BR112020021259A2 - process for converting c2-c5 hydrocarbons into mixtures of gasoline and diesel fuel - Google Patents

Abstract

"process for converting c2-c5 hydrocarbons in gasoline and diesel fuel blends". a process for converting c2-5 alkanes into higher value c5-24 hydrocarbon fuels and blends. 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 break down, oligomerize and cyclize the olefins to the fuel products which are then recovered. , 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 TO CONVERT C2-C5 HYDROCARBONS INTO GASOLINE AND DIESEL FUEL MIXTURES"

FIELD

[001] The field of this invention is the low-cost production of performance grade gasoline and combustible products distilled from light hydrocarbon feed streams rich in C2-C5 alkane. The field relates more particularly to a thermal olefin reaction which converts C2-C5 alkanes to alkenes and subsequent cracking, olefinisation and / or cyclization of the alkenes to form fuel formulations and mixtures. A particular application of the invention is in the tailored derivation of performance grade fuels and fuel mixtures of readily available low value hydrocarbon streams.

FUNDAMENTALS

[002] Although the total US demand for gasoline is stable or at a small level of decline, there is a growing demand for premium gasoline blends to meet the needs of new, more efficient and more compressed spark ignition engines. There is also an increasing demand for performance-grade, ultra-low sulfur diesel fuel mixtures with high cetane values and effective cold temperature fluidity properties used in compression ignition diesel engines and gas turbine engines.

These demands exist while surplus light hydrocarbons are trapped in certain markets with no supply chain options, despite being available from medium-current facilities, refineries and petrochemicals for transformation into high-fuel products.

[003] According to the US Energy Information Administration (EIA), sources of natural gas and liquid liquids in the mid-stream industry are abundant across the country. See, for example, Table 1. Note that this picture of NGL volumes can underestimate the rejected ethane sold with methane.

Any separation of natural gas from natural gas liquids, for example, through demethanisation, leaves an alkane-rich additive of light hydrocarbon compounds (typically C2-C5 + natural gas liquids (NGL's). These can undergo additional separations, for example , deethanization, depropanization, gas and liquid de-butanisation This invention is particularly aimed at any C2-C5 alkane rich source of NGLs (preferably NGLs without ethane rejection), or similar industrial gases comprising such light hydrocarbons, to transform rich feed streams in alkane in high-value fuel products, thus avoiding the need for such separations C2, C3, C4.

Table 1 US GAS PRODUCTION UNIT 2 year average (BBL / DAY) ETHANE 1,577,870 PROPAN 1,323,455 n-BUTANE 340,604 iso-BUTANE 370,782 PENTANES + 478,112

[004] The petrochemical industry, a major consumer of ethane and propane, uses extremely complex, high precision and capital-intensive methods to separate and purify compounds of chemical quality, such as ethylene and propylene. For example, the conversion of propane to propylene or ethane to ethylene requires cryogenic separation (-100 ° C) followed by ultrapure, dry and uncontaminated hydrogenation processing to eliminate very close boiling molecules (eg, butadiene, propine, acetylene ) which can be highly reactive to chemical processing and / or poison polymerization catalysts. None of these is a concern for the process of this invention.

SUMMARY

[005] The invention comprises a process of thermal and chemical reactions that provide a high conversion of hydrocarbon feed streams

C2-C5 rich in alkane comprising ethane, propane, butanes, or pentanes, or any additives thereof, in performance grade gasoline and distilled combustible products. The process includes a specialized non-catalytic method of converting certain alkane feeds to olefins by means of low-cost, non-catalytic alkane dehydrogenation reactions, called "thermal olefinization". The process combines this olefin process with cracking, oligomerization and / or cyclization reactions of olefins in high-fuel products using zeolite catalysts. In embodiments, the process includes useful variations in converting alkene-rich feed streams.

[006] The process can be organized in appropriate sequences with thermal and catalytic reactors operating in parallel or in series and using recycling methods based on the characteristics of the raw material, operating conditions and desired products.

[007] Thermal and catalytic reactors use innovative low-cost methods to minimize the accumulation of carbon through specialized regeneration techniques.

[008] Liquid fuel products produced from the process can be targeted specifically by operating conditions and catalyst choices to produce any desired range of C4 to C12 gasoline compounds (ie, high octane paraffins, olefins and aromatics), or to produce performance grade C9 to C16 + compounds of medium distillates (eg zero sulfur, high cetane, low pour point for use in ultra low sulfur diesel fuel) that achieve pre-specified fuel performance targets .

[009] The process also accommodates any C2-C5 light hydrocarbon feed streams rich in alkene comprised of ethylene, propene, butenes or pentenes, or any mixture thereof, which are convertible into fuel mixtures using the same process and thermal reactions and catalytic, although re-sequenced as described in this invention.

[010] Other objects and advantages will be evident from the description that follows.

BRIEF DESCRIPTION OF THE DRAWINGS

[011] Figure 1 is a schematic showing the process flow and system components of the method and conversion system of the present invention.

[012] Figure 2 is a graph showing yield versus conversion to pentane processing according to the method in Figure 1.

[013] Figure 3 is a more detailed flow diagram of an LG2F Process modality.

[014] Figure 4 is a simplified version of the flow diagram in Figure 3, modified to include an Extraction Unit between the R1 and R2 reactors.

[015] Figure 5a is a graph showing selectivity of product distribution of aliphatics as a function of spatial speed.

[016] Figure 5b is a graph showing selectivity of product distribution of aliphatics as a function of temperature.

[017] Figure 6a is a graph showing selectivity of aromatics product distribution as a function of spatial speed.

[018] Figure 6b is a graph showing selectivity of aromatic product distribution as a function of temperature.

[019] Figure 7 is a graph showing percentages of hydrocarbon mass for Jet A medium fuel.

[020] Figure 8 is a graph of percentages of mass in a typical carbon distribution for diesel fuel.

[021] Figure 9 is a flow diagram of an alternative modality of the LG2F Process including series oligomerization reactors.

[022] Figure 10 is a flow diagram of an alternative modality of the LG2F Process including a combination with the I2FE process.

[023] Figure 11 is a flow diagram of an alternative modality of the LG2F Process including direct alkene feed to the R2 oligomerization reactor.

[024] Figure 12 is a graph showing a single pass yield of propene according to the flow diagram in Figure 11.

[025] Figure 13 is a flow diagram showing optimal elimination of benzene from gasoline mixtures produced by methods here.

[026] Figure 14 is a diagram showing typical construction elements of single and double reactors.

[027] Figure 15 is a diagram of a dewaxing process flow according to the present disclosure.

DESCRIPTION

[028] For the purpose of promoting an understanding of the principles of the invention, reference will now be made to the modalities illustrated here and specific language will be used to describe them. However, it will be understood that no limitation on the scope of the invention is thus intended. Any further changes and modifications to the described modalities, and any additional applications of the principles of the invention, as described in this document, are contemplated as would normally occur to a person skilled in the art to which the invention relates.

The modalities 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 here are percentages by weight, unless otherwise noted.

[029] One aspect of this disclosure, commonly referred to here as the Light Hydrocarbon Gas for Fuel Process, or “LG2F Process”, converts feed streams rich in alkane hydrocarbons comprising 2 to 5 carbons, or any additives of compounds of hydrocarbon C2-5, in fuel grade hydrocarbons C4 to C16 +. The process uses a non-catalytic thermal olefin reaction followed by catalyzed cracking, olefinization and / or acid cyclization reactions. The process can be carried out in a variety of sequences using single or multiple bed reactors, subject to the characteristics of the supply current, operating parameters and targeted products. As used in this document, the term LG2F Process includes all corresponding processes and systems that are within the scope of this disclosure.

[030] This invention uses a thermal olefin reactor that produces a series of dehydrogenation and cracking reactions to update any source of alkane-rich compounds in the light hydrocarbon gas phase (ie,> 90% alkanes) to produce a effluent flow of light gas rich in olefin. The low boiling olefin rich gas compounds are then transformed to produce a longer spectrum of alkanes and / or alkenes and / or aromatics, using zeolite catalysts in a controlled temperature and pressure catalyst reactor.

This transformation of gases rich in light alkanes results in unique high value liquid streams, including high-octane compounds targeted for use as gasoline blends or longer chain compounds and high cetane content for use as diesel blends.

[031] The LG2F process is extremely efficient and does not use complex multi-stage distillation or fractionation columns, multi-stage cryogenic separation or hydrogenation processing (for chemical purification in the basic petrochemical industry), while producing a diverse molecular spectrum of mixtures C4 to C16 + with targeted performance characteristics ideal for transport fuels with up to 60% less capital investment.

[032] The process employs a thermal olefin technique to prevent traditional catalytic dehydrogenation and / or the use of steam cracking, while taking advantage of a light gas recycling system to maximize the finished product yield of performance grade fuel products .

[033] LG2F reactor systems can utilize a unique two-stage reactor cleaning and regeneration process to eliminate the need for steam cracking, boilers and water separation processes. An automated in-line regeneration process allows reactor operability to be extended for up to 3 to 10 years, while thermal activation and catalyst activity levels are maintained at high levels.

[034] The LG2F process can also convert streams of demethanized gas and alkane-rich waste gas industrial compounds into liquid fuels and thereby minimize production losses attributed to low-value waste gas compounds. Due to market / location imbalances, compounds like methane vs. NGLs, or even varying degrees of gasoline or diesel, may have varying economic values, allowing location arbitration by introducing an additional factor in assessing the ideal configuration of power supplies, operating conditions, and market dynamics impacting product portfolios. and targeted by-products. The availability of light hydrocarbon feed streams (for example, alkane-rich, alkene-rich) and the appropriate sequencing of the thermal olefin and catalytic processes of this invention are adapted to produce high octane gasoline blends or diesel fuel blends of high cetane to meet the specific market for fuel specification requirements based on performance and regulation.

Overview

[035] The present disclosure is based on a unique and efficient process for converting light paraffins into performance grade fuel components. The foods rich in selected alkanes undergo thermal olefin reactions in a first reactor, transforming the light paraffin compounds into olefins. The olefins of the thermal olefin reactions are then catalytically transformed into a second reactor in a fuel grade mixture. This combination of specific thermal olefin and catalytic conversion reactions is referred to herein as the LG2F Process. This process converts light hydrocarbon gases into high-grade transport fuels that span selected ranges of hydrocarbon compounds that have targeted fuel compositions and performance characteristics.

Industrial Need

[036] Due to the increase in the production of C2-C5 light hydrocarbons and shale gas on a global scale, there is an excess supply and an increasing displacement of the light hydrocarbon market with limited paths to the petrochemical markets (for example, ethane crackers) ). As a result, there is a growing interest in converting and upgrading these lower value light hydrocarbons to components in the higher value C6-C24 + fuel range as ready-to-perform fuel products, leveraging the existing fuel supply chain. This requires that fuel components are produced to meet critical performance specifications for gasoline and diesel, so that they can be mixed with existing supply chain paths.

Solution

[037] The LG2F process provides a technique for producing any number of hydrocarbon fuels or fuel mixtures in the gasoline and medium distillates spectrum that are capable of meeting the fuel performance criteria defined by the industry. This allows the fuels produced by this invention to be homogeneous with the fuels in the existing supply chain and available for immediate blending or other boutique blends with some added commercial value.

[038] The basic LG2F process is exemplified in Figure 1. A feed stream rich in light gas C2-5 alkane is directed to the thermal olefin reactor (R1), in which C2-5 alkanes are converted to olefins. Cracking, oligomerization and / or aromatic cyclization occurs in a second, catalytic conversion reaction (R2). Upon completion of the catalytic process, the resulting hydrocarbon stream is cooled and partially condensed, and evaporated to recover liquid from the fuel grade mixture product. The hydrogen and methane in the cooled light gases in the catalytic reactor are separated (or purged) from the C2 + gases, which can be recycled to the thermal olefin reactor.

[039] Fuel grade hydrocarbons, preferably mixture C4-C12 for gasoline and mixture C9-C24 for diesel fuel are recovered. As a result, selecting light C1 + alkanes are transformed into any constituent of C4 to C16 + hydrocarbon constituents for use in various transport fuels, with methane and hydrogen as by-products. Another characteristic of light gas transformation is the creation of aromatic hydrocarbons that add energy density and bring a higher octane value to the gasoline mixture and contribute to the thermal stability and cold current properties for diesel fuels.

C2-5 Alkane Power Chains

[040] The thermal olefin reactor receives and processes alkanes including 2 to 5 carbon atoms, that is, ethane, propane, butane and / or pentane. As used in this document, the term "C2-5 alkane" is used to refer to alkanes having specifically 2 to 5 carbon atoms. The term "Supply Chain" refers to a reactor supply that does not include any recycling component.

The term "C2-5 alkane feed stream" refers to a feed stream comprising C2-5 alkanes. For example, a typical C2-5 alkane feed stream can include ethane, propane, n-butane, iso-butane and n-pentane. As described hereinafter, in a preferred aspect the C2-5 alkane feed stream is obtained as an effluent stream from existing commercial operations.

