system for housing a homogeneous oligomerization catalyst.

[0045] Examples of catalysts used in the first oligomerization 104 may include, but are not limited to: (a) homogeneous catalysts, including (a1) homogeneous catalysts containing organic aluminum, nickel, titanium and / or zirconium or (a2) Ziegler type, wherein (a1) or (a2) may optionally contain a ligand for activating the metal, and may optionally contain a solvent such as a hydrocarbon or an ionic liquid cyclohexane; (b) heterogeneous catalysts, such as (b1) solid phosphoric acid, (b2) microporous materials, such as zeolites, for example, ZSM-5 catalysts, ZSM-57 catalysts, ZSM-22 catalysts, ZSM-48 catalysts, ZSM-12 catalysts, or (b3) silicoaluminophosphate (SAPO) molecular sieves; (c) the like; and (d) any mixture thereof.

[0046] The first oligomerization 104 may utilize a homogeneous organometallic catalyst. This may include, for example, nickel and other metal coordination catalysts, such as described in "Oligomerization of Monoolefins by Homogeneous Catalysts", A. Forestière, Oil & Gas Science and Technology-Rev. IFP, Vol. 64 (2009), No. 6, pp. 649-667. It may be optimal to limit the concentration of C10+ olefins to a small amount (e.g., not more than about 15 wt% of the total C4+ oligomer product) for feeding the stream to the second oligomerization 110. This can be accomplished by using a catalyst known as The ethylene oligomerization process and the one licensed by UOP are called The second oligomerization 110 can be implemented with an ethylene oligomerization process of the reactor system. The second oligomerization 110 can operate acceptably well with C10+ olefins in the reactor system feed, but can operate most efficiently when the concentration of those components is relatively low. The C10+ molecules are already in the carbon number range of distillate products such as diesel and jet fuel, so the main benefit of feeding them to the second oligomerization 110 is to provide alkyl branches to the molecules (by adding lighter olefins) to lower their freezing point, but there is a risk of increased harmful cracking reactions that the higher carbon number olefins are susceptible to.

[0047] The contact between the ethylene stream 102 and the first oligomerization catalyst can be carried out under conditions suitable for oligomerization of ethylene. For example, the temperature can be from about 25° C. to about 300° C. (or from about 50° C. to about 200° C.). For example, the pressure can be from about 100 psia to about 2000 psia (or from about 200 psia to about 1200 psia, or from about 250 psia to about 1000 psia).

[0048] The propylene / C4+ olefin stream 108 and the C4+ olefin stream 106 undergo a second oligomerization 110 (e.g., in a second oligomerization unit) to produce an iso-olefin stream 112. Although shown as entering the second oligomerization 110 separately, the process may include mixing (or otherwise blending) the propylene / C4+ olefin stream 108 and the C4+ olefin stream 106 prior to undergoing the second oligomerization 110.

[0049] The second oligomerization 110 to produce the isoolefin stream 112 may optionally utilize the process described in U.S. Patent 7,692,049, which is incorporated herein by reference in its entirety.

[0050] Propylene / C4+ olefin stream 108 can contain any single C3 to C9 olefin or any ratio thereof.Propylene / C4+ olefin stream 108 can contain at least 50wt% C3+ olefin.C3+ olefin can be present in propylene / C4+ olefin stream 108 with at least 50wt%, at least 60wt%, or at least 70wt%, or at least 80wt%, or 50wt% to 95wt%, or 50wt% to 80wt%, or 60wt% to 90wt%, or 70wt% to 90wt%, or 80wt% to 95wt% amount.The distribution of the carbon number of C3+ olefin can change based on the source of propylene / C4+ olefin stream 108.For example, propylene / C4+ olefin stream 108 can include at least 5wt% propylene, at least 5wt% C4 olefin and C5+ olefin, so that C3+ olefin concentration is at least 50wt% of propylene / C4+ olefin stream 108. The 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 from 5 wt% to 80 wt%, or from 5 wt% to 30 wt%, or from 10 wt% to 50 wt%, or from 25 wt% to 75 wt%, or from 40 wt% to 80 wt% of the propylene / C4+ olefin stream 108. The 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 from 5 wt% to 80 wt%, or from 5 wt% to 30 wt%, or from 10 wt% to 50 wt%, or from 25 wt% to 75 wt%, or from 40 wt% to 80 wt% of the propylene / C4+ olefin stream 108. The C5 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 from 5 wt% to 80 wt%, or from 5 wt% to 30 wt%, or from 10 wt% to 50 wt%, or from 25 wt% to 75 wt%, or from 40 wt% to 80 wt% of the propylene / C4+ olefin stream 108. The 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 from 5 wt% to 80 wt%, or from 5 wt% to 30 wt%, or from 10 wt% to 50 wt%, or from 25 wt% to 75 wt%, or from 40 wt% to 80 wt% of the propylene / C4+ olefin stream 108. In a non-limiting example, the propylene / C4+ olefin stream 108 may include propylene, at least 5 wt% C4 olefins, at least 40 wt% C5 olefins, and at least 10 wt% C6 olefins.In another non-limiting example, the propylene / C4+ olefin stream 108 may include propylene, at least 20 wt% of C4 olefins, at least 40 wt% of C5 olefins, and at least 10 wt% of C6 olefins. In yet another non-limiting example, the propylene / C4+ olefin stream 108 may include propylene, at least 40 wt% of C4 olefins, at least 40 wt% of C5 olefins, and at least 10 wt% of C6 olefins.

[0051] The propylene / 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 fluid catalytic cracker (FCC), a methanol catalytic conversion reaction commonly referred to as "methanol to olefins (MTO), and the like, and any combination of sources.

[0052] The second oligomerization 110 may occur in an oligomerization unit, which may include a fixed bed adiabatic reactor housing (or otherwise containing) an oligomerization catalyst, or an isothermal tubular reactor housing (or otherwise containing) an oligomerization catalyst.

[0053] Examples of oligomerization catalysts that can be used for the second oligomerization 110 may include, but are not limited to, zeolite families, including MWW family (e.g., MCM-22), *BEA family (e.g., zeolite β), FAU catalysts, 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, etc., and any mixtures thereof.

[0054] The contacting of the propylene / C4+ olefin stream 108 and the C4+ olefin stream 106 (introduced as a mixture or separately) with the second oligomerization catalyst can be carried out under conditions suitable for oligomerizing the olefins. For example, the temperature can be from about 150° C. to about 300° C. (or from about 150° C. to about 250° C., or from about 200° C. to about 300° C.). For example, the pressure can be from about 600 psia to about 2000 psia (or from about 600 psia to about 1200 psia, or from about 1000 psia to about 2000 psia).

[0055] The second oligomerization unit or a unit between the second oligomerization unit and the hydroprocessing unit can remove at least one light olefin (e.g., C3-C9 olefin, or C3 to C6 olefin, or C3 to C8 olefin) from the iso-olefin stream 112. The light olefin can be recycled back as part of the feed to the oligomerization unit along with the propylene / C4+ olefin stream 108 and the C4+ olefin stream 106.

[0056] The second oligomerization 110 produces an iso-olefin stream 112. The composition of the iso-olefin stream 112 depends on, among other things, the conditions of the second oligomerization 110, the composition of the propylene / C4+ olefin stream 108, the composition of the C4+ olefin stream 106, and the catalyst.

[0057] The isoolefin stream 112 may contain primarily C6+ olefins (or C8+ olefins, or C9+ olefins). For example, the isoolefin 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 60 wt% 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 more than 20 wt% C5-olefins (or no more than 10 wt% C5-olefins, or no more than 5 wt% C5-olefins). In another example, the iso-olefin stream 112 can 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 60 wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) C8+ olefins (e.g., C8 to C20 olefins) with no more than 20 wt% C7-olefins (or no more than 10 wt% C7-olefins, or no more than 5 wt% C7-olefins). In yet another example, the iso-olefin stream 112 can 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 60 wt% 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 more than 20 wt% C8-olefins (or no more than 10 wt% C8-olefins, or no more than 5 wt% C8-olefins).

[0058] At least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or from 50 wt% to 99 wt%, or from 50 wt% to 80 wt%, or from 60 wt% to 90 wt%, or from 70 wt% to 90 wt%, or from 80 wt% to 99 wt%, or from 94 wt% to 99 wt%) of the olefins in the iso-olefin stream 112 may be iso-olefins.

[0059] For example, 80wt% or more, or 90wt% or more, or 94wt% or more, or 97wt% or more of isoolefin stream 112 can be composed of C9 to C20 isoolefins. Further, 2.0wt% to 25wt%, or 2.0wt% to 15wt%, or 5.0wt% to 25wt%, or 5.0wt% to 15wt%, or 2.0wt% to 10wt% of isoolefin stream 112 can be composed of C9 olefins (e.g., C9 isoolefins). Further, 1.0wt% to 15wt%, or 2.5wt% to 15wt% of isoolefin stream 112 can be composed of C17+ olefins (e.g., C17+ isoolefins). In some aspects, 1.0wt% to 15wt%, or 2.5wt% to 15wt%, or 1.0wt% to 10wt%, or 2.5wt% to 10wt% of isoolefin stream 112 can be composed of C17 and / or C18 olefins (e.g., C17 and / or C18 isoolefins). Further, isoolefin stream 112 can contain 5.0wt% or less, or 3.0wt% or less, or 1.0wt% or less of C19+ olefins (e.g., C19+ isoolefins), such as being as low as substantially free of C19+ hydrocarbons. Further, isoolefin stream 112 can contain 5.0wt% or less, or 3.0wt% or less, or 1.0wt% or less, or 0.5wt% or less of C8-olefins, such as being as low as 0.1wt% or possibly still lower (i.e., being substantially free of C8-olefins).

[0060] In another example, the isoolefin stream 112 may contain 60 wt% to 90 wt% C11 to C18 olefins (e.g., C11 to C18 isoolefins). Additionally or alternatively, the isoolefin stream 112 may contain 50 wt% to 75 wt% C12 to C16 olefins (e.g., C12 to C16 isoolefins). This is particularly advantageous for being suitable for additional processing (e.g., hydroprocessing), where the resulting product can be flexibly used as aviation or diesel fuel.

[0061] The isoolefin stream 112 may contain reduced or minimal amounts of aromatic compounds. This may correspond to 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 of aromatic compounds, such as down to substantially no aromatic compounds.

