METHODS AND SYSTEMS OF RENEWABLE NAPHTHA WITH INCREASED OCTANE NUMBER

Abstract

The present application is directed to a process for increasing Anti-Knock Index (AKI) rating in a renewable naphtha having an initial AKI rating. The process comprises fractionating the renewable naphtha under conditions sufficient to form a light renewable naphtha fraction and a heavy renewable fraction. The light renewable fraction often comprises C4-C6 normal paraffins while the heavy renewable naphtha fraction usually comprises C7-C9 normal paraffins. Advantageously, the light renewable naphtha fraction has an AKI rating which is above the initial AKI rating of the renewable naphtha making the light renewable fraction more suitable for blending into gasoline at higher amounts.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. provisional application 63/825,125 filed on Jun. 17, 2025, which application is incorporated herein by reference.

This application is also a continuation-in-part and for U.S. purposes claims priority to pending PCT application PCT/US25/24604 filed Apr. 14, 2025 entitled “RENEWABLE GASOLINE BLENDS” which application is incorporated herein by reference. More specifically, the products of the processes described herein may be employed in the renewable fuel compositions of PCT application PCT/US25/24604.

FIELD OF THE INVENTION

This application relates to renewable fuels and more specifically methods for increasing octane number, i.e., Anti-Knock Index (AKI), of renewable naphtha.

BACKGROUND AND SUMMARY OF THE INVENTION

Renewable naphtha is a common byproduct of producing fuels such as renewable diesel and sustainable aviation fuel. There is a desire to find new uses of the renewable naphtha byproduct. Unfortunately, it is challenging to, for example, blend renewable naphtha into gasoline because it typically has a much lower octane number, i.e., Anti-Knock Index (AKI), than fossil or petroleum naphtha. Accordingly, what is needed are new methods of usefully employing the renewable naphtha byproduct. It would further be beneficial if such new methods included a way to blend renewable naphtha into fuels to reduce the fuel's carbon intensity. It would also be beneficial if such fuels could include higher amounts of renewable naphtha than in the prior art yet still meet market-required Anti-Knock Index (AKI) ratings and other standards such as ASTM D4814 and/or EN228.

Advantageously, the present application meets one or more up to all of the aforementioned desires. The present application is directed to a process for increasing Anti-Knock Index (AKI) rating in a renewable naphtha having an initial AKI rating. The process comprises fractionating the renewable naphtha under conditions sufficient to form a light renewable naphtha fraction and a heavy renewable fraction. The light renewable fraction often comprises C4-C6 normal paraffins while the heavy renewable naphtha fraction usually comprises C7-C9 normal paraffins. Advantageously, the light renewable naphtha fraction has an AKI rating which is above the initial AKI rating of the renewable naphtha making the light renewable fraction more suitable for blending into gasoline at higher amounts.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows cut points vs. octane rating for a light renewable naphtha fraction and a heavy renewable naphtha fraction.

FIG. 2 shows cut points vs. AKI for a light renewable naphtha fraction.

FIG. 3 shows relative carbon number distribution for various cuts points in a light renewable naphtha fraction.

FIG. 4 shows cumulative octane number increase (%) by cut point and step octane number increase (%) by cut point.

FIG. 5 shows a bar graph for carbon number and compositions at representative cut point.

FIG. 6 shows a bar graph for carbon number and compositions at representative cut point.

FIG. 7 shows a bar graph for carbon number and compositions at representative cut point.

FIG. 8 shows a bar graph for carbon number and compositions at representative cut point.

FIG. 9 shows a bar graph for carbon number and compositions at representative cut point.

FIG. 10 shows a bar graph for carbon number and compositions at representative cut point.

DETAILED DESCRIPTION OF THE INVENTION

Herein is described a method for increasing Anti-Knock Index (AKI) rating in a renewable naphtha. In this manner the renewable naphtha with increased AKI rating may be more useful for blending into useful fuels such as gasoline.

Petroleum based commercial gasoline is made up of a variety of components termed blendstocks. Blendstocks are mixed together to create a finished gasoline blend that has specific desired chemical (such as sulfur content), physical (such as vapor pressure) and performance properties (such as octane). The blendstocks are produced from a variety of refining processes, with a non-exhaustive list of examples being straight-run naphtha, FCC naphtha, reformate, isomerate, alkylate, and hydrobate. The blendstocks possess different chemical, physical and performance properties with respect to each other, and can vary themselves due to changes in feedstocks and processing conditions. Blendstocks can also be generated using renewable feedstocks that undergo either similar refining processes as petroleum based blendstocks or can undergo different processes, relevant to the renewable feedstock.

