WO2019204365A1

WO2019204365A1 - Process for converting c2-c5 hydrocarbons to gasoline and diesel fuel blendstocks

Info

Publication number: WO2019204365A1
Application number: PCT/US2019/027766
Authority: WO
Inventors: Jeffrey Miller; Kurtis SLUSS; Benjamin WEGENHART; Chris D'acosta
Original assignee: Swift Fuels, Llc
Priority date: 2018-04-16
Filing date: 2019-04-16
Publication date: 2019-10-24
Also published as: AU2019255251A1; EP3781651A4; MX2020010902A; BR112020021259A2; EP3781651A1; CA3097546A1; CN112543800A

Abstract

A process for converting C2-5 alkanes to higher value C5-24 hydrocarbon fuels and blendstocks. The C2-5 alkanes are converted to olefins by thermal olefination, without the use of a dehydrogenation catalyst and without the use of steam. The product olefins are fed to an oligomerization reactor containing a zeolite catalyst to crack, oligomerize and cyclize the olens to the fuel products which are then recovered. Optionally, hydrogen and methane are removed from the product olefin stream prior to oligomerization. Further optionally, C2-5 alkanes are removed from the product olefin stream prior to oligomerization.

Description

PROCESS FOR CONVERTING C2-C5 HYDROCARBONS TO

GASOLINE AND DIESEL FUEL BLENDSTOCKS

F1ELD

The field of this invention is the low-cost production of performance-grade gasoline and distillate fuel products from C2-C5 alkane-rich light hydrocarbon feedstreams. The field more particularly relates to a thermal olefination reaction converting C2-C5 alkanes to alkenes and subsequent cracking, oligomerizing and/or cyclizing of the alkenes to form fuel formulations and blendstocks. A particular application of the invention is in the tailored derivation of performance-grade fuels and fuel blendstocks from readily-available, lower-value, hydrocarbon streams.

BACKGROUND

While the total U.S. demand for gasoline is steady or in a small level of decline, there is a rising demand for premium gasoline blendstocks to meet the needs of new, more efficient, higher-compression spark-ignited engines. There is also a rising demand of high-performance, ultra-low sulfur, diesel fuel blendstocks with high cetane values and effective cold-temperature flowability properties used in compression- ignition diesel engines and gas turbine engines. These demands exist while surplus light hydrocarbons are stranded in certain markets without supply-chain options, despite being available from midstream, refinery and petrochemical facilities for transformation to fuel grade products.

According to the US Energy lnformation Administration (EIA), sources of natural gas and gas liquids in the midstream industry are abundant across the nation. See, for example, Table 1. Note that this portrayal of NGL volumes may under-report rejected ethane sold with methane. Any separation of natural gas from natural gas liquids, e.g. via de-methanization, leaves an alkane-rich admixture of light hydrocarbon compounds (typically C2 - C5+ natural gas liquids (NGL’s). These may undergo further separations, e.g., de-ethanization, de-propanization, de-butanization of gases and liquids. This invention particularly targets any C2-C5 alkane rich source of NGL’s (preferably NGL’s without ethane rejection), or similar industrial gases comprising such light

hydrocarbons, to transform alkane-rich feedstreams to high-value fuel products, thereby avoiding the need for such C2, C3, C4 separations. Table 1

The petrochemical industry, a major consumer of ethane and propane, uses extremely complex, high-precision and capital-intensive methods to separate and purify chemical grade compounds such as ethylene and propylene. For example, conversion of propane to propylene, or ethane to ethylene, requires cryogenic separation (-100°C) followed by ultrapure, dry, non-contaminated hydrogeneration processing to eliminate very-close boiling molecules (e.g., butadiene, propyne, acetylene) that can be highly reactive to chemical processing and/or poison polymerization catalysts. None of these are a concern for the process of this invention.

SUMMARY

The invention comprises a process of thermal and chemical reactions which provide a high-conversion of alkane-rich C2-C5 hydrocarbon feedstreams comprising ethane, propane, butanes, or pentanes, or any admixture thereof, to performance-grade gasoline and distillate fuel products. The process includes a specialized, non-catalytic method of converting certain alkane feeds to olefins by way of low-cost, non-catalytic, alkane dehydrogenation reactions called "thermal olefination". The process combines this olefination process with cracking, oligomerization and/or cyclization reactions of olefins to fuel-grade products using zeolite catalysts ln embodiments, the process includes variations useful in the conversion of alkene-rich feedstreams.

The process can be arranged in appropriate sequences with thermal and catalytic reactors operating in parallel or in series and utilizing recycling methods based upon feedstock characteristics, operating conditions and desired products.

The thermal and catalytic reactors utilize innovative low-cost methods to minimize carbon build-up via specialized regeneration techniques.

The liquid fuel products produced from the process can be specifically targeted by operating conditions and catalyst choices to yield any desired range of C₄ to C12 gasoline compounds (i.e., high octane paraffins, olefins and aromatics), or to yield C₉ to Ci₆₊ high-performance middle distillate compounds (e.g., zero sulfur, high cetane, low pour point for use in ultra-low-sulfur diesel fuel) that achieve pre-specified fuel performance targets.

The process also accommodates any alkene-rich C2 - C5 light hydrocarbon feedstreams comprised of ethene, propene, butenes or pentenes, or any admixture thereof, which are convertible to fuel blendstocks using the same thermal and catalytic process and reactions albeit re-sequenced as outlined in this invention.

Further objects and advantages will be apparent from the description which follows.

BR1EF DESCRIPTION OF THE DRAW1NGS

F1G. 1 is a schematic showing the process flow and system components of the conversion method and system of the present invention.

F1G. 2 is a graph showing yield versus conversion for processing of pentane in accordance with the method of F1G. 1.

F1G. 3 is a more detailed flow diagram of an embodiment of the LG2F Process.

F1G. 4 is a simplified version of the flow diagram of F1G. 3, modified to include a Knockout Unit between the R1 and R2 reactors.

F1G. 5a is a graph showing selectivity of product distribution of aliphatics as a function of space velocity.

F1G. 5b is a graph showing selectivity of product distribution of aliphatics as a function of temperature.

F1G. 6a is a graph showing selectivity of product distribution of aromatics as a function of space velocity.

F1G. 6b is a graph showing selectivity of product distribution of aromatics as a function of temperature.

F1G. 7 is a graph showing mass percentages of hydrocarbons for Average Jet A fuel.

F1G. 8 is a graph of mass percentages in a typical carbon distribution for diesel fuel.

F1G. 9 is a flow diagram of an alternate embodiment of the LG2F Process including series oligomerization reactors.

F1G. 10 is a flow diagram of an alternate embodiment of the LG2F Process including a combination with the 12FE process.

F1G. 11 is a flow diagram of an alternate embodiment of the LG2F Process including direct alkene feed to the R2 oligomerization reactor.

F1G. 12 is a graph showing a single pass yield of propene in accordance with the flow diagram of F1G. 11.

F1G. 13 is a flow diagram showing optimal elimination of benzene from gasoline blendstocks produced by methods herein.

F1G. 14 is a diagram showing construction elements typical of single and dual reactors. F1G. 15 is a diagram of a dewaxing process flow in accordance with the present disclosure.

DESCRIPTION

For the purpose of promoting an understanding of the principles of the invention, reference will now be made to the embodiments illustrated herein and specific language will be used to describe the same lt will nevertheless be understood that no limitation of the scope of the invention is thereby intended. Any alterations and further modifications in the described embodiments, and any further applications of the principles of the invention as described herein are contemplated as would normally occur to one skilled in the art to which the invention relates. Embodiments of the invention are shown in detail, but it will be apparent to those skilled in the relevant art that some features that are not relevant to the present invention may not be shown for the sake of clarity. All percentages used herein are weight percentages, unless indicated otherwise.

An aspect of this disclosure, referred to herein generally as the Light

Hydrocarbon Gas to Fuel Process, or "LG2F Process", converts alkane-rich feedstreams of hydrocarbons comprising 2-5 carbons, or any admixture of C2-5 hydrocarbon compounds, to C₄to Ci₆₊ fuel grade hydrocarbons. The process uses a non-catalytic thermal olefination reaction followed by acid-catalyzed cracking, oligomerizing and/or cyclizing reactions. The process may be performed in a variety of sequences using single or multi-bed reactors subject to the feedstream characteristics, operating parameters and targeted products. As used herein, the term LG2F Process includes all processes, and corresponding systems, coming within the scope of the present disclosure.

This invention utilizes a thermal olefination reactor producing a series of dehydrogenation and cracking reactions to upgrade any source of light hydrocarbon gas phase alkane-rich compounds (i.e., > 90% alkanes) to produce an olefin-rich light gas effluent stream. Low-boiling olefin-rich gas compounds are then transformed to produce a spectrum of longer alkanes and/or alkenes and/or aromatics, by using zeolite catalysts in a temperature and pressure controlled catalytic reactor. This

transformation of light alkane-rich gases results in unique, higher-valued liquid streams including targeted high-octane compounds for use as gasoline blendstocks or longer- chain, high-cetane compounds for use as diesel blendstocks. The LG2F Process is extremely efficient and utilizes no complex multi-stage distillation or fractionation columns, multi-stage cryogenic separation, or

hydrogenation processing (for chemical purification in the base petrochemical industry), while producing a diverse molecular spectrum of C₄ to Ci₆₊ blendstocks with targeted performance characteristics ideal for transportation fuels with up to 60% less capital investment.

The Process employs a thermal olefination technique to avoid traditional catalytic dehydrogenation and/or the use of steam cracking, while leveraging a light-gas recycle system to maximize finished product yields of targeted high-performance fuel products.

The LG2F reactor systems may utilize a unique, two-step reactor regeneration and cleansing process to eliminate the need for steam cracking, boilers and water separation processes. An automated, in-line regeneration process allows operability of the reactors to be extended up to 3-10 years while thermal activation and catalyst activity levels are maintained at high levels.

The LG2F process can also convert de-methanized gas streams and industrial alkane-rich off-gas compounds to liquid fuels, and thereby minimize production losses attributed to low-value off-gas compounds. Due to market/location imbalances, compounds such as methane vs. NGL’s, or even various grades of gasoline or diesel, may have economic values which vary, allowing location arbitrage introducing an additional factor in assessing the optimal configuration of feed sources, operating conditions, and market dynamics impacting targeted product and byproduct portfolios. The availability of light hydrocarbon feedstreams (e.g., alkane-rich, alkene-rich) and the appropriate sequencing of the thermal olefination and catalytic processes of this invention are tailored to yield high-octane gasoline blendstocks or high cetane diesel fuel blendstocks to meet specific market-based, performance-based, and regulatoiy-driven fuel specification requirements.

Overview

The present disclosure is based upon a unique and efficient process for the conversion of light paraffins into performance-grade fuel components. Selected alkane- rich feeds undergo thermal olefination reactions in a first reactor, transforming the light paraffin compounds to olefins. The olefins from the thermal olefination reactions are then catalytically transformed in a second reactor into fuel-grade blendstock. This combination of the specific thermal olefination and catalytic conversion reactions is referred to herein as the LG2F Process. This process converts light hydrocarbon gases into high-grade transportation fuels that span select ranges of hydrocarbon compounds possessing targeted fuel compositions and performance characteristics.

lndustry Need

Due to the increase in C2 - C5 light hydrocarbons and shale gas production on a global scale there is a surplus supply and growing market dislocation of light

hydrocarbons with limited pathways to petrochemical markets (e.g. ethane crackers). Accordingly there is growing interest in converting and upgrading such lower value light hydrocarbons to higher-value C6 - C24+ fuel range components as performance- ready consumable fuel products leveraging the existing fuels supply chain. This requires that fuel components be produced to match critical performance specifications for gasoline and diesel fuels such that they can be blended into existing supply chain pathways.

Solution

The LG2F process provides a technique to produce any number of hydrocarbon fuels or fuels blendstocks in the gasoline and middle distillate spectrum that are capable of meeting fuel performance criteria set by the industry. This allows the fuels produced by this invention to be homogeneous with fuels in the existing supply chain and available for immediate blending or other boutique blends with some added

commercial value.