[0062] The composition of the isoolefin stream 112 or a portion or fraction thereof may be a suitable product for various applications, or suitable for further processing into suitable products for various applications. For example, the isoolefin stream 112 may be suitable for further processing to produce a blend composition (e.g., a jet fuel blend stock, a diesel fuel blend stock, a distillate blend stock, a kerosene blend stock, etc.), specialty chemicals (e.g., surfactants, lubricants, solvents, hydraulic and other working fluids, etc.), etc. In a non-limiting example, a portion or all of the isoolefin stream 112 may be further subjected to hydroprocessing 114 to produce an isoparaffin stream 116 (preferably with an olefin content of no more than 10 wt %).

[0063] Mild hydrotreating can generally convert isoolefins to isoparaffins while reducing or minimizing the amount of reduction in carbon chain size in the fraction. In addition to converting isoolefins to isoparaffins, hydrotreating of the kerosene fraction can also be used for desulfurization, denitrogenation, saturation of olefins, saturation of aromatic compounds, and / or for other purposes.

[0064] During hydroprocessing, a feedstock consisting partially or entirely of a jet fuel boiling range fraction is treated in a hydroprocessing (or other hydroprocessing) reactor comprising one or more hydroprocessing stages or beds. Optionally, the reaction conditions in the hydroprocessing stage may be conditions suitable for reducing the sulfur content of the feed stream, such as conditions suitable for reducing the sulfur content of the feed stream to 500 wppm or less, or 100 wppm or less, or 10 wppm or less, such as as low as 0.5 wppm or possibly still lower. The reaction conditions may comprise 0.1 to 20.0 hr -1 The reaction conditions preferably include a LHSV of about 50 psig (0.34 MPag) to about 3000 psig (20.7 MPag) of hydrogen partial pressure, a process gas containing at least about 50% hydrogen, and a temperature of about 450°F (232°C) to about 800°F (427°C). Preferably, the reaction conditions include about 0.3 to about 5 hr -1 The reactor has an LHSV of about 100 psig (0.69 MPag) to about 1000 psig (6.9 MPag), and a temperature of about 700°F (371°C) to about 750°F (399°C).

[0065] Optionally, a hydroprocessing reactor operating at a relatively low total pressure value may be used, such as a total pressure of about 200 psig (1.4 MPag) to about 800 psig (5.5 MPag). For example, the pressure in a certain stage in the hydroprocessing reactor may 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 certain stage in the hydroprocessing reactor may be about 800 psig (5.5 MPag) or less, or about 700 psig (4.8 MPag) or less, or about 600 psig (4.1 MPa) or less.

[0066] The catalyst in the hydroprocessing stage can be a conventional hydroprocessing catalyst, such as a catalyst consisting of a VIB group metal and / or a VIII group metal on a carrier. Suitable metals include cobalt, nickel, molybdenum, tungsten or a combination thereof. Preferred metal combinations include nickel and molybdenum or nickel, cobalt and molybdenum. Suitable carriers include silicon dioxide, silicon dioxide-alumina, aluminum oxide and titanium dioxide.

[0067] The isoparaffin stream 116 from the hydroprocessing 114 can be suitable for producing a blend composition (e.g., a jet fuel blend stock, a diesel fuel blend stock, a distillate blend stock, a kerosene blend stock, etc.). Advantageously, the isoolefin stream 112 and the resulting isoparaffin stream 116 can have a low aromatic content, which can be advantageous for producing a low aromatic content fuel (e.g., jet fuel, a jet fuel blend stock).

[0068] The isoparaffin stream 116 may have a carbon number distribution similar to that of the isoolefin stream 112, but as paraffins rather than olefins. Thus, the isoparaffin stream 116 may contain primarily C6+ isoparaffins (or C8+ isoparaffins, or C9+ isoparaffins). For example, the isoparaffin 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 60 wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) of C6+ paraffins (e.g., C6 to C20 paraffins) with no more than 20 wt% of C5-paraffins (or no more than 10 wt% of C5-paraffins, or no more than 5 wt% of C5-paraffins). In another example, the isoparaffin stream 116 can 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 60 wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) of C8+ paraffins (e.g., C8 to C20 paraffins) with no more than 20 wt% C7-paraffins (or no more than 10 wt% C7-paraffins, or no more than 5 wt% C7-paraffins). In yet another example, the isoparaffin stream 116 can 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 60 wt% to 90 wt%, or 70 wt% to 90 wt%, or 80 wt% to 99 wt%, or 94 wt% to 99 wt%) of C9+ paraffins (e.g., C9 to C20 paraffins) with no more than 20 wt% C8-paraffins (or no more than 10 wt% C8-paraffins, or no more than 5 wt% C8-paraffins).

[0069] At least 50 wt% (or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or from 50 wt% to 99 wt%, or from 50 wt% to 80 wt%, or from 60 wt% to 90 wt%, or from 70 wt% to 90 wt%, or from 80 wt% to 99 wt%, or from 94 wt% to 99 wt%) of the paraffins in the isoparaffin stream 116 may be isoparaffins.

[0070] For example, 80 wt% or more, or 90 wt% or more, or 94 wt% or more, or 97 wt% or more of the isoparaffin stream 116 may consist of C9 to C20 isoparaffins. Further, 2.0 wt% to 25 wt%, 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% of the isoparaffin stream 116 may consist of C9 paraffins (e.g., C9 isoparaffins). Further, 1.0 wt% to 15 wt%, or 2.5 wt% to 15 wt% of the isoparaffin stream 116 may consist of C17+ paraffins (e.g., C17+ isoparaffins). In some aspects, 1.0 wt% to 15 wt%, or 2.5 wt% to 15 wt%, or 1.0 wt% to 10 wt%, or 2.5 wt% to 10 wt% of the isoparaffin stream 116 can be composed of C17 and / or C18 paraffins (e.g., C17 and / or C18 isoparaffins). Further, the isoparaffin stream 116 can contain 5.0 wt% or less, or 3.0 wt% or less, or 1.0 wt% or less of C19+ paraffins (e.g., C19+ isoparaffins), such as down to substantially free of C19+ hydrocarbons. Further, the isoparaffin stream 116 can contain 5.0 wt% or less, or 3.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less of C8-paraffins, such as down to 0.1 wt% or possibly still lower (i.e., substantially free of C8-paraffins).

[0071] In another example, the isoparaffin stream 116 can contain 60 wt% to 90 wt% C11 to C18 paraffins (e.g., C11 to C18 isoparaffins). Additionally or alternatively, the isoparaffin stream 116 can contain 50 wt% to 75 wt% C12 to C16 paraffins (e.g., C12 to C16 paraffins). This is particularly advantageous for being suitable for additional processing (e.g., hydroprocessing), where the resulting product can be flexibly used as aviation or diesel fuel.

[0072] The isoparaffin stream 116 may contain reduced or minimal amounts of aromatic compounds. This may correspond to 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 of aromatic compounds, such as down to substantially no aromatic compounds.

[0073] Although Figure 1 The description of provides non-limiting examples of sources of ethylene stream 102 and propylene / C4+ olefin stream 108, but Figure 1 The source of said is not stated. Figure 2Non-limiting examples are presented that include processes for converting oxygenates to olefins and then separating the olefin products to produce both an ethylene stream and a propylene / C4+ olefin stream as potential sources.

[0074] Figure 2 A non-limiting exemplary method 200 of the present disclosure is presented, which shows an oxygenate to olefin reaction 220, followed by separation 226 of the products from the oxygenate to olefin process 220, a first oligomerization 204, and a second oligomerization 210. In short, an oxygenate stream 218 (e.g., including methanol and optionally dimethyl ether) undergoes an oxygenate to olefin reaction 220, which produces a water stream 222 and a raw olefin stream 224. 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 produce a C4+ olefin stream 206. The propylene / C4+ olefin stream 208 and the C4+ olefin stream 206 can then be used for various applications. In the illustrated example, the propylene / C4+ olefin stream 208 and the C4+ olefin stream 206 are inputs to the second oligomerization 210 to produce an isoolefin stream 212. In alternative embodiments, the second oligomerization may be eliminated and the propylene / C4+ olefins stream 208 and the C4+ olefins stream 206 may be used as feeds to other processes.

[0075] Oxygenated compound stream 218 can come from any suitable source. In non-limiting examples, oxygenated compounds (e.g., methanol) can be produced by reforming natural gas, reforming coal, reforming municipal waste, reforming biomass, fermenting biomass, electrolyzing water to produce hydrogen for reacting with carbon monoxide and / or carbon dioxide, etc. and any combination thereof. Typically, electrolyzing water produces hydrogen and oxygen. The hydrogen can then react with carbon monoxide and / or carbon dioxide to produce methanol.

[0076] Examples of methanol conversion catalysts that can be used for oxygenate-to-olefin reaction 220 can include, but are not limited to, microporous materials such as zeolites, SAPO and ALPO materials. Such materials can include, but are not limited to, zeolite families, including MWW family (e.g., MCM-22), *BEA family (e.g., zeolite β), 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 SAPO-34 (CHA) or mixtures thereof (including intergrowths).

[0077] The contacting of the oxygenate stream 218 with the methanol conversion catalyst can be carried out under conditions suitable for producing olefins. For example, the inlet temperature can be from about 300° C. to about 625° C. (or from about 400° C. to about 600° C., or from about 450° C. to about 550° C.). For example, the pressure can be from about 20 psia to about 300 psia (or from about 30 psia to about 250 psia, or from about 50 psia to about 150 psia).

[0078] The oxygenate to olefin reaction 220 may occur in a fixed bed adiabatic reactor housing (or otherwise containing) a methanol conversion catalyst and receiving an input of the oxygenate stream 218 .

[0079] The gained original olefin stream 224 can comprise ethene, propylene and C4+ olefin, wherein at least 10wt% of all olefins in the stream can be ethene.Original olefin stream 224 can further comprise the methane and ethane of at least 1000wppm separately, and carbon monoxide and hydrogen of at least 100wppm separately.In other aspects, original olefin stream 224 can comprise other components of volatility range from hydrogen to butane, such as propane or dimethyl ether.The definite composition of original olefin stream 224 will depend on the concrete method that produces original olefin stream 224, and further depend on the concrete means of operating these methods.