Gasoline blendstocks derived from petroleum are comprised of a variety of classes of hydrocarbons, such as paraffins, isoparaffins, naphthenes, aromatics and olefins. Also, blendstocks will often contain structural isomers, which are hydrocarbons with the same molecular formula (i.e. number of carbons and hydrogen atoms), but which have different chemical structures and properties, and will usually be members of the different classes (e.g., paraffins, isoparaffins, naphthenes, aromatics and olefins). Molecular isomers (structural isomers by carbon number) often have been found to increase as carbon number increases. Blendstocks derived from renewable feedstocks are usually comprised of the same classes and structures of molecules found in conventional petroleum derived gasoline components, although often with less variety in molecular structure. For both petroleum and renewable derived blendstocks, the classes and carbon numbers present may depend on the feedstock, process and process conditions (such as alkylate versus reformate).

Distillation employed here is a process where a complex hydrocarbon mixture can be simplified by separating into different fractions or distillation “cuts” which have a defined boiling temperature range defined by the beginning and end distillation temperatures. Each hydrocarbon within the distillation fraction will possess individual boiling points constrained by the distillation cutpoints. Hydrocarbons with lower carbon number will often possess relatively lower boiling points when compared to the same class (i.e. paraffins, isoparaffins . . . , etc.), but isomers with the same carbon number but of a different class may have a larger boiling range and variability (for example C5 isoparaffins typically have a lower boiling point than C5 paraffin). It has been found that with increasing carbon number, the possibility for molecular isomers and classes increases, as well as usually increasing the boiling range.

Octane is a performance property defined by a gasoline's (i.e. hydrocarbons mixture) resistance to knock under specific engine conditions and within a Cooperative Fuel Research (CFR) engine. While octane rating is measured for the gasoline, each hydrocarbon isomer present in a gasoline may be considered to be a complex hydrocarbon mixture, where each individual hydrocarbon contributes towards the octane value of the whole gasoline. Furthermore, the classes of hydrocarbons have been observed to usually possess general trends towards octane (i.e. aromatic and olefin isomers tend to possess higher octane values than paraffin or isoparaffin isomers with the same carbon number). The relationship between the octane contributions of each individual hydrocarbon is complex and non-linear with respect to the octane of the whole gasoline, but distillation can be used to define hydrocarbon classes and carbon numbers for fractions (based on boiling points), distillation by extension can be used to generate gasoline fractions with different octane values than the original mixture (octane contribution is related to carbon number and class). Throughout this application, all octane values presented are calculated based on the sample's molecular structure, rather than measured used the ASTM D2699 & D2700 procedures. This was necessary as many of the samples could not be measured using the procedures outlined in D2699 & D2700 due to the sample's volatility, or its low octane number, or both.

Depending on renewable feedstock and process, it has been discovered that renewable naphthas can be generated that are enriched in paraffin and isoparaffin content, without aromatics or olefins, and slight amount of naphthenes. A similar petroleum derived blendstock, such as hydrobate will usually contain a broader distribution of paraffins, isoparaffins, naphthenes and aromatics. It has been discovered that since renewable naphtha usually has less diversity of classes present, generating fractions by distillation yields larger shifts (e.g., in some embodiments this shift can be on the order of at most 10 octane units for a single 10 °F (5.6 °C) step in final distillation temperature, or up to 22 octane units over a broader 120 °F (66.7 °C) change in final distillation temperature) in octane than with respect to a petroleum based hydrobate. The present processes takes advantage of the effect of lower carbon number (lower distillation cut points), less isomer diversity, less potential boiling range, and less octane diversity in renewable derived naphtha as it is deficient in naphthenes, olefins and aromatics. That is, for petroleum derived feedstocks, due to the relatively larger diversity of hydrocarbon classes and isomers, changes in octane contribution are relatively small when shifting distillation cutpoints. In contrast, as discovered here renewable naphtha can be made to have large shifts in octane for distillation fractions.

The practice of creating distillation fractions of renewable naphthas with optimized octane content as taught here can be used in a number of ways. With the intention to maximize practical blending limits of renewable naphtha blendstock into finished gasoline blends, the renewable naphtha can advantageously be distilled to create a desirable octane fraction that contributes favorably (at least about 60, at least about 65, at least about 70, up to about 80, or up to about 75 octane units) as a blendstock to finished gasoline blends. The remaining commensurate renewable naphtha distillation fraction can be used for purposes less dependent on octane, such as a denaturant for blending ethanol or in, for example, ethanol fuel blends (E85). The techniques described here may also be used to provide flexibility for the blendable yield of renewable naphtha. For example, adjusting the distillation cutpoint such as to decrease octane to a suitable target, thereby achieving an increase in the volume of the renewable naphtha fraction.