The basic LG2F Process is exemplified in FIG.1. A C2-5 light gas alkane-rich feedstream is directed to thermal olefination reactor (Rl), wherein C2-5 Alkanes are converted into olefins. Cracking, oligomerization and/or aromatic cyclization take place in a second, catalytic conversion reactor (R2). Upon completion of the catalytic process, the resulting hydrocarbon stream is cooled and partially condensed, and flashed for liquid recovery of the fuel-grade blendstock product. The hydrogen and methane in the cooled light gases from the catalytic reactor are separated (or purged) from the C2+ gases, which may be recycled to the thermal olefination reactor.

Fuel-grade hydrocarbons, preferably C₄ -C12 blendstock for gasoline and C₉ - C₂₄₊ blendstock for diesel fuel are recovered. As a result, select Ci+ light alkanes are transformed to any range of C₄ to Ci₆₊ hydrocarbon constituents for use in various transportation fuels, with methane and hydrogen as byproducts. Another feature of the light gas transformation is the creation of aromatic hydrocarbons which add energy density and bring a higher-octane value to the gasoline blendstock and contribute to thermal stability and cold-flow properties for diesel fuels.

C2-5 Alkane Feedstreams

The thermal olefination reactor receives and processes alkanes including 2-5 carbon atoms, namely, ethane, propane, butane and/or pentane. As used herein, the term "C2-5 Alkane" is used to refer to alkanes having specifically from 2 to 5 carbon atoms. The term "Feedstream" refers to a reactor feed not including any recycle component. The term "C2-5 Alkane Feedstream" refers to a Feedstream comprising C2- 5 alkanes. For example, a typical C2-5 Alkane Feedstream may include ethane, propane, n-butane, iso-butane and n-pentane. As described hereafter, in a preferred aspect the C2-5 Alkane Feedstream is sourced as an effluent stream from existing commercial operations lt may have been the subject of pretreatments, and it may also be formed from the combination of more than one feed source.

The LG2F Process specifically uses a C2-5 Alkane Feedstream which is "alkane- rich", meaning that at least 90% of the Feedstream comprises C2-5 Alkanes ln another aspect, the alkane-rich, C2-5 Alkane Feedstream includes at least 95%, and preferably at least 98%, C2-5 Alkanes.

ln particular embodiments, the C2-5 Alkane components are specific subsets of all C2-5 Alkanes. For example, certain embodiments utilize a C2-5 Alkane Feedstream constituting a single C2-5 Alkane, namely any one of ethane, propane, butane or pentane ln a particular aspect, the LG2F Process uses ethane as the C2-5 Alkane Feedstream. ln other embodiments, the C2-5 Alkane Feedstream contains at least 90%, preferably at least 95%, and more preferably at least 98% ethane ln an alternative embodiment, the C2-5 Alkane Feedstream comprises 80-100% ethane and 0-20% propane. Ethane and propane are less expensive alkanes and there is thus a greater value in upgrading them to use in fuels ln another aspect, the C2-5 Alkane Feedstream comprises at least 90% of a mixture of ethane, propane and butane. Other Feedstream Constituents

The C2-5 Alkane Feedstream contains at least 90% by weight of C2-5 Alkanes. Therefore, in certain embodiments the Feedstream includes other constituents. These other constituents may, for example, include other hydrocarbons, contaminants and inert materials.

The additional components may include other hydrocarbons. Methane may be present in the Feed Stream, particularly depending on the source. Methane is preferably kept to a low amount (preferably less than 5-10%) as it is unreactive and therefore unproductive in the LG2F Process. Controlled accumulations of methane via recycle can be productive for dispersing consumed and generated heat in the R1 and R2 reactors, respectively ln an embodiment, methane gas may be used as a diluent to sustain heat for the R1 thermal olefination reactor (an endothermic reaction) ln a related embodiment, methane gas may be used as a diluent to disperse heat in the R2 oligomerization reactor (an exothermic reaction) ln another embodiment, it is possible to utilize a membrane or other (non-distillation) gas separation unit prior to the thermal olefination reaction to remove unproductive quantities of methane from the feedstream for higher purity C2-C5 feedstreams. Higher alkanes may be present and can be thermally cracked in the LG2F Process, but they are also useful as gasoline constituents and there is therefore limited value in including them in the Alkane Feed Stream. Accordingly, in a similar embodiment, an option exists to capture C6+ liquids from the C2-C5 feedstream in a liquid/vapor flash drum prior to the thermal olefination reaction to minimize cracking of these compounds. Light hydrocarbon feedstreams with smaller quantities of alkenes and alkynes are to be avoided as they are destructive to the yield (making benzene and methane), and they tend to coke the R1 reactor. Note that LG2F alternatives exist to handle feedstreams with larger quantities of alkenes via use of the R2 reaction. Therefore, alkenes and alkynes preferably comprise less than 5%, and more preferably less than 2%, of the C2-5 Alkane Feed Stream.

ln practice, some field sources of the C2-5 Alkanes may contain contaminants ln this setting, a contaminant may be any component that adversely affects the LG2F Process or its system components. For example, contaminants may include ammonia, hydrogen sulfide, nitrogen, sulfur and/or water. Some source streams are not scrubbed to reduce such contaminants. These contaminants could poison later-used catalysts or cause accelerated corrosion to downstream (e.g., refining or petrochemical) processing units.

Significant concentrations of these contaminants are preferably removed in advance by conventional pre-treatments. The C2-5 Alkane Feedstream preferably contains less than 1%, and more preferably less than 0.5% contaminants. However, pre-treatment is not necessary when using clean light gas feedstocks, e.g., cracked gases from reformate, as these light hydrocarbon streams are treated upstream and contain ultra-low quantities of contaminants.

lnert components (e.g., nitrogen, argon, helium) are by definition non-reactive in the LG2F Process. However, it remains preferable to keep the inert components in limited amounts prior to being purged (e.g. via membrane) from the LG2F Process. Accordingly, the C2-5 Alkane Feedstream (excluding methane) preferably contains less than 1%, and more preferably less than 0.5% inert materials.

A given C2-5 alkane-rich hydrocarbon source may be processed as obtained, or it may be combined with other available light gas streams for transformation to targeted gasoline or diesel-range transportation fuel blendstocks. Blending streams from 2 or more sources, or augmenting a source stream with one or more added components, is one manner of directing the compositions of the final products.

Example C2-5 Alkane Sources

There are many diverse sources of C₂ to C5 light hydrocarbon gas streams.

Sources include NGL’s, gas condensate, industrial fuel gas, petroleum gases and liquified petroleum gases (LPG), which are available across the oil, gas & petrochemical industry. Suitable C2-5 Alkane sources are typically found in refineries, oil & gas extraction facilities, gas processing plants, petrochemical plants, and liquid petroleum gas (LPG) storage facilities. C2-5 Alkane sources also include any light hydrocarbon gases output of catalytic cracking or catalytic reforming, or streams exiting any paraffin cracking unit. Additional examples include light hydrocarbon gases from hydrotreating and

hydrodesulfurization units. These and other C2-5 sources are all eligible to be thermally and catalytically converted to C5+ constituents to maximize liquid volume yield of gasoline or diesel fuel blendstocks.

Such streams are light gas compounds, typically containing ethane, propane, butane, pentane or any mixtures thereof. Pentane and butane/pentane mixtures may also be in liquid form at ambient temperatures and pressures. Some sources may be an isolated stream of virtually one compound (e.g. propane). Any combination of suitable C2-5 alkane gas streams can be merged together to utilize this transformative LG2F Process.

The LG2F Process thus provides enhanced utilization of available plant effluents. For example, a cracked, long-chain paraffin byproduct having between 3% and 14% hydrocarbon gases upgrades from low-value industrial fuel uses to a higher-value gasoline blendstockby the LG2F Process. Similar gas constituents (predominately C₂+ with hydrogen) from the outputs of catalytic reformers create the opportunity for even larger liquid volume yields of high-octane gasoline blendstocks using the LG2F Process. Any such gas streams can be pretreated if necessary, and processed individually or merged with any number of other available C2-C5 alkane-rich gas streams.

Thermal Olefination

Using an alkane-rich feedstream comprised of >90% alkanes, the production of liquid fuels in one embodiment starts with the alkanes being largely converted to olefins via a dehydrogenation step. The LG2F Process uses a thermal olefination reaction for this purpose.

Thermal Olefination utilizes endothermic reactions which suitably occur, for example, in an isothermal reactor operating with a constant supply of heat. The

Thermal Olefination reactor converts the C2-5 Alkanes into olefins having 2 or more carbons ("C2₊"). Various light gas compounds are produced as byproducts, depending on the Alkane Feedstream. For example, pentane may be cracked into olefins and paraffins as illustrated by the following examples:

C5H12 ® C4H8 (olefin) + CH₄ (paraffin)

C5H12 ® C3H6 + C2H6

C5H12 ® C2H4 + C3H8

C5H12 ® C5H10 + H₂

As another example, ethane may be cracked into ethene, with small quantities of methane and hydrogen as light gas byproducts.

The results of the Thermal Olefination reactions therefore depend largely upon the composition of the alkane-rich C2-5 Alkane Feedstream. The intermediate product is a mix comprised of C2 to C5 olefins, along with a lesser amount of Cl-5 alkanes and hydrogen as byproducts. The conversion is selected to maximize gasoline or diesel fuel yields.

As used herein, the term "Thermal Olefination" refers to the conversion of alkanes to olefins in relation to controllable variables including the Feedstream composition, temperature, pressure and space velocity. As used herein, thermal olefination does not comprise the use of either catalytic or steam cracking. The absence of any dehydrogenation catalyst avoids the high cost and marginal value of managing such dehydrogenation catalysts. The absence of steam eliminates the burden of handling water, steam and fractionation columns. Further, water is known to be a hindrance to the downstream use of zeolite catalysts in the subsequent catalytic process. This invention thus uses a low-cost, non-catalytic dehydrogenation technique targeting alkane-rich feedstreams.

The results of an exemplary, single-pass LG2F processing of a C5 alkane

(pentane) feedstock is shown in FIG. 2. This demonstrates the dependence of the product mix on operating parameters of the LG2F Process. That is, modification of the C2-5 Alkane Feedstream and/or of the operating conditions allows control of the product mix. For example, it is apparent from FIG. 2 that the production of ethene as compared to methane reached an optimal point for product yield lt is also shown that going to 100% conversion was disadvantageous in view of the increased production of methane and the consequent reduction in ethene.

The LG2F Process utilizes thermal olefination reactors configured to

dehydrogenate the C2-5 Alkanes to form olefins without the requirement of any catalyst. The thermal olefination reactor may be of conventional design, including as simple as a tubular chamber. To minimize carbon build-up, a protective layer may be crafted onto the internal surface area of the entire reactor via plating (e.g., chemical or electroplating) to produce a superficial layer of aluminum that is oxidized to alumina. Alumina has known chemical and heat resistive properties up to 1700°C in the absence of high-temperature steam and will thereby inhibit deposition of carbon onto the inner tube surface by preventing chemical access to iron surface atoms. This specialized aluminum/alumina coating thus increases the process lifecycle by reducing coke accumulation.

14

Olefination Operating Conditions

The thermal olefination reaction is performed at a high-temperature, with no catalyst or steam utilized. The thermal olefination reactor is preferably operated at a temperature above 600°C, an internal pressure of 0 - 1500 psig, and a gas weight hourly space velocity of 30 - 1000 hr¹. The thermal olefination process does not materially affect methane or hydrogen in the Feedstream. The presence of steam as a byproduct of the R1 thermal olefination reaction with light hydrocarbons must be avoided as it can be damaging to the subsequent R2 catalytic reaction. Table 2 - Thermal Olefination Reactions

The thermal olefination reaction is effective to convert to olefins at least 20%, preferably at least 25%, of the C2-5 Alkanes per pass ln some embodiments the conversion is in the range of 25% to 65% conversion per pass ln addition, unconverted C2-5 Alkanes are preferably recycled to the thermal olefination reactor. Overall, conversion of the C2-5 Alkanes from the initial Alkane Feedstream to hydrocarbon fuels is preferably at least 65%, more preferably at least 80%, and most preferably at least 95%.

Reactor Regeneration - R1

The LG2F thermal olefination system may include integrated reactor

regeneration and cleaning sequences (RRC). Operability of the thermal olefination reactor(s) is dependent upon reactor life-cycles and the resulting amount of thermal resistance that may occur from carbon build-up on reactor walls. This RRC sequence is performed to reduce or eliminate carbon buildup (coking). Regeneration and cleaning of the reactor(s) operating at high temperatures involves a unique series of steps, during which the light hydrocarbon feedstream flow is paused, in order to restore active levels of the reactor(s). Two methods for regenerating and cleansing the

Thermal Olefination reactors are provided, which can be used with a single reactor, or with multiple units operated in parallel, and/or series.