It may have been the subject of pre-treatments and may also be formed from the combination of more than one power source.

[041] The LG2F process specifically uses a C2-5 alkane feed stream which is "rich in alkane", means that at least 90% of the feed stream comprises C2-5 alkanes. In another aspect, the C2-5 alkane-rich alkane feed stream includes at least 95%, and preferably at least 98%, C2-5 alkanes.

[042] In particular embodiments, the C2-5 alkane components are specific subsets of all C2-5 alkanes. For example, certain embodiments use a C2-5 alkane feed stream constituting a single C2-5 alkane, that is, any one of ethane, propane, butane or pentane. In a particular aspect, the LG2F process uses ethane as the C2-5 alkane feed stream. In other embodiments, the C2-5 alkane feed stream contains at least 90%, preferably at least 95%, and more preferably at least 98% ethane. In an alternative embodiment, the C2-5 alkane feed stream comprises 80 to 100% ethane and 0 to 20% propane. Ethane and propane are less expensive alkanes and therefore there is a greater value in upgrading them for use in fuels. In another aspect, the C2-5 alkane feed stream comprises at least 90% of a mixture of ethane, propane and butane.

Other Constituent Supply Chains

[043] The C2-5 alkane feed stream contains at least 90% by weight of C2-5 alkanes. Therefore, in certain embodiments, the supply chain includes other constituents. Such other constituents may, for example, include other hydrocarbons, contaminants and inert materials.

[044] Additional components may include other hydrocarbons. Methane may be present in the supply stream, particularly depending on the source. Methane is preferably kept in a low amount (preferably less than 5 to 10%), as it is not reactive and, therefore, unproductive in the LG2F Process. Controlled methane accumulations through recycling can be productive to disperse the heat consumed and generated in the R1 and R2 reactors, respectively. In one embodiment, methane gas can be used as a diluent to maintain heat for the R1 thermal olefin reactor (an endothermic reaction). In a related embodiment, methane gas can be used as a diluent to disperse heat in the R2 oligomerization reactor (an exothermic reaction). In another embodiment, it is possible to use a membrane or other gas separation unit (non-distillation) before the thermal olefin reaction to remove unproductive amounts of methane from the feed stream for higher purity C2-C5 feed streams. Higher alkanes may be present and may be thermally cracked in the LG2F Process, but they are also useful as constituents of gasoline and therefore there is limited value in including them in the alkane feed stream. Therefore, in a similar modality, there is an option to capture C6 + liquids from the C2-C5 feed stream in a liquid / vapor flash drum prior to the thermal olefin reaction to minimize cracking of these compounds. Light hydrocarbon feed streams with lower amounts of alkenes and alkynes should be avoided, as they are destructive to yield (producing benzene and methane) and tend to coke the reactor R1. Note that LG2F alternatives exist to deal with feed currents with higher amounts of alkenes through the 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.

[045] In practice, some field sources of C2-5 alkanes may contain contaminants. In this scenario, a contaminant can be any component that adversely affects the LG2F process or its system components. For example, contaminants can include ammonia, hydrogen sulfide, nitrogen, sulfur and / or water. Some source streams are not cleaned to reduce these contaminants. These contaminants can poison later-used catalysts or cause accelerated corrosion to downstream processing units (for example, refining or petrochemicals).

[046] Significant concentrations of these contaminants are preferably removed in advance by conventional pretreatments.

The C2-5 alkane feed stream preferably contains less than 1%, and more preferably less than 0.5% of contaminants. However, pretreatment is not necessary when using clean light gas raw materials, for example, broken reformed gases, as these light hydrocarbon streams are treated upstream and contain ultra-low amounts of contaminants.

[047] Inert components (eg, nitrogen, argon, helium) are, by definition, non-reactive in the LG2F Process. However, it remains preferable to keep the components inert in limited quantities before being purged (for example, through the membrane) of the LG2F Process. Consequently, the C2-5 alkane feed stream (excluding methane) preferably contains less than 1%, and more preferably less than 0.5% of inert materials.

[048] A given source of hydrocarbon rich in C2-5 alkane can be processed as obtained, or it can be combined with other light gas streams available for transformation into target gasoline or diesel fuel for the transportation of diesel strips. Combining chains from 2 or more sources, or increasing a source chain with one or more components added, is a way to target the compositions of the final products.

Examples of C2-5 Alkane Sources

[049] There are many different sources of C2 to C5 light hydrocarbon gas streams. Sources include NGL, gas condensate, industrial fuel gas, petroleum gases and liquefied petroleum gas (LPG), which are available throughout the oil, gas and petrochemical industry. Suitable C2-5 alkane sources are typically found in refineries, fuel and gas extraction facilities, gas processing facilities, petrochemical facilities and liquefied petroleum gas (LPG) facilities. The C2-5 alkane sources also include any outlet of light hydrocarbon gases from catalytic cracking or catalytic reform, or currents 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 the net volume yield of gasoline or diesel mixtures.

[050] These streams are composed of light gas, typically containing ethane, propane, butane, pentane or any mixtures thereof. Pentane and butane / pentane mixtures can also be in liquid form at ambient temperatures and pressures. Some sources can be a current isolated from virtually a compound (eg, propane). Any combination of suitable C2-5 alkane gas streams can be combined to use this transformer LG2F Process.

[051] The LG2F process, therefore, provides better use of available plant effluents. For example, a cracked long-chain paraffin by-product containing between 3% and 14% hydrocarbon gases is upgraded from low-value industrial fuel used for a high-value gasoline mixture by the LG2F Process. Similar gas constituents (predominantly C2 + with hydrogen) from the catalytic reformer outlets create the opportunity for even higher liquid volume yields from high-octane gasoline mixtures using the LG2F Process. Any gas streams can be pretreated if necessary and processed individually or combined with any number of other available C2-C5 alkane-rich gas streams.

Thermal Olefination

[052] Using an alkane-rich feed stream composed of ≥ 90% alkanes, the production of liquid fuels in one mode begins with the alkanes being largely converted to olefins through a dehydrogenation step. The LG2F Process uses a thermal olefin reaction for this purpose.

[053] Thermal olefin uses endothermic reactions that occur properly, for example, in an isothermal reactor operating with a constant supply of heat. The thermal olefin reactor converts C2-5 alkanes to olefins with 2 or more carbons (“C2 +”). Various light gas compounds are produced as by-products, depending on the alkane feed stream.

For example, pentane can 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

[054] As another example, ethane can be cracked into ethylene, with small amounts of methane and hydrogen as by-products of light gas.

[055] The results of thermal olefin reactions, therefore, largely depend on the composition of the alkane-rich C2-5 feed stream. The intermediate product is a mixture composed of C2 to C5 olefins, together with a smaller amount of C1-5 alkanes and hydrogen as by-products. The conversion is selected to maximize gasoline or diesel fuel yields.

[056] As used in this document, the term "Thermal Olefination" refers to the conversion of alkanes to olefins in relation to controllable variables, including the composition of the supply current, temperature, pressure and space speed. As used herein, thermal olefin does not include the use of catalytic cracking 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. In addition, water is known to be an obstacle to the use downstream of zeolite catalysts in the subsequent catalytic process. This invention, therefore, uses a low cost non-catalytic dehydrogenation technique directed to alkane-rich feed streams.

[057] The results of an exemplary single-pass LG2F processing of a C5 alkane raw material (pentane) are shown in Figure

2. This demonstrates the dependence of the product mix on the operational parameters of the LG2F Process. In other words, the modification of the C2-5 alkane supply current and / or the operating conditions allows the control of the product mix. For example, it is evident from Figure 2 that the production of ethylene in comparison with methane has reached an ideal point for the yield of the product. It is also shown that going to 100% conversion was disadvantageous in view of the increase in methane production and the consequent reduction in ethylene.

[058] The LG2F process uses thermal olefin reactors configured to dehydrogenate the C2-5 alkanes to form olefins without the need for any catalyst. The thermal olefin reactor can be of conventional design, including as simple as a tubular chamber. To minimize the accumulation of carbon, a protective layer can be worked on the internal surface area of the entire reactor by means of galvanizing (for example, chemical or electroplating) to produce a surface layer of aluminum that is oxidized to alumina. Alumina has known chemical and heat-resistant properties of up to 1700 ° C in the absence of high temperature steam and, therefore, will inhibit the deposition of carbon on the surface of the inner tube, preventing chemical access to the atoms on the iron surface. This specialized aluminum / alumina coating increases the life cycle of the process by reducing the accumulation of coke.

Olefining Operating Conditions

[059] The thermal olefin reaction is carried out at a high temperature, with no catalyst or steam used. The thermal olefin reactor is preferably operated at a temperature above 600 ° C, an internal pressure of 0 to 1500 psig and an hourly gas weight space velocity of 30 to 1000 h-1. The process of thermal olefin does not materially affect methane or hydrogen in the feed stream. The presence of steam as a by-product of the thermal olefin reaction of R1 with light hydrocarbons should be avoided, as it can be harmful to the subsequent catalytic reaction of R2.

Table 2 - Thermal Olefination Reactions Examples of Thermal Olefination Reactions Execution of 018 018 118 118 118 118 218 218 218 Test # -1 -3 -1 -2 -3 -4 -1 -2 -3 Zone 1 SP ° C 400 400 400 400 400 400 400 400 400 400

Ç

Zone 2 SP ° C 400 400 400 400 400 400 400 400 400 Zone 3 SP ° C 800 800 800 800 800 800 810 820 830 Ethane, sccm 1580 790 1185 1580 790 790 790 790 790 Pressure, psig 30 18 19 19 14 0 0 0 0 39.5 45.6 35.1 29.5 46.9 37.1 39.6 47.8 54.3% Conv. 2 4 8 9 0 7 6 1 1 Methane 5.74 9.30 5.48 4.03 9.25 4.13 4.85 6.59 8.22 28.0 33.5 27.5 23.7 34 , 7 31.4 33.1 39.1 43.6% Yield Ethene 2 3 6 1 7 8 6 4 9 60.8 54.6 65.0 70.6 53.3 63.0 60.6 52, 4 45.9 Ethane 9 2 7 4 8 9 1 7 7 Propylene 1.69 1.21 0.89 0.71 1.22 0.60 0.61 0.81 0.92 Propane 0.22 0.14 0 , 18 0.24 0.12 0.16 0.15 0.11 0.11 Benzene 1.05 0.27 0.13 0.08 0.33 0.06 0.09 0.16 0.26 14, 5 20.3 15.5 13.6 19.7 11.1 12.2 13.7 15.1% Selectivity Methane 1 7 7 3 3 0 3 9 3 70.9 73.4 78.3 80.1 74.1 84.6 83.6 81.8 80.4 Ethene 2 6 5 4 4 9 3 7 4 Propylene 4.27 2.64 2.52 2.41 2.61 1.61 1.55 1.70 1.69 Propane 0.55 0.31 0.51 0.82 0.27 0.44 0.38 0.24 0.21

[060] The thermal olefin reaction is effective for converting at least 20%, preferably at least 25%, of the C2-5 alkanes per pass into olefins.

In some modalities, the conversion is in the range of 25% to 65% conversion per pass. In addition, unconverted C2-5 alkanes are preferably recycled to the thermal olefin reactor. In general, the conversion of C2-5 alkanes from the initial alkane feed stream to hydrocarbon fuels is preferably at least 65%, more preferably at least 80%, and most preferably at least 95%.

Reactor Regeneration - R1

[061] The LG2F thermal olefin system can include integrated reactor regeneration and cleaning sequences (RRC). The operability of the thermal olefin reactor (s) depends on the life cycles of the reactor and the resulting amount of thermal resistance that can occur from the accumulation of carbon in the reactor walls. This RRC sequence is performed to reduce or eliminate the accumulation of carbon (coke). The regeneration and cleaning of the reactor (s) operating at high temperatures involves a unique series of steps, during which the light hydrocarbon feed stream is paused in order to restore the active levels of the reactor (s) ). Two methods for regenerating and cleaning thermal olefin reactors are provided, which can be used with a single reactor or with multiple units operated in parallel and / or in series.

[062] Reactor regeneration intentionally avoids the potential for harmful amounts of high temperature steam impacting the thermal olefin reactor and prevents water contaminants from passing into the downstream catalytic oligomerization reactor (s). This avoids permanent catalytic deactivation of the downstream zeolite-based catalysts used in the oligomerization reactor (s). The removal of the generated water (through the hydrogen / carbon reaction at low temperature) avoids the harmful effects on the zeolite catalysts (through the reduction of the active site and de-alumination) used downstream in the oligomerization reaction.

[063] Traditionally, alkane dehydrogenation reactors have used 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. In LG2F Processes, regeneration is carried out without the use of steam or steam / air mixtures, making the LG2F System more durable and economical. The absence of added water (for example, by means of steam) improves the operation of the LG2F System.

Low Temperature Hydrogen and High Temperature Carbon

[064] A reactor regeneration sequence for the regeneration of thermal olefin reactors is carried out requires two steps. This sequence is specifically designed to (1) safely react hydrogen with oxygen to form water and (2) allow removal of water from the system, before conducting a high temperature carbon / oxygen reaction to clean the reactor.