In some embodiments, a compositional measurement of the renewable naphtha may first be determined using industry methods that provide such information as group types (PIONA) and hydrocarbon speciation (DHA). In this manner, one may employ the compositional measurement in determining how to more effectively fractionate the renewable naphtha to achieve the desired octane increase and/or other desired properties.

Renewable Naphtha

The renewable naphtha that may be useful in the methods described here is not particularly limited. As used herein, the term “naphtha” means a mixture of hydrocarbons generally having between 4 and 12 carbon atoms and having a boiling point in the range of 30 to 200 °C (86 °F to 392 °F). The term naphtha is inclusive of both light naphtha generally having between 4 and 7 carbon atoms and having a boiling point in the range of 30 to 100 °C (86 °F to 212 °F) and heavy naphtha generally having between 8 and 12 carbon atoms and having a boiling point in the range of 100 to 200 °C (212 °F to 392 °F).

The term “renewable naphtha” may also be referred to as renewable naphtha distillate or biorenewable naphtha. As used herein “renewable naphtha” is meant a naphtha fraction which contains bio-based carbon atoms as determined according to ASTM method D6866-24 entitled “Standard Test Methods for Determining the Biobased Content of Solid, Liquid and Gaseous Samples using Radiocarbon Analysis” or as determined by ISO 16620-2. The renewable content may then be determined by isotopic distribution involving 14C, 13C and/or 12C as described in ASTM D6866.

The renewable naphtha component of the present application can be prepared according to the methods provided in international patent applications WO2018/069137, WO2018/234187, WO2009/148909, U.S. Pat. No. 9,885,000B2, or U.S. Patent Publications 2009/0300971A1 and 2023/0227742A1, all of which are incorporated herein by reference in their entirety. These references also provide further details of the chemical and physical properties of the renewable naphtha component.

Renewable naphtha as used herein may comprise reformed or isomerized reprocessed renewable naphtha, a bio-naphtha derived from one or more of the following feedstocks and processes: ketopyrolysis-derived renewable naphtha from lipids, ketopyrolysis-derived renewable naphtha from cellulosic feedstocks, renewable naphtha or its derivatives produced from hydrothermal liquefaction of cellulosic material which is subsequently hydrotreated and potentially further upgraded, renewable naphtha or its derivatives produced from fast pyrolysis of cellulosic material which is subsequently hydrotreated and potentially further upgraded, or any mixture thereof. The renewable naphtha starting component typically has an initial AKI rating which is lower than a light renewable naphtha fraction that results from the process.

Fractionating

As described above, it may be useful in some embodiments to conduct a compositional measurement of the renewable naphtha using a convenient method to determine, for example, the compounds present, amounts, group types, and/or hydrocarbon speciation. If desired, an octane number analysis may be conducted of various components, distillation cuts, or both to assist with determining proper fractionation cuts to achieve desired benefits.

The processes of the present application typically fractionate the renewable naphtha using any convenient method. The methods employed may vary depending upon the specific components and amounts in the renewable naphtha, desired fractions, and desired properties of the fractions. Typical fractionation methods may comprise, for example, distilling the renewable naphtha. Whether distilling or another method is employed the fractionation conditions often may comprise those conditions sufficient to form a light renewable naphtha fraction comprising C4-C6 normal paraffins and a heavy renewable naphtha fraction comprising C7-C9 normal paraffins.

Distillation conditions may differ depending upon, for example, the specific components and amounts in the renewable naphtha, desired fractions, and desired properties of the fractions. In some embodiments, the distilling may comprise distilling at a final distillation temperature of 145 °F to 170 °F (62.8 °C to 76.7 °C), preferably about 160 °F (71.1 °F) to form the light renewable naphtha fraction and then, if desired, removing the light renewable naphtha fraction.

In some embodiments the light renewable naphtha fraction has an AKI rating which is at least 42% above the initial AKI rating of the starting renewable naphtha, and in other embodiments 38% higher or 21% higher. In some embodiments the light renewable naphtha fraction has an AKI rating which is (1) at least 7% higher than the initial AKI rating of the renewable naphtha; or (2) at least 51% higher than an AKI rating of the heavy renewable naphtha fraction; or (3) both (1) and (2). On the other hand, the heavy renewable naphtha fraction or fractions typically has a lower AKI rating than the light fraction, with embodiments ranging from 41 AKI to 50 AKI. Despite the lower octane ratings of the heavy renewable naphtha fraction than the light renewable naphtha fraction, the heavy fraction can be put to productive use in a number of applications, including: blending of the heavy renewable naphtha fraction into gasoline blends with lower octane number requirements, such as those being sold as mid-level ethanol blends (16-50% ethanol); use of heavy renewable naphtha as the hydrocarbon blendstock in E85, a fuel with 51-83% ethanol content; use of heavy renewable naphtha as a feedstock in the petrochemicals industry.