The Reactor Regeneration intentionally avoids the potential for deleterious amounts of high-temperature steam impacting the thermal olefination reactor, and prevents water contaminants passing to the downstream catalytic oligomerization reactor(s). This is to prevent permanent catalytic deactivation of the downstream zeolite-based, catalysts used in the oligomerization reactor(s). The removal of generated water (via low-temperature the hydrogen/carbon reaction) avoids the detrimental effects on the zeolite catalysts (via active site reduction and dealumination) used downstream in the oligomerization reaction.

Traditionally, alkane dehydrogenation reactors have used either catalytic or steam cracking methods. Steam or steam/air methods were used to reduce or eliminate coking. However, such methods require large capital investments to manage water, steam boilers and water separation techniques ln the LG2F Processes, regeneration is performed without the use of steam or steam/air mixtures, making the overall LG2F System long-lived and cost efficient. The absence of added water (e.g., by way of steam) enhances operation of the LG2F System.

A. Low Temperature Hydrogen and High Temperature Carbon One Reactor Regeneration sequence for regeneration of the Thermal Olefination reactors is conducted requires two-steps. This sequence is specifically designed to (1) safely react hydrogen with oxygen to form water, and (2) then allowing the removal of water from the system, before conducting a high-temperature carbon/oxygen reaction to cleanse the reactor.

Step 1: Low Temperature Hydrogen Removal

The first step in the regeneration sequence is initiated by flowing a low concentration of oxygen, e.g., in air, through the thermal olefination reactor. The oxygen comprises preferably no more than 21% v/v, and more preferably no more that 10% v/v, and even more preferably no more than 5% v/v. A diluent gas, such as nitrogen or argon, is used to decrease the concentration of combustible oxygen for the water production phase. The reduced oxygen concentration in this burndown feedstream allows for a smaller temperature flame front.

This oxygen-containing feed gas is heated up in the thermal olefination reactor until a flame front is observed in the reactor. This flame front is strictly due to the combustion of hydrogen to water at a lower temperature than that of combusting carbon. The flame front remains until no hydrogen is present, and the hydrogen burndown process is then complete. The generated water is collected as a liquid in a condensing chamber, while allowing for other non-combusted and combusted gases to be fed back into the LG2F System via a recycle loop.

Step 2: High Temperature Carbon Removal in the Absence of Hydrogen The second step is a carbon combustion cleansing sequence performed once the water has been appropriately purged from the system. While an oxygenated gaseous stream is still being passed through the R1 reactor system the temperature is increased from its initial water removal step to a temperature at which a second flame front is observed. This second flame front is largely devoid of water as the first burndown sequence combusted preferably at least 90% of the hydrogen, more preferably at least 95%, and even more preferably at least 99% of the hydrogen. The only combustion product resulting from the second carbon combustion sequence is therefore primarily due to the production of carbon dioxide, with little to no carbon monoxide. This flame front is followed through the R1 reactor until a flame front is no longer observed. Once the flame front is no longer being produced, the reaction chamber of the thermal olefination units is sufficiently devoid of coke.

This two-step sequence can be conducted at any level of carbon build-up, but preferably not more than at 50% of the unit’s lifecycle, more preferably not more that 30% of the unit’s life cycle, and most preferably not more than 20% of the unit’s lifecycle. This 2-step sequence can be performed in-situ, offline from the hydrocarbon flow, on an individual reactor operating in parallel with other thermal olefination reactors, to assure a continuous LG2F Process ln another embodiment, duplicate reactors of the same type are used in parallel with different burndown time rotations so at least one unit can be online continuously. The procedure can be fully automated to allow the starting and stopping of the regeneration sequence and the resumption of the hydrocarbon feedstream to continue thermal olefination reaction.

B. Compressed Air

A second option for the Reactor Regeneration method involves stopping the hydrocarbon feed before substantial coke formation occurs, then introducing compressed air into the reactor zone at 0-50°C below the typical unit operating temperature. The regeneration proceeds for a short time duration, which may be limited by the effects of exothermic heat. This regeneration cycle is preferably designed to limit exothermic heat, by using a frequent regeneration cycle which keeps carbon build-up at low levels. Within minutes, the carbon build-up is purged. The process thereby emits C0₂, H₂0 and excess air for venting to the atmosphere.

While any regeneration cycle can be used, a higher frequency regeneration cycle (e.g., 15 minutes every 1 -15 days) allows for minimal water partial pressure in the combusted products as carbon and hydrogen become the limiting reactants, rather than oxygen ln general, the frequency of the regeneration is dependent on the feedstream quality which impacts the level and/or rate of coke formation.

C2-5 Olefin Catalytic Processing

The thermal olefination results in a product stream which is passed to a catalytic reactor in which the olefins are converted into a broad spectrum of fuel grade hydrocarbons. The conversion involves chemical reactions comprising cracking, oligomerization and/or aromatic cyclization, and transforms the olefins without affecting lighter (C₂/C3) paraffins in the Feedstream. ln one sense, the catalytic conversion may be affected in any manner known in the art to be effective in cracking, oligomerizing and/or cyclizing C2-5 olefins. Particularly preferred catalytic processes are disclosed herein.

As used herein, the term "Olefin Feedstream" refers to a Feedstream comprising C2-5 olefins. The Olefin Feedstream may comprise all or a portion of the product stream of the thermal olefination reactor. For example, methane and hydrogen present in the olefination product may be separated prior to passing the stream to the catalytic reactor. Similarly, C2-5 Alkanes present in the product stream, particularly ethane and propane, may be separated out and recycled to the thermal olefination reactor - either combined with the C2-5 Alkane Feedstream, or separately. An Olefin Feedstream derived from the product stream of the thermal olefination reactor will contain C2-5 olefins.

ln one aspect, the C2-5 Olefin Feedstream is input to the catalytic reactor. As used herein, the term "catalytic reactor" is used to refer to a reactor using a catalyst and operating under conditions so as to cause cracking, oligomerizing and, in many conditions, cyclizing of the feed olefins to form higher hydrocarbons, namely higher- carbon alkanes, alkenes and aromatics suitable for gas or diesel blending stocks.

lt will be appreciated that these reactions may occur in various combinations and orders, with some molecules undergoing several such reactions. Thus, reactions leading to the end products may act on the olefins in the feed, or may act on the olefins after they have already undergone one or more reactions lt is therefore contemplated, and is to be understood, that reference to reactions of the feed olefins refers generally to reaction of any molecule that was originally fed to the catalytic reactor as a C2-5 olefin.

The catalytic reactor uses a zeolite catalyst and operates above 200°C, at 0 -1500 psig, and a weight hourly space velocity (WHSV) between 0.5 and 10 (preferably about 1). This reactor produces multi-iterative, random-sequenced chemical reactions to crack, oligomerize, and in many conditions, cyclize the broad-spectrum of hydrocarbons comprising olefins and olefin-derived compounds. The catalytic process can be caused to produce any range of fuel grade products, including for example, C5₊ or C₆₊ or C7₊ gasoline ranges (primarily paraffins, olefins, and aromatics), or C9₊ or C10₊ or C12₊ ranges of light gas oil or middle distillate hydrocarbons (for use primarily as diesel fuel blendstocks).

The chemical reactions in the catalytic reactor (R2) comprise multi-iterative, building, degrading and sometimes cyclizing of different molecular formations creating a portfolio of hydrocarbons that can be selectively tailored to any specific carbon range of products. The end products can be affected, for example, based on the composition of the C2-5 Alkane Feedstream, the configuration of a recycle loop, and various other operating conditions of the overall LG2F Process. For example, operating conditions (e.g., T, P, WHSV) are varied depending upon the desired product - gasoline grade or middle distillate grade fuel blendstocks.

Catalysts

The catalytic reactions disclosed herein utilize catalysts that crack, oligomerize, and in many conditions cyclize the olefins with high efficiency. The catalyst used in the LG2F Process generally contains a strongly acidic zeolite, with a high surface area support, for example, alumina. Additionally, there may be a weakly active metal, for example molybdenum, which saturates cracked olefins without saturation of aromatic compounds in certain specialized embodiments. By comparison, traditional catalytic naphtha reforming technology uses catalysts that contain platinum (Pt) on chloride alumina, often promoted with either tin (Sn) or rhenium (Re) for better yield and stability, respectively. These reforming catalysts are compositionally very different from the LG2F catalysts.

The LG2F Process uses catalysts which are functional to substantially crack, oligomerize, and under some conditions cyclize the olefins in the feedstream, while not significantly affecting other components of value in the feedstream. A catalyst is functional to substantially crack, oligomerize, and/or cyclize the olefins if it transforms at least 65%, preferably at least 80%, and more preferably at least 95% of the olefins to fuel grade compounds in a single-pass yield.

ln one embodiment, the catalytic reaction is performed using a zeolite catalyst. The acidic cites in zeolite catalyze cracking reactions more rapidly than other components. The reactions can be conducted both with and without metal

impregnation. The metal allows hydrogen to add across olefinic compounds which can be strategically implemented to saturate olefins in the latter half of the R2 reactor or in a separate hydrogenation step entirely. This can function with internally generated or supplemental hydrogen.

ln one aspect, the processes use a zeolite catalyst having a pore size of 2 to 8 Angstroms. Exemplary surface areas for the catalyst are 400 to 800 m²/gram.

Examples of the zeolite catalysts include Si, Al and 0, preferably with an Si: Al ratio of 10 to 300. Zeolite catalysts with properties outside of these limitations may also be useful. The catalyst is preferably selected to substantially catalyze the olefins while not significantly affecting other components of value in the feed stream.

ln embodiments, the catalyst is Zeolite ZSM-5, Zeolite Beta or Zeolite Mordenite. lmpregnations of these catalysts all use the same metal at varying concentrations for activity. Molybdenum trioxide is used to impregnate the zeolite catalyst with molybdenum. This creates a bifunctional catalyst that is an acid and metal. Zeolites are characterized in the following ways: pore size - 3 to 8 angstroms usually; pore structure - many types; and chemical structure - combination of Si, Al, and 0. All have

ammonium cations (except one version of mordenite) until impregnation and all have molar Si/Al ratios of 10 to 300.

Zeolite Beta has the following properties: 2 - 7 angstroms pore size, Si02 to A1203 molar ratio (Si/Al) ranging from 20 to 50, intergrowth of polymorph A and B structures, and surface area between 600 and 800 m²/gram.

Zeolite Mordenite has the following properties: 2 - 8 angstroms pore size, sodium and ammonium nominal cation forms, Si/Al ratio of 10 to 30, and surface area between 400 and 600 m2/gram.

ln a particular embodiment, the catalyst is Zeolite ZSM-5. ZSM-5 has the following properties: 4 - 6 angstroms pore size, pentasil geometry forming a 10-ring- hole configuration, Si/Al ratio of 20 to 560, and surface area between 400 and 500 m²/gram. Various impregnations may use between 1% and 2% molybdenum. The ZSM-5 is the preferred catalyst for its ability to support the R2 transformation reaction while preserving the chemical composition of the aromatic compounds. The reaction can be conducted both with and without metal impregnation. The metal allows hydrogen to add across olefinic compounds that are produced during the cracking mechanism. The smaller pore size of the ZSM-5 catalyst results in far less undesired saturation of aromatic compounds, which are generally desired constituents in both gasoline and diesel blendstocks.

Zeolite Catalyst Example

The proprietary acid-based (ZSM-5 zeolite) catalyst specifically targets C2-rich hydrocarbon streams (e.g., one embodiment: 80:1 silica on alumina ratio). The process design may also have catalyst beds which favor C₂ reactions more than C₃ reactions or C₄ reactions, etc., resulting in layers or sequences of oligomerization and cracking reactions with different conditions to maximize the yield and performance properties of the fuel products.