Step 1: Low Temperature Hydrogen Removal

[065] The first stage in the regeneration sequence is initiated by flowing a low concentration of oxygen, for example, in the air, through the thermal olefin reactor. Oxygen preferably comprises not more than 21% v / v, and more preferably not more than 10% v / v, and even more preferably not 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 desiccant feed stream allows for a lower temperature of the flame front.

[066] This feed gas containing oxygen is heated in the thermal olefin reactor until a flame front is observed in the reactor. This flame front is strictly due to the combustion of hydrogen in water at a lower temperature than that of burning carbon. The flame front remains until no hydrogen is present, and the hydrogen extinguishing process is then completed. The water generated is collected as a liquid in a condensation chamber, allowing other flared and unburned gases to be fed back into the LG2F System through a recycling cycle.

Step 2: High Temperature Carbon Removal in the Absence of Hydrogen

[067] The second stage is a carbon combustion cleaning sequence carried out after the water has been properly purged from the system. While a stream of oxygenated gas is still being passed through the reactor system

R1, the temperature is increased from its initial step of removing water to a temperature at which a second flame front is observed. This second flame front is largely devoid of water, since the first sequence of desiccant preferably burned 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, mainly due to the production of carbon dioxide, with little or no carbon monoxide. This flame front is followed through reactor R1 until a flame front is no longer observed.

Since the flame front is no longer being produced, the reaction chamber of the thermal olefin units is sufficiently devoid of coke.

[068] This two-step sequence can be conducted at any level of carbon accumulation, but preferably not more than 50% of the unit's life cycle, more preferably not more than 30% of the unit's life cycle and more preferably not more than 20% of the unit's life cycle. This 2-step sequence can be performed in situ, disconnected from the hydrocarbon stream, in an individual reactor operating in parallel with other thermal olefin reactors, to ensure a continuous LG2F Process. In another embodiment, duplicate reactors of the same type are used in parallel with different blocking time revolutions, so that at least one unit can be connected continuously. The procedure can be fully automated to allow the start and stop of the regeneration sequence and the resumption of the hydrocarbon feed stream to continue the thermal olefin reaction.

B. Compressed Air

[069] A second option for the reactor regeneration method involves interrupting the hydrocarbon supply before substantial coke formation occurs, then introducing compressed air into the reactor zone at 0 to 50 ° C below temperature typical operating unit. Regeneration proceeds for a short period of time, which can be limited by the effects of exothermic heat. This regeneration cycle is preferably designed to limit exothermic heat, using a frequent regeneration cycle that keeps carbon accumulation at low levels. Within minutes, the carbon build-up is eliminated. The process, therefore, emits CO2, H2O and excess air to release to the atmosphere.

[070] Although any regeneration cycle can be used, a higher frequency regeneration cycle (for example, 15 minutes every 1 to 15 days) allows a minimum partial pressure of water in the burned products, as carbon and hydrogen become the limiting reagents, instead of oxygen. In general, the frequency of regeneration depends on the quality of the feed that impacts the level and / or rate of coke formation.

Catalytic Processing of Olefin C2-5

[071] Thermal olefin results in a product stream that is passed to a catalytic reactor in which the olefins are converted into a wide spectrum of fuel grade hydrocarbons. The conversion involves chemical reactions comprising cracking, oligomerization and / or aromatic cyclization, and transforms the olefins without affecting the lightest paraffins (C2 / C3) in the food. In a sense, catalytic conversion can be affected in any way known in the art to be effective in cracking, oligomerization and / or cyclization of C2-5 olefins. Particularly preferred catalytic processes are disclosed herein.

[072] As used in this document, the term "Olefine Feed Stream" refers to a feed stream comprising C2-5 olefins. The olefin feed stream may comprise all or a portion of the product stream from the thermal olefin reactor. For example, methane and hydrogen present in the olefin product can be separated before passing the current to the catalytic reactor. Likewise, the C2-5 alkanes present in the product stream, particularly ethane and propane, can be separated and recycled to the thermal olefin reactor combined with the C2-5 alkane feed stream, or separately. An olefin feed stream derived from the product stream of the thermal olefin reactor will contain C2-5 olefins.

[073] In one aspect, the C2-5 olefin feed stream is inserted into the catalytic reactor. As used in this document, the term “catalytic reactor” is used to refer to a reactor using a catalyst and operating under conditions to cause cracking, oligomerization and, in many conditions, cyclization of the feed olefins to form higher hydrocarbons, namely carbon alkanes, alkenes and aromatics suitable for gas or diesel mixture stocks.

[074] It will be appreciated that these reactions can occur in various combinations and orders, with some molecules going through several of these reactions.

Thus, the reactions that lead to the final products can act on the olefins in the food, or they can act on the olefins after having already suffered one or more reactions.

Therefore, it is contemplated, and must be understood, that the reference to reactions of the feed olefins generally refers to the reaction of any molecule that was originally fed to the catalytic reactor as a C2-5 olefin.

[075] The catalytic reactor uses a zeolite catalyst and operates above 200 ° C, at 0 to 1500 psig, and a space speed of weight per hour (WHSV) between 0.5 and 10 (preferably about 1). This reactor produces random, multi-iterative sequenced chemical reactions to break down, oligomerize and, in many conditions, cyclize the broad spectrum of hydrocarbons comprising olefins and compounds derived from olefins. The catalytic process can be done to produce any range of fuel grade products, including, for example, C5 + or C6 + or C7 + gas ranges (mainly paraffins, olefins and aromatics), or C9 + or C10 + ranges or

C12 + of light diesel or medium hydrocarbon distillate (for use mainly as diesel fuel mixtures).

[076] The chemical reactions in the catalytic reactor (R2) comprise multi-iterative, construction, degradation and sometimes cyclization of different molecular formations, creating a portfolio of hydrocarbons that can be selectively adjusted for any specific carbon range of products. The end products can be affected, for example, based on the composition of the C2-5 alkane feed stream, the configuration of a recycling cycle and various other operational conditions of the general LG2F Process. For example, operating conditions (for example, T, P, WHSV) are varied depending on the desired gasoline grade product or medium distillate grade fuel mixtures.

Catalysts

[077] The catalytic reactions disclosed in this document use catalysts that break, oligomerize and, in many conditions, cyclize olefins with high efficiency. The catalyst used in the LG2F Process generally contains a highly acidic zeolite, with a high surface area support, for example, alumina. In addition, there may be a weakly active metal, for example molybdenum, which saturates cracked olefins without saturation of aromatic compounds in certain specialized modalities. In comparison, traditional catalytic naphtha reform technology uses catalysts that contain platinum (Pt) in alumina chloride, often promoted with tin (Sn) or rhenium (Re) for better performance and stability, respectively. These reform catalysts are compositionally very different from LG2F catalysts.

[078] The LG2F process uses catalysts that are functional to substantially break, oligomerize and, under some conditions, cyclize the olefins in the feed stream, although they do not significantly affect other valuable components in the feed stream. A catalyst is functional to substantially break, oligomerize, and / or cyclize the olefins to transform at least 65%, preferably at least 80%, and more preferably at least 95% of the olefins into fuel grade compounds in a single pass yield .

[079] In one embodiment, the catalytic reaction is carried out using a zeolite catalyst. Acid citations in zeolite catalyze cracking reactions more quickly than other components. The reactions can be conducted with and without metal impregnation. The metal allows hydrogen to join olefinic compounds that can be strategically implemented to saturate olefins in the last half of the R2 reactor or in a separate hydrogenation step entirely. This can work with internally generated or supplemented hydrogen.

[080] In one aspect, the processes use a zeolite catalyst with a pore size of 2 to 8 Angstroms. Exemplary surface areas for the catalyst are 400 to 800 m2 / gram. Examples of zeolite catalysts include Si, Al and O, preferably with a Si: Al ratio of 10 to 300. Zeolite catalysts with properties outside these limitations can also be useful. The catalyst is preferably selected to substantially catalyze the olefins while not significantly affecting other valuable components in the feed stream.

[081] In modalities, the catalyst is Zeolite ZSM-5, Zeolite Beta or Zeolite Mordenite. All impregnations of these catalysts use the same metal in 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 a metal. Zeolites are characterized in the following ways: pore size, usually 3 to 8 angstroms; pore structure, many types; and chemical structure, combination of Si, Al and O. All have ammonium cations

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

[082] Zeolite Beta has the following properties: pore size from 2 to 7 angstroms, molar ratio of SiO2 to Al2O3 (Si / Al) ranging from 20 to 50, intergrowth of polymorphic structures A and B and surface area between 600 and 800 m2 / gram.

[083] Zeólito Mordenita has the following properties: pore size from 2 to 8 angstroms, nominal sodium and ammonium cation forms, Si / Al ratio from 10 to 30 and surface area between 400 and 600 m2 / gram.

[084] In a particular embodiment, the catalyst is Zeolite ZSM-5. The ZSM-5 has the following properties: pore size of 4 to 6 angstroms, pentasil geometry forming a configuration of 10 ring holes, Si / Al ratio of 20 to 560 and surface area between 400 and 500 m2 / gram. Various impregnations can use between 1% and 2% of molybdenum. ZSM-5 is the preferred catalyst for its ability to withstand the R2 transformation reaction while preserving the chemical composition of aromatic compounds. The reaction can be carried out with or without metal impregnation. The metal allows hydrogen to aggregate into olefinic compounds that are produced during the cracking mechanism. The smaller pore size of the ZSM-5 catalyst results in much less unwanted saturation of aromatic compounds, which are generally desired constituents in both gasoline and diesel mixtures.

Example of Zeolite Catalyst

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

Reactor Regeneration - R2

[086] The operability of the catalytic reactor depends on the reactor and catalyst life cycles and the resulting amount of deactivation or thermal resistance that can occur from the accumulation of carbon in the catalysts or in the reactor walls. The regeneration and cleaning of any 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 catalytic reactor. It has been determined that the regeneration methods previously described in this document are also useful with the catalytic reactor and the regeneration time can be determined on a similar basis.

[087] Both of the regeneration methods described here can be adapted to operate in any suitable reactor, especially any alkane dehydrogenation reactor or zeolite-based oligomerization reactor. These methods advantageously eliminate the need for steam-based regeneration methods, economically eliminate excess carbon accumulation and restore the process activation levels.

LG2F system

[088] With reference to Figure 3, a process flow for the LG2F process is shown. The raw material stream (1) mainly comprises alkanes rich in C2-C5 paraffin. 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 production gasoline and diesel fuel and / or to optimize feed composition. The raw material stream (1) is combined with a light recycled stream (13) composed of a C1-C5 mixture including mainly n-paraffins and i-paraffins with some olefins and the combined current (2) is fed into the heat exchanger heat (EX-1). As described later, light gas supply streams that are mainly rich in olefins (eg FCC exhaust gases, propylene, etc.) can be fed directly into R-2 via line (7), bypassing the thermal olefin phase. The combined current (2) is exchanged on the EX-1 with the current (8), to recover the heat produced in the catalytic reactor of R-2. The output current (3) of EX-1 is fed into another cross exchanger, EX-2, to further preheat the feed to R-

1.

[089] The preheated current (4) is fed into a thermal olefin furnace (R-1) operating normally at 600 to 1100 ° C and 0 to 1500 psig. The thermal olefin reactor (R-1) conducts an endothermic reaction to produce olefinic compounds through carbon cracking and dehydrogenation. Excess heat from the reaction is used as the hot current (5) for EX-2. The hot current (6) coming out of EX-2 may require additional cooling for the second reaction stage (R-2). EX-3 is an optional air-water or refrigerant cooling unit for the system, depending on the heating requirements. It is useful here to conduct the appropriate heat transfer step to ensure adequate conditions for the entry of R-2 at the set point. A deviation can be implemented between chains (6) and (7) and chains (9) and (10) instead of the cooling utility for EX-3 and EX-4 for dynamic operability between diesel and gasoline production. An optional extraction step can be incorporated before the R-2 reactor in the stream (7) to capture entrained liquid droplets and remove all C6 + compounds from entering R-2. See Figure 4.

[090] R-2 is a catalytic reactor, typically operating at 200 to 1000 ° C and 0 to 1500 psig, which breaks, oligomerizes, and, under some conditions, cyclizes olefinic compounds in multi-iterative reactions to produce a wide spectrum of n -parafins, i-

paraffins, naphthenes and aromatics mainly in the range of C4 to C16, resulting in high octane gasoline or products in the diesel spectrum with a high cetane content.

Depending on the desired final product, the excess of 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 internal cooling or integrated to prevent overheating. Excess heat from the reacted stream (8) is used in EX-1 as the hot current input to increase the temperature for the combined feed (2).

[091] The hot outlet (9) can support optional cooling for proper flashing on the D-1 flash drum. For this reason, the EX-4 may not be necessary, but it can be an air cooler, water cooler, etc. to conduct the appropriate heat exchange. The power of the flash drum (10) is maintained at the system pressure and is used to purge the light components directed from the mixed product stream. The main function of D-1 is to control the pressure of the system. Light components (11, 14) mainly consist of H2 and C1-C3 compounds that can be purged (14) from the system or directly recycled (11) back into the system, combining with the light current from the flash drum (D-2 ) (16) before the compressor, C-1.