In some embodiments, the light renewable naphtha fraction has an AKI rating of 70 or more and/or the heavy renewable naphtha fraction has an AKI rating of 55 or less. In another embodiment, the light renewable naphtha fraction has an AKI rating of 79 or more, and the heavy renewable naphtha fraction has an AKI rating of 51 or less. In a third embodiment, the light renewable naphtha fraction has an AKI rating of 81 or more, and the heavy renewable naphtha fraction has an AKI rating of 50 or less. The light renewable naphtha fraction may comprise any amount of C4 to C6 isoparaffins depending upon the application but in some embodiments C4 to C6 isoparaffins comprise at least about 20% or more by weight of the total weight of the light renewable naphtha fraction. In another embodiment, the C4 to C6 isoparaffins comprise at least 34% of the light renewable naphtha fraction. In a third embodiment, the C4 to C6 isoparaffins comprise at least 40% of the light renewable naphtha fraction. Similarly, the light renewable naphtha fraction may comprise various amounts of C4 to C6 n-paraffins and/or C5 to C7 naphthenes depending upon the application. In some embodiments the light renewable naphtha fraction may comprise at least about 36% or more by weight of C4 to C6 n-paraffins based on the total weight of the light renewable naphtha fraction and/or the light renewable naphtha fraction may comprise at least about 3% or more by weight of C5 to C7 naphthenes based on the total weight of the light renewable naphtha fraction. Other embodiments might comprise 57% or 61% or more by weight of C4 to C6 n-paraffins based on the total weight of the light renewable naphtha fraction and/or the light renewable naphtha fraction may comprise at least about 3% or more by weight of C5 to C7 naphthenes based on the total weight of the light renewable naphtha fraction

The heavy renewable naphtha fraction may comprise any amount of C7 to C9 isoparaffins, C7 to C9 n-paraffins, C7 to C9 naphthenes, and/or aromatics. In some embodiments, the heavy renewable naphtha fraction comprises at least about 20% or more by weight of C7 to C9 isoparaffins based on the total weight of the heavy renewable naphtha fraction, at least about 15% or more by weight of C7 to C9 n-paraffins, at least about 14% or more by weight of C7 to C9 naphthenes, and/or at least about 5% or more by weight of aromatics based on the total weight of the heavy renewable naphtha fraction.

Due to the different AKI ratings (among other differences) the light and heavy fractions may be used for different purposes. Thus, in some embodiments at least a portion of the heavy renewable naphtha fraction may be blended into a gasoline comprising 10% or more ethanol based on total liquid gasoline volume while at least a portion of the light renewable naphtha fraction may be blended into a gasoline comprising 10% or less ethanol based on total liquid gasoline volume. That is, the light renewable naphtha fraction may be used in a traditional blended gasoline before oxygenate blending (BOB) comprising renewable content and in some embodiments the blended gasoline before oxygenate blend meets all applicable ASTM D4814 and/or EN228 specifications and after appropriate oxygenate blending has a minimum Anti-Knock Index (AKI) rating of at least 85, and preferably 87.

Advantageously, employing the light renewable naphtha fraction made according to the methods described here may allow the incorporation of a higher renewable naphtha fraction than a comparable blended gasoline comprising renewable naphtha that has not been distilled to remove a heavy renewable naphtha fraction. For example, the higher renewable naphtha fraction in the BOB at least about 10% higher by volume in the blended gasoline than the renewable naphtha that has not been distilled in the comparable blended gasoline. It was also surprising and unexpected that (1) the blended gasoline with light renewable naphtha fraction before oxygenate blend meets all applicable ASTM D4814 and/or EN228 specifications and after appropriate oxygenate blending has a minimum Anti-Knock Index (AKI) rating of at least 85 or minimum Research Octane Number (RON) of at least 91 and/or the gasoline demonstrates lower particulate emissions relative to an ASTM D4814 and/or EN228 compliant gasoline whose BOB comprises only petroleum derived components and lacks renewable components. The particulate emissions may be measured in a convenient manner such as, for example, using an FTP, an HWFE, or US06 EPA regulatory drive cycle.

When Applicant discloses or claims a range of any type, Applicant's intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein, unless otherwise specified. Numerical end points of ranges disclosed herein are approximate, unless excluded by proviso.

Values, ranges, or features may be expressed herein as “about”, from “about” one particular value, and/or to “about” another particular value. When such values, or ranges are expressed, other embodiments disclosed include the specific value recited, from the one particular value, and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that there are a number of values disclosed therein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. In another aspect, use of the term “about” means+20% of the stated value, +15% of the stated value, +10% of the stated value, +5% of the stated value, +3% of the stated value, or +1% of the stated value.