Reactor Regeneration - R2

Operability of the catalytic reactor is dependent upon reactor and catalyst life- cycles, and the resulting amount of deactivation or thermal resistance that may occur from carbon build-up on catalysts or reactor walls. Regeneration and cleaning of any such reactor or catalyst operating at high temperatures involves a unique series of steps to restore active levels and prevent permanent catalytic deactivation of the downstream zeolite-based catalytic reactor lt has been determined that the regeneration methods previously described herein are also useful with the catalytic reactor, and the timing of regeneration may be determined on a similar basis.

Both regeneration methods outlined herein can be tailored to operate in any suitable reactor, especially any alkane dehydrogenation reactor or zeolite-based oligomerization reactor. These methods beneficially eliminate the need for steam- based regeneration methods, eliminate excess carbon build-up in a cost-effective manner, and restore process activation levels.

LG2F System

Referring to FIG. 3, there is shown a process flow for the LG2F Process.

Feedstock stream (1) comprises mostly C2-C5 paraffin-rich alkanes. Pretreatment (not shown) of the feed (1) can be conducted to remove excess methane (via membrane system), C6+ hydrocarbons (via liquid-vapor flash drum), or any contaminants to support gasoline and diesel fuel production and/or to optimize feed composition.

Feedstock stream (1) is combined with a recycled light stream (13) comprised of a C1-C5 mixture primarily including n-paraffins and i-paraffins with some olefins and the combined stream (2) is fed into heat exchanger (EX-1). As described later, light gas feedstreams that have primarily olefin-rich content (e.g., FCC off-gases, propylene, etc.) may be fed directly into R-2 via line (7), bypassing the thermal olefination step. The combined stream (2) is cross exchanged in EX-1 with stream (8), to recover heat produced in the catalytic reactor R-2. The outlet stream (3) of EX-1 is fed into another cross exchanger, EX-2, to further pre-heat the feed for R-l.

The pre-heated stream (4) is fed into a thermal olefination furnace (R-l) typically operating at 600 - 1100 °C and 0 - 1500 psig. Thermal olefination reactor (R- 1) conducts an endothermic reaction to produce olefinic compounds via carbon cracking and dehydrogenation. Excess heat from the reaction is used as the hot stream (5) for EX-2. The hot stream (6) exiting EX-2 may require additional cooling for the second reaction stage (R-2). EX-3 is an optional air-water or refrigerant-based cooling unit for the system depending upon heating requirements lt is useful here to conduct the appropriate heat transfer step to ensure proper set-point R-2 inlet conditions. A bypass can be implemented between streams (6) and (7) and streams (9) and (10) in lieu of cooling utility for EX-3 and EX-4 for dynamic operability between diesel and gasoline production. An optional knockout step may be incorporated prior to the R-2 reactor in stream (7) to capture entrained liquid droplets and remove all C6+ compounds from entering R-2. See FIG.4.

R-2 is catalytic reactor, typically operating at 200 - 1000 °C and 0 - 1500 psig, that cracks, oligomerizes, and under some conditions cyclizes olefinic compounds in multi-iterative reactions to produce a broad spectrum of n-paraffins, i-paraffins, naphthenes, and aromatics primarily across the C₄ to Ci₆₊ range, resulting in high- octane gasoline or high-cetane diesel spectrum products. Depending upon the final product desired, excess C₂ to C12 compounds from this catalytic reaction can be recycled into fuel grade constituents. The reaction is very exothermic and can be configured with or without inter-stage or integrated cooling to prevent overheating. The excess heat from the reacted stream (8) is used in EX-1 as the hot stream inlet to step up temperature for the combined feed (2).

The hot outlet (9) can support optional cooling for proper flashing in flash drum D-l. For this reason, EX-4 may not be required but it could be an air-cooler, water cooler, etc. to conduct appropriate heat exchange. The flash drum feed (10) is kept at the pressure of the system and is used to purge targeted light components from the mixed product stream. The primary function of D-l is to control the pressure of the system. Light components (11, 14) consist of mostly H2 and C1-C3 compounds that can either be purged (14) from the system or directly recycled (11) back into the system by combining with the flash drum (D-2) lights stream (16) prior to compressor, C-l.

D-l light streams will have H2 and Cl components which are unreactive for the system and will cause accumulation in the recycle if not properly removed. H2 and Cl can be purged (14) with other light components to stabilize the recycle system or a separator, such as a membrane, can be utilized to selectively remove H2 and Cl. The liquid bottoms (15) from D-l are fed into D-2 which is set at a lower pressure to remove mostly C3 and C4 compounds from the liquid stream (15). Lights (16) from D-2 are combined with lights (11) from D-l to form stream (12) which is compressed in C-l and recycled for further reaction. Recyclable light hydrocarbons (16) from D-2 (typically C₂ - C₄ if targeting gasoline; C₂ - Cio if targeting diesel) will be fed back to the thermal reaction, unless the constituents are olefin-rich which can optionally be fed directly into R-2 to increase process efficiency. The resulting flashed liquid stream (17) exiting the bottoms of D-2 is the final product of the process which can be targeted to produce any range of C₄-Ci₂ high-octane gasoline blendstock or C9-16₊ high-cetane diesel fuel blendstock.

Recycle

Following the R2 catalytic reaction, the alkane-rich light gas recycle stream exiting the flash drum condensation unit can be directed back to the C₂₊ thermal olefination reactor to be merged with other incoming light hydrocarbon streams as depicted in the process flow FIG. 1. The constituents outside the selected array are gathered into a single-loop recycling configuration. This recycle process maximizes the yield profile and performance properties of any type of the liquid effluent produced for transportation fuel use. Typically, for all compounds not used in a targeted gasoline range or diesel fuel range the process will direct the lighter byproducts (e.g. < C5 for gasoline or < Ce for diesel) to be recycled for further upgrading. Operating with a continuous recycle loop with R2 effluent achieves high product yields, for example ranging from 65% to 95%. Each recycle loop is continuous to allow the random redistribution of C₆₊ liquid hydrocarbons yielded from the LG2F Process to unite in various formations (e.g., paraffins, olefins, aromatics) needed for a fuel based upon specific performance characteristics. Such performance characteristics for gasoline might include octane, vapor pressure, density, net heat of combustion, etc., while such characteristics for diesel fuel might include cetane, thermal stability, cold flowability, and others.

Referring to FIG.4, there is shown a simplified schematic for an LG2F system in accordance with the present invention. The system is generally the same as shown in FIG. 3, except a "Knockout" is provided between reactors R1 and R2. As previously mentioned, the Knockout unit operates to remove entrained liquids and C6+

compounds from entering R2.

By way of example, the fully-recycled thermal and chemical reactions from processing a feed of 80% C2 (ethane) and 20% C5 (pentane) are depicted in a material balance as shown below in Table 3a. The process follows the steps in FIG. 4.

The resulting C₆₊ gasoline compounds yielded a 66% mass conversion of high- performance gasoline with a 25% (17 /66% mass as aromatics) from the C2/C5 feed and resulted in an unexpectedly high 101.7 Research Octane number (using ASTM D2699 Test Method). This illustration using C2 and C5 as the feed to thermal olefination demonstrates the broad range of gasoline blend compositions that are possible.

Table 3a - Production of Gasoline Blendstock from C2 & C5 feedstock

A similar example shown in Table 3b depicts 100% C2 (ethane) with an 84% mass conversion to C5+ gasoline (for standard RVP) with a 25% (21/84% mass as aromatics). This demonstrates the broad spectrum of molecular outcomes typical of all C2-5 feedstreams. The C₂ to C5 feedstocks can be fully recycled and converted to gasoline range molecules based upon the unique operating conditions of the reactor. The process follows the steps in FIG. 4. Table 3b - Production of Premium Gasoline Blendstock from C2 (ethane) feedstock

This illustration also depicts how specific operating conditions can be used to control the resulting slate of compounds. The temperature of Reactor 2 was 250°C 5 which resulted in a 25% m/m aromatic content. The aromatic content is variable and can be used to increase octane values of gasoline blendstocks. Surplus C6+ aromatics can be captured from the knockout as byproducts for petrochemical processing lncreasing the temperature of reactor 2 from 250°C to 400°C doubles the content of desirable aromatics in the gasoline blendstock and thereby increases the resulting 0 octane. The lights purge (via flash drum and membrane separation) allows methane and hydrogen byproducts to be reused in other downstream processes. Table 3c is similar for a C6+compounds (> 98 RON with low RVP) gasoline with a total yield of 79% from 100% ethane; aromatics were 35% (28/79) of the total yield. The process follows the steps in FIG. 4.

Table 3c - Production of Gasoline from C2 (ethane) feedstock

The oligomerization reactions are effective to convert a significant amount of the olefins received from the thermal olefination reactor. Conversion of the received olefins with the R1 and R2 Process, with recycle, is preferably at least 60%, more preferably at least 80%, and most preferably at least 90%. Conversions at least up to 95% are also possible. Product Selectivity

The LG2F process uses the feed composition, the thermal olefination reaction, and the oligomerization operating conditions (T, P, WHSV) to establish a predictable result to various fuel performance criteria described on industry fuel specifications. The following outlines how this technique is achieved. Also, see FIGS. 5 and 6.

ln one aspect, the process is configured to produce a desirable, broad-range of fuel products. The fuel products are typically in the C5-24+ range of hydrocarbon fuels or fuel blendstocks. The range of fuel products depends in part on the C2-C5 alkane feedstream, and is controlled based on operation of the LG2F Process ln one approach, the fuel products are determined in the following manner. First, the available feedstream is analyzed in relation to the desired fuel target. Then a baseline is established taking into account the nature of the feedstream and typical operating conditions for the LG2F Process. For example, it can be established that a given feedstream, e.g., 100% ethane, will produce a predictable array of fuel products with the operation of the Process at certain conditions of temperature, pressure, space velocity and recycle.

lt can further be determined that changes to these conditions will move the product mix in one direction or another. For example, raising the temperature in the oligomerization reactor R2 (or R2L) will increase cracking of the hydrocarbons and the production of lighter aromatics, resulting in a lower final boiling point of the targeted fuel. A higher pressure used in R2L will increase the chain-length of middle distillate compounds produced, also impacting final boiling point of diesel fuel. Higher space velocities result in a higher exotherm temperature which produces lighter compounds (as depicted in Fig. 5a and 6a). Higher reactor temperatures at a fixed space velocity and pressure reflect a similar tendency to produce lighter compounds (as depicted in Fig. 5b and 6b). ln this manner, it is possible to identify baseline reactor operating conditions and then adjust from there to produce differing product mixes.

Upper Boiling Limit

The temperature of the oligomerization reaction is used to prescribe the cut- point of the fuel product, which determines the limit of the final boiling point of the fuel. For example, a fuel specification may call for a final boiling point of 340°C or 225°C or 180°C and the reactor conditions can be set to limit the upper boiling condition to a specific temperature.

Table 4

Lower Boiling Limit

The use of a single stage flash-drum with a preset liquid-vapor temperature limit can establish any lower bound to the liquid fuel without the expense of cryogenics or complex multi-stage fractionation columns. The flash-drum temperature is set at a predetermined point, e.g., for C4 butane (high RVP), for the preferred liquid / vapor cut. The level of precision can be enhanced by using a 2-stage drum.

Table 5

Benzene Knock-Out

The thermal olefination reaction is known to cause some production of benzene, which has a control limit in fuels. Accordingly, the LG2F Process utilizes a liquid-vapor knockout flash drum set at 75°C to capture any light aromatics exiting thermal olefination. Since C2 - C5 hydrocarbons are generally cracked into C5 and smaller compounds, the primary exception to this is the production of the liquid C6H6 aromatic (albeit valued in select markets) which can then be largely eliminated from the final BO fuel. This compound can be marketed as BTX or reacted with olefins to make C7+ alky- aromatics to increase octane in gasoline.

Aromatics Content in Gasoline

The temperature of the oligomerization reaction is used to pre-determine the level of activation which directly effects aromatic production. Accordingly, the higher octane gasoline formulations favor a C7 - CIO aromatic content of up to 50%.