[092] D-1 light chains will have H2 and C1 components that are not reactive to the system and will cause accumulation in recycling if not removed properly. H2 and C1 can be purged (14) with other lightweight components to stabilize the recycling system or a separator, such as a membrane, can be used to selectively remove H2 and C1. The liquid bottoms (15) of D-1 are fed into D-2, which is adjusted to a lower pressure to remove mainly compounds C3 and C4 from the liquid stream (15). Levels (16) of D-2 are combined with light (11) of D-1 to form the chain (12) which is compressed into C-1 and recycled for further reaction. The recyclable light hydrocarbons (16) from D-

2 (usually C2 - C4 if directed towards gasoline; C2 - C10 if directed towards diesel) will be fed back to the thermal reaction, unless the constituents are rich in olefins, which can optionally be fed directly into R-2 to increase the process efficiency. The resulting instantaneous liquid stream (17) coming out of the bottom of D-2 is the end product of the process that can be directed to produce any range of high octane gasoline mixture C4-C12 or high-grade diesel fuel mixture. cetane C9-16 +.

Recycling

[093] After the R2 catalytic reaction, the alkane-rich light gas recycling stream exiting the flash drum condensing unit can be directed back to the C2 + thermal olefin reactor to be fused with other light hydrocarbon streams of input, as represented in the process stream of Figure 1. The constituents outside the selected matrix are assembled in a single-circuit recycling configuration. This recycling process maximizes the performance profile and performance properties of any type of liquid effluent produced for use as transport fuel. Typically, for all compounds not used in a targeted gasoline range or diesel fuel range, the process will target the lighter by-products (for example, ≤ C5 for gasoline or ≤ C8 for diesel) to be recycled for later update. Operating with a continuous recycling cycle with R2 effluent achieves high product yields, for example, ranging from 65% to 95%.

[094] Each recycling cycle is continuous to allow random redistribution of liquid C6 + hydrocarbons produced from the LG2F Process to join together in various formations (eg paraffins, olefins, aromatics) needed for a fuel based on characteristics of specific performance. These performance characteristics for gasoline may include octane, vapor pressure, density, liquid heat of combustion, etc., while such characteristics for diesel fuel may include cetane, thermal stability, cold flow and others.

[095] With reference to Figure 4, a simplified scheme for an LG2F system according to the present invention is shown. The system is generally the same as shown in Figure 3, except that an “Extraction” is provided between reactors R1 and R2. As mentioned earlier, the extraction unit operates to remove entrained liquids and C6 + compounds from entering R2.

[096] For example, the fully recycled thermal and chemical reactions from processing a feed of 80% C2 (ethane) and 20% C5 (pentane) are represented in a material balance as shown below in Table 3a. The process follows the steps in Figure 4.

[097] The resulting C6 + gasoline compounds produced a 66% mass conversion of high performance gasoline with 25% (17/66% by weight as aromatics) of the C2 / C5 feed and resulted in a search octane number of 101.7 unexpectedly high (using the ASTM D2699 Test Method).

This illustration using C2 and C5 as the thermal olefin feed demonstrates the wide range of gasoline blend compositions that are possible.

Table 3a - Production of Gasoline Mixture of raw material C2 & C5 Step 1 1 3 3 4 5 6 7 8 9 Process LG2F w / C2 + C5 R2 s Flash act Light oline Recycling m Lb / h H2 5.59 5.59 5.59 5.59 5.59 C1 19.10 19.10 19.11 19.11 19.11 148.8 149.6 149 , 6 C2 80 148.82 149.68 2 8 8 C2 = 75.43 75.43 0.00 C3 0.65 0.65 5.55 5.55 5.55 C3 = 9.54 9.54 0, 00 C4 0.61 0.61 14.24 14.24 14.24 C4 = 2.21 2.21 2.65 2.65 2.65 C5 20 0.00 0.00 14.27 14.2

C5 = 0.97 0.97 4.15 4.15 11.1 C6 0.13 0.13 11.19 9 C7 7.33 7.33 C8 6.01 6.01 C9 4.07 4.07 C10 1.46 1.46 C11 0.48 0.48 C12 0.61 0.61 A6 4.83 4.83 0.19 0.19 A7 1.60 1.60 1.45 1.45 A8 3.64 3.64 A9 5.45 5.45 A10 4.17 4.17 A11 0.94 0.94 Unknown 2.65 2.65 0.82 0.82 acid 272.1 263.0 172.1 66.2 Total 100 9.08 263.05 196.82 24.69 3 5 2 3

[098] A similar example shown in Table 3b represents 100% C2 (ethane) with a mass conversion of 84% into C5 + gasoline (for standard RVP) with 25% (mass of 21/84% as aromatics). This demonstrates the broad spectrum of molecular results typical of all C2-5 feed currents. Raw materials C2 to C5 can be fully recycled and converted into gasoline molecules based on the reactor's unique operating conditions. The process follows the steps in Figure 4.

Table 3b - Production of Premium Gasoline Blend from raw material C2 (ethane) Step 1 2 3 4 5 6 7 8 9 Process LG2F: C2 w / Recycle Alime Fora Extr Alimentaç Fora Cover Recycle Purging R1 action R2 R2 R2 Flash act Light oline Lb / h H2 4.67 4.67 4.67 4.67 4.67 C1 10.68 10.68 10.69 10.69 10.69 238.4 239.3 239.3 C2 100 238.41 239.32 1 2 2 108.3 C2 = 108.32 0.00 0.00 0.00 2

C3 1.11 1.11 7.36 7.36 7.36 C3 = 2.33 2.33 C4 0.88 0.88 18.71 18.71 18.71 C4 = 1.77 1.77 3, 39 3.39 3.39 22.9 C5 22.94 4 14.3 C6 0.22 0.22 14.35 5 C7 9.39 9.39 C8 7.70 7.70 C9 5.22 5.22 C10 1.87 1.87 C11 0.62 0.62 C12 0.78 0.78 A6 0.39 0.39 0.24 0.24 A7 1.86 1.86 A8 4.66 4.66 A9 6 , 99 6.99 A10 5.35 5.35 A11 1.21 1.21 Unknown 1.05 1.05 acid 368.7 368.3 268.7 84.2 Total 100 0.39 368.39 284.14 15.36 8 9 8 5

[099] This illustration also describes how specific operating conditions can be used to control the resulting list of compounds. The temperature of Reactor 2 was 250 ° C, which resulted in an aromatic content of 25% w / w. The aromatic content is variable and can be used to increase the octane values of gasoline mixtures. Surplus C6 + aromatics can be captured from extraction as by-products of petrochemical processing.

Raising the temperature of reactor 2 from 250 ° C to 400 ° C doubles the desirable aromatics content in the gasoline mixture and thus increases the resulting octane rating. Light purging (via flash drum and membrane separation) allows methane and hydrogen by-products to be reused in other downstream processes. Table 3c is similar for gasoline with C6 + compounds (> 98 RON with low RVP) with a total yield of 79% from 100% ethane; aromatics represented 35% (28/79) of the total yield. The process follows the steps in Figure 4.

Table 3c - Production of gasoline from raw material C2 (ethane) Stage of the 1 2 3 4 5 6 7 8 9 Process LG2F: C2 Alime Fora Extr Alimentaç Fora Cover Recycled Purgo Gas w / Recycling of R1 action of R2 of R2 s Flash act Light olina gem Lb / h H2 6.09 6.09 6.09 6.09 6.09 C1 13.94 13.94 13.95 13.95 13.95 311.1 312.6 312.6 C2 100 311.16 312.63 6 3 3 141.3 C2 = 141.38 8 C3 1.45 1.45 9.61 9.61 9.61 C3 = 3.04 3.04 C4 1.15 1, 15 24.94 24.94 24.94 C4 = 2.31 2.31 4.45 4.45 4.45 C5 29.68 29.68 29.68 18.6 C6 0.28 0.28 18.60 0 12.1 C7 12.17 7 C8 9.98 9.98 C9 6.76 6.76 C10 2.42 2.42 C11 0.80 0.80 C12 1.01 1.01 A6 0.51 0, 51 0.31 0.31 A7 2.42 2.42 A8 6.04 6.04 A9 9.06 9.06 A10 6.93 6.93 A11 1.57 1.57 Unknown 1.36 1.36 acid 481.3 480.8 381.3 79.4 Total 100 0.51 480.80 401.36 20.05 1 0 1 4

[0100] Oligomerization reactions are effective in converting a significant amount of the olefins received from the thermal olefin reactor. The conversion of olefins received with the R1 and R2 Process, with recycling, is preferably at least 60%, more preferably at least 80%, and most preferably at least 90%. Conversions of at least up to 95% are also possible.

Product Selectivity

[0101] The LG2F process uses the feed composition, thermal olefin reaction and oligomerization operating conditions (T, P, WHSV) to establish a predictable result for various fuel performance criteria described in the fuel specifications of the industry. The following describes how this technique is achieved. In addition, see Figures 5 and 6.

[0102] In one aspect, the process is configured to produce a desirable wide range of fuel products. Fuel products are typically in the C5-24 + range of hydrocarbon fuels or fuel mixtures. The range of fuel products depends in part on the supply current of C2-C5 alkane and is controlled based on the operation of the LG2F Process. In one method, the fuel products are determined as follows. First, the available supply current is analyzed against the desired fuel target. Then, a baseline is established taking into account the nature of the supply current and the typical operating conditions for the LG2F Process. For example, it can be established that a given feed stream, for example, 100% ethane, will produce a predictable matrix of fuel products with the operation of the Process under certain conditions of temperature, pressure, space speed and recycling.

[0103] In addition, it can be determined that changes in these conditions will move the product mix in one direction or the other. For example, increasing the temperature in the R2 (or R2L) oligomerization reactor will increase the cracking of hydrocarbons and the production of lighter aromatics, resulting in a lower final boiling point of the target fuel. A higher pressure used in R2L will increase the length of the chain of intermediate distillate compounds produced, also impacting the final boiling point of diesel fuel. Higher spatial velocities result in a higher exothermic temperature that produces lighter compounds (as shown in Figures 5a and 6a). Higher reactor temperatures at a fixed space speed and pressure reflect a similar tendency to produce lighter compounds (as illustrated in Figures 5b and 6b). In this way, it is possible to identify the operating conditions of the baseline reactor and then adjust from there to produce different combinations of products.

Upper Boiling Limit

[0104] The temperature of the oligomerization reaction is used to prescribe the cutoff point of the fuel product, which determines the limit of the final boiling point of the fuel. For example, a fuel specification may require a final boiling point of 340 ° C or 225 ° C or 180 ° C and reactor conditions can be defined to limit the boiling condition above a specific temperature.

Table 4 Boiling point R2 - Operational condition of higher ratio Oligomerization Baseline reactor - 275 to 325 ° C To include C12 FBP 225 ° C (cold / less cracking) To include C11 FBP 215 ° C Baseline reactor - 325 to 375 ° C Baseline reactor - 400 ° C To include C10 FBP 200 ° C (hot / more cracking) Baseline R2 reactor - (hot / more To include C18 Medium aromatic cetane) Best R2 Reactor Point of baseline - (minus To include hot flowing C17) Baseline R2 reactor - (cold / minus To include C16 High Cetan aromatics) Lower Boiling Limit

[0105] The use of a single stage flash drum with a predefined liquid vapor temperature limit can establish any lower limit for liquid fuel without the expense of cryogenics or complex multi-stage fractionation columns. The temperature of the flash drum is set at a predetermined point, for example, for butane C4 (high RVP), for the preferred liquid / vapor cut. The level of accuracy can be increased using a 2-stage drum.

Table 5 Low Boiling Point Ratio Flash point Flash To include C4 RVP high set flash at 0 ° C To include C5 RVP medium set flash at 27 ° C To include C6 RVP Low set flash at 50 ° C To include C7 Aromatic Cut Set flash at 105 ° C To include C9 High Cetane set flash at 125 ° C To include C10 High Cetane set flash at 150 ° C Benzene extraction

[0106] The thermal olefin reaction is known to cause some production of benzene, which has a control limit on fuels.

Consequently, the LG2F Process uses a liquid vapor extraction flash drum set to 75 ° C to capture any light aromatics that come out of thermal olefin. Since C2-C5 hydrocarbons are generally broken down into C5 and smaller compounds, the main exception to this is the production of aromatic liquid C6H6 (although valued in selected markets) which can then be largely eliminated from the final fuel. This compound can be marketed as BTX or reacted with olefins to make C7 + alkylaromatics to increase octane in gasoline.

Gasoline Aromatics Content

[0107] The temperature of the oligomerization reaction is used to pre-determine the level of activation that directly affects the production of aromatics.

Consequently, high-octane gasoline formulations favor a C7 to C10 aromatic content of up to 50%.