Although embodiments described herein are made with reference to example embodiments, it should be appreciated by those skilled in the art that various modifications are well within the scope of this disclosure. Those skilled in the art will appreciate that the example embodiments described herein are not limited to any specifically discussed application and that the embodiments described herein are illustrative and not restrictive. From the description of the example embodiments, equivalents of the elements shown therein will suggest themselves to those skilled in the art, and ways of constructing other embodiments using the present disclosure will suggest themselves to practitioners of the art. Therefore, the scope of the example embodiments is not limited herein.

Examples

The composition of a representative renewable naphtha that may be employed herein is shown in the table below with a representative heavy and light renewable fraction shown after employing the methods described herein. FIG. 1 shows cut points vs. octane rating (RON and MON) for a light renewable naphtha fraction and a heavy renewable naphtha fraction separated via distillation as described herein. RON refers to Research Octane Number while MON refers to Motor Octane Number. AKI or anti-knock index is (RON+MON)/2.

FIG. 2 shows cut points vs. AKI for a light renewable naphtha fraction.

FIG. 3 shows relative carbon number distribution for various cuts points in a light renewable naphtha fraction.

FIG. 4 shows cumulative octane number increase (%) by cut point and step octane number increase (%) by cut point.

Representative Renewable Naphtha Composition

Carbon		Iso-		Naph-
#	Paraffins	paraffins	Olefins	thenes	Aromatics	Total
C3	1.1	0.0	0.0	0.0	0.0	1.1
C4	3.7	1.6	0.0	0.0	0.0	5.3
C5	9.0	5.7	0.0	0.2	0.0	14.9
C6	15.4	8.7	0.0	1.1	0.0	25.1
C7	16.2	11.1	0.0	0.8	0.1	28.1
C8	13.0	10.0	0.0	0.4	0.1	23.5
C9	0.3	1.5	0.0	0.0	0.0	1.8
C10	0.1	0.1	0.0	0.0	0.0	0.2
C11	0.1	0.0	0.0	0.0	0.0	0.1
C12	0.0	0.0	0.0	0.0	0.0	0.0
Total	58.8	38.6	0.0	2.5	0.2	100.0

Representative Light Renewable Naphtha Composition

Carbon		Iso-		Naph-
#	Paraffins	paraffins	Olefins	thenes	Aromatics	Total
C3	0.0	0.0	0.0	0.0	0.0	0.0
C4	9.5	2.2	0.0	0.0	0.0	11.7
C5	51.2	32.6	0.0	0.0	0.0	83.8
C6	0.4	4.1	0.0	0.0	0.0	4.5
C7	0.0	0.0	0.0	0.0	0.0	0.0
C8	0.0	0.0	0.0	0.0	0.0	0.0
C9	0.0	0.0	0.0	0.0	0.0	0.0
C10	0.0	0.0	0.0	0.0	0.0	0.0
C11	0.0	0.0	0.0	0.0	0.0	0.0
C12	0.0	0.0	0.0	0.0	0.0	0.0
Total	61.1	38.9	0.0	0.0	0.0	100.0

Representative Heavy Renewable Naphtha Composition

Carbon		Iso-		Naph-
#	Paraffins	paraffins	Olefins	thenes	Aromatics	Total
C3	0.0	0.0	0.0	0.0	0.0	0.0
C4	0.2	0.1	0.0	0.0	0.0	0.2
C5	1.0	0.2	0.0	0.1	0.0	1.3
C6	18.6	9.2	0.0	2.0	0.0	29.7
C7	20.4	13.9	0.0	1.1	0.1	35.6
C8	16.7	12.8	0.0	0.7	0.1	30.4
C9	0.4	1.6	0.0	0.3	0.1	2.4
C10	0.1	0.1	0.0	0.0	0.0	0.2
C11	0.1	0.0	0.0	0.0	0.0	0.1
C12	0.0	0.0	0.0	0.0	0.0	0.0
Total	57.5	37.9	0.0	4.2	0.4	100.0

Representative Cutpoint 1 is shown in the chart below with a corresponding bar chart at FIG. 5.

Carbon		Iso-		Naph-
#	Paraffins	paraffins	Olefins	thenes	Aromatics	Total
C3	0.9	0.0	0.0	0.0	0.0	0.9
C4	14.7	5.5	0.0	0.0	0.0	20.2
C5	34.9	23.3	0.0	0.0	0.0	58.2
C6	9.0	11.6	0.0	0.0	0.0	20.7
C7	0.0	0.0	0.0	0.0	0.0	0.0
C8	0.0	0.0	0.0	0.0	0.0	0.0
C9	0.0	0.0	0.0	0.0	0.0	0.0
C10	0.0	0.0	0.0	0.0	0.0	0.0
C11	0.0	0.0	0.0	0.0	0.0	0.0
C12	0.0	0.0	0.0	0.0	0.0	0.0
Total	59.6	40.4	0.0	0.0	0.0	100.0

Representative Cutpoint 2 is shown in the chart below with a corresponding bar chart at FIG. 6.