[0080] The raw olefin stream 224 may have been processed by various methods (e.g., in or downstream of the unit where the oxygenate to olefin reaction 220 occurs) to remove some of the byproducts produced by a given olefin production process. Such methods and related systems may be used for the raw olefin stream 224 within the scope of the present disclosure, but are not described in detail herein. Figure 2 In the embodiment of the present invention, the present invention is shown in Figure 2. The example of such method can include but is not limited to reactor effluent quenching and large amount of water removal, gas compression, washing with caustic solution to remove carbon dioxide, gas drying to complete drying, C5+ species and C4 species separation or saturation with hydrogen selectivity to remove acetylene and methylacetylene, and other methods fully recorded in this area. Those skilled in the art can easily modify the present disclosure to use the original olefin stream 224 derived from multiple olefin production processes. It is also useful to merge the olefin streams from different sources or processes. In non-limiting examples, the ethylene derived from the ethanol dehydration reaction can be merged with hydrogen, CO, propylene, unreacted propane and C4+ by-products derived from the propane dehydrogenation reaction to produce the original olefin stream 224.

[0081] The raw olefin stream 224 then undergoes separation 226 to produce an ethylene stream 202 and a propylene / C4+ olefin stream 208. The separation 226 may occur in a separation system. Examples of separation devices that may be included in the separation system may include, but are not limited to, fractionators, membranes, and the like, and any combination thereof.

[0082] Separation 226 may occur in the same unit as oxygenate to olefin reaction 220 or in a downstream unit.

[0083] Separation 226 involves differences in component volatility using equipment such as flash tanks and distillation columns, which can be configured in a variety of ways to produce ethylene stream 202 exiting separation 226. Hydrogen, carbon monoxide, propylene, and C4+ olefins can be separated from raw olefin stream 224 to produce ethylene stream 202. The ethylene stream 202 may contain at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 20 wppm each of carbon monoxide and hydrogen (or (i) at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 5 wppm each of carbon monoxide and hydrogen, or (ii) at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 1 wppm each of carbon monoxide and hydrogen), and at least 95 wt% of all ethylene in the original 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 original olefin stream 224. Separation 226 creates separate lines for less volatile components such as propylene and C4+ olefins to be separated from the ethylene and ethane in ethylene stream 202, which exit separation as propylene / C4+ olefins stream 208. The separation process may also include membranes and absorption systems in lieu of or in addition to distillation columns. Figure 1 The composition of the ethylene stream 102 is described as applicable to Figure 2 of ethylene stream 202.

[0084] Figure 2 The propylene / C4+ olefin stream 208 after separation 226 is shown as a single stream, but the propylene / C4+ olefin stream 208 can be two separate streams (e.g., a first stream comprising relatively pure propylene and a second stream comprising relatively pure C4+ olefins). This additional separation can be performed with an additional distillation column and can include separating propylene from propane and similar or less volatile components such as dimethyl ether. This process, known in the art as a "propylene concentrator," is particularly useful if the olefin source is oxygenate conversion, which can produce significant amounts of dimethyl ether, or catalytic cracking, which can produce significant amounts of propane, neither of which is particularly desirable to provide to the optional second oligomerization 210.

[0085] Figure 1 The disclosure of ethylene stream 102, first oligomer 104, C4+ olefin stream 106, propylene / C4+ olefin stream 108, second oligomer 110, and isoolefin stream 112 is applicable to Figure 2ethylene stream 202, first oligomerization 204, C4+ olefin stream 206, propylene / C4+ olefin stream 208, second oligomerization 210, and isoolefin stream 212. Additional embodiments may include additional processing of isoolefin stream 212, as discussed with respect to additional processing of isoolefin stream 112, including hydroprocessing to produce an isoparaffin stream.

[0086] Figure 3 A non-limiting example of a method 300 of the present disclosure is shown, wherein a non-limiting example separation 326 is described. Figure 1 and / or Figure 2 The disclosure of steps, streams, processes, units, etc. having the last two reference numerals corresponding to the preceding reference numerals in FIG. 1 (e.g., propylene / C4+ olefin stream 108) is applicable to steps, streams, processes, units, etc. having the same reference numerals as those in FIG. Figure 3 The last two reference numerals in the same reference numeral correspond to the steps, streams, processes, units, etc. (e.g., propylene / C4+ olefin stream 308). However, in Figure 3 The separation 326 shown in FIG. 1 is a non-limiting example of a separation, and is one of many possible separations that may be used for the separations shown in any other figures in this disclosure.

[0087] As shown, the raw olefin stream 324 undergoes separation 326 to remove hydrogen, carbon monoxide, propylene, and C4+ olefins from ethylene and ethane. Briefly, separation 326 produces three separate streams, wherein (1) higher volatility components (e.g., methane, hydrogen, and carbon monoxide) form a high volatility stream 334, (2) lower volatility components (e.g., propylene and C4+ olefins) form a propylene / C4+ olefin stream 308, and (3) medium volatility components (e.g., ethylene and ethane) form an ethylene stream 302.

[0088] In separation 326, the raw olefin stream 324 is first introduced into a deethanizer distillation column 328, which separates lower volatility components (e.g., propylene and C4+ olefins) from higher and medium volatility components (e.g., ethylene, ethane, methane, carbon monoxide, and hydrogen) to produce a 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 higher volatility components from medium volatility components to produce a high volatility stream 334 and an ethylene stream 302. The ethylene stream 302 may contain at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 20 wppm each of carbon monoxide and hydrogen (or (i) at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 5 wppm each of carbon monoxide and hydrogen, or (ii) at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 1 wppm each of carbon monoxide and hydrogen), and at least 95 wt% of all ethylene in the original olefin stream 324 may be recovered in the ethylene stream 302. In this embodiment, the ethylene stream 302 may also contain at least 90% of the ethane present in the original olefin stream in the pipeline 324, which eliminates the need for a distillation column (referred to in the art as a "C2 splitter") for separating ethylene from ethane.

[0089] 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 feeds in a second oligomerization 310. As shown, the C4+ olefin stream 306 is combined with the propylene / C4+ olefin stream 308 into a feed stream 338, which enters the second oligomerization 310. The second oligomerization 310 produces a desired isoolefin stream 312. Additional embodiments may include additional processing of the isoolefin stream 312, as discussed with respect to the additional processing of the isoolefin stream 112, including hydroprocessing to produce an isoparaffin stream.

[0090] Figure 4 A non-limiting example of a method 400 of the present disclosure is shown, wherein a non-limiting example first oligomerization 404 is described. Figure 1 , Figure 2 and / or Figure 3 The disclosure of steps, streams, processes, units, etc. having the last two reference numerals corresponding to the preceding reference numerals in FIG. 1 (e.g., propylene / C4+ olefin stream 108) is applicable to steps, streams, processes, units, etc. having the same reference numerals as those in FIG. Figure 3 The last two reference numerals in the same reference numeral correspond to the steps, streams, processes, units, etc. (e.g., propylene / C4+ olefin stream 308). However, in Figure 4 The first oligomerization 404 shown in FIG. 4 is a non-limiting example of a separation, and is one of many possible separations that may be used for the separations shown in any of the other figures in this disclosure.

[0091] Briefly, a raw olefin stream 424 undergoes separation 426 to produce at least two streams: an ethylene stream 402 and a propylene / C4+ olefin stream 408, and optionally a high volatility stream 434 (e.g., when Figure 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 into a C4+ olefin stream 406. The C4+ olefin stream 406 may contain no more than 10 wt% of combined methane, ethylene, and ethane (or (i) no more than 5 wt% of combined methane, ethylene, and ethane, or (ii) no more than 2000 wppm of combined methane, ethylene, and ethane, or (iii) no more than 1000 wppm of combined methane, ethylene, and ethane, or (iv) at least 10 wt% and no more than 10 wt% (or 2000 wppm or 1000 wppm) of combined methane, ethylene, and ethane). The C4+ olefin stream 406 and the propylene / C4+ olefin stream 408 then undergo a second oligomerization 410. Although optional, as shown, streams 406 and 408 are combined into feed stream 438 prior to second oligomerization 410 to produce isoolefin stream 412. Additional embodiments may include additional processing of isoolefin stream 412, as discussed with respect to additional processing of isoolefin stream 112, including hydroprocessing to produce an isoparaffin stream.

[0092] The process of the first oligomerization 404 can include introducing the ethylene stream 402 into the reactor 442, in which the oligomerization reaction of the ethylene stream 402 to the intermediate C4+ olefin stream 444 occurs. The oligomerization can convert at least 95% of the ethylene in the ethylene stream 402 into C4+ oligomers when passing through the reactor 442 once. The first oligomerization unit can include two or more reactors arranged in series, wherein the hydrocarbon product from one reactor containing some product oligomers and unreacted ethylene is sent as a feed to the next reactor in series to convert additional ethylene into oligomer products. Alternatively, the first oligomerization unit can include two or more reactors arranged in parallel, for example, the feed is divided into two streams to enter two independent reactors, increasing the overall capacity of the first oligomerization unit. Further, a mixture of the above reactors can be included in the first oligomerization unit, wherein some reactors are arranged in parallel, and others are arranged in series.

[0093] Then the intermediate C4+olefin stream 444 from reactor 442 is introduced into a light-removing tower 446 to remove components with higher volatility than butenes, as well as potential small amounts of butenes, to produce a light fuel gas stream 436. The higher volatile components in the light fuel gas stream 436 may mainly include methane, ethane, and unreacted ethylene. Using a light-removing tower 446 to separate saturated hydrocarbons such as methane and ethane from the intermediate C4+olefin stream 444 may advantageously reduce energy intensity and / or require less complex components, compared to separating saturated hydrocarbons from more proximal volatile ethylene in an earlier separation 426. That is, the upstream separation may produce only two streams, wherein the higher volatile components are retained in the ethylene stream. Then, the higher volatile components may be removed in the first oligomerization by including a light-removing tower downstream of the oligomerization reactor. The light-removing tower may be in the first oligomerization unit or downstream thereof.

[0094] Another advantage of including a light removal column downstream of reactor 442 is that the first oligomerization reaction and the first oligomerization catalyst can be largely unaffected by saturated hydrocarbons because saturated hydrocarbons are substantially inert in the first oligomerization reaction. Therefore, the requirement to separate saturated hydrocarbons in separation 426 can be relaxed or eliminated, which has significant energy usage benefits and cost benefits.