This results in the following operating conditions:

Table 6

Aromatics Content in Distillate

The temperature of the oligomerization reaction is used to pre-determine the level of activation which directly affects aromatic production. Accordingly, the higher cetane formulations favor lower aromatic content of less than 25%. The aromatic content of diesel fuel is limited to not exceed 35% and the presence of C16+ aromatics can impede the cetane performance. So the diesel fuel spectrum is generally targeted to C9 - C16 range compounds and aromatic content is limited to < 35%, resulting in the following operating conditions:

Table 7

Gasoline performance was measured using ethylene with baseline operating at 320°C, atm (0 psig) and 0.75 WHSV. Space velocity graphs using aliphatics and aromatics were performed at atm (0 psig) at temperature 284°C, 293°C, 318°C and 343°C. All results demonstrate the core principles for determining the appropriate R2 reactor operating conditions to produce performance fuels. The actual operating parameters will vary depending upon the feedstream. Diesel fuels follow the same basic chemistry and thermodynamic principles as gasoline spectrum reactions.

Control of operating parameters (Temperature, Pressure, Space Velocity) can directly impact the scope and range of molecules produced in a catalytic

oligomerization unit. Temperature directly impacts the level of cracking that occurs during oligomerization. An increased temperature causes more cracking to occur which will result in smaller molecules to be produced. Lower temperature will produce longer chained molecules as they crack less while coupling still occurs.

High pressures are preferred for diesel range production as a higher gas concentration will allow for more opportunities for coupling. Locally, more molecules will occupy a given area at high pressure allowing for more reactions to occur in a given time frame. Modifying pressure will have a direct impact on the boiling point of the product as more pressure would create longer molecules. However, more reactions due to high pressure will significantly increase the exotherm so the energy would need to be removed at the rate of generation to minimize cracking.

The same applies for space velocity where an increased space velocity gives a shorter duration of residence time on the catalyst but more reactions per second that will increase temperature as well. Chain propagation can be reduced at high space velocities at the expense of an increased exotherm. Thus, proper heat management can dynamically control product slate, distribution and final boiling point while modifying pressure and space velocity.

Commercial Significance

The LG2F Process and System allows for the midstream or refinery production of performance-grade fuels which are tailored to meet ever-changing industry

performance criteria in areas where stranded light hydrocarbons are not accessible to traditional fuel supply chains. The US NGL market currently rejects approximately 407,000 BPD of ethane (~ 10% of the total production NGL’s) by selling ethane as natural gas where an ethane market does not exist, despite ethane’s higher volumetric BTU value. Eliminating the "ethane rejection" mode opens up the opportunity for more cost efficient gasoline and diesel fuel production from NGL's and streamlines otherwise stranded, shut-in, or flared methane gas reserves. LG2F also offers a low-cost pathway to upgrade ethane, propane and butane+ compounds to performance-grade fuel values. Producing gasoline and diesel to a fuel performance standard reduces unnecessary logistics costs and allows fuels to enter markets via the existing finished product fuel supply chains.

The LG2F thermal olefination reaction (Rl) along with the chemical reaction (R2) and recycle loop can be used independently and can be interchangeably tailored based upon feedstock composition and desired end products to produce gasoline blendstocks and/or diesel fuel blendstocks. The process is flexible to allow the reactor operating conditions to be established to produce the desired blend components and compositional features to meet fuel performance requirements (e.g. aromatics for gasoline octane value, cetane for diesel performance). The byproducts of the reaction may include methane and hydrogen.

The tailoring effects of the gasoline and diesel fuel reactions include a variety of factors including the final boiling point cut-off of the product, the lower cut-off of the product - both of which are based on the operating conditions for any given feedstream. Other factors include the % m/m of C6 aromatics, the % of C5 used in the gasoline (RVP index), the cetane number, the % aromatics, the % C18+ compounds, etc.

A major feature of the LG2F Process is the targeting of performance grade fuel products. Rather than indiscriminately producing a stream of random hydrocarbons, this invention serves to tailor the process and operating conditions for specific purposes. For example, when targeting gasoline, C4 and C5 compounds typically have higher vapor pressure and lower octane values than preferred C6 - C12 compounds, so too much concentration of C4/C5 compounds in the targeted fuel will result in a low- grade off-spec fuel. Similarly, high-performance gasoline with more than 50%

aromatics, while high in octane, can be undesirable for environmental emissions. Yet other users of the process may prefer to produce a very high concentration of aromatics in a constrained market - only to be used as blendstocks with other surplus

components (e.g. before blending into a final fuel at a refinery) ln yet another example, the presence of excess benzene can also be on operating limitation to some fuel specifications. Diesel fuel requires a high proportion of C9 - C16 compounds with relatively high cetane values; diesel also requires less presence of low-melting point compounds. Accordingly, this invention offers a wide variety of process techniques and optionality for the user to configure the catalytic operating conditions to meet the intended performance-grade product outcomes.

An optional feature of LG2F is to produce C₄ and C5 alkanes which may be useful for increasing the volatility and raising the vapor pressure in gasoline, although often at the expense of octane levels. Thus, some or all the C4-5 alkanes may be targeted for production into the gasoline blendstock. Alternatively, C4 or C4-C5 production may be avoided, in which case the process directs < C₄ or < C5 byproducts to be recycled for further upgrading.

ltwill be appreciated that the LG2F Process can include split multi-iterative variations of both R1 and R2 that may require more than a single recycle loop for optimal operation. As an example, R2 may be separated into two or more reaction sequences with some form of separation between and after the operations. The separation off-gas may be merged or recycled independently and at different locations from one another.

LG2F Products

The LG2F Process converts C2-5 Alkanes into a broad-range of fuel products constituting higher-value Cs-2₄₊ hydrocarbon fuels and fuel blendstocks. This refers to the fact that a variety of fuel products may be derived using this Process with the products containing one or more compounds within the Cs-2₄₊ range. A typical fuel product is a gasoline blendstock including one or more compounds selected from hydrocarbons having 4 to 12 carbons. Another typical product is a C9_₂₄₊ hydrocarbon blendstock suitable for diesel fuel. A number of other possible LG2F Process products have been identified herein, and it is distinct feature of the present invention that a broad-range of different fuel products may be formed.

However, this does not mean that the reference materials must include each of the compounds in the recited range. Accordingly, as used herein, a reference to the LG2F Process providing a fuel product identified as a range, e.g., C4-12, includes both a product including all of the hydrocarbons in that range, as well as fewer than all, e.g., 1 or 4, hydrocarbons in that range. Similarly, a reference to a range such as in regards to the alkane feedstream including C2-5 alkanes is a reference to a feedstream having one or more of the C2 to C5 alkanes.

The process configuration utilizes a recycle loop to produce a specified range, for example C5 to C12 gasoline compounds or C₉ to C20 diesel fuel compounds for use as blendstocks in high grade transportation fuels. Using the LG2F process, the liquid yields using recycling can range, for example, from 65% to 95+ % of the initial feedstream depending upon the severity of operating conditions. This process offers flexibility in making paraffinic molecules of higher yield, or olefinic molecules and aromatic hydrocarbons of somewhat lower yields for gasoline range products, or alternatively, it can be switched to create a blend of middle distillates (primarily paraffins, olefins and aromatics) primarily for diesel range products. As an alternative, excess methane can be used as process fuel or recycled into fuels.

Gasoline Blendstocks

ln one aspect the LG2F Process is tailored to the production of gasoline blendstocks, as exemplified in the foregoing discussion. As used herein, the term "gasoline blendstock" refers to a formulation comprising n-paraffins, iso-paraffins, cyclo-paraffins, olefins and aromatics having 4 to 12 carbons. The gasoline blendstocks from this invention preferably have 5-12 carbons, and more preferably comprise 6-11 or 7-10 carbons. The gasoline blendstocks also typically have branched-chain paraffins and aromatic hydrocarbons having 6 to 11 carbons, preferably 7 to 10 carbons ln preferred embodiments, the LG2F Process yields a product containing at least about 65% C5-10 branched-chain paraffins and at least 25% C7-9 aromatic hydrocarbon compounds. The following examples further demonstrate the ability to tailor the LG2F Process depending on the C2-5 feedstream and the desired end product(s).

Table 8 - Typical Gasoline Composition

While the gasoline blendstocks described as the products of LG2F in this invention may be comprised of varying chemical compounds, the compounds output from this invention is not randomly indiscriminate. This is accomplished as described herein by, inter alia, selection of C2-5 Alkane Feedstreams, operating parameters and recycle between the R1 and R2 reactors. The production of high-performance gasoline requires the adherence to a minimum set of performance conditions for gasoline grade products. The LG2F Process produces, for example, fuel compositions and blendstocks including the following:

In one embodiment, the gasoline compound is > 95 research octane number (RON) with no ethanol, with a > 9 psi vapor pressure (RVP) but < 13.5 psi, aromatic content < 50% m/m and with benzene content below 1.30% (v/v), and a final boiling point < 225°C .

ln one embodiment, the gasoline compound is > 95 RON with no ethanol, with a vapor pressure > 9psi but < 13.5 psi, aromatic content < 55% m/m and with benzene content below 1.30% (v/v), and a final boiling point < 225°C.

In one embodiment, the gasoline compound is > 91 [using R+M/2] with no ethanol, with a vapor pressure > 9psi but < 13.5 psi, aromatic content > 35% m/m and with benzene content below 1.30% (v/v), and a final boiling point < 225°C.

In one embodiment, the gasoline compound is > 89 [using R+M/2] with no ethanol, with a vapor pressure >9psi but < 13.5 psi, aromatic content < 35% m/m and with benzene content below 1.30% (v/v), and a final boiling point < 225°C.

In one embodiment, the gasoline compound is > 87 [using R+M/2] with no ethanol, with a vapor pressure >9 psi but < 13.5 psi, aromatic content < 30% m/m and with benzene content below 1.30% (v/v), and a final boiling point < 225°C.

In one embodiment, the gasoline compound is > 84 [using R+M/2] with no ethanol, with a vapor pressure > 9 psi but < 15.0 psi, aromatic content < 25% m/m and with benzene content below 1.30% (v/v), sulfur content below 0.008% (m/m), and a final boiling point < 225°C.

C2-5 Hydrocarbons to C6-8 Aromatics

ln an embodiment, the LG2F Process is tailored by isolating the catalytic R2 reaction to convert C₂ - C5 light olefin feedstocks into aromatic hydrocarbons comprising a narrow range of C₆ to Ce aromatics for use as a high-octane fuel blendstock or petrochemical use. This is done by use of operating conditions to obtain an aromatic yield up to the upper boiling limit of o-xylene, for example 145°C, and recycling all byproducts in the flash drum with boiling points below benzene at 80°C. The yield of C₆ to C₈ aromatics is valuable to the petrochemical market as a base aromatic feedstream to aromatics fractionation or as an alternative, if the BTX product stream is first processed by a hydrodealkylation step to decouple and remove ethyl- propyl and butyl- aromatic constituents leaving only methyl-aromatic products.

C2-5 Hydrocarbons to C7-8 Aromatics

ln another embodiment, this invention can be tailored by isolating the catalytic R2 reaction to convert C₂ - Cs light olefin feedstocks into aromatic hydrocarbons in a narrow range of C₇ to Cs aromatics. Again, this is done by targeting the aromatic yield up to the upper boiling limit of o-xylene, for example 145°C, and recycling all

byproducts in the flash drum with boiling points below toluene at 110°C. The yield of C₇ and Cs aromatics have a very high-octane value and a very high energy density in the absence of benzene and are useful gasoline blendstocks to meet premium high-octane grades.

C2-5 Hydrocarbons to C8 Aromatics

ln another embodiment, the LG2F Process is tailored by isolating the catalytic R2 reaction to convert C₂ - Cs light olefin feedstocks into aromatic hydrocarbons in a narrow range of solely Cs aromatics by targeting operating conditions for the aromatic yield up to the upper boiling limit of o-xylene, for example 145°C, and recycling all byproducts in the flash drum with boiling points below p-xylene at 138°C. The yield of Cs aromatics will have a very high-octane value and a very high energy density which can be a useful gasoline blendstock to meet premium high-octane grades ln addition, these Cs compounds may be further valuable to the petrochemical market, particularly if they are produced by a hydrodealkylation step to decouple and remove any close boiling ethyl-aromatic constituents and produce methyl-aromatic products.

C2-5 Hydrocarbons to C7-9 Aromatics

ln one embodiment, this invention is tailored by isolating the catalytic R2 reaction to convert C₂ - Cs light olefin feedstocks into aromatic hydrocarbons in the C₇ to C₉ range by specifying operating conditions for the aromatic yield up to the upper boiling limit of trimethylbenzenes, for example 175°C, and recycling all byproducts in the flash drum with boiling points below toluene at 110°C. The yield of C₇ to C₉ aromatics will have a very high-octane value and a very high energy density, without the presence of benzene, and can be a useful gasoline blendstock to meet premium high- octane grades.