Carbon		Iso-		Naph-
#	Paraffins	paraffins	Olefins	thenes	Aromatics	Total
C3	0.0	0.0	0.0	0.0	0.0	0.0
C4	0.0	0.0	0.0	0.0	0.0	0.0
C5	0.1	0.0	0.0	0.0	0.0	0.2
C6	15.6	4.5	0.0	1.3	0.0	21.4
C7	23.3	16.0	0.0	1.3	0.2	40.8
C8	18.9	14.3	0.0	1.0	0.2	34.4
C9	0.5	1.9	0.0	0.3	0.1	2.8
C10	0.2	0.1	0.0	0.0	0.0	0.3
C11	0.1	0.0	0.0	0.0	0.0	0.1
C12	0.0	0.0	0.0	0.0	0.0	0.0
Total	58.7	36.9	0.0	4.0	0.4	100.0

Representative Cutpoint 3 is shown in the chart below with a corresponding bar chart at FIG. 7.

Carbon		Iso-		Naph-
#	Paraffins	paraffins	Olefins	thenes	Aromatics	Total
C3	1.2	0.0	0.0	0.0	0.0	1.2
C4	7.1	2.8	0.0	0.0	0.0	9.9
C5	20.3	12.4	0.0	0.4	0.0	33.1
C6	32.3	19.6	0.0	1.8	0.0	53.7
C7	0.1	2.0	0.0	0.0	0.0	2.1
C8	0.0	0.0	0.0	0.0	0.0	0.0
C9	0.0	0.0	0.0	0.0	0.0	0.0
C10	0.0	0.0	0.0	0.0	0.0	0.0
C11	0.0	0.0	0.0	0.0	0.0	0.0
C12	0.0	0.0	0.0	0.0	0.0	0.0
Total	61.0	36.8	0.0	2.1	0.0	100.0

Representative Cutpoint 4 is shown in the chart below with a corresponding bar chart at FIG. 8.

Carbon		Iso-		Naph-
#	Paraffins	paraffins	Olefins	thenes	Aromatics	Total
C3	0.0	0.0	0.0	0.0	0.0	0.0
C4	0.0	0.0	0.0	0.0	0.0	0.0
C5	0.0	0.0	0.0	0.0	0.0	0.1
C6	2.6	0.3	0.0	0.5	0.0	3.4
C7	29.0	18.3	0.0	1.7	0.2	49.2
C8	23.6	17.9	0.0	1.3	0.3	43.1
C9	0.6	2.4	0.0	0.5	0.1	3.6
C10	0.2	0.1	0.0	0.0	0.0	0.4
C11	0.1	0.1	0.0	0.0	0.0	0.1
C12	0.0	0.0	0.0	0.0	0.0	0.1
Total	56.2	39.2	0.0	4.0	0.6	100.0

Representative Cutpoint 5 is shown in the chart below with a corresponding bar chart at FIG. 9.

Carbon		Iso-		Naph-
#	Paraffins	paraffins	Olefins	thenes	Aromatics	Total
C3	0.5	0.0	0.0	0.0	0.0	0.5
C4	4.5	1.6	0.0	0.0	0.0	6.1
C5	14.9	8.8	0.0	0.3	0.0	24.0
C6	26.8	16.2	0.0	1.9	0.0	43.9
C7	9.1	15.9	0.0	0.5	0.0	25.5
C8	0.0	0.0	0.0	0.0	0.0	0.0
C9	0.0	0.0	0.0	0.0	0.0	0.0
C10	0.0	0.0	0.0	0.0	0.0	0.0
C11	0.0	0.0	0.0	0.0	0.0	0.0
C12	0.0	0.0	0.0	0.0	0.0	0.0
Total	55.7	41.5	0.0	2.8	0.1	100.0

Representative Cutpoint 6 is shown in the chart below with a corresponding bar chart at FIG. 10.