[0095] Figure 5 A non-limiting example of a method 500 of the present disclosure is shown, wherein a non-limiting example second oligomer 510 is described. Figure 1 , Figure 2 , Figure 3 and / or Figure 4 The disclosure of steps, streams, processes, units, etc. having the last two reference numerals corresponding to the preceding reference numerals in FIG. 1 (e.g., propylene / C4+ olefin stream 108) is applicable to steps, streams, processes, units, etc. having the same reference numerals as those in FIG. Figure 3 The last two reference numerals in the same reference numeral correspond to the steps, streams, processes, units, etc. (e.g., propylene / C4+ olefin stream 308). However, in Figure 5 The second oligomer 510 shown in FIG. 5 is a non-limiting example of a separation, and is one of many possible separations that may be used for the separations shown in any of the other figures in this disclosure.

[0096] As shown, raw olefin stream 524 enters separation 526 which produces ethylene stream 502 and propylene / C4+ olefin stream 508, and optionally high volatility stream 534 (e.g., when Figure 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 (e.g., when a light removal tower is used, such as the first oligomerization 504, which may be based on Figure 4 The first oligomerization 404 occurs).

[0097] The C4+ olefin stream 506 and the propylene / C4+ olefin stream 508 then undergo a second oligomerization 510. Although optional, as illustrated, the streams 506 and 508 are combined into a feed stream 538 prior to the second oligomerization 510 to produce an iso-olefin stream 512.

[0098] The second oligomerization 510 is shown as occurring in a second oligomerization unit comprising a reactor 552 , a mogas / distillate fractionator 556 , and a debutanizer fractionator 562 .

[0099] Feed stream 538 is combined with top recycle stream 568 and bottom recycle stream 566 to form a combined second oligomerization reactor feed stream 550 comprising C4-C10+ olefins that may contain not greater than about 10 wt% C10+ olefins. Combined feed stream 550 is provided to reactor 552, which produces a reactor product 554 rich in distillate range C10+ olefins (e.g., C10+ iso-olefins), as well as unreacted and newly produced C4-C9 olefins of various isomers.

[0100] The reactor product 554 is directed to a mercury / distillate fractionator 556, which separates a C9- or C10- first mercury stream 558 from a C10+ isoolefin stream 512. The C10+ isoolefin stream 512 is removed from the second oligomerization unit 510 and can be used in a variety of applications. The C9- first mercury stream 558 is split into two streams, typically most of which becomes a top recycle stream 568, and the remainder becomes a debutanizer feed stream 560. The debutanizer feed stream 560 is sent to a debutanizer fractionator 562, which separates a C4- purge stream 540 from a C5+ second mercury stream 564. A C4 − purge stream 540 is removed from the second oligomerization unit 510 , while a C5+ second mercury stream 564 is split into two streams, typically most becoming a bottoms recycle stream 566 and the remainder becoming a mercury product purge stream 548 which is also removed from the second oligomerization unit 510 .

[0101] As described above, propylene / C4+ olefin stream 508 and C4+ olefin stream 506 can be introduced into reactor 552 separately. In the variation within the scope of the present disclosure, depending on the exact composition involved, including olefins and potential low concentrations of contaminants, it may be desirable to provide each of streams 506 and 508 to a separation point within the second oligomerization unit. For example, C4+ olefin stream 508 can contain up to 15wt% or even more C10+ olefins that are already in the distillate range. In order to minimize the load on reactor 552, propylene / C4+ olefin stream 508 can be the feed gas to reactor 552, and C4+ olefin stream 506 can be added directly to the mercury / distillate fractionator 556. In this manner, the Merck / distillate fractionator 556 separates the C10+ molecules in the C4+ olefin stream 506 directly into the iso-olefin stream 512, and separates the lower carbon number molecules in the C4+ olefin stream 506 into Merck range materials 558, most of which will become the recycle feed to the reactor 552 to produce additional iso-olefin stream 512.

[0102] Additional embodiments may include additional processing of the isoolefin stream 512, as discussed with respect to the additional processing of the isoolefin stream 112, including hydroprocessing to produce an isoparaffin stream.

[0103] Isoparaffin blending component of jet / kerosene boiling range products for blending

[0104] In various aspects, the isoparaffin blend component (e.g., Figure 1-5 All or a portion of the isoparaffin stream discussed in ) can be used to form a blended product that can correspond to a jet fuel and / or a jet fuel blending component. Optionally, an isoolefin blending component can be used instead of or in addition to the isoparaffin blending component.

[0105] In this discussion, for an isoparaffin blend component or an isoolefin blend component, a fraction will contain 50 wt% or more, or 60 wt% or more, or 70 wt% or more, or 80 wt% or more of the combined weight of isoparaffins and isoolefins, such as up to a fraction consisting essentially of isoparaffins and isoolefins (i.e., less than 5.0 wt%, or less than 3.0 wt%, or less than 1.0 wt% of other types of hydrocarbons / compounds, such as as low as zero). In addition to the foregoing, an isoparaffin blend component refers to a fraction containing less than 5.0 wt% isoolefins and 80 wt% or more, or 85 wt% or more, or 90 wt% or more of isoparaffins (relative to the weight of the fraction), such as up to essentially all of the fraction corresponding to isoparaffins. The iso-olefin blend component refers to a fraction that: a) meets the combined amount requirements of iso-olefins and iso-paraffins; and b) contains 5.0 wt% or more, or 25 wt% or more, or 50 wt% or more, or 70 wt% or more of iso-olefins, such as up to substantially all of the fraction corresponding to iso-olefins.

[0106] In various aspects, the isoparaffin blend component and / or the isoolefin blend component can have one or more of the following properties. In some aspects, 80 wt% or more, or 90 wt% or more, or 94 wt% or more, or 97 wt% or more of the blend component is C 9 To C 20 In some aspects, 2.0 wt% to 25 wt%, 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% of the blended components consists of C 9 In some aspects, 1.0 wt% to 15 wt%, or 2.5 wt% to 15 wt% of the blended components consist of C 17 In some aspects, 1.0 wt% to 15 wt%, or 2.5 wt% to 15 wt%, or 1.0 wt% to 10 wt%, or 2.5 wt% to 10 wt% of the blended components consists of C 17 and / or C 18 In some aspects, the blended components may contain 5.0 wt% or less, or 3.0 wt% or less, or 1.0 wt% or less of C 19+ Hydrocarbons, such as low to essentially free of C 19+ In some aspects, the blended components may contain 5.0 wt% or less, or 3.0 wt% or less, or 1.0 wt% or less, or 0.5 wt% or less of C 8- Hydrocarbons, such as as low as 0.1 wt% or possibly still lower (i.e., substantially free of C 8-In some aspects, the specific gravity of the blended components at 15° C. is 0.730 g / cm 3 Up to 0.775g / cm 3 .

[0107] In some aspects, the blend components may contain 60 wt % to 90 wt % of C 11 To C 18 Additionally or alternatively, the blend component may contain 50 wt % to 75 wt % of C 12 To C 16 This is particularly advantageous for the flexible use of the composition as aviation or diesel fuel.

[0108] In various aspects, the blend components can contain reduced or minimal amounts of aromatic compounds. This can correspond to containing 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 of aromatic compounds, such as down to substantially no aromatic compounds.

[0109] In various aspects, the flash point of the blend components can be 38° C. or higher, or 40° C. or higher, or 45° C. or higher, or 50° C. or higher, or 55° C. or higher, such as up to 60° C. or potentially still higher. Additionally or alternatively, when tested alone (i.e., before blending with another fraction), the Jet Fuel Thermal Oxidation Test (JFTOT) breakpoint results of the blend components can be 260° C. or higher, or 270° C. or higher, or 280° C. or higher, such as up to 320° C. or potentially still higher.

[0110] In some aspects, the conductivity of the blend component can be 10 pS / m or less (according to ASTM test method D2624) before any additives are added, such as as low as substantially no conductivity. Note that the isoparaffin blend component as described herein has a good response to conductive additives. After adding conventional additives for conductivity, the conductivity of the isoparaffin blend component can be 50 pS / m to 600 pS / m.

[0111] The isoparaffin blend component can be blended with one or more other fractions to form a kerosene / jet boiling range product. Examples of fractions that can be blended with the isoparaffin blend component include, but are not limited to, conventional jet fractions, mineral naphthas and / or jet and / or diesel boiling range fractions, and various types of synthetic naphthas, jet and / or diesel boiling range fractions, such as sustainable aviation fuel fractions and / or Fischer-Tropsch fractions. Other challenging fractions, at least a portion of which corresponds to a jet and / or diesel boiling range component, can also be blended with the isoparaffin blend component.

[0112] In various aspects, the blended product may contain 1.0 vol% or more, or 10 vol% or more, or 30 vol% or more, or 50 vol% or more, or 65 vol% or more, or 75 vol% or more of the isoparaffin blend component, such as up to 99 vol% or possibly still higher. In some aspects, such blended products may contain 1.0 vol% to 20 vol%, or 1.0 vol% to 15 vol%, or 5.0 vol% to 20 vol%, or 5.0 vol% to 15 vol%, or 10 vol% to 20 vol% of the isoparaffin blend component. In other aspects, such blended components may contain 30 vol% to 99 vol%, or 30 vol% to 95 vol%, or 30 vol% to 80 vol%, or 30 vol% to 60 vol%, or 30 vol% to 45 vol%, or 50 vol% to 99 vol%, or 50 vol% to 95 vol%, or 50 vol% to 80 vol%, or 70 vol% to 99 vol% of the isoparaffin blend component.

[0113] In some aspects, 0.1 wt% to 15 wt%, or 1.0 wt% to 15 wt%, or 2.5 wt% to 15 wt%, or 0.1 wt% to 10 wt%, or 1.0 wt% to 10 wt%, or 2.5 wt% to 10 wt%, or 1.0 wt% to 6.0 wt%, or 2.5 wt% to 6.0 wt%, or 1.0 wt% to 3.0 wt%, or 0.1 wt% to 6.0 wt%, or 0.1 wt% to 3.0 wt% of the resulting blended product may be C 17 + hydrocarbons. In some aspects, 0.1 wt% to 15 wt% of the resulting blended product may be C 17 and / or C 18 For example, the resulting blended product may contain 0.1 wt% or more, or 1.0 wt% or more, or 1.5 wt% or more, or 2.0 wt% or more, or 4.0 wt% or more, or 6.0 wt% or more, or 10 wt% or more of C 17 -C 18 In some aspects, the resulting blended product may contain 5.0 wt% or less, or 3.0 wt% or less, or 1.0 wt% or less, or 0.1 wt% or less of C 19+ Hydrocarbons, such as low to essentially free of C 19+ hydrocarbon.