C2-5 Hydrocarbons to lsooctane

One specialized technique to produce high-octane gasoline blendstocks is the use of LG2F in a truncated fashion - by setting the operating conditions of the catalytic R2 chemical reaction to the targeted upper temperature on the desired product stream. All light hydrocarbon gases below a lower targeted boiling point limit are recycled, creating a desired range of product. This technique allows production of a simple narrow band of desirable hydrocarbons that may be particularly valuable to the fuel blending process of a particular LG2F production facility.

One such example of the optionality is the targeting of isobutane, a high-octane compound typically used to add vapor pressure (RVP) to gasoline blending, but also used as a feedstock to any traditional paraffin alkylation process. The catalytic R2 chemical reaction favors the production of branched-chain paraffins, which reduces the likelihood of producing n-paraffins which boil on either side of isobutane. Accordingly, as a result of the tailored LG2F R2 reaction, isobutane (C4H10) can be isolated using a high-pressure separation vessel. The target is a narrow boiling range of between -40°C and -2°C at atmospheric conditions, which can be pressurized to partially liquify the stream and extract C₄ iso-paraffins. All the lights below -40°C (notably ethane and propane) are recycled to maximize the yield of branched paraffins within the

temperature band.

ln a similar example, the LG2F R1 thermal olefination reactor in this invention can be targeted to produce any combination of C3 - C5 olefins (propene, butene and/or amylene) from any C3 - C5 light gas alkanes which can then be directly applied into any traditional paraffin alkylation unit with the additional feed of isobutane (from any source) for production of high-octane, branched-chain paraffinic hydrocarbons, particularly 2,2,4-trimethylpentane (lsooctane).

ln a combined example, the LG2F R1 thermal olefination reaction can be processed using any C3-C5 alkane gases to produce C3-C5 olefins. The < C3 stream can be extracted and processed by R2 (with the option to add additional light olefin streams) to target the production of isobutane or isobutene as described above. Any C6+ byproducts from the R1 reaction can be captured by liquid-vapor knockout for surplus gasoline or reuse. This tailored configuration results in the critical feedstreams necessary for input to paraffin alkylation.

Diesel Blendstocks

Diesel fuel has several key performance characteristics which depend upon the chemical composition of the fuel. Diesel fuels are generally comprised of n-paraffins, iso-paraffins, cycloparaffins and aromatics in such a way as to meet key performance requirements of the fuel. For example, in a diesel engine, cetane number is the measure of the speed of the compression ignition upon injection of the fuel, as well as the quality of the fuel burn in the combustion chamber. Accordingly, a high-performance diesel fuel is preferred to have an aggregate cetane index value (using ASTM D613) of at least 40 and as high as 60.

ln addition, very low sulfur levels are also highly desirable in diesel fuel to eliminate corrosive wear-and-tear and prevent engine emission control system issues. Jet fuel and diesel fuel, both derived from middle distillates, share many common features. See FIG. 7 and FIG. 8. However, ASTM lnternational fuel specifications call for different performance-based fuel test results impacting cetane, lubricity, viscosity, low temperature flowability, sulfur content, heating value, and more. The performance requirements are what dictate the composition and operating requirements to produce the desired fuel.

Generally, Cg₊ n-paraffins, iso-paraffins and cycloparaffins have higher cetane values than aromatics and are key constituents in the diesel blendstock to achieving high cetane measures (e.g. 40 - 60) for good fuel performance. Cetane Values for various n-paraffins are shown below in Table 8. Table 8 - C9+ n-Paraffin Compounds Have Highest Cetane Values

However, while C14+ n-paraffins have high Cetane Values, their melting point is above low ambient temperatures. See Table 10. Specialized pour point, cloud point and cold filter plugging tests often call for a reduction of heavier n-paraffinic compounds in middle distillates (often via dewaxing) to improve the cold flowability and operability of a diesel fuel ln addition, n-paraffins have lower volumetric heating value (btu/gal) in comparison to aromatics.

Table 10 - C14+ n-Paraffin Compounds Melting Points

Unlike gasoline for spark-ignited piston engines, which depend upon C7-C9 high- octane aromatics to retard early ignition, C10 to C20 aromatics provide diesel engines thermal stability, heating value (btu/gallon) and desirable elastomer swell

characteristics. Unfortunately, these aromatics generally have low cetane values which can impede effective diesel engine performance. The right balance of aromatic vs. aliphatic compounds will impact the performance characteristics of the diesel blendstock. See Table 11.

Table 11 - C10+ Aromatic Compounds Cetane Values

lt is therefore desirable to be able to produce diesel blendstocks that primarily contain high Cetane Value components (e.g. Cg-Cie₊ n-paraffins) with lesser targeted amounts of aromatics (e.g. Cg-Cie) whose lower melting points help increase cold flowability of the fuel.

Olefins are also a product of the R1 and R2 reactions and play a key role in diesel fuel blendstocks. The Cetane Values of Cg to C20 olefins are moderately high (above 50) and the C9-C15 melting points tend to be cooler than ambient temperatures helping to improve cold flowability, making them ideal compounds for diesel fuel. See Table 12. Table 12

These varying factors and fuel requirements call for flexibility in the

compositions of diesel fuels ln an aspect, the LG2F Process is tailored to the production of diesel blendstocks. As used herein, the term "diesel blendstock" refers to a formulation comprising n-paraffins, iso-paraffins, cyclo-paraffins, olefins and aromatics having 9 to 24 carbons. The diesel blendstocks preferably have 10-20 carbons preferably have less than 35 wt% aromatic hydrocarbons, and more preferably less than 30 wt%. The following discussion further demonstrates the ability to tailor the LG2F Process depending on the C2-5 feedstream and the desired diesel product(s).

This invention can be tailored by isolating the LG2F R2 chemical reaction to convert C₂ - C5 light olefin-rich feedstocks into any range of C₉ to C₂₄₊ middle distillate hydrocarbons used in jet fuel/kerosene, heating oil, marine gasoil, and ideally for high- value diesel fuel blending. When using olefin-rich feedstocks from any source with the LG2F R2 reactor for producing diesel fuel blendstocks, the acid-based chemical reaction produces a broad-spectrum of paraffin, iso-paraffin, cycloparaffin, olefin and aromatic output in a normal (gaussian) distribution. The distribution of the final product can be wide (e.g. C₉ to C₂₄₊) or narrowed (e.g. C 10 to C17) depending upon the desired performance characteristics of the middle distillate blendstock.

For example, one embodiment targets the LG2F R2 product yield by setting the operating conditions to produce hydrocarbons up to the upper boiling limit of n- hexadecane for example 295°C and recycling all byproducts in the flash drum with boiling points just above C₉ n-nonane at for example 145°C. This will yield a very high cetane blendstock with limited need for dewaxing. This can be a very useful premium diesel fuel blendstock, particularly if processed in the absence of any sulfur

contaminates (e.g. using the optional C₂ - C5 light gas feeds from the 12FE long-chain cracking process). The lower carbon paraffins have low freezing points which improve fuel flowability in cold weather (pour point). Many other LG2F R2 operating conditions may also be modified to optimize the fuel performance characteristics (e.g. cetane, pour point, density, heat of combustion, thermal stability, etc.) of the R2 product as a blendstock in comparison with other possible middle distillate blending components. The LG2F R1 and R2 reactions can be used together in a recycle loop or independently depending upon the availability of the alkane or alkene light gas feedstreams. Assessing the middle distillate product requirements in relation to the feedstream quality available will determine the targeted operating conditions and product yields from LG2F processing. Table 8 depicts the varying range of carbon numbers that would include n-paraffin, iso-paraffins, cyclo-paraffins, olefins and aromatic compounds found in the middle distillate fuel. Using the operating conditions to select the upper boiling point and lower boiling point directly impacts the resulting cetane values, melting point and flowability attributes of the all-hydrocarbon blendstock. Selecting 3 ranges of carbon numbers C9 - C14 results in excellent low-temperature flowability

characteristics, selecting C10-C20 has a lower cetane value, selecting C12 - C16 is a boutique diesel fuel blend with very high cetane values.

Table 13 - Targeting C9-20 Paraffins, Olefins & Aromatics

ln one embodiment, the LG2F Process is tailored to produce a narrow range of C9 to C14, high-cetane paraffins with few low-melting compounds, thereby minimizing any need for dewaxing. This product is a desirable diesel fuel blendstock due to its speed of starting, clean combustion and low temperature flowability.

Examples - Diesel Blendstocks

This same fully-recycled LG2F Process can be operated at conditions to produce any targeted range (e.g. Cg₊) of hydrocarbons for use as middle distillate, marine fuel, jet fuel or for diesel fuel blendstocks. The thermal olefination reaction creates a spectrum of C₂ to C5 olefin-rich hydrocarbons, and the acid-catalyzed chemical reactor uses operating conditions which favor the Cg to C₂₄₊ range of hydrocarbon compounds used in diesel fuel blendstocks largely via the dimerization, trimerization, etc. of reacted C2 - C5 olefin compounds. Selecting the C₂ to Ce range of molecules output from the R2 catalytic reaction for recycle or aromatic reuse, and setting the appropriate operating conditions (T, P, WHSV) allows a tailored outcome of middle distillate with high cetane and low pour point values ideal for diesel fuel blendstocks. Byproducts of the reaction include methane, hydrogen and aromatic surplus. In one embodiment, the R2 feedstream is comprised of > 60% m/m ethene and is subjected to a high-pressure, low-temperature catalytic reaction just above activation energy to allow additional thermodynamic control over the reaction. This embodiment utilizes an integrated cooling/dilution mechanism and/or a deactivating agent to minimize the exothermic reaction.

In one embodiment, the R2 feedstream is comprised of > 40% m/m ethene and > 10% propene and is subjected to a high-pressure, low-temperature catalytic reaction just above activation energy to allow additional thermodynamic control over the reaction. This embodiment utilizes an integrated cooling/dilution mechanism and/or a deactivating agent to minimize the exothermic reaction.

In one embodiment, the R2 feedstream is comprised of > 50% m/m any C2/C3 olefins and is subjected to a high-pressure, low-temperature catalytic reaction just above activation energy to allow additional thermodynamic control over the reaction. This embodiment utilizes an integrated cooling/dilution mechanism and/or a deactivating agent to minimize the exothermic reaction.

In one embodiment, the R2 feedstream is comprised of > 50% m/m any C3/C4 olefins and is subjected to a high-pressure, low-temperature catalytic reaction just above activation energy to allow additional thermodynamic control over the reaction. This embodiment utilizes an integrated cooling/dilution mechanism and/or a deactivating agent to minimize the exothermic reaction.

In one embodiment, the R2 feedstream is comprised of > 50% m/m any C3-C5 olefins and is subjected to a high-pressure, low-temperature catalytic reaction just above activation energy to allow additional thermodynamic control over the reaction. This embodiment utilizes an integrated cooling/dilution mechanism and/or a deactivating agent to minimize the exothermic reaction.

By-Products

ln all LG2F embodiments, excess methane and hydrogen are byproducts of the thermal olefination reaction. Since methane and hydrogen are unreactive to the LG2F process, there is no restriction on their being present in the light hydrocarbon gas feedstream.

The LG2F Process will produce varying amounts of methane (e.g. 5-20%) subject to operational and economic choices, which may have utility as process fuel particularly in remote operating locations or returned for credit as dry gas to pipelines or refineries. Depending upon the C₂+ feedstock quality, the LG2F process provides the option of extracting excess methane and hydrogen via membrane separation. Byproduct methane can also be recycled via MTO to maximize finished product yields from a given light gas feedstream.

Produced H₂ is highly desirable if reusable as a byproduct, particularly in refining and petrochemical applications lf membrane separation is not feasible then a purge stream of the same composition as the recycle loop can be drawn to prevent byproduct accumulation.