[0108] This results in the following operational conditions: Table 6 Ratio Level Aromatic in Gasoline activation High octane (RON Up to 55% aromatics C7 +; Baseline + High> 95) 60 - 100 ° C Medium octane Up to 20% aromatics C7 + ; Baseline + Medium (RON> 91) 20 - 60 ° C Low octane Up to 15% aromatics C7 +; Low line reactor (RON> 89) base at 320 ° C Aromatics content in distillate

[0109] The temperature of the oligomerization reaction is used to pre-determine the level of activation that directly affects the production of aromatics.

Consequently, higher cetane formulations favor a lower aromatic content of less than 25%. The aromatic content of diesel fuel is limited to not exceeding 35% and the presence of C16 + aromatics can impede the performance of cetane.

Therefore, the diesel fuel spectrum is generally directed to compounds in the C9 to C16 range and the aroma content is limited to <35%, resulting in the following operational conditions: Table 7 Aroma Ratio Level in Distillate activation Low cetane Up to 35% aromatics in C9 + distillate; High Line (> 40) base + 100 to 175 ° C Medium cetane Up to 30% aromatics in C9 + distillate; Medium Line (> 45) base + 50 to 100 ° C High Cetane Up to 25% aromatics in C9 + distillate; Baseline Reactor Low (> 50) Conditions

[0110] Gasoline performance was measured using baseline ethylene operating at 320 ° C, atm (0 psig) and 0.75 WHSV. The spatial velocity graphs using aliphatics and aromatics were performed in atm (0 psig) at temperatures of 284 ° C, 293 ° C, 318 ° C and 343 ° C. All results demonstrate the basic principles for determining the appropriate R2 reactor operating conditions to produce performance fuels. Actual operating parameters will vary depending on the supply current. Diesel fuels follow the same basic principles as the chemistry and thermodynamics of reactions in the gasoline spectrum.

[0111] The control of operational parameters (temperature, pressure, speed of space) can directly impact the scope and range of molecules produced in a catalytic oligomerization unit. The temperature directly impacts the cracking level that occurs during oligomerization. An increase in temperature causes more cracking, which will result in the production of smaller molecules. The lower temperature will produce longer chain molecules, as they break less while coupling still occurs.

[0112] High pressures are preferred for production in the diesel range, as a higher gas concentration will allow more coupling opportunities. Locally, more molecules will occupy a certain area at high pressure, allowing more reactions to occur in a given period of time.

Modifying the 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 the high pressure will significantly increase the exotherm, so that the energy would need to be removed at the generation rate to minimize cracking.

[0113] The same applies to space speed, where an increased space speed provides a shorter residence time in the catalyst, but more reactions per second that also increase the temperature. The spread of the chain can be reduced at high spatial speeds at the expense of an increase in exotherm. Thus, proper heat management can dynamically control the product's slate, distribution and final boiling point while modifying pressure and spatial speed.

Commercial Significance

[0114] The LG2F Process and System allows for medium current or performance grade fuel refinery production that are adapted to meet the constantly changing industry performance criteria in areas where stranded light hydrocarbons are not accessible to supply chains. traditional fuel supplies. The US NGL market currently rejects approximately 407,000 BPD of ethane (~ 10% of total NGLs production) with the sale of ethane as natural gas where an ethane market does not exist, despite the higher volumetric BTU value than ethane.

[0115] Eliminating the “ethane rejection” mode opens the opportunity for more economical production of gasoline and diesel from NGL and optimizes methane gas reserves that would otherwise be stranded, closed or burned. The LG2F also offers a low-cost way to update ethane, propane and butane + compounds to performance-level fuel values. The production of gasoline and diesel with a fuel performance standard reduces unnecessary logistics costs and allows fuels to enter markets through existing finished product fuel supply chains.

[0116] The thermal olefin reaction of LG2F (R1) together with the chemical reaction (R2) and the recycling cycle can be used independently and can be adapted interchangeably based on the composition of the raw material and final products desired for produce stocks of gasoline and / or diesel fuel mixtures. The process is flexible to allow reactor operating conditions to be established to produce the desired mixing components and compositional characteristics to meet fuel performance requirements (for example, aromatics for the octane value of gasoline, cetane for performance diesel). The by-products of the reaction can include methane and hydrogen.

[0117] The adaptation effects of gasoline and diesel fuel reactions include a variety of factors, including the final boiling point of the product, the lowest boiling point of the product, both based on the operating conditions for any Supply stream. Other factors include% w / w aromatics C6,% C5 used in gasoline (RVP index), cetane number,% aromatics,% C18 + compounds, etc.

[0118] An important feature of the LG2F Process is the segmentation of fuel products with a performance level. Rather than indiscriminately producing a stream of random hydrocarbons, this invention serves to adapt the process and operational 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 target fuel will result in a low grade out of fuel specifications. Likewise, high performance gasoline with more than 50% aromatics, although with a high octane content, may be undesirable for environmental emissions. However, other users of the process may prefer to produce a very high concentration of aromatics in a restricted market only to be used as mixtures with other surplus components (for example, before mixing into a final fuel in a refinery). In yet another example, the presence of excess benzene can also be an operational limitation for some fuel specifications. Diesel fuel requires a high ratio of C9-C16 compounds with relatively high cetane values; diesel also needs less presence of low melting point compounds. Consequently, this invention offers a wide variety of process techniques and optionality for the user to configure the catalytic operating conditions to meet the intended results of the performance grade product.

[0119] An optional feature of LG2F is to produce C4 and C5 alkanes that can be useful to increase volatility and increase vapor pressure in gasoline, although often at the expense of octane levels. Thus, some or all of the C4-5 alkanes can be targeted for production in the gasoline mixture.

Alternatively, the production of C4 or C4-C5 can be avoided, in which case the process directs ≤ C4 or ≤ C5 by-products to be recycled for later update.

[0120] It will be appreciated that the LG2F Process may include split multi-iterative variations of R1 and R2 that may require more than a single recycling cycle for optimal operation. As an example, R2 can be separated into two or more reaction sequences with some form of separation between and after operations. The residual separation gas can be melted or recycled independently and at different locations.

LG2F products

[0121] The LG2F process converts C2-5 alkanes into a wide range of combustible products constituting higher value C5-24 + hydrocarbon fuels and fuel mixtures. This refers to the fact that a variety of fuel products can be derived using this Process with products that contain one or more compounds within the C5-24 + range. A typical fuel product is a mixture of gasoline including one or more selected hydrocarbon compounds with 4 to 12 carbons. Another typical product is a mixture of C9-24 + hydrocarbons suitable for diesel fuel. Several other possible products of the LG2F Process have been identified here, and it is a distinct feature of the present invention that a wide range of different fuel products can be formed.

[0122] However, this does not mean that the reference materials should include each of the compounds in the recited range. Therefore, as used in this document, a reference to the LG2F Process providing a fuel product identified as a range, for example, C4-12, includes a product including all hydrocarbons in that range, as well as less than all, for example , 1 or 4, hydrocarbons in that range. Likewise, a reference to a range such as with respect to the alkane feed stream including C2-5 alkanes is a reference to a feed stream having one or more of the C2 to C5 alkanes.

[0123] The process configuration uses a recycling cycle to produce a specified range, for example, C5 to C12 gasoline compounds or C9 to C20 diesel fuel compounds for use as mixtures in high grade transport fuels. Using the LG2F process, net yields from recycling can vary, for example, from 65% to 95+% of the initial supply current, depending on the severity of the operating conditions. This process offers flexibility in the production of higher yielding paraffinic molecules or slightly lower yielding olefinic and aromatic hydrocarbons for products in the gasoline range or, alternatively, can be exchanged to create a mixture of middle distillates (mainly paraffins, olefins and aromatics) for products in the diesel range. Alternatively, excess methane can be used as a process fuel or recycled into fuels.

Gasoline Blends

[0124] In one aspect, the LG2F Process is adapted for the production of gasoline mixtures, as exemplified in the previous discussion. As used herein, the term "gasoline mixture" refers to a formulation comprising n-paraffins, iso-paraffins, cycloparaffins, olefins and aromatics with 4 to 12 carbons.

The gasoline mixtures of this invention preferably have 5 to 12 carbons and more preferably comprise 6 to 11 or 7 to 10 carbons. Gasoline blends also typically have branched-chain paraffins and aromatic hydrocarbons with 6 to 11 carbons, preferably 7 to 10 carbons. In preferred embodiments, the LG2F Process produces a product containing at least about 65% branched-chain paraffins C5 to 10 and at least 25% aromatic hydrocarbon compounds C7 to 9. The following examples further demonstrate the ability to adapt o LG2F Process, depending on the C2-5 feed and the desired end product (s).

Table 8 - Typical Gasoline Composition Typical Constituents of C4 C5 C6 C7 C8 C9 C10 C11 C12 Gasoline n-paraffins X X X X O O O O O iso-paraffins X X X X X X X O O cycloparaffins X X X X X X O O olefins X X X X X X O O aromatic X X X O X

[0125] Although the gasoline mixtures described as LG2F products in this invention may consist of several chemical compounds, the compounds produced in this invention are not indiscriminate at random. This is done as described in this document, inter alia, selection of the C2-5 alkane supply currents, operational parameters and recycling between reactors R1 and R2. The production of high performance gasoline requires adherence to a minimum set of performance conditions for gasoline grade products. The LG2F Process produces, for example, fuel compositions and mixtures including the following:

[0126] In one embodiment, the gasoline compound is ≥ 95 research octane number (RON) without ethanol, with a vapor pressure ≥ 9 psi (RVP), but ≤ 13.5 psi, aromatic content ≤ 50% m / m and benzene content below 1.30% (v / v), and a final boiling point <225 ° C.

[0127] In one embodiment, the gasoline compound is> 95 RON without ethanol, with a vapor pressure ≥ 9 psi, but ≤ 13.5 psi, aromatic content <55% w / w and benzene content below 1, 30% (v / v), and a final boiling point <225 ° C.

[0128] In one embodiment, the gasoline compound is ≥ 91 [using R + M / 2] without ethanol, with a vapor pressure ≥ 9 psi but ≤ 13.5 psi, aromatic content ≥ 35% w / w and content of benzene below 1.30% (v / v), and a final boiling point <225 ° C.

[0129] In one embodiment, the gasoline compound is ≥ 89 [using R + M / 2] without ethanol, with a vapor pressure ≥ 9 psi but ≤ 13.5 psi, aromatic content ≤ 35% w / w and content of benzene below 1.30% (v / v), and a final boiling point <225 ° C.

[0130] In one embodiment, the gasoline compound is ≥ 87 [using R + M / 2] without ethanol, with a vapor pressure ≥ 9 psi but ≤ 13.5 psi, aromatic content ≤ 30% w / w and content of benzene below 1.30% (v / v), and a final boiling point <225 ° C.

[0131] In one embodiment, the gasoline compound is ≥ 84 [using R + M / 2] without any ethanol, with a vapor pressure ≥ 9 psi but ≤ 15.0 psi, aromatic content ≤ 25% w / w and content benzene below 1.30% (v / v), sulfur content below 0.008% (w / w), and a final boiling point <225 ° C.

C2-5 Hydrocarbons for C-8 Aromatics

[0132] In one embodiment, the LG2F Process is adapted by isolating the R2 catalytic reaction to convert raw materials for C2-C5 light olefins into aromatic hydrocarbons comprising a narrow range of C6 to C8 aromatics for use as a fuel mixture. high octane or petrochemical use.

This is done using the operating conditions to obtain an aromatic yield up to the upper boiling limit of o-xylene, for example 145 ° C, and recycling all by-products in the flash drum with boiling points below benzene at 80 ° C.

The yield of aromatics C6 to C8 is valuable for the petrochemical market as a base aromatics feed stream for aromatic fractionation or as an alternative, if the BTX product stream is first processed by a hydrodesalkylation step to uncouple and remove constituents ethyl-propyl and butyl-aromatics leaving only methyl-aromatic products.

C2-5 Hydrocarbons for C7-8 Aromatics

[0133] In another embodiment, this invention can be adapted by isolating the catalytic reaction of R2 to convert raw materials of light olefins C2-C5 into aromatic hydrocarbons in a narrow range of aromatics C7 to C8. Again, this is done aiming at the aromatic yield up to the upper boiling limit of oxylene, for example 145 ° C, and recycling all by-products in the flash drum with boiling points below toluene at 110 ° C. The yield of aromatics C7 and C8 have a very high octane value and a very high energy density in the absence of benzene and are mixtures of gasoline useful to meet premium grades of high octane.

C2-5 Hydrocarbons for C8 Aromatics

[0134] In another modality, the LG2F Process is adapted by isolating the catalytic reaction of R2 to convert raw materials of light olefins C2-C5 into aromatic hydrocarbons in a narrow range of aromatics only C8, aiming at operating conditions for yield aromatic to the upper boiling limit of o-xylene, for example 145 ° C, and recycle all by-products in the flash drum with boiling points below p-xylene at 138 ° C. The performance of C8 aromatics will have a very high octane value and a very high energy density that can be a useful gasoline blend to meet premium octane ratings. In addition, these C8 compounds can be even more valuable for the petrochemical market, particularly if they are produced by a hydrodesalkylation step to decouple and remove any boiling point ethyl aromatic constituents and produce methyl aromatic products.