[0114] In some aspects, the resulting blended product can have an unexpectedly high content of C 9In such aspects, the resulting blended product may contain 5.0 wt% or more, or 10 wt% or more, or 15 wt% or more of C 9 Hydrocarbons, such as up to 25 wt% or possibly still higher.

[0115] In various aspects, the resulting blended product may have a specific gravity of 0.775 g / cm at 15°C. 3 Up to 0.840g / cm 3 . Additionally or alternatively, the flash point of the resulting blended product may be 38°C or higher, or 40°C or higher, or 45°C or higher, or 50°C or higher, such as up to 60°C or possibly still higher. Further additionally or alternatively, the Jet Fuel Thermal Oxidation Test (JFTOT) breakpoint result of the resulting blended product may be 260°C or higher, or 270°C or higher, or 280°C or higher, such as up to 320°C or possibly still higher. Still further additionally or alternatively, the freezing point of the resulting blended product may be -40°C or lower, or -47°C or lower, or -50°C or lower, or -55°C or lower, such as as low as -70°C or possibly still lower.

[0116] In some aspects, the final boiling point of the resulting blended product can be 300° C. or less, even if the resulting blended product contains 1.0 wt % or more of C 17+ hydrocarbon.

[0117] In various aspects, the resulting blended product can contain reduced or minimal aromatic compounds. This can correspond to containing 15wt% or less, or 10wt% or less, or 5.0wt% or less, or 3.0wt% or less, or 1.0wt% or less, or 0.5wt% or less, or 0.1wt% or less aromatic compounds, such as being as low as substantially free of aromatic compounds. Additionally or alternatively, the sulfur content can be 500wppm or less, or 250wppm or less, or 100wppm or less, or 10wppm or less, such as being as low as 0.5wppm or possibly still lower.

[0118] In some aspects, the product of the obtained blending can include at least a portion of one or more conventional jet fuels. Conventional jet fuel is defined herein as a fraction that has been qualified as jet fuel according to at least one of ASTM D1655, British Ministry of Defense Standard 91-091 and Canadian General Standards Committee 3.23. In such aspects, the product of the obtained blending can include 1.0vol% to 99vol%, or 1.0vol% to 90vol%, or 1.0vol% to 70vol%, or 1.0vol% to 50vol%, or 1.0vol% to 30vol%, or 1.0vol% to 10vol%, or 10vol% to 70vol%, or 10vol% to 50vol%, or 10vol% to 30vol%, or 30vol% to 70vol% conventional jet fuel fractions. Thus, in some aspects, the resulting blended product can contain 50 vol% or less, or 30 vol% or less, or 10 vol% or less of conventional jet fuel fractions, such as as low as 1.0 vol% or possibly still less.

[0119] In some aspects, the product of the obtained blending can include at least a portion of one or more mineral kerosene / jet boiling range fractions. In such aspects, the product of the obtained blending can include 1.0vol% to 99vol%, or 1.0vol% to 90vol%, or 1.0vol% to 70vol%, or 1.0vol% to 50vol%, or 1.0vol% to 30vol%, or 1.0vol% to 10vol%, or 10vol% to 70vol%, or 10vol% to 50vol%, or 10vol% to 30vol%, or 30vol% to 70vol% jet / kerosene boiling range fractions. Therefore, in some aspects, the product of the obtained blending can include 50vol% or less, or 30vol% or less, or 10vol% or less jet / kerosene boiling range fractions, such as as low as 1.0vol% or may still be lower.

[0120] In some aspects, the resulting blended product can include at least a portion of one or more synthetic jet boiling range fractions, optionally as defined in ASTM D7566. In these aspects, the resulting blended product can include 1.0 vol% to 99 vol%, 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 70 vol%, or 10 vol% to 50 vol%, or 10 vol% to 30 vol%, or 30 vol% to 70 vol% of a synthetic jet boiling range fraction. Therefore, in some aspects, the resulting blended product can include 50 vol% or less, or 30 vol% or less, or 10 vol% or less of a synthetic jet boiling range fraction, such as as low as 1.0 vol% or possibly still lower.

[0121] Note that the isoparaffins and / or components can be blended with a variety of different types of fractions. For example, in some aspects, the blended product can include two or more (or three or more) of a conventional jet fuel fraction, a mineral jet boiling range fraction, and a synthetic fraction. Examples of synthetic fractions include bio-derived fractions, sustainable aviation fuels, and / or Fischer-Tropsch fractions.

[0122] In some aspects, after the components are blended together to form the kerosene / jet fuel boiling range fraction, it may be desirable to further process the kerosene / jet boiling range fraction for any convenient reason. Examples of additional processing methods may include, but are not limited to, wet processing, clay processing, acid and / or caustic processing, mercaptan oxidation, salt drying, and hydroprocessing.

[0123] Distribution of carbon atom types in isoparaffin streams and related blend components and blends

[0124] In some aspects, the isoparaffin stream formed according to the process has a distribution of carbon atom types within the hydrocarbons of the isoparaffin stream that is different from the distribution of carbon atom types of an isoparaffin-containing fraction formed by another process, such as by isomerization of an n-paraffin feed. This difference in carbon atom types can be characterized using various types of nuclear magnetic resonance (NMR) analysis, including 1 H NMR and 13 C NMR.

[0125] 1 H NMR can be used to roughly characterize the CH 3 Group (primary carbon or terminal carbon), CH 2 The amount of hydrogen corresponding to the CH group (secondary carbon) and the CH group (tertiary carbon). This is only an approximate representation, because the presence of aromatic rings can change the resonance position of some types of hydrogen. However, this effect of aromatic rings is the same for all types of 1H NMR is universal and for any sample containing less than 60 wt% aromatic compounds, CH 3 Group, CH 2 The change in the number of detected CH groups and CH groups is minimal. 1 H NMR can be used to characterize CH in a sample in a reproducible manner. 3 Group, CH 2 The content of CH groups.

[0126] generally, 1 H NMR can be used to characterize the CH in a sample in the following way 3 Group, CH 2 The number of groups and CH groups. Based on the peak position, 1 H NMR can generally characterize hydrogen in a hydrocarbon (or hydrocarbon-like) sample as falling into one of six types of groups: 1) hydrogen attached to an aromatic ring; 2) hydrogen attached to a carbon that is part of an olefinic bond; 3) hydrogen attached to a carbon that is alpha to the aromatic ring (i.e., the hydrogen is attached to the first carbon that is attached to the second carbon that is part of the aromatic ring); 4) hydrogen attached as a CH 3 5) as part of the hydrogen of CH 2 The peaks corresponding to these 6 types of hydrogen can then be integrated. This provides the relative ratios of the amount of each type of hydrogen present. These ratios can then be used to determine the relative percentages of the corresponding types of carbon present in the sample. Specifically, for peaks corresponding to CH 3 Group and CH 2 The amount of hydrogen present needs to be divided by 3 or 2, respectively, in order to convert the relative amount of hydrogen detected by NMR to CH 3 Group or CH 2 The relative number of groups.

[0127] In this discussion, “CH 3 A "group" is defined as 1 Alkanes / aliphatic CH determined by H NMR 3 This is determined by integrating the hydrogen peaks corresponding to the peaks in the NMR spectrum as CH 3 Note that any CH 3 The hydrogen of the group is not part of this peak, where CH 3 The carbon of the group is in the α or β position relative to the aromatic ring (e.g., CH 3 is part of a methyl or ethyl group attached to an aromatic ring). Here, CH in the side chain of the aromatic ring in the γ position or further away is included. 3Therefore, for the presence of aromatic compounds, based on 1 CH detected by H NMR 3 The amount of the group may be slightly lower than that of CH 3 The actual content of CH groups. However, for samples with aromatic compound content less than 60 wt%, this is a small error. Therefore, in this discussion, the CH 3 The reference of a group is defined as 1 HNMR detected CH 3 groups without attempting to correct the NMR values ​​based on this possible undercounting error due to the presence of aromatic compounds.

[0128] In this discussion, “CH 2 A "group" is defined as 1 Alkanes / aliphatic CH determined by H NMR 2 This is determined by integrating the hydrogen peaks corresponding to the peaks in the NMR spectrum as CH 2 Note that any CH 2 The hydrogen of the radical is not part of this peak. Additionally, the peak from the CH 3 The hydrogen of the group is also included in this peak. Therefore, the presence of aromatic compounds is based on 1 H NMR detected CH 2 The amount of the group may be slightly less than, slightly greater than, or equal to CH 2 The actual content of CH groups. However, for samples with aromatic compound content less than 60 wt%, this is a small error. Therefore, in this discussion, the CH 2 The reference of a group is defined as 1 CH detected by H NMR 2 groups without attempting to correct the NMR values ​​based on possible undercounting and / or overcounting errors due to the presence of aromatic compounds. Note that the CH 2 The group contains CH 2 NMR peak.

[0129] In this discussion, a "CH group" is defined as 1Alkane / aliphatic CH groups determined by H NMR. This is determined by integrating the hydrogen peaks corresponding to the peaks in the NMR spectrum that correspond 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, note that hydrogens from any CH groups located alpha or beta to the aromatic ring are not part of this peak. Further, hydrogens from CH groups located beta to the aromatic ring are not part of this peak. 2 The hydrogen of the group is also included in this peak. Therefore, the presence of aromatic compounds is based on 1 The amount of CH groups detected by H NMR may be slightly lower, slightly higher, or equal to the actual amount of CH groups. However, for samples with less than 60 wt% aromatics, this is a small error. Therefore, in this discussion, references to CH groups in a sample are defined as 1 The paraffinic / aliphatic CH groups detected by H NMR were not attempted to correct the NMR values ​​based on possible undercounting and / or overcounting errors due to the presence of aromatic compounds. Note that CH groups that are part of the cycloalkane ring are included in the CH NMR peaks.