Middle Distillates - R2^L

Low-Pressure/High Pressure Catalytic Reaction

The LG2F catalytic reaction sequence can also be configured to combine a low- pressure and high pressure reaction sequence to target the conversion of light olefinic gases (e.g., C₂-Cs) from the thermal olefination reaction, to chemically transform into longer-chain components through intermediary low-molecular coupling. This pressure and conversion control method produces high-grade distillates used particularly in middle distillates, jet fuel and diesel fuel blendstocks with added quality control by utilizing a high-pressure catalytic reaction sequentially following a low-pressure catalytic reactor.

ln one such embodiment, the R1 thermal olefination reaction occurs upon receipt of alkane-rich C₂ to C5 light gases at high temperatures (e.g., above 700°C) operating at low pressure (e.g., 0-200 psig) and producing a C₂₊ olefin-rich mixed gaseous yield. These gases are cooled and proceed to the initial R2 catalytic reactor which operates at temperatures between about 200 - 500°C and low pressure (e.g. 0- 200 psig) to avoid using expensive compression techniques. Using R2 with a WHSV above 30 and a residence time < 1.0 second produces many molecular combinations (dimers, trimers, etc.) in the R2 gas-phase effluent.

A compressor is utilized downstream of R2 and the pre heat-exchanger to compress the gas phase effluent into a phase separation flash drum whereby condensed liquids are captured, methane and hydrogen are separated or purged, and C₂ - C₄₊ residual light gases are recycled back to Rl. The liquid phase from R2’s condensed effluent, which comprises C4+ hydrocarbons (suitable for Y-grade gasoline), can be further pressurized by a pump operating at from 100 to 1000+ psig for processing into another oligomerization reactor R2^L. R2^L operates at similar temperatures (e.g. 150 - 300°C) and uses a zeolite catalyst which may be the same or different as used in R2, but in a high-pressure environment, resulting in a high concentration reaction. This high concentration reaction maximizes long-chain molecule formation (e.g., C_B+ which are ideal for various middle distillates). The resulting R2^L reactions produce an effluent which then undergoes vapor/liquid flash drum separation to remove C₄ and lighter gaseous components for recycle back upstream of R2^L, and yields performance grade diesel fuel or targeted C₆-Cio gasoline blendstocks. This low-pressure / high-pressure catalytic method provides a more controllable coupling of light olefinic gases to produce longer-chain molecules thereby enhancing the tailoring of middle distillates,

particularly those used in any targeted range of C¾ to Ci_&+ diesel fuel blendstocks or tailored gasoline blendstocks. See FIG. 9.

Similar to the previously described two-reaction (R1 and R2) sequence, there also exists an acceptable configuration for two R2 oligomerization reactions (here depicted as R2 and R2L) operating in series with a low and high-pressure configuration for increased molecular concentration thereby improving longer-chain reactions targeting fuels.

The R1 feedstream is similarly comprised of the indicated C2-C5 light alkane components that render the process productive. These alkanes are combined with recycled light alkanes that are unreacted or formed downstream. A combined feed is then preheated in a heat exchanger (E-100) with the recycled gas outlet from R1 and then fed into the Thermal Olefination reactor (Rl). R1 has operating conditions similar to previous embodiments where this high temperature reaction is conducted between 600 and 1100 0C and 0-1500 psig. Rl's products consist of thermally dehydrogenated alkenes that are suitable for the next iteration of reactions. The outlet of the reactor has integrated heat with E-100 as described during heat exchange previously. It is expected that the stream will need to be further cooled after cross exchange before entering the catalytic oligomerization reactor (R2). E-101 will further cool the stream to an appropriate operation temperature and pressure for R2. R2 operates to largely dimerize, trimerize, and tetramerize the incoming olefinic components to produce a partially condensable stream at high pressure. The R2 effluent is then combined with a recycle stream originating downstream in the final flash drum (D-101). There should be enough suction head from C-100 to return the compressed gas from the downstream drum otherwise additional compression may be necessary. The combined stream is then compressed to a pressure resulting in some initial liquification of C3+ components (200 - 1000 psig) that are then further liquified in a cooler (E-102). lt shall be appreciated that further heat integration can occur to increasingly preheat the feed into the first reactor as the temperature will notably increase post compression. A flash separator (D-100) is used to remove any vaporous light alkanes that can be further processed by Rl. The light alkane stream that contains mostly ethane, propane, methane, and hydrogen is fed into a compressor (C- 101) to ensure consistent flow through the recycle loop. C-101 may be unnecessary depending on operating conditions and this high-pressure gas may have enough head to proceed through the loop unaided before being stepped down with a valve. The outlet of C-101 is led into a separator (S-100) where it can either be simply purged or passed through a membrane(s) to remove methane and hydrogen byproducts. After mass removal the first recycle loop is then fed back upstream in the process.

The high-pressure liquid of D-100 is pumped (P-100) to very-high-pressure (>1000 psig) as a liquid to mitigate the need for expensive veiy-high-pressure compression. This veiy-high-pressure liquid is fed into a third reactor (R2L) where the liquid is vaporized and further oligomerized to heavy molecular weight components. A heated expansion chamber pre-R2L may be needed to ensure appropriate vaporization. Heavy molecular weight production under this pressure will result in a largely condensed stream down-flow of the third reactor. This heavy molecular weight stream exiting the third reactor is then cooled in E-103 where it is further cooled/liquified to a temperature that is appropriate for vapor/liquid separation. D-101 separates the unliquified gases that may contain some mid-range olefinic components. Regardless of alkane/alkene composition, the tops of D-101 are fed upstream to be re-compressed, cooled, and separated. Any recycled byproducts downstream that are C2 or less will consequently be recycled through the initial recycle loop. Finally, a liquid stream is recovered from D-101 that resembles a diesel or gasoline spectrum product produced via a three-reactor, pressure swing process for veiy-high-pressure and high

concentration oligomerization ln a related embodiment, a source comprising about 70% ethane gas can be processed in the R1 thermal olefination reactor to primarily produce ethylene which is then processed in R2 at low pressure with a fast residence time to create dimers, trimers and tetramers from the olefin-rich feedstream. The exiting light gases are then cleaved away for recycle and the remaining C4+ liquid, a low-grade natural gasoline product, is available for the next processing step. The R2 liquid effluent from the low-pressure reaction may optionally serve as a finished product in this example with higher value than ethane, or it may be further processed as a pressurized liquid at high concentration into the R2^L reactor where longer-chain coupling occurs. The high molecular concentration in the liquid phase and the low residence time of the R2^L reaction produce a premium grade distillate for use in diesel fuel blendstocks or targeted gasoline blendstocks. The unused compounds from R2^L are recycled based upon targeted hydrocarbon cut-points and moved upstream of the liquid/gas condenser and the liquid pump. Unprocessed light gases from R2 are recycled back to R1 and methane and hydrogen are purged for reuse.

ln a similar embodiment, a low-value ethane/propane mixture is processed into R1 and the same options and features of the invention result in either C5₊ gasoline grade fuel blendstocks (from R2) and/or high-performance distillate (from R2^L) which can be targeted to produce any range of fuel grade molecules, e.g., C₉ to Ci₆₊ for use in diesel fuel blendstocks or targeted gasoline blendstocks. ln processing R2^L for diesel fuel, the C₈ and lighter pressurized stream is recycled for reprocessing. The light compounds from R2 are recycled, and the byproduct methane and hydrogen are purged for reuse. ln another embodiment, two R2 reactors performing in series can be operated at the same pressure as R1 thermal olefination with intermediary separation of light gases. This will increase the concentration of hydrogen and methane in the gaseous stream for easier membrane separation or less yield loss from purge. Generated byproducts in the second R2 catalytic reactor can then be recycled directly into R1 without removal of unreactive hydrogen and methane since they will be unremarkable in stream composition.

ln an environmentally distinct embodiment, a modification of the gas phase reaction of R2 can be conducted as a very-high-pressure liquid or supercritical phase reaction (>500 psig) to even further increase its concentration past that of high- pressure gas. Configurationally, the LG2F system can also operate with multiple R1 thermal olefination reactions and a single R2 catalytic reaction. Stepping temperature up and down from the first R1 to the second R1 will give more selective control of olefinic product distributions and also serve to limit heavy coking of a single R1 reactor system.

A further embodiment is the LG2F process is a multi-stage R1 configuration and multi-stage R2 catalytic reactions with low/high pressure optionality to produce a more optimized product distribution and yield. These two-, three- and four-step LG2F reactor designs embodied herein allow for the interchangeable production of C4 -C12 gasoline blendstocks and/or C9-C16+ diesel fuel blendstocks from alkane-rich light gases.

The LG2F process conditions are easily convertible to switch processing methods which offers a unique capability to adjust the production of key transportation fuels depending upon ever-changing market conditions. A particular feature of the LG2F process is the option to produce gasoline blendstocks at one set of operating conditions and/or switch to produce middle distillate blendstocks at a different set of (R2) reactor operating conditions. Depending upon the availability of downstream processing often available at refining plants, the timing of the process switching can be tailored using distinctive cuts to eliminate the need for any distillation of the

blendstocks.

ln one embodiment, the process is solely devised to produce middle distillate grade product blendstocks of a high cetane and net heat value ln a different

embodiment, the process is solely devised to produce higher octane gasoline

blendstocks. ln yet another embodiment, the process is set to produce higher octane gasoline blendstocks during one period, then switched and reconfigured to produce middle distillate blendstocks in another period ln yet another embodiment, the process is set to produce a full spectrum of, for example, C5+ or C₆₊ or C7+ fuel products which could be distilled downstream for different commercial uses. Once again, the preferred end product of the reaction (e.g., the targeted performance requirements of a fuel blendstock) may have a determining factor on the ideal operating conditions (T,P,WHSV) and choice of the R2 catalyst.

While the diesel fuel blendstocks described as the products of LG2F in this invention may be comprised of varying chemical compounds, targeted performance grade diesel fuels can be tailored by feed characteristics, catalyst choices and operating conditions to achieve a minimum set of performance conditions for diesel grade products.

In one embodiment, the diesel fuel product is > 40 cetane number, with aromatic content < 35% m/m, satisfactory cloud point and cold temperature flowability, lubricity

< 520 microns at 60°C, and distillation temperature < 338°C at 90% point.

ln one embodiment, the diesel fuel product is > 50 cetane number, with aromatic content < 35% m/m, satisfactory cloud point and cold temperature flowability, lubricity

< 520 microns at 60°C, and distillation temperature < 338°C at 90% point,

ln one embodiment, the diesel fuel product is > 55 cetane number, with aromatic content < 35% m/m, satisfactory cloud point and cold temperature flowability, lubricity

< 520 microns at 60°C, and distillation temperature < 338°C at 90% point.

Another distinguishing feature of the LG2F process is that the composition and performance characteristics of the C9+ distillate products do not require a

hydrogenation step. However, some tailored fuel applications may favor a more paraffinic composition in which case a hydrogenation reaction is included as an optional embodiment.

The LG2F process also offers a wide range of modular configurations (e.g., to eliminate benzene or increase octane or increase energy density or increase net heat of combustion or lower vapor pressure) when processing C2 to C5 light gases which allows for the tailoring of the operating conditions resulting in a specified composition of gasoline blendstock. ln one embodiment, the LG2F R1 + R2 reaction with recycling is specified to produce only C7 to CIO aliphatic and aromatic hydrocarbons between the boiling point range of 85° (above benzene) up to 200°C. This results in a well-balanced high-octane gasoline blendstock with no benzene ln another embodiment, the LG2F R1 + R2 reactions with recycling is specified to produce C5 to CIO aliphatic (favoring paraffins and olefins) with virtually no aromatics. This results in a lower octane blendstock, but with higher volumetric yields ln another embodiment, the LG2F R1 + R2 reaction is specified to produce primarily C7 to CIO high octane aromatics with only a minor content of aliphatic hydrocarbons. This results in a high-octane gasoline blendstock, in the absence of benzene, and a high energy density. This modular functionality in designing tailored hydrocarbon product streams from C2 - C5 light gas streams is a major feature of this invention. This tailoring can be applied to adjust to ever-changing market conditions and locational arbitrage opportunities. The LG2F R1 and R2 reactors can operate independently or in an integrated fashion. Any available source of olefins can be used in the R2 reaction once the feedstock composition is assessed for the ideal temperature, pressure and reaction time for a given product specification. The product high (final) boiling point is specified by the R2 operating conditions and the product low (initial) boiling point is set by the flash drum cut point which eliminates any need for distillation.

Combined I2FE and LG2F

Another aspect of the LG2F Process is the ability to combine the process with another process which provides a source of C2-5 hydrocarbons useful as a feed to the LG2F Process. This other process is described in a co-pending application, US Serial No. 16/242,465, also owned by Applicant. This other process is referred to as the process for Increase to Fuel Economy, or "I2FE". This combined process is presented in FIG. 10.