C2-5 Hydrocarbons for C7-9 Aromatics

[0135] In one embodiment, this invention is adapted by isolating the R2 catalytic reaction to convert raw materials of light olefins C2-C5 into aromatic hydrocarbons in the range of C7 to C9 specifying the operational conditions for the aromatic yield up to the boiling limit of trimethylbenzenes, for example, 175 ° C, and recycle all by-products in the flash drum with boiling points below toluene at 110 ° C. The yield of aromatics C7 to C9 will have a very high octane value and a very high energy density, without the presence of benzene, and can be a useful gas mixture to meet premium octane ratings.

C2-5 Hydrocarbons for Isooctane

[0136] A specialized technique for producing high octane gasoline mixtures is the use of LG2F in a truncated form defining the operational conditions of the chemical reaction of catalytic R2 to the desired upper temperature in the desired product stream. All light hydrocarbon gases below a lower target boiling point limit are recycled, creating a desired range of products. This technique allows the production of a simple narrow band of desirable hydrocarbons that can be particularly valuable for the fuel mixing process of a particular LG2F production facility.

[0137] An example of optionality is the targeting of isobutane, a high-octane compound typically used to add vapor pressure (RVP) to the gasoline mixture, but also used as a raw material for any traditional paraffin alkylation process. The catalytic chemical reaction of R2 favors the production of branched-chain paraffins, which reduces the probability of producing n-paraffins that boil on both sides of the isobutane. Therefore, as a result of the adapted R2's LG2F reaction, the isobutane (C4H10) can be isolated using a high pressure separation vessel. The target is a narrow boiling range between -40 ° C and -2 ° C in atmospheric conditions, which can be pressurized to partially liquefy the current and extract the C4 iso-paraffins.

All lighters below -40 ° C (mainly ethane and propane) are recycled to maximize the yield of branched paraffins within the temperature range.

[0138] In a similar example, the LG2F thermal olefin reactor of R1 in this invention can be directed to produce any combination of C3-C5 olefins (propene, butene and / or amylene) from any C3- light gas alkanes C5 which can then be applied directly to any traditional paraffin alkylation unit with the additional supply of isobutane (from any source) for the production of high octane branched chain paraffinic hydrocarbons, particularly 2,2,4-trimethylpentane (Isooctane) .

[0139] In a combined example, the LG2F thermal olefin reaction of R1 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 of adding additional light olefin streams) to direct the production of isobutane or isobutene as described above. Any C6 + by-products of the R1 reaction can be captured by extracting liquid vapor for surplus gasoline or reuse. This tailored configuration results in the critical supply currents necessary for entering paraffin alkylation.

Diesel Blends

[0140] Diesel fuel has several main performance characteristics that depend on the chemical composition of the fuel. Diesel fuels are generally composed of n-paraffins, isoparaffins, cycloparaffins and aromatics in order to meet the main performance requirements of the fuel. For example, in a diesel engine, the cetane number is a measure of the compression ignition speed in the fuel injection, as well as the quality of the fuel burning in the combustion chamber. Therefore, 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.

[0141] In addition, very low levels of sulfur are also highly desirable in diesel fuel to eliminate corrosive wear and avoid problems in the engine's emission control system. Aircraft fuel and diesel oil, both derived from middle distillates, share many common characteristics. See Figure 7 and Figure 8. However, ASTM International's fuel specifications require different performance-based fuel test results that affect cetane, lubricity, viscosity, low temperature fluidity, sulfur content, heating value and much more. Performance requirements are what dictate the composition and operational requirements to produce the desired fuel.

[0142] Generally, n-paraffins, iso-paraffins and C9 + cycloparaffins have higher cetane values than aromatics and are key constituents in the diesel mixture to achieve high cetane measurements (eg 40 to 60) for good fuel performance. The cetane values for various n-paraffins are shown below in Table 8.

Table 8 - C9 + n-Paraffin Compounds Have Higher Cetane Values n-Paraffin Point C9 to C20 Formula Cetane # Boiling (° C) Fusion (° C) N-NONANO C9H20 150 -48 72 N-DECANO C10H22 174 -30 76 N-UNDECAN C11H24 196 -26 81 N-DODECAN C12H26 216 -10 87 N-TRIDECAN C13H28 235 -5 90

N-TETRADECAN C14H30 254 6 95 N-PENTADECAN C15H32 271 10 96 N-HEXADECAN C16H34 287 18 100 N-HEPTADECAN C17H36 302 22 105 N-OCTADECAN C18H38 316 28 106 N-NONADECANO C19H40 336 32 110 N-ICOSANO 36 110

[0143] However, while C14 + n-paraffins have high cetane values, their melting point is above low ambient temperature. See Table 10. Specialized pour point, cloud point and cold filter clogging tests generally require a reduction of heavier n-paraffinic compounds in medium distillates (usually by dewaxing) to improve cold flow and the operability of a diesel fuel. In addition, n-paraffins have a lower volumetric heating value (btu / gal) compared to aromatics.

Table 10 - Melting points of n-paraffin compounds C14 + n-Paraffins C9 to Point Point of Formula Cetane # C20 Boiling (° C) Melting (° C) N-NONANO C9H20 150 -48 72 N-DECANO C10H22 174 - 30 76 N-UNDECAN C11H24 196 -26 81 N-DODECAN C12H26 216 -10 87 N-TRIDECAN C13H28 235 -5 90 N-TETRADECAN C14H30 254 6 95 N-PENTADECAN C15H32 271 10 96 N-HEXADECANO C16H34 287 18 100 N-HEPTEC C17H36 302 22 105 N-OCTADECANO C18H38 316 28 106 N-NONADECANO C19H40 336 32 110 N-ICOSANO C20H42 344 36 110

[0144] Unlike gasoline for spark-ignited piston engines, which rely on high octane aromatics C7-C9 to delay early ignition, aromatics C10 to C20 provide diesel engines with thermal stability, heating value (btu / gallon) and desirable elastomer expansion characteristics. Unfortunately, these aromatics generally have low cetane values that can impede the effective performance of the diesel engine. The right balance of aromatic compounds vs. aliphatics will affect the performance characteristics of the diesel mixture. Refer to Table 11.

Table 11 - C10 Values of Aromatic Compounds C10 + Aroma Point Point C10 to C20 Boiling Formula Cetane # Fusion (° C) (° C) N-BUTYLENZENE C10H8 183 -88 6 1-METHYLNAPHTHALENE C11H10 245 -30 0 N-PENTILBENZENE C11H16 205 -75 8 N-HEXYLBENZENE C12H18 226 -61 19 N-HEPTYLBENZENE C13H20 246 -48 35 1-N-BUTYLNAPHTHALENE C14H16 289 -20 6 N-OCTYLBENZENE C14H22 264 -36 32 N-NONILEN C16H26 298 -14 N-UNDECYLBENZENE C17H28 313 -5 2-N-OCTYLNAPHTHALENE C18H24 352 -2 18 N-DODECYLBENZENE C18H30 328 3 68 N-TRIDECYLBENZENE C19H32 341 10 N-TETRADECILBENZEN34

[0145] Therefore, it is desirable to be able to produce diesel blends that contain mainly high cetane components (eg, C9-C16 + n-paraffins) with lower desired amounts of aromatics (eg, C9-C16), whose lower melting points help to increase the cold fluidity of the fuel.

[0146] Olefins are also a product of reactions R1 and R2 and play a key role in diesel fuel mixtures. The cetane values of C9 to C20 olefins are moderately high (above 50) and C9-C15 melting points tend to be cooler than room temperature, helping to improve cold fluidity, making them ideal compounds for diesel fuel.

Refer to Table 12.

Table 12 Point of Point of Olefin Compounds Formula Boiling Cetane # Fusion ° C ° C 1-NONENE C9H18 146.87 -81 51 1-DECENO C10H20 170.57 -66 56 1-UNDECENO C11H22 192.67 -49 65 1- DODECENO C12H24 213.36 -35 71 1-TRIDECENO C13H26 232.78 -13 1-TETRADECENO C14H28 251.10 -12 80 1-PENTADECENO C15H30 268.39 -3 1-HEXADECENO C16H32 284.87 4 86 1-HEPTADENO , 33 11 1-OCTADECENO C18H36 314,82 14 90 1-NONADECENO C19H38 329,10 23 1-EICOSENO C20H40 342,40 26

[0147] These variable fuel requirements and factors require flexibility in the composition of diesel fuels. In one aspect, the LG2F Process is adapted for the production of diesel blends. As used in this document, the term "diesel blend" refers to a formulation that comprises n-paraffins, iso-paraffins, cycloparaffins, olefins and aromatics with 9 to 24 carbons. Diesel blends preferably have 10 to 20 carbons, preferably have less than 35% by weight of aromatic hydrocarbons and, more preferably, less than 30% by weight. The following discussion further demonstrates the ability to adapt the LG2F Process depending on the C2-5 supply current and the desired diesel product (s).

[0148] This invention can be adapted by isolating the chemical reaction of LG2F R2 to convert raw materials rich in C2-C5 light olefins into any range of C9 to C24 + medium distillate hydrocarbons used in jet fuel / kerosene, heating oil, marine diesel and, ideally, for high value diesel fuel mix. When using olefin-rich raw materials from any source with the LG2F R2 reactor for the production of diesel fuel mixtures, the acid-based chemical reaction produces a broad spectrum of paraffin, iso-paraffin, cycloparaffin, olefin and outlet of aromatics in a normal (Gaussian) distribution. The distribution of the final product can be wide (for example, C9 to C24 +) or reduced (for example, C10 to C17), depending on the desired performance characteristics of the medium distillate mixture.

[0149] For example, one modality targets the yield of the LG2F product from R2 by setting the operating conditions to produce hydrocarbons up to the upper boiling limit of n-hexadecane, for example, 295 ° C and recycling all by-products in the flash drum with boiling points just above C9 n-nonane at, for example, 145 ° C. This will produce a very high cetane mixture with limited need for dewaxing. This can be a very useful premium diesel fuel mixture, particularly if processed in the absence of any sulfur contaminants (for example, using the optional C2-C5 light gas feeds from the I2FE long chain cracking process). Low carbon paraffins have low freezing points that improve the fluidity of the fuel in cold climates (pour point). Many other operating conditions of R2's LG2F can also be modified to optimize the performance characteristics of the fuel (eg cetane, pour point, density, heat of combustion, thermal stability, etc.) of the R2 product as a mixture in comparison with other possible mixture of medium distillate components. The LG2F reactions of R1 and R2 can be used together in a recycling cycle or independently, depending on the availability of the alkane or light alkane gas feed streams. Assessing the requirements of the average distilled product in relation to the quality of the available feed stream will determine the desired operating conditions and yields of the LG2F processing product. Table 8 describes the variable range of carbon numbers that would include n-paraffin, isoparaffins, cycloparaffins, olefins and aromatics found in the medium distilled fuel. Using operating conditions to select the upper boiling point and the lower boiling point directly impacts the resulting cetane values, melting point and fluidity attributes of the hydrocarbon mixture. Selecting 3 ranges of carbon numbers C9-C14 results in excellent flow characteristics at low temperature, 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 Paraffins, Olefins and Aromatics C9-20 Fluidity in Wide Mixture Carbon # low High Cethane Custom spectrum temperature 9 XX 10 XXX 11 XXX 12 XXXX 13 XXXX 14 XXXX 15 XXX 16 XXX 17 XX 18 XX 19 XX 20 XX 21 X 22 X 23 X

[0150] In one embodiment, the LG2F Process is adapted to produce a narrow range of high cetane paraffins from C9 to C14, with few low melting point compounds, thus minimizing any need for dewaxing.

This product is a desirable mixture of diesel fuel due to its starting speed, clean combustion and low temperature fluidity.

Examples - Diesel Blends

[0151] This same fully recycled LG2F Process can be operated under conditions to produce any target range (for example, C9 +) of hydrocarbons for use as medium distillate, marine fuel, aviation fuel or for diesel fuel mixtures. The thermal olefin reaction creates a spectrum of hydrocarbons rich in C2 to C5 olefins, and the acid-catalyzed chemical reactor uses operating conditions that favor the C9 to C24 + range of hydrocarbon compounds used in diesel fuel mixtures mainly through dimerization, trimerization, etc. of reacted C2-C5 olefin compounds. Selecting the C2 to C8 range of output molecules from the R2 catalytic reaction for aromatic recycling or reuse and defining the appropriate operating conditions (T, P, WHSV) allows a personalized result of medium distillate with high cetane and pour point values low, ideal for diesel fuel mixtures. The by-products of the reaction include methane, hydrogen and aromatic surplus.

[0152] In one embodiment, the supply current of R2 is composed of ≥ 60% m / m of ethylene and is subjected to a catalytic reaction of high pressure and low temperature just above the activation energy to allow additional thermodynamic control over the reaction. This modality uses an integrated cooling / dilution mechanism and / or a deactivating agent to minimize the exothermic reaction.