[0130] In various aspects, the isoparaffin stream (e.g., Figure 1-5 The CH 3 Groups (such as those based on 1 HNMR confirmed) and CH 2 Groups (such as those based on 1 The ratio of CH4 to CH6 (determined by H NMR) can be from 1.01 to 1.35, or from 1.01 to 1.25, or from 1.10 to 1.35, or from 1.10 to 1.25. By blending at least a portion of the isoparaffin stream (also referred to as the isoparaffin blend component) with another fraction, a CH4 to CH6 fraction can be formed. 3 Group and CH 2 Groups (both based on 1 H NMR) ratio 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. Note that CH 3 With CH 2The ratio of the groups can vary depending on the type of fraction with which the isoparaffin blend component is blended. For example, blending an isoparaffin blend component with a mineral jet boiling range fraction, a mineral distillate boiling range fraction, or a Fischer-Tropsch fraction and / or a fraction having a high n-paraffin content will tend to result in a blend having a lower ratio. In contrast, blending an isoparaffin blend component with a fraction that is highly isomerized during a catalytic dewaxing / isomerization process will tend to result in a blend having a higher ratio.

[0131] In addition to characterizing the hydrogen content of the entire sample, 13 C NMR is also used to characterize the C 12 For this type of measurement, gas chromatography can be used to separate the C 12 The compound is separated from the remaining hydrocarbons. It can be used to form C 12 A direct method of fractionation is the n-paraffin (or straight-chain alkane) gas chromatography method. That is, for a suitable gas chromatograph with a separation column of sufficient resolution, it is assumed that n-paraffins of a given carbon number depict a peak, above which species can be assumed to have carbon numbers up to and including the peak of the next higher carbon number n-paraffin. For example, all peaks of material eluting between the peaks of n-decane and n-undecane are assumed to be C 11 Species.

[0132] Then you can use 13 C NMR characterization of the obtained C 12 It has been found that the C of the isoparaffin blend component prepared according to the process described herein is greater than that of the fraction prepared by catalytic isomerization of n-paraffins. 12 The fraction can have an unexpectedly low quaternary carbon content. In such aspects, the C of the isoparaffin blend component 12 The quaternary carbon content of the fraction can be 12 1.5% or less, or 1.4% or less, or 1.3% or less, such as as low as 1.0% or possibly still less, of the total carbon in the fraction.

[0133] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and the like used in the present specification and the associated claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximations that may vary depending upon the desired properties sought to be obtained by the embodiments of the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0134] One or more illustrative embodiments in conjunction with one or more inventive elements are presented herein. For the sake of clarity, all features of physical embodiments are not described or shown in this application. It should be understood that in the development of physical embodiments in conjunction with one or more elements of the present invention, many decisions specific to the embodiments must be made to achieve the developer's goal, such as meeting system-related, business-related, government-related and other constraints, which vary with the embodiments and time. Although the developer's efforts may be time-consuming, this effort will be a routine task for those of ordinary skill in the art who benefit from the disclosure.

[0135] Although compositions and methods are described herein as "comprising" various components or steps, the compositions and methods may also "consist essentially of" or "consist of" the various components and steps.

[0136] Other embodiments

[0137] Example 1. A method for producing a blended jet boiling range composition stream, the method comprising: oligomerizing an ethylene stream into a C4+ olefin stream in a first olefin oligomerization unit comprising a series reactor and a lightness removal column, wherein the C4+ olefin stream contains no more than 10 wt% of combined methane, ethylene and ethane; wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 20 wppm of carbon monoxide and hydrogen each; oligomerizing the C4+ olefin stream and a propylene / C4+ olefin stream in a second oligomerization unit to produce an isoolefin stream; subjecting at least a portion of the isoolefin stream to a hydroprocessing process using hydrogen as a treat gas to produce an olefin stream containing an isoparaffin stream in an amount not greater than 10 wt %; and using at least a portion of the isoparaffin stream to produce the blended jet boiling range composition, the blended jet boiling range composition comprising: 30 vol % to 99 vol % of an isoparaffin blend component, the isoparaffin blend component being derived from the isoparaffin stream, the isoparaffin stream containing 80 wt % or more of isoparaffins, 5.0 wt % or less of olefins, and 5.0 wt % or less of C19+ hydrocarbons; 1.0 vol % to 70 vol % of a mineral jet boiling range fraction; and a T10 distillation point of 205° C. or less, a final boiling point of 300° C. or less, a freezing point of -40° C. or less, and 2.0 wt % or more of C17-C18 hydrocarbons.

[0138] Embodiment 2. The method according to embodiment 1, wherein the C4+ olefin stream contains no more than 5 wt% of combined methane, ethylene and ethane.

[0139] Embodiment 3. The method according to any one of embodiments 1 to 2, wherein the C4+ olefin stream contains no more than 2000 wppm of combined methane, ethylene and ethane.

[0140] Embodiment 4. The method according to any one of embodiments 1 to 3, wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 5 wppm each of carbon monoxide and hydrogen.

[0141] Embodiment 5. The method of any one of embodiments 1 to 4, wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 1 wppm each of carbon monoxide and hydrogen.

[0142] Embodiment 6. The process of any one of embodiments 1 to 5, wherein the C4+ olefin stream and the propylene / C4+ olefin stream are combined prior to the second oligomerization.

[0143] Embodiment 7. The method of any one of embodiments 1 to 6, wherein the first oligomerization unit utilizes a homogeneous catalyst, and wherein the second oligomerization unit utilizes a heterogeneous catalyst.

[0144] Embodiment 8. The process according to any one of embodiments 1 to 7, wherein the second oligomerization recycles a portion of the unoligomerized C4+ olefin stream to pass it through the second oligomerization again.

[0145] Embodiment 9. A method according to any one of embodiments 1 to 8, further comprising: converting methanol into 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 contains at least 1000 wppm of methane and ethane each, and at least 100 wppm of carbon monoxide and hydrogen each; 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.

[0146] Embodiment 10. The method of embodiment 9, wherein the ethylene stream contains at least 90% of the ethane present in the original olefin stream.

[0147] Embodiment 11. The method according to embodiment 9, wherein the methanol is converted to olefins using a silicoaluminophosphate catalyst, an aluminosilicate catalyst or steam cracking.

[0148] Embodiment 13. A method for producing a blended jet boiling range composition, the method comprising: providing a raw olefin stream, the 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 comprising at least 1000 wppm of methane and ethane each, and at least 100 wppm of carbon monoxide and hydrogen each; 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 more than 1000 wppm methane, and no more than 20 wppm of carbon monoxide and hydrogen each, wherein at least 95 wt% of all ethylene in the raw olefin stream is recovered in the ethylene stream; providing at least a portion of the ethylene stream to a first olefin oligomerization unit comprising one or more series reactors and a lightness remover to convert at least 90% of the ethylene contained in the ethylene stream into a combined olefin stream containing no more than 10 wt% of ethylene in a single pass through the series reactors. The invention relates to a method for preparing a second C4+ olefin stream of methane, ethylene and ethane; providing at least a portion of each of the propylene and the C4+ olefins removed from the original olefin stream and at least a portion of the second C4+ stream to a second olefin oligomerization unit to produce an isoolefin stream; and subjecting at least a portion of the isoolefin stream to a hydrotreatment process using hydrogen as a treatment gas to produce an isoparaffin stream having an olefin content of not more than 10 wt %; and using at least a portion of the isoparaffin stream to produce the blended jet boiling range composition, wherein the blended jet boiling range composition The invention discloses a novel isoparaffin stream comprising: 30 vol% to 99 vol% of an isoparaffin blend component, the isoparaffin blend component being derived from the isoparaffin stream, the isoparaffin stream containing 80 wt% or more of isoparaffins, 5.0 wt% or less of olefins and 5.0 wt% or less of C19+ hydrocarbons; 1.0 vol% to 70 vol% of a mineral jet boiling range fraction; and a T10 distillation point of 205°C or less, a final boiling point of 300°C or less, a freezing point of -40°C or less, and 2.0 wt% or more of C17-C18 hydrocarbons.

[0149] Embodiment 14. The method of embodiment 13, wherein the C4+ olefin stream contains no greater than 5 wt% of combined methane, ethylene, and ethane.

[0150] Embodiment 15. The method of any one of embodiments 13 to 14, wherein the C4+ olefin stream contains no greater than 2000 wppm of combined methane, ethylene, and ethane.

[0151] Embodiment 16. The method of any one of embodiments 13 to 15, wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 5 wppm each of carbon monoxide and hydrogen.

[0152] Embodiment 17. The method of any one of embodiments 13 to 16, wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no greater than 1000 wppm methane, and no greater than 1 wppm each of carbon monoxide and hydrogen.

[0153] Embodiment 18. The process of any one of embodiments 13 to 17, wherein the ethylene stream contains at least 90% of the ethane present in the original olefin stream.

[0154] Embodiment 19. A method according to any one of embodiments 13 to 18, wherein the separation operation includes: a deethanizer distillation tower for separating propylene and C4+ from the original olefin stream; and a demethanizer distillation tower for separating methane, hydrogen and carbon monoxide from the original olefin stream to produce the ethylene stream.

[0155] Embodiment 20. The method of embodiment 19, further comprising: an additional distillation column in the separation operation, wherein the propylene is separated from the C4+ olefins and then further separated from propane and components of similar or lower volatility.

[0156] Embodiment 21. The method of any one of embodiments 13 to 20, wherein the first oligomerization unit utilizes a homogeneous catalyst, and wherein the second oligomerization unit utilizes a heterogeneous catalyst.

[0157] Embodiment 22. The method according to any one of embodiments 13 to 21, wherein the second oligomerization unit comprises: a series of reactors; a distillate fractionation column outputting the iso-olefin stream; and a debutanizer fractionation column purging C4-olefins.

[0158] Embodiment 23. A method according to embodiment 22, wherein the distillate fractionator also outputs C9-olefins, a first portion of which is recycled to the series reactor and a second portion is sent to a debutanizer fractionator.

[0159] Embodiment 24. A method according to embodiment 22, wherein the debutanizer fractionator also outputs C5+ olefins, a first portion of which is recycled to the series reactor and a second portion is purged.

[0160] Embodiment 25. A method according to embodiment 22, wherein when entering the second oligomerization unit, the second C4+ stream first goes to the distillate fractionation tower, and the propylene and the C4+ olefins removed from the original olefin stream first go to the series reactor.

[0161] Embodiment 26. The method according to any one of embodiments 13 to 25, further comprising: converting methanol into olefins to produce a raw olefin stream.

[0162] Embodiment 27. The method of embodiment 26, wherein the methanol is converted to olefins using a silicoaluminophosphate catalyst, an aluminosilicate catalyst, or steam cracking.

[0163] In order to facilitate a better understanding of the embodiments of the present invention, the following preferred or representative embodiments are given. The following examples should not be construed as limiting or defining the scope of the present invention.