The 12FE process can be designed to consume a small amount of hydrogen to maintain the longevity of the metal catalyst. Depending upon design configurations, hydrogen byproduct from LG2F may offset on-purpose hydrogen consumed in 12FE, if these two processes are used together. The design of both units can be balanced and optimized to be hydrogen natural or a net producer of hydrogen, depending upon the needs of the business operation.

ln this combined embodiment, the LG2F Process converts the clean light gas compounds (C₂+) specifically from the 12FE process to produce C6+ blendstocks using thermal olefination (Rl) followed by a multi-iterative, acid-catalyzed cracking, oligomerizing and/or cyclizing reactions (R2) in a single or multi-bed reactor configuration with a recycle loop ln one embodiment, for example, the process is used to yield any range of Cg to C₂4+, zero-sulfur, middle distillate compounds with effective performance properties for use in diesel fuel and other transportation fuel blendstocks. The same process can be performed targeting a narrower range of middle distillate compounds such as Ci₀-C₂₀, or Ci₂-Ci₈, or C9-C14, etc. depending upon the performance requirements of the finished product. A byproduct of this process depending upon the configuration is unused hydrogen, methane and surplus aromatics. Another embodiment of this LG2F invention converts the clean light gas compounds (C₂+) specifically from the 12FE process, with or without reformer off-gases, to produce gasoline range blendstocks using only thermal olefination and a multi- iterative acid-catalyzed oligomerization, cyclization and cracking reaction in a single or multi-bed reactor configuration with a recycle loop. This process is designed to handle excess hydrogen to yield any C₄to C12 range gasoline compounds (i.e., paraffins, olefins and aromatics) for use with other gasoline blendstocks. All gasoline products in this embodiment are very-low benzene, sulfur-free and nitrogen-free. A byproduct of this process depending upon the configuration is unused hydrogen, methane and surplus aromatics.

Another embodiment of this LG2F invention converts the clean light gas compounds (C₂+) specifically from the 12FE process to produce gasoline range blendstocks using thermal cracking (Rl) and multi-iterative, acid catalyzed reactions (R2) in a single or multi -bed reactor configuration along with a recycle loop. This process is designed without excess hydrogen to yield C₄to Ci₂ range gasoline

compounds (i.e., paraffins, olefins and aromatics) for use with other gasoline

blendstocks. All gasoline products in this embodiment are sulfur-free and nitrogen- free. Alternatively, this process is designed to provide excess hydrogen for reuse.

Depending upon the configuration, methane and surplus aromatics may be byproducts of the reaction.

Direct Alkene Feeds

The LG2F Process is also useful with other sources of the C2 - C5 alkenes processed in the catalytic reactor (R2). For example, FCC cat-cracked gasoline byproducts including C3 alkenes and LPG can be utilized as feedstocks directly into the catalytic reactor of the LG2F Process. Another source comes from any methane activation process, such as oxidative coupling of methane, or methane pyrolysis and hydrogenation of acetylene, or any other technique known in the art to produce ethene from methane. The presence of > 50% alkenes in the light hydrocarbon feedstock allows the use first of the acid-catalyzed chemical reaction in the LG2F process.

Referring to FIG. 11, the basic LG2F Process is shown. However, the Process is augmented by having the C2-5 alkene feed directed first into the R2 catalytic reactor, bypassing the thermal olefination reactor and going straight into the multi-iterative, acid-catalyzed reactions in a single or multi-bed reactor configuration with a recycle loop. This feedstream is processed as previously described to yield C6+ fuel-grade blendstocks. Light gases from the catalytic process (often containing C₃₊ olefinic compounds, e.g., propylene) are then sent to the R1 reactor to proceed through the system as previously described, thereby producing additional gasoline range

blendstocks. This process is designed to provide excess hydrogen to yield C₆to Cn range gasoline compounds (i.e., paraffins, olefins and aromatics) for use with other gasoline blendstocks. All gasoline products in this embodiment are very-low benzene, sulfur-free and nitrogen-free. A byproduct of this process is unused hydrogen.

As an illustration of the processing of alkene gases, a single pass yield of the C₂₊ acid-based chemical reaction, shown in FIG. 12, is from a C₃ olefin feedstock and demonstrates the production of gasoline grade compounds. This reaction was made at 45 psig and 3 WHSV across a range of temperatures. As illustrated, the aromatic hydrocarbon content (A₆₊) varied by the reaction temperature, which can be used to increase octane values of gasoline blendstocks.

Another embodiment of this LG2F invention receives the byproduct light gases from the catalytic cracking process (often containing C₃₊ olefinic compounds, e.g.

propylene) to produce diesel range fuel blendstocks. This embodiment again bypasses the initial thermal olefination and goes straight into the multi-iterative, acid-catalyzed reactions in a single or multi -bed reactor configuration with an R2 catalyst tailored for the feedstream before re-entering the LG2F recycle loop. This process is designed to provide excess hydrogen and to yield any specified range of C₄ to C12 gasoline blendstocks or Cg to C₂₄ middle distillate for use as diesel fuel blendstocks. A byproduct of this process is unused hydrogen.

The foregoing processes are examples of a range of processes using alkene feeds, further including the following:

• C₂+ alkene gas streams exiting the catalytic cracking unit are transformed to C₆+ gasoline constituents first via LG2F chemical reaction (R2), followed by a recycle loop that restarts thermal olefination and a chemical reaction loop resulting in higher liquid gasoline yields;

• C₂₊ light hydrocarbon streams with primarily olefinic compounds are merged to increase the available volume of light gas compounds for conversion via R2 processing with recycle loops to R1 + R2 to produce gasoline blendstocks using the LG2F process;

• C₂₊ light hydrocarbon streams with primarily olefinic compounds are merged to increase the available volume of light gas compounds for conversion to light gas oil or diesel fuel blendstocks using LG2F.

Reducing Benzene

Another major feature of this light gas transformation to transportation fuel is the selective reduction of benzene, which makes the resulting products excellent for gasoline blending due to low specification limits placed on benzene for use in fuels ln the case where there is an unwanted surplus of benzene-rich C6+ aromatics extracted by liquid-vapor knockout from the R1 thermal olefination effluent, an added feature of LG2F is to combine light alkene compounds (e.g. C2-C3) from the R1 reaction with the surplus C6+ aromatic compounds into a simple low-temperature acid-catalyzed reaction to create alkyl-benzenes. See FIG. 13. This processing will convert benzene via electrophilic substitution to become productive gasoline grade blendstocks that adhere to existing limitations in gasoline specifications for high-octane aromatic compounds. This process may utilize aluminum chloride and hydrogen chloride catalysts. This process will further increase the value of the gasoline blendstock.

Dewaxing

Another aspect of this invention is a simplified method to dewax paraffinic compounds from Ci₄ to C₄₀ hydrocarbon streams using a single-stage, low-severity, acid-catalyzed reaction process to both hydrocrack and hydrotreat middle-to-heavy grade distillate feedstocks to produce a higher-value, higher-grade middle distillate with higher fuel performance properties.

Catalytic dewaxing is typically referred to as a process that selectively removes Ci₄₊ paraffinic compounds from middle- to heavy-distillate hydrocarbon streams. This technology is usually applied to hydrocarbons used in diesel fuel and heating oils to improve its physical properties including cloud point, pour point and cold flowability. lncreasing quality reduces the need of using fuel additives to improve properties and allows for more detailed control of blending specifications. The primary alternative technology to catalytic dewaxing is solvent based dewaxing which applies a solvent extraction method to heavy paraffinic compounds that preserves the chemical structure.

Configurations of traditional dewaxing units vary but are most often categorized in two categories: a single or dual bed reactor. The choice in configuration depends on preference for hydrotreating integration into the dewaxing catalytic system. The inlet streams have higher concentrations of sulfur and nitrogen which will deactivate noble metal catalysts. So, a hydrotreating bed is typically integrated before the dewaxing catalyst to ensure minimal degradation of performance.

Traditional Dewaxing Methods

Traditional refinery dewaxing catalysts are nickel- or platinum-based selective zeolites, which is a molecular sieve catalyst. By controlling pore size, these methods control the types of molecules that enter the catalytically active sites. Specifically, the pore sizes are set to allow n-paraffinic compounds but not isoparaffinic compounds (0.6 nm). Traditional hydrotreating catalysts commonly use Ni/Mo metal combination to perform the hydrogenation of nitrogen and sulfur-based compounds. The configuration of these catalyst depends on the level of protection needed in a dewaxing unit lf there are lower than normal catalyst poisons, then a single reactor can be used with a protective bed above the dewaxing bed. However, if poisons are an issue then a separate hydrotreating bed will be beneficial to sustained catalyst life. A comparison between typical single and dual bed catalysts is shown in Table 14.

Table 14

Traditional methods for dewaxing require a separation between two catalytic beds with one performing hydrotreating and the other selectively cracking n-paraffinic compounds. Noble metal catalysts propose too high of a risk for poisoning from hydrogen sulfide and ammonia, hence the removal of these gases before dewaxing. However, base metal catalysts lack the activity needed to dewax a hydrocarbon stream effectively and require larger utility costs. This invention utilizes a unique, low-severity method for hydrocracking the C14- to C₄₀₊ paraffins or any targeted range of n-paraffins compounds using a specialized zeolite catalyst with the capability to simultaneously hydrotreat the feedstream thereby removing the sulfur and nitrogen-based compounds and cracking the low-melting paraffins in a single step process. This unique method reduces total costs of processing and eliminates the need for additives used in the field. The main target is cracking broad scope n-paraffinic compounds since even n-tetradecane (C14) melts above low ambient temperatures. Having even a single branch significantly reduces the melting point by ~80 F while still having a cetane value of 67.

While the invention has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character, it being understood that only the preferred embodiment has been shown and described and that all changes, equivalents, and modifications that come within the spirit of the inventions defined by following claims are desired to be protected.

Claims

CLA1MS What is claimed is:

1. A two-stage process for converting C_2-5 alkanes to a broad-range of fuel products constituting higher-value C_5-24+ hydrocarbon fuels or fuel blendstocks, comprising:

delivering a C2-5 alkane feedstream into a thermal olefination reactor, the C2-5 alkane feedstream containing at least 90 wt% feed alkanes having two to five carbons, the thermal olefination reactor operating at a temperature, pressure and space velocity to convert at least 80% of the feed alkanes to product olefins in a product olefin stream, without using a dehydrogenation catalyst and without using steam;

delivering at least a portion of the product olefin stream to an oligomerization reactor containing a zeolite catalyst functional to crack, oligomerize and cyclize the product olefins to form the fuel products; and

recovering the fuel products.

2. The method of claim 1 and which comprises converting the product olefins to form a C4-12 hydrocarbon blendstock for gasoline.

3. The method of claim 1 and which comprises converting the product olefins to form a C9-24+ hydrocarbon blendstock for diesel fuel.

4. The method of claim 1 and which includes removing hydrogen and methane from the product olefin stream prior to delivering the product olefin stream to the oligomerization reactor.

5. The method of claim 1 and which includes removing C2-5 alkanes from the product olefin stream prior to delivering the product olefin stream to the

oligomerization reactor.

6. The method of claim 1 in which the C2-5 alkane feedstream includes less than 2% alkenes and alkynes.

7. The method of claim 1 in which the C2-5 alkane feedstream comprises 80- 100% ethane and 0-20% propane.

8. The method of claim 1 in which the C2-5 alkane feedstream comprises 100% ethane.

9. The method of claim 1 in which the oligomerization reactor operates without hydrogenation of the olefins.

10. A method for converting C2-5 alkanes in a feedstream to a range of C5-24₊ fuel products, comprising:

olefinating the alkanes in an alkane-rich feedstream in a thermal olefination reactor at a temperature, pressure and space velocity operable to convert at least 80% of the alkanes to product olefins without use of a dehydrogenation catalyst and without use of steam, the alkane-rich feedstream containing at least 90 wt% feed alkanes having two to five carbons;

converting the product olefins into the fuel products by contacting the product olefins with a zeolite catalyst in an oligomerizing reactor at a temperature, pressure and space velocity operable to crack, oligomerize and cyclize the product olefins to form ; and

recovering the fuel products.