Carbon		Iso-		Naph-
#	Paraffins	paraffins	Olefins	thenes	Aromatics	Total
C3	0.0	0.0	0.0	0.0	0.0	0.0
C4	0.2	0.1	0.0	0.0	0.0	0.2
C5	1.0	0.5	0.0	0.0	0.0	1.5
C6	1.8	1.0	0.0	0.1	0.0	2.9
C7	26.1	5.7	0.0	1.4	0.2	33.4
C8	30.7	23.6	0.0	1.4	0.4	56.1
C9	0.7	3.5	0.0	0.4	0.1	4.9
C10	0.3	0.3	0.0	0.0	0.0	0.6
C11	0.1	0.1	0.0	0.0	0.0	0.2
C12	0.1	0.0	0.0	0.0	0.0	0.1
Total	61.0	34.8	0.0	3.4	0.8	100.0

Embodiments

• • 1. A process for increasing Anti-Knock Index (AKI) rating in a renewable naphtha having an initial AKI rating comprising:
  • separating the renewable naphtha under conditions sufficient to form a light renewable naphtha fraction comprising C4-C6 normal paraffins, preferably a light renewable naphtha fraction comprising C4-C6 normal and iso paraffins which is substantially free of aromatics, e.g., has less than about 1% aromatic compounds by volume and a heavy renewable naphtha fraction comprising C7-C9 normal and iso paraffins and a heavy renewable naphtha fraction comprising C7-C9 normal paraffins;
    wherein the light renewable naphtha fraction has an AKI rating which is above the initial AKI rating of the renewable naphtha.
  • 2. The process of embodiment 1 wherein the separating comprises distilling.
  • 3. The process of embodiment 1 wherein the light renewable naphtha fraction has an AKI rating which is:
  • (1) at least 19% higher than the initial AKI rating of the renewable naphtha; or
  • (2) at least 39% higher than an AKI rating of the heavy renewable naphtha fraction; or
  • (3) both (1) and (2).
  • 4. The process of embodiment 1 which further comprises blending at least a portion of the light renewable naphtha fraction into a gasoline comprising 10% or less ethanol based on total liquid gasoline volume.
  • 5. The process of embodiment 1 which further comprises blending at least a portion of the heavy renewable naphtha fraction into a gasoline comprising 10% or more ethanol based on total liquid gasoline volume, or alternatively blending heavy renewable naphtha into E85, a fuel containing 51%-83% ethanol, or alternatively using heavy renewable naphtha as a feedstock to the petrochemicals industry.
  • 6. The process of embodiment 1 wherein the light renewable naphtha fraction has an AKI rating of 70 or more.
  • 7 The process of embodiment 1 wherein the heavy renewable naphtha fraction has an AKI rating of 55 or less.
  • 8. The process of embodiment 1 wherein the light renewable naphtha fraction comprises at least about 50% or more by weight of C4 to C6 isoparaffins based on the total weight of the light renewable naphtha fraction.
  • 9. The process of embodiment 1 wherein the light renewable naphtha fraction comprises at least about 15% or more by weight of C4 to C6 n-paraffins based on the total weight of the light renewable naphtha fraction.
  • 10. The process of embodiment 1 wherein the heavy renewable naphtha fraction comprises at least about 29% or more by weight of C7 to C9 isoparaffins based on the total weight of the heavy renewable naphtha fraction.
  • 11. The process of embodiment 1 wherein the heavy renewable naphtha fraction comprises at least about 30% or more by weight of C7 to C9 n-paraffins based on the total weight of the heavy renewable naphtha fraction.
  • 12. The process of embodiment 1 wherein the heavy renewable naphtha fraction comprises at least about 3% or more by weight of C7 to C9 naphthenes based on the total weight of the heavy renewable naphtha fraction.
  • 13. The process of embodiment 2 wherein the distilling comprises distilling at a temperature of up to 160 °F to form the light renewable naphtha fraction.
  • 14. The process of embodiment 13 which further comprises removing the light renewable naphtha fraction.
  • 15. The process of embodiment 14 which further comprises blending at least a portion of the light renewable naphtha fraction into a gasoline comprising 10% or less ethanol based on total liquid gasoline volume.
  • 16. The process of embodiment 15 wherein the blended gasoline before oxygenate blending meets all applicable ASTM D4814 specifications and after appropriate oxygenate blending has a minimum Anti-Knock Index (AKI) rating of at least 85.
  • 17. The process of embodiment 16 wherein the blended gasoline before oxygenate blending comprises a higher renewable naphtha fraction than a comparable blended gasoline comprising renewable naphtha that has not been distilled to remove a heavy renewable naphtha fraction.
  • 18. The process of embodiment 17 wherein the higher renewable naphtha fraction is at least about 10% higher by volume in the blended gasoline than the renewable naphtha that has not been distilled in the comparable blended gasoline.
  • 19. The process of embodiment 1 wherein the renewable naphtha comprises reformed or isomerized reprocessed renewable naphtha, a bio-naphtha derived from one or more of the following feedstocks and processes: ketopyrolysis-derived renewable naphtha from lipids, ketopyrolysis-derived renewable naphtha from cellulosic feedstocks, renewable naphtha or its derivatives produced from hydrothermal liquefaction of cellulosic material which is subsequently hydrotreated and potentially further upgraded, renewable naphtha or its derivatives produced from fast pyrolysis of cellulosic material which is subsequently hydrotreated and potentially further upgraded, or any mixture thereof.
  • 20. The process of embodiment 15 wherein the gasoline demonstrates lower particulate emissions relative to an ASTM D4814 compliant gasoline whose BOB comprises only petroleum derived components and lacks renewable components, wherein the particulate emissions are measured using an FTP, and HWFE, or US06 EPA regulatory drive cycle.