[0164] Examples

[0165] Example 1 - Carbon Chain Length Distribution in Isoparaffin Blend Components

[0166] One of the unusual features of the isoparaffin blend components as described herein is that the isoparaffin blend components may contain C 17+ The present invention relates to a method for preparing a substantially isoparaffinic hydrocarbon blend component comprising a substantially isoparaffinic hydrocarbon, while still forming a blend having a final boiling point of 300° C. or less, as measured according to ASTM D86. To illustrate this point, samples of several different isoparaffinic blend components were formed using the synthetic methods described herein. Table 1 shows the volume percentage of hydrocarbon chain length in the resulting isoparaffinic blend component. The samples are referred to as IPB 1, 2, and 3 (for isoparaffinic blend components). For comparison, the hydrocarbon chain length distribution in a representative JET A-1 sample is also shown.

[0167] Table 1 - Hydrocarbon chain length distribution

[0168] [vol%] C8 C9 C10 C11 C12 C13 / 14 C15 / 16 C17 / 18 C19 / 20 JET A-1 1.7 3.2 7.3 12.7 15.2 27.4 13.4 1.5 0.0 IPB 1 0.3 3.8 6.6 12.3 24.3 14.3 10.7 2.9 1.4 IPB 2 0.2 15.1 5.5 10.3 20.1 11.9 8.9 2.4 1.1 IPB 3 0.2 9.6 9.6 10.9 17.4 14.2 9.9 3.3 1.2

[0169] As shown in Table 1, a representative JET A-1 sample contains less than 2.0 vol% C 17 -C 18 components and does not contain C 19 or C 20 In contrast, each of the isoparaffin blend components contains more than 3.0 vol% of C 17 -C 18 Hydrocarbons, and more than 4.5 vol% C 17+ hydrocarbon.

[0170] C in isoparaffin blend components17+ An increase in hydrocarbon concentration may result in a decrease in the C 17+ Tables 2-4 show the volume percentages of hydrocarbons of various chain lengths to be incorporated into blended products containing 70 vol% (Table 2), 50 vol% (Table 3), 30 vol% (Table 4) of the isoparaffin blend component.

[0171] Table 2-70 vol% contribution to the blend

[0172] [vol%] C8 C9 C10 C11 C12 C13 / 14 C15 / 16 C17 / 18 C19 / 20 JET A-1 1.2 2.3 5.1 8.9 10.6 19.2 9.4 1.0 0.0 IPB 1 0.2 2.7 4.7 8.6 17.0 10.0 7.5 2.1 1.0 IPB 2 0.2 10.6 3.9 7.2 14.1 8.3 6.2 1.7 0.8 IPB 3 0.1 6.7 6.7 7.7 12.2 10.0 7.0 2.3 0.9

[0173] Table 3-50 vol% contribution to the blend

[0174] [vol%] C8 C9 C10 C11 C12 C13 / 14 C15 / 16 C17 / 18 C19 / 20 JET A-1 0.8 1.6 3.6 6.3 7.6 13.7 6.7 0.7 0.0 IPB 1 0.1 1.9 3.3 6.2 12.1 7.2 5.4 1.5 0.7 IPB 2 0.1 7.6 2.8 5.1 10.1 5.9 4.5 1.2 0.6 IPB 3 0.1 4.8 4.8 5.5 8.7 7.1 5.0 1.6 0.6

[0175] Table 4-30 vol% contribution to the blend

[0176] [vol%] C8 C9 C10 C11 C12 C13 / 14 C15 / 16 C17 / 18 C19 / 20 JET A-1 0.5 1.0 2.2 3.8 4.5 8.2 4.0 0.4 0.0 IPB 1 0.1 1.1 2.0 3.7 7.3 4.3 3.2 0.9 0.4 IPB 2 0.1 4.5 1.7 3.1 6.0 3.6 2.7 0.7 0.3 IPB 3 0.0 2.9 2.9 3.3 5.2 4.3 3.0 1.0 0.4

[0177] As shown in Tables 2-4, a blend containing 70 vol% of an isoparaffin blend component may contain 1.6 vol% or more, or 2.0 vol% or more of a C 17 -C 18 For a 50% blend, the isoparaffin blend component may contribute 1.2 vol% or more of the C 17 -C 18 Hydrocarbons, such as up to 1.6 vol%. Based on the typical C 17 -C 18 content, it is clear that the isoparaffin blend components described herein can allow for a higher volume percentage of C 17 -C 18 The hydrocarbons are incorporated into the potential blended jet fuel product.

[0178] Example 2 - Blends with Conventional Jet Fuel

[0179] The isoparaffin blend components corresponding to IPB 1 and IPB 2 in Example 1 are used in combination with conventional jet fuel (JETA-1 or JP-5) to form a blended jet boiling range product. Even for blends having 50 vol% or more, or 70 vol% or more of the isoparaffin blend component, the resulting blended jet boiling range product still meets the specifications of the corresponding type of jet fuel.

[0180] Figure 6Results of characterization of a conventional JET A-1 sample, a sample of IPB 1, a blend formed of 30 vol% IPB 1 and 70 vol% JET A-1, and a blend formed of 70 vol% IPB 1 and 30 vol% JET A-1 are shown. Figure 6 As shown in Figure 1, IPB 1 alone does not meet all the standard requirements of JET A-1 jet fuel. However, the blended product obtained by blending 70 vol% IPB 1 with 30 vol% conventional JET A-1 meets the requirements of the JET A-1 jet fuel. Figure 6 All JET A-1 requirements are shown, except for conductivity. However, the conductivity of the potential jet fuel product can be easily increased using conventional additives to meet the required standards.

[0181] As explained in Example 1, a blend containing 70 vol% IPB 1 contains at least 2.0 vol% C 17 -C 18 hydrocarbons, even without considering the contribution from JET A-1. The blend containing 70 vol% IPB 1 also provides a higher JFTOT breakpoint temperature and a higher smoke point. Combined with the generally beneficial cold flow properties of the isoparaffin blend component, Figure 6 The value of an isoparaffin blend component as described herein for potentially restoring an off-spec jet fuel sample to specification is shown.

[0182] Similar characterization was performed on JET A-1 samples, IPB 2, blends of 30 vol% IPB 2 and 70 vol% JET A-1, and blends of 70 vol% IPB 2 and 30 vol% JET A-1. The characterization results of these blend products are given in Figure 7 As shown in Figure 6 Similarly, blending 50 vol% or more, or 70 vol% or more of the isoparaffin blend component with a conventional jet fuel sample may still meet the blended product. Figure 7 All required standards shown.

[0183] Example 3 - Isoparaffin blend component as lubricity improver

[0184] It has been found that the blended product comprises at least 10 vol% of a mineral jet boiling range fraction and 40 vol% or more (or 50 vol% or more) of an isoparaffin blend component, and the blended product can have unexpectedly improved lubricity. Lubricity can be measured based on the wear scar diameter determined according to ASTM D5001. For example, such blended products can comprise 10 vol%-50 vol%, or 10 vol% to 60 vol%, or 20 vol% to 50 vol%, or 20 vol% to 60 vol% of a mineral jet boiling range fraction. Such blended components can also comprise 40 vol% to 90 vol%, or 50 vol% to 90 vol%, or 40 vol% to 80 vol%, or 50 vol% to 80 vol% of an isoparaffin blend component.

[0185] The unexpected nature of the lubricity improvement when 50 vol% or more of an isoparaffin blend component is added to a mineral jet boiling range fraction can be understood by comparing the lubricity behavior of the blends shown in Table 5. Table 5 shows the results of testing various jet boiling range fractions to determine the wear scar diameter according to the method of ASTM D5001. In Table 5, the first two samples correspond to pure samples of JET A-1 and JP-5. The remaining samples are blends of an isoparaffin blend component (IPB-1 or IPB-2) with JET A-1 or JP-5. Traditionally, it is expected that adding a highly paraffin blend component to a mineral jet boiling range fraction will result in poor lubricity performance. For comparison, note that some diesel fuel standards have a maximum wear scar diameter of 0.85 mm or less according to ASTM D5001.

[0186] Table 5 - Measured Lubricity Values ​​for Jet Boiling Range Fractions

[0187]

[0188] As shown in Table 5, when the blend amount of IPB-1 or IPB-2 with the JET A-1 machine is 30 vol%, if a linear weighted average model is used to describe the wear scar diameter results of the blend, the linear weighted average model predicts that the wear scar diameter of IPB-1 or IPB-2 alone is about 0.60 mm. In contrast, for blends containing 50 wt% or more of IPB-1 or IPB-2, the linear weighted average model predicts a wear scar diameter below 0.60 mm. Further note that for blends of higher levels of isoparaffin blend components with the JET A-1 sample (such as 50 vol% or more of isoparaffin blend components), the wear scar diameter of the blended composition is reduced by 10% or more relative to the wear scar diameter of the mineral jet boiling range fraction alone.

[0189] Similarly, for a 25 vol% blend of IPB-1 and JP-5, the linear weighted average model predicts a wear scar diameter of about 0.63 mm for IPB-1. In fact, the addition of IPB-1 appears to increase the wear scar diameter when mixed with JP-5, which is consistent with conventional expectations. However, increasing the amount of IPB-1 in this blend to 50 wt% results in a decrease in the wear scar diameter relative to pure JP-5, with a predicted wear scar diameter of about 0.58 mm for pure IPB-1.

[0190] Based on Table 5, for blends having 50% or greater isoparaffin blend component, a synergistic effect is observed, wherein an unexpected reduction in wear scar diameter is achieved at greater amounts of isoparaffin blend component in the blend.

[0191] Example 4 - Blended Components 1 H NMR analysis

[0192] An isoparaffin blend component IPB-1 is formed according to the process described herein, wherein the isoolefin blend component is formed by olefin oligomerization. A portion of the isoolefin blend component is then exposed to hydroprocessing conditions to saturate the portion, thereby forming an IPB-1 sample. In addition to forming the isoparaffin blend component, the other two portions of the isoolefin blend component are exposed to conditions of partial saturation of the olefins, such that the components contain approximately 30 wt% olefins / 70 wt% paraffins and 70 wt% olefins / 30 wt% paraffins.