[0153] In one embodiment, the supply current of R2 is composed of ≥ 40% m / m of ethylene and ≥ 10% of propene and is subjected to a catalytic reaction of high pressure and low temperature just above the activation energy for allow additional thermodynamic control over the reaction. This modality uses an integrated cooling / dilution mechanism and / or a deactivating agent to minimize the exothermic reaction.

[0154] In one embodiment, the supply current of R2 is composed of ≥ 50% w / w of any C2 / C3 olefins and is subjected to a high pressure, low temperature catalytic reaction just above the activation energy to allow control additional thermodynamic effect on the reaction. This modality uses an integrated cooling / dilution mechanism and / or a deactivating agent to minimize the exothermic reaction.

[0155] In one embodiment, the supply current of R2 is composed of ≥ 50% w / w of any C3 / C4 olefins and is subjected to a high pressure, low temperature catalytic reaction just above the activation energy to allow control additional thermodynamic effect on the reaction. This modality uses an integrated cooling / dilution mechanism and / or a deactivating agent to minimize the exothermic reaction.

[0156] In one embodiment, the supply current of R2 is composed of ≥ 50% w / w of any C3-C5 olefins and is subjected to a high pressure, low temperature catalytic reaction just above the activation energy to allow control additional thermodynamic effect on the reaction. This modality uses an integrated cooling / dilution mechanism and / or a deactivating agent to minimize the exothermic reaction.

[0157] In all LG2F modalities, excess methane and hydrogen are by-products of the thermal olefin reaction. Since methane and hydrogen do not react to the LG2F process, there is no restriction on their presence in the feed stream of the light hydrocarbon gas.

[0158] The LG2F process will produce varying amounts of methane (for example, 5 to 20%) subject to operational and economic choices, which can be useful as a process fuel particularly in remote operating locations or returned for credit as dry gas for pipelines or refineries.

Depending on the quality of the raw material C2 +, the LG2F process offers the option of extracting excess methane and hydrogen through membrane separation.

The methane by-product can also be recycled through MTO to maximize the yields of the finished product for a given light gas supply stream.

[0159] H2 produced is highly desirable if reusable as a by-product, particularly in refining and petrochemical applications. If membrane separation is not feasible, then a purge stream of the same composition as the recycling cycle can be designed to prevent the accumulation of by-products.

Medium Distillates - R2L Low Pressure / High Pressure Catalytic Reaction

[0160] The LG2F catalytic reaction sequence can also be configured to combine a low pressure and high pressure reaction sequence to direct the conversion of light olefinic gases (eg C2-C5) from the thermal olefin reaction, to transform chemically into longer chain components through intermediate coupling of low molecular weight. This method of pressure control and conversion produces high-grade distillates used particularly in medium distillates, jet fuel and diesel fuel mixtures with added quality control, using a high pressure catalytic reaction sequentially after a low pressure catalytic reactor.

[0161] In such a modality, the thermal olefin reaction of R1 occurs after receiving C2 to C5 alkane-rich light gases at high temperatures (for example, above 700 ° C) operating at low pressure (for example, 0 to 200 psig) and producing a C2 + rich olefin in gas mixture. These gases are cooled and proceed to the initial R2 catalytic reactor, which operates at temperatures between about 200 to 500 ° C and low pressure (for example, 0 to 200 psig) to avoid the use of 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 R2's gas phase effluent.

[0162] A compressor is used downstream of R2 and the heat exchanger to compress the gas phase effluent into a phase separation flash drum, in which condensed liquids are captured, methane and hydrogen are separated or purged and the residual light gases C2-C4 + are recycled back to R1. The liquid phase of the R2 condensed effluent, which comprises C4 + hydrocarbons (suitable for grade Y gasoline), can additionally be pressurized by a pump operating from 100 to 1000+ psig for processing in another R2L oligomerization reactor. R2L operates at similar temperatures (for example, 150 to 300 ° C) and uses a zeolite catalyst that can be the same or different from that used in R2, but in a high pressure environment, resulting in a high concentration reaction. This high concentration reaction maximizes the formation of long chain molecules (for example, C8 + which are ideal for several medium distillates). The resulting R2L reactions produce an effluent that then undergoes vapor / liquid flash drum separation to remove C4 and lighter gaseous components to recycle back upstream from R2L and produces performance grade diesel fuel or C6- gasoline mixtures. Targeted C10. This low pressure / high pressure catalytic method provides a more controllable coupling of light olefinic gases to produce longer chain molecules, thus improving the adaptation of medium distillates, particularly those used in any target range of C9 to C16 + diesel fuel mixtures. or custom gasoline blends. See Figure 9.

[0163] Similar to the two reaction sequence (R1 and R2) described earlier, there is also an acceptable configuration for two oligomerization reactions of R2 (represented here as R2 and R2L) operating in series with a low and high pressure setting to increase molecular concentration thereby improving the longest chain reactions targeting fuels.

[0164] The feed stream of R1 is similarly composed of the indicated C2-C5 light alkane components that make the process productive. These alkanes are combined with light recycled alkanes that have not reacted 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 olefin reactor (R1). R1 has operating conditions similar to the previous modalities, where this high temperature reaction is conducted between 600 and 1100 ° C and 0 to 1500 psig. R1 products consist of thermally dehydrogenated alkenes that are suitable for the next iteration of reactions. The reactor outlet has heat integrated with E-100, as described during the heat exchange earlier. It is expected that the current will need to be further cooled after cross-switching before entering the catalytic oligomerization reactor (R2). The E-101 will further cool the chain to an operating temperature and pressure suitable for R2. R2 operates extensively to dimerize, trimerize and tetramerize the incoming olefinic components to produce a partially condensable current at high pressure.

[0165] The effluent from R2 is then combined with a recycling stream originating downstream in the final flash drum (D-101). There must be enough suction head on the C-100 to return the compressed gas from the downstream drum, otherwise additional compression may be required. The combined stream is then compressed to a pressure resulting in some initial liquefaction of C3 + components (200 to 1000 psig) which are then liquefied in a cooler (E-102). It should be appreciated that more heat integration can occur to preheat the feed to the first reactor more and more, as the temperature will increase noticeably after compression. A flash separator (D-100) is used to remove any light vaporous alkanes that can be further processed by R1. The light alkane stream that contains mainly ethane, propane, methane and hydrogen is fed into a compressor (C-101) to ensure a consistent stream through the recycling cycle. The C-101 may be unnecessary depending on the operating conditions and this high pressure gas may be of sufficient pressure to proceed through the circuit without assistance before being reduced with a valve. The outlet of the C-101 is routed to a separator (S-100) where it can be simply purged or passed through a membrane to remove methane and hydrogen by-products. After removing the dough, the first recycling cycle is then fed back upstream in the process.

[0166] The high pressure liquid of the D-100 is pumped (P-100) to very high pressure (> 1000 psig) as a liquid to mitigate the need for expensive very high pressure compression. This extremely high pressure liquid is fed into a third reactor (R2L) where the liquid is vaporized and then oligomerized into heavy molecular weight components. A pre-R2L heated expansion chamber may be required to ensure proper vaporization. The production of high molecular weight under this pressure will result in a largely condensed current downstream of the third reactor. This high molecular weight stream leaving the third reactor is then cooled in E-103, where it is then cooled / liquefied to a temperature that is suitable for vapor / liquid separation. D-101 separates the non-liquefied gases that may contain some mid-range olefinic components.

Regardless of the alkane / alkene composition, the tops of D-101 are fed upstream to be re-compressed, cooled and separated.

Any by-products recycled downstream that are C2 or less will consequently be recycled through the initial recycling cycle. Finally, a liquid stream is recovered from D-101 that resembles a product in the diesel or gasoline spectrum produced by means of a three-reactor pressure oscillation process for high-pressure, high-concentration oligomerization. In a related embodiment, a source comprising about 70% ethane gas can be processed in the R1 thermal olefin reactor to produce mainly ethylene, which is then processed into R2 at low pressure with a fast residence time to create dimers, trimers and tetramers of the olefin-rich diet. The light outgoing gases are then cleaved for recycling 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 can optionally serve as a finished product in this example with a higher value than ethane, or it can be further processed as a pressurized liquid in high concentration in the R2L reactor where the most stringent coupling occurs long.

The high molecular concentration in the liquid phase and the low residence time of the R2L reaction produce a premium quality distillate for use in diesel fuel mixtures or targeted gasoline mixtures. Unused R2L compounds are recycled based on targeted hydrocarbon cut points and moved upstream of the liquid / gas condenser and liquid pump. R2's unprocessed light gases are recycled back to R1 and methane and hydrogen are purged for reuse.

[0167] In a similar modality, a low value ethane / propane mixture is processed in R1 and the same options and characteristics of the invention result in C5 + (R2) gasoline and / or high performance distillate fuel mixtures (from R2L) that can be targeted to produce any range of fuel grade molecules, for example, C9 to C16 + for use in diesel fuel mixtures or targeted gasoline mixtures. In R2L processing for diesel fuel, the C8 and the lighter pressurized chain are recycled for reprocessing. The light compounds in R2 are recycled and the by-product methane and hydrogen are purged for reuse.

[0168] In another modality, two R2 reactors acting in series can be operated at the same pressure as the thermal olefin of R1 with intermediate separation of light gases. This will increase the concentration of hydrogen and methane in the gas stream to facilitate membrane separation or decrease the loss of purge yield. The by-products generated in the second catalytic reactor in R2 can then be recycled directly into R1 without removing non-reactive hydrogen and methane, since they will not be noticeable in the composition of the stream.

[0169] In an environmentally distinctive modification, a modification of the R2 gas phase reaction can be conducted as a high pressure liquid or supercritical phase reaction (> 500 psig) to further increase its concentration after that of the high pressure gas .

[0170] Configurationally, the LG2F system can also operate with multiple thermal olefin reactions from R1 and a single catalytic reaction from R2.

Increasing and decreasing the temperature from the first R1 to the second R1 will give a more selective control of the distribution of olefinic products and will also serve to limit the heavy coking of a single R1 reactor system.

[0171] Another modality is the LG2F process is a configuration of multi-stage R1 and catalytic reactions of multi-stage R2 with low / high pressure option to produce a more optimized distribution and product yield. These two-, three- and four-stage LG2F reactor designs incorporated in this document enable the interchangeable production of C4-C12 gasoline mixtures and / or C9-C16 + diesel fuel mixtures from alkane-rich light gases.

[0172] The LG2F process conditions are easily convertible into alternate processing methods, which offers a unique ability to adjust the production of the main transport fuels, depending on changing market conditions. A particular feature of the LG2F process is the option to produce gasoline mixtures under a set of operating conditions and / or alternate to produce mixtures of medium distillate under a different set of reactor operating conditions (R2). Depending on the availability of downstream processing often available in refining plants, the process changeover time can be adjusted using separate cuts to eliminate the need for any distillation of the mixtures.

[0173] In one embodiment, the process is exclusively designed to produce mixtures of medium distillate grade products with a high cetane value and liquid heat. In a different modality, the process is designed exclusively to produce high octane gasoline blends. In yet another modality, the process is defined to produce high octane gasoline blends during one period, then exchanged and reconfigured to produce intermediate distillate blends in another period. In yet another embodiment, the process is defined to produce a full spectrum of, for example, C5 + or C6 + or C7 + fuel products that can be distilled downstream for different commercial uses. Again, the preferred end product of the reaction (for example, the target performance requirements of a fuel mixture) may have a determining factor in the ideal operating conditions (T, P, WHSV) and choice of the R2 catalyst.

[0174] While the diesel fuel mixtures described as the LG2F products in this invention may be composed of several chemical compounds, targeted performance grade diesel fuels can be adapted by the power characteristics, catalyst choices and operating conditions to achieve a minimum set of performance conditions for grade diesel products.

[0175] In one embodiment, the diesel fuel product is ≥ 40 cetane number, with aromatic content ≤ 35% m / m, satisfactory cloud point and fluidity in cold temperature, lubricity ≤ 520 microns at 60 ° C and temperature of distillation ≤ 338 ° C at 90% point.

[0176] In one embodiment, the diesel fuel product is ≥ 50 cetane number, with aromatic content ≤ 35% m / m, satisfactory cloud point and fluidity in cold temperature, lubricity ≤ 520 microns at 60 ° C and temperature distillation ≤ 338 ° C at 90% point.

[0177] In one embodiment, the diesel fuel product is ≥ 55 cetane number, with aromatic content ≤ 35% m / m, satisfactory cloud point and fluidity in cold temperature, lubricity ≤ 520 microns at 60 ° C and temperature of distillation ≤ 338 ° C at 90% point.

[0178] Another distinguishing feature of the LG2F process is that the composition and performance characteristics of C9 + distilled products do not require a hydrogenation step. However, some custom fuel applications may favor a more paraffinic composition, in which case a hydrogenation reaction is included as an optional modality.

[0179] The LG2F process also offers a wide range of modular configurations (for example, to eliminate benzene or increase octane or increase energy density or increase liquid heat of combustion or reduce vapor pressure) when processing gases lightweight C2 to C5, which allows adaptation of the operation conditions that result in a specified composition of gasoline mixture. In one embodiment, the LG2F reaction of R1 + R2 with recycling is specified to produce only aliphatic and aromatic C7 to C10 hydrocarbons between the boiling point range of 85 ° (above benzene) to 200 ° C. This results in a well-balanced, high-octane gasoline blend without benzene. In another embodiment, the LG2F reactions of R1 + R2 with recycling are specified to produce aliphatic C5 to C10 (favoring paraffins and olefins) with virtually no aromatics. This results in a lower octane mix, but with higher volumetric yields. In another embodiment, the LG2F reaction of R1 + R2 is specified to produce mainly high octane aromatics C7 to C10 with only a small content of aliphatic hydrocarbons. This results in a mixture of high-octane gasoline, in the absence of benzene, and a high energy density.

[0180] This modular functionality in the design of customized hydrocarbon product streams from C2-C5 light gas streams is a major feature of this invention. This adaptation can be applied to adjust to constantly changing market conditions and opportunities for location arbitrage. The LG2F reactors of R1 and R2 can operate independently or integrated. Any available source of olefins can be used in the R2 reaction, since the composition of the raw material is evaluated for the ideal temperature, pressure and reaction time for a given product specification. The high (final) boiling point of the product is specified by the operating conditions of R2 and the low (initial) boiling point of the product is defined by the flash drum cut-off point which eliminates any need for distillation.

I2FE and LG2F Combined

[0181] Another aspect of the LG2F Process is the ability to combine the process with another process that provides a source of C2-5 hydrocarbons useful as feed for the LG2F Process. This other process is described in a co-pending application, Serial No. US 16 / 242,465, also owned by the Claimant. This other process is known as the Fuel Economy Increase or “I2FE” process. This combined process is shown in Figure 10.

[0182] The I2FE process can be designed to consume a small amount of hydrogen to maintain the longevity of the metal catalyst.

Depending on the project settings, the LG2F hydrogen by-product can compensate for the intentional hydrogen consumed in the I2FE, if these two processes are used together. The design of both units can be balanced and optimized to be natural hydrogen or a liquid hydrogen producer, depending on the needs of the commercial operation.

[0183] In this combined modality, the LG2F Process converts clean light gas compounds (C2 +) specifically from the I2FE process to produce C6 + mixtures using thermal olefin (R1) followed by multi-iterative, acid-catalyzed cracking reactions, oligomerization and / or cyclization (R2) in a single or multiple bed reactor configuration with a recycling cycle. In one embodiment, for example, the process is used to produce any range from C9 to C24 +, zero-sulfur, medium distillate compounds with effective performance properties for use in diesel fuel and other transport fuel mixtures. The same process can be carried out aiming at a narrower range of medium distillate compounds, such as C10-C20, or C12-C18 or C9-C14, etc., depending on the performance requirements of the finished product. A by-product of this process, depending on the configuration, is unused hydrogen, methane and surplus aromatics.

[0184] Another embodiment of this LG2F invention converts clean light gas compounds (C2 +) specifically from the I2FE process, with or without residual reformer gases, to produce mixtures of the gasoline range using only thermal olefin and an oligomerization catalyzed by multi-iterative acid, cyclization and cracking reaction in a single or multiple bed reactor configuration with a recycling cycle. This process is designed to handle excess hydrogen to produce any gasoline compound in the C4 to C12 range

(ie paraffins, olefins and aromatics) for use with other gasoline blends.

All gasoline products in this modality are very low in benzene, without sulfur and without nitrogen. A by-product of this process, depending on the configuration, is unused hydrogen, methane and surplus aromatics.

[0185] Another embodiment of this LG2F invention converts clean light gas compounds (C2 +) specifically from the I2FE process to produce mixtures of the gasoline range using thermal cracking (R1) and multi-iterative acid catalyzed (R2) reactions into a single bed or multiple configuration reactor together with a recycling circuit. This process is designed without excess hydrogen to produce gasoline compounds in the C4 to C12 range (ie paraffins, olefins and aromatics) for use with other gasoline blends. All gasoline products in this modality are free of sulfur and nitrogen.

Alternatively, this process is designed to provide excess hydrogen for reuse. Depending on the configuration, methane and excess aromatics can be by-products of the reaction.

Direct Alkene Feeds

[0186] The LG2F process is also useful with other sources of C2-C5 alkenes processed in the catalytic reactor (R2). For example, gasoline by-products cracked by the FCC, including C3 and LPG alkenes, can be used as raw materials directly in the LG2F Process catalytic reactor. Another source comes from any methane activation process, such as oxidative methane coupling, or methane pyrolysis and acetylene hydrogenation, or any other technique known in the art to produce ethylene from methane. The presence of> 50% of alkenes in the light hydrocarbon feedstock allows the first use of the acid-catalyzed chemical reaction in the LG2F process.

[0187] With reference to Figure 11, the basic LG2F Process is shown.

However, the Process is increased by having the C2-5 alkene fed first into the R2 catalytic reactor, bypassing the thermal olefin reactor and going straight to the multi-iterative acid catalyzed reactions in a single or multiple bed reactor configuration. recycling cycle. This feed stream is processed as previously described to produce C6 + fuel grade mix stocks. The light gases from the catalytic process (often containing C3 + olefinic compounds, for example, propylene) are then sent to reactor R1 to proceed through the system as previously described, thus producing additional mixtures of the gasoline range. This process is designed to supply excess hydrogen to produce gasoline compounds in the range of C6 to C11 (ie paraffins, olefins and aromatics) for use with other gasoline mixtures. All gasoline products in this modality are very low in benzene, without sulfur and without nitrogen. A by-product of this process is unused hydrogen.

[0188] As an illustration of the processing of alkene gases, a single pass yield of the chemical reaction based on C2 + acid, shown in Figure 12, is a C3 olefin feedstock and demonstrates the production of gasoline grade compounds . This reaction was done at 45 psig and 3 WHSV over a temperature range. As illustrated, the aromatic hydrocarbon content (A6 +) varied with the reaction temperature, which can be used to increase the octane values of gasoline mixtures.

[0189] Another embodiment of this LG2F invention receives light by-product gases from the catalytic cracking process (often containing olefinic C3 + compounds, for example, propylene) to produce diesel fuel mixtures. This mode again ignores the initial thermal olefin and goes straight to acid-catalyzed multi-iterative reactions in a single-bed or multi-bed reactor configuration with an R2 catalyst adapted to the feed stream before entering the cycle again recycling

LG2F. This process is designed to supply excess hydrogen and produce any specified range of C4 to C12 gasoline mixtures or C9 to C24 intermediate distillates for use as diesel fuel mixtures. A by-product of this process is unused hydrogen.

[0190] The foregoing processes are examples of a variety of processes using alkene feeds, including the following:  C2 + alkene gas streams leaving the catalytic cracking unit are transformed into constituents of C6 + gasoline first through the reaction LG2F (R2) chemistry, followed by a recycling cycle that restarts thermal olefin and a chemical reaction cycle resulting in higher yields of liquid gasoline;  C2 + light hydrocarbon chains with mainly olefinic compounds are combined to increase the available volume of light gas compounds for conversion through R2 processing with recycling cycles to R1 + R2 to produce gasoline mixtures using the LG2F process;  C2 + light hydrocarbon chains with mainly olefinic compounds are combined to increase the available volume of light gas compounds for conversion to light diesel or diesel fuel mixtures using LG2F.

Reducing Benzene

[0191] Another key feature of this transformation of light gas into transport fuel is the selective reduction of benzene, which makes the resulting products excellent for mixing gasoline due to the low specification limits imposed on benzene for use in fuels. In the event that there is an unwanted excess of C6 + aromatics rich in benzene extracted by extracting liquid vapor from the thermal olefin effluent of R1, an additional feature of LG2F is to combine light alkene compounds (eg C2-C3) from the R1 reaction with the excess C6 + aromatic compounds in a simple reaction catalyzed by low temperature acid to create alkyl benzenes. See Figure 13. This processing will convert benzene through electrophilic substitution into productive grade gasoline mixtures that adhere to existing limitations in gasoline specifications for high-octane aromatics. This process can use aluminum chloride and hydrogen chloride catalysts.

This process will further increase the value of the gasoline mixture.

Dewaxing

[0192] Another aspect of this invention is a simplified method for dewaxing paraffinic compounds from C14 to C40 hydrocarbon streams using a low-gravity, acid-catalyzed reaction process, both for hydrocracking and for hydrotreating raw materials from medium to heavy grade distillates to produce a high value, high grade medium distillate with superior fuel performance properties.

[0193] Catalytic dewaxing is commonly referred to as a process that selectively removes C14 + paraffinic compounds from hydrocarbon streams of medium to heavy distillates. This technology is generally applied to hydrocarbons used in diesel oil and heating oils to improve their physical properties, including cloud point, pour point and cold pour point. The increase in quality reduces the need to use fuel additives to improve properties and allows for more detailed control of mixing specifications. The main alternative technology for catalytic dewaxing is solvent-based dewaxing, which applies a solvent extraction method to heavy paraffinic compounds that preserve the chemical structure.

[0194] The configurations of traditional dewaxing units vary, but in most cases they are categorized into two categories: a single or double bed reactor. The choice of configuration depends on the preference for the integration of hydrotreatment in the dewaxing catalytic system. Inlet streams have higher concentrations of sulfur and nitrogen, which deactivate noble metal catalysts. Thus, a hydrotreating bed is normally integrated before the dewaxing catalyst to ensure minimal performance degradation.

Traditional Dewaxing Methods

[0195] Traditional refinery dewaxing catalysts are selective zeolites based on nickel or platinum, which is a molecular sieve catalyst. By controlling the size of the pores, these methods control the types of molecules that enter catalytically active sites. Specifically, the pore sizes are adjusted to allow for non-paraffinic compounds, but not isoparaffinic compounds (0.6 nm). Traditional hydrotreating catalysts generally use the Ni / Mo metal combination to perform the hydrogenation of nitrogen and sulfur-based compounds. The configuration of these catalysts depends on the level of protection required in a dewaxing unit.

However, if poisons are a problem, a separate hydrotreating bed will be beneficial for the long life of the catalyst. A comparison between typical single and double bed catalysts is shown in Table 14.

Table 14 Product Distribution (% Single Stage (SDD-800) Second Stage (SDD-821) by weight) C1-C4 4.3 0.2 C5-177 ° C 9.2 5.9 177 ° C + 86.7 94.5 Total 100.2 100.6

[0196] Traditional dewaxing methods require a separation between two catalytic beds, one performing hydrotreating and the other by selectively breaking n-paraffinic compounds. Noble metal catalysts pose a very high risk of poisoning by hydrogen sulfide and ammonia, hence the removal of these gases before dewaxing. However, base metal catalysts lack the activity required to effectively unscrew a hydrocarbon stream and require higher utility costs.

[0197] This invention uses a unique low-gravity method to hydrocrack C14- to C40 + paraffins or any target range of n-paraffin compounds using a specialized zeolite catalyst with the ability to simultaneously hydrate the feed stream, thereby removing sulfur and nitrogen-based compounds and break down low-melting paraffins in a single step process. This unique method reduces total processing costs and eliminates the need for additives used in the field. The main objective is to crack wide-range n-paraffinic compounds, since even n-tetradecane (C14) melts above low ambient temperatures.

Even having a single branch significantly reduces the melting point by ~ 80 F, although it still has a cetane value of 67.

[0198] Although the invention has been illustrated and described in detail in the drawings and in the previous description, it should be considered as illustrative and not restrictive in character, it being understood that only the preferred modality was shown and described and that all changes, equivalent, and modifications that come within the spirit of the inventions defined by the following claims must be protected.

Claims (10)

1. Two-stage process for converting C2-5 alkanes into a wide range of combustible products constituting higher value C5-24 + hydrocarbon fuels or fuel mixtures, FEATURED by the fact that it comprises: distributing a C2 alkane feed stream -5 in a thermal olefin reactor, the C2-5 alkane feed stream containing at least 90% by weight of feed alkanes having two to five carbons, the thermal olefin reactor operating at a temperature, pressure and space speed to convert at least 80% of the feed alkanes to product olefins into a product olefin stream, without using a dehydrogenation catalyst and without using steam; distributing at least a portion of the product olefin stream to an oligomerization reactor containing a functional zeolite catalyst to break, oligomerize and cyclize the product olefins to form the combustible products; and recover fuel products. 2. Method, according to claim 1, and CHARACTERIZED by the fact that it comprises converting the product olefins to form a mixture of C4-12 hydrocarbon to gasoline. 3. Method according to claim 1, and CHARACTERIZED by the fact that it comprises converting the product olefins to form a mixture of C9-24 + hydrocarbon for diesel fuel. 4. Method according to claim 1, and CHARACTERIZED by the fact that it includes removing hydrogen and methane from the product olefin stream before distributing the product olefin stream to the