Claims

1. A process for increasing Anti-Knock Index (AKI) rating in a renewable naphtha having an initial AKI rating comprising: wherein the light renewable naphtha fraction has an AKI rating which is above the initial AKI rating of the renewable naphtha.

separating the renewable naphtha under conditions sufficient to form a light renewable naphtha fraction comprising C4-C6 normal and iso paraffins and a heavy renewable naphtha fraction comprising C7-C9 normal and iso paraffins;

2. The process of claim 1 wherein the separating comprises distilling.

3. The process of claim 1 wherein the light renewable naphtha fraction has an AKI rating which is:

(1) at least 7% higher than the initial AKI rating of the renewable naphtha; or

(2) at least 51% higher than an AKI rating of the heavy renewable naphtha fraction; or

(3) both (1) and (2).

4. The process of claim 1 which further comprises blending at least a portion of the light renewable naphtha fraction into a gasoline comprising 10% or less ethanol based on total liquid gasoline volume.

5. The process of claim 1 which further comprises blending at least a portion of the heavy renewable naphtha fraction into a gasoline comprising 10% or more ethanol based on total liquid gasoline volume.

6. The process of claim 1 wherein the light renewable naphtha fraction has an AKI rating of 70 or more.

7. The process of claim 1 wherein the heavy renewable naphtha fraction has an AKI rating of 55 or less.

8. The process of claim 1 wherein the light renewable naphtha fraction comprises at least about 20% or more by weight of C4 to C6 isoparaffins based on the total weight of the light renewable naphtha fraction.

9. The process of claim 1 wherein the light renewable naphtha fraction comprises at least about 35% or more by weight of C4 to C6 n-paraffins based on the total weight of the light renewable naphtha fraction.

10. The process of claim 1 wherein the heavy renewable naphtha fraction comprises at least about 35% or more by weight of C7 to C9 isoparaffins based on the total weight of the heavy renewable naphtha fraction.

11. The process of claim 1 wherein the heavy renewable naphtha fraction comprises at least about 45% or more by weight of C7 to C9 n-paraffins based on the total weight of the heavy renewable naphtha fraction.

12. The process of claim 1 wherein the heavy renewable naphtha fraction comprises at least about 3% or more by weight of C7 to C9 naphthenes based on the total weight of the heavy renewable naphtha fraction.

13. The process of claim 2 wherein the distilling comprises distilling at a temperature of up to 160 °F to form the light renewable naphtha fraction.

14. The process of claim 13 which further comprises removing the light renewable naphtha fraction.

15. The process of claim 14 which further comprises blending at least a portion of the light renewable naphtha fraction into a gasoline comprising 10% or less ethanol based on total liquid gasoline volume.

16. The process of claim 15 wherein the blended gasoline before oxygenate blending meets all applicable ASTM D4814 specifications and after appropriate oxygenate blending has a minimum Anti-Knock Index (AKI) rating of at least 85.

17. The process of claim 16 wherein the blended gasoline before oxygenate blending comprises a higher renewable naphtha fraction than a comparable blended gasoline comprising renewable naphtha that has not been distilled to remove a heavy renewable naphtha fraction.

18. The process of claim 17 wherein the higher renewable naphtha fraction is at least about 10% higher by volume in the blended gasoline than the renewable naphtha that has not been distilled in the comparable blended gasoline.

19. The process of claim 1 wherein the renewable naphtha comprises reformed or isomerized reprocessed renewable naphtha, a bio-naphtha derived from one or more of the following feedstocks and processes: ketopyrolysis-derived renewable naphtha from lipids, ketopyrolysis-derived renewable naphtha from cellulosic feedstocks, renewable naphtha or its derivatives produced from hydrothermal liquefaction of cellulosic material which is subsequently hydrotreated and potentially further upgraded, renewable naphtha or its derivatives produced from fast pyrolysis of cellulosic material which is subsequently hydrotreated and potentially further upgraded, or any mixture thereof.

20. The process of claim 15 wherein the gasoline demonstrates lower particulate emissions relative to an ASTM D4814 compliant gasoline whose BOB comprises only petroleum derived components and lacks renewable components, wherein the particulate emissions are measured using an FTP, and HWFE, or US06 EPA regulatory drive cycle.