[0193] use 1 H NMR characterization of isoolefin blend components, isoparaffin blend components and two partially saturated components to characterize CH 3 Group and CH 2 The ratio of the groups, as given by 1 The results of H NMR confirmed. Figure 8 Shows 1 The results of H NMR analysis. Figure 8 In the first column of data, the data corresponds to the data of the substantially fully saturated isoparaffin blend component (IPB-1). The second and third columns show partially saturated products, while the last column corresponds to the data of the isoolefin blend component produced by the oligomerization process.

[0194] like Figure 8 As shown, the isoolefin blend component (before any saturation) has the highest CH 3 Group and CH 2 As saturation increases, CH 3 Group and CH 2 The ratio of the CH 3 Group and CH 2The ratio of groups (such as based on 1 H NMR determined) was 1.18.

[0195] In order to Figure 8 , and also use 1 Various other fractions were characterized by H NMR to determine CH 3 Group and CH 2 Table 6 shows the values ​​obtained from these various other types of fractions. Where a range is given, this indicates that a number of different samples were characterized, with the range corresponding to the minimum and maximum values.

[0196] Table 6 - If passed 1 The CH of other components determined by H NMR 3 / CH 2 ratio

[0197] Sample type <![CDATA[CH 3 With CH 2 Ratio of]]> JET A-1 0.75 diesel fuel 0.57-1.00 Gas Oil 0.54 Mainly isoparaffinic liquids (formed by catalytic isomerization) 2.50-3.21 Mainly normal paraffin liquid 0.24-0.33 Cycloparaffinic liquids (petroleum distillates) 2.35 Fischer-Tropsch liquid 0.37

[0198] As shown in Table 6, CH 3 With CH 2 The ratios of CH4 and CH6 are often well below 1.00. Commercial fuel products usually have ratios below 1.00, although high isoparaffin / low aromatics diesel can approach 1.00. Fluids containing high levels of cycloparaffins have CH4 and CH6 ratios of less than 1.00. 3 With CH 2 The ratio of CH 3 With CH 2 The ratio is above 2.30, where the isoparaffin content is formed by catalytic isomerization.

[0199] Example 5 - Quaternary Carbon Content

[0200] A sample of IPB-1 was separated using a gas chromatograph to form C 12 Fraction. Use 13 C NMR analysis of 12 fractions to determine the amount of quaternary carbon in the sample. For comparison, after exposing the source to deep catalytic isomerization, C 12 Fractions were also formed from two other mineral sources. Table 7 shows the C 12 Results of the analysis of the fractions.

[0201] Table 7-C 12 Fraction 13 C NMR analysis

[0202] <![CDATA[C 12 Comparison No. 1]]> <![CDATA[C 12 Comparison No. 2]]> <![CDATA[C from IPB-1 12 > Average carbon number (by GC) 11.95 11.88 12.0 Cycloalkane content 8 8 0 Number of branches per molecule 2.97 2.39 2.78 Quaternary carbon (% of total carbon) 1.64 1.77 1.35

[0203] As shown in Table 7, C12 The quaternary carbon content of the fraction is substantially lower than that of the other fractions. For the two comparative samples, relative to the total amount of carbon in the sample, C 12 The quaternary carbon content of the fraction is greater than 1.60%, while the C 12 The quaternary carbon content of the fraction is 1.60% or less, or 1.50% or less, or 1.40% or less, such as as low as 1.20% or possibly still lower.

[0204] Therefore, the present invention is well suited for achieving the mentioned purposes and advantages as well as the inherent purposes and advantages thereof. The specific examples and configurations disclosed above are illustrative only, as the present invention can be modified and practiced in different but equivalent ways that are obvious to those skilled in the art who benefit from the teachings herein. In addition, it is not intended to limit the details of the construction or design shown herein, except for the limitations described in the claims below. Therefore, it is obvious that the specific illustrative examples disclosed above can be changed, combined or modified, and all such changes are considered to be within the scope and spirit of the present invention. The present invention disclosed illustratively herein can be appropriately practiced in the absence of any element not specifically disclosed herein and / or any optional element disclosed herein. Although compositions and methods are described with "comprising", "containing" or "including" various components or steps, compositions and methods can also be "essentially composed of various components or steps" or "composed of various components or steps". All numbers and ranges disclosed above can differ by a certain amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any numerical value and any included range falling within the range are specifically disclosed. Specifically, each value range disclosed herein (in the form of "about a to about b" or equivalently "about a to b" or equivalently "about ab") should be understood to list each number and range covered within the broader value range. Moreover, unless otherwise explicitly and clearly defined by the patentee, the terms in the claims have their ordinary, common meaning. In addition, the indefinite articles "a / an" used in the claims are defined herein to mean one or more than one of the elements they introduce.

Claims

1. A method for producing a blended jet boiling range composition stream, the method comprising: oligomerizing an ethylene stream into a C4+ olefin stream in a first olefin oligomerization unit comprising a series reactor and a lightness removal column, wherein the C4+ olefin stream contains no more than 10 wt% of combined methane, ethylene and ethane; wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more 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 isoolefin stream; subjecting at least a portion of the isoolefin stream to a hydrotreating process using hydrogen as a treat gas to produce an isoparaffin stream having an olefin content of no more than 10 wt%; and using at least a portion of the isoparaffin stream to produce the blended jet boiling range composition, the blended jet boiling range composition comprising: 30 vol% to 99 vol% of an isoparaffin blend component, the isoparaffin blend component being derived from the isoparaffin stream, the isoparaffin stream containing 80 wt% or more of isoparaffins, 5.0 wt% or less of olefins, and 5.0 wt% or less of C19+ hydrocarbons; 1.0 vol% to 70 vol% of a mineral jet boiling range fraction; and a T10 distillation point of 205°C or less, a final boiling point of 300°C or less, a freezing point of -40°C or less, and 2.0 wt% or more of C17-C18 hydrocarbons.

2. A method for producing a blended jet boiling range composition, the method comprising: Providing a raw olefin stream, the 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 methane and ethane each, and at least 100 wppm of carbon monoxide and hydrogen each; 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 more than 1000 wppm methane, and no more than 20 wppm of carbon monoxide and hydrogen each, wherein at least 95 wt% of all ethylene in the raw olefin stream is recovered in the ethylene stream; providing at least a portion of the ethylene stream to a first olefin oligomerization unit comprising one or more series reactors and a lightness remover to convert at least 90% of the ethylene contained in the ethylene stream into a second C4+ olefin stream containing no more than 10 wt% of combined methane, ethylene and ethane in a single pass through the series reactors; providing at least a portion of each of said propylene and said C4+ olefins removed from said original olefin stream and at least a portion of said second C4+ stream to a second olefin oligomerization unit to produce an isoolefin stream; and subjecting at least a portion of the isoolefin stream to a hydrotreating process using hydrogen as a treat gas to produce an isoparaffin stream having an olefin content of no greater than 10 wt %; and using at least a portion of the isoparaffin stream to produce the blended jet boiling range composition, the blended jet boiling range composition comprising: 30 vol% to 99 vol% of an isoparaffin blend component, the isoparaffin blend component being derived from the isoparaffin stream, the isoparaffin stream containing 80 wt% or more of isoparaffins, 5.0 wt% or less of olefins, and 5.0 wt% or less of C19+ hydrocarbons; 1.0 vol% to 70 vol% of a mineral jet boiling range fraction; and a T10 distillation point of 205°C or less, a final boiling point of 300°C or less, a freezing point of -40°C or less, and 2.0 wt% or more of C17-C18 hydrocarbons.

3. The process according to any one of claims 1 to 2, wherein the C4+ olefin stream contains no more than 5 wt% of combined methane, ethylene and ethane.

4. The process of any one of claims 1 to 3, wherein the C4+ olefin stream contains no more than 2000 wppm of combined methane, ethylene and ethane.

5. The process according to any one of claims 1 to 4, wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane and no more than 5 wppm each of carbon monoxide and hydrogen.

6. The process of any one of claims 1 to 5, wherein the ethylene stream contains at least 50 wt% ethylene, at least 2000 wppm ethane, no more than 1000 wppm methane, and no more than 1 wppm each of carbon monoxide and hydrogen.

7. The process according to any one of claims 1 to 6, a) wherein the C4+ olefin stream and the propylene / C4+ olefin stream are combined prior to the second oligomerization; b) wherein the first oligomerization unit utilizes a homogeneous catalyst, and wherein the second oligomerization unit utilizes a heterogeneous catalyst; or c) a combination of a) and b).

8. The process according to any one of claims 1 to 7, wherein the second oligomerization recycles a portion of the unoligomerized C4+ olefin stream to pass it through the second oligomerization again.

9. The method according to any one of claims 1 to 8, further comprising: converting methanol to olefins to produce a raw olefin stream; wherein the original olefin stream comprises ethylene, propylene and C4+ olefins, wherein at least 10 wt% of all olefins in the original olefin stream are ethylene, and further contains at least 1000 wppm of methane and ethane each, and at least 100 wppm of carbon monoxide and hydrogen each; and separating the original olefin stream to remove hydrogen, carbon monoxide, propylene and C4+ olefins from the original olefin stream and produce the ethylene stream.

10. The process of claim 9, wherein the ethylene stream contains at least 90% of the ethane present in the original olefin stream.

11. The process according to claim 2 or 9, wherein the methanol is converted to olefins using a silicoaluminophosphate catalyst, an aluminosilicate catalyst or steam cracking.

12. The method according to claim 2, wherein the separation operation comprises: a deethanizer distillation column for separating propylene and C4+ from said raw olefin stream; and a demethanizer distillation column for separating methane, hydrogen and carbon monoxide from the raw olefin stream to produce the ethylene stream, the process optionally further comprising an additional distillation column in the separation operation wherein the propylene is separated from the C4+ olefins and then further separated from propane and components of similar or lower volatility.

13. The method of claim 2, wherein the second oligomeric unit comprises: Reactors in series; a distillate fractionation tower for outputting the isoolefin stream; and a debutanizer fractionator to purge C4-olefins.

14. The process of claim 13, i) wherein the distillate fractionator also outputs C9- olefins, a first portion of which is recycled to the series reactor and a second portion is sent to a debutanizer fractionator; ii) wherein the debutanizer fractionator also outputs C5+ olefins, a first portion of which is recycled to the series reactor and a second portion is purged; or iii) wherein upon entering the second oligomerization unit, the second C4+ stream first goes to the distillate fractionator, while the propylene and the C4+ olefins removed from the original olefin stream first go to the series reactor.

15. The method according to claim 2, further comprising: The methanol is converted to olefins to produce a raw olefin stream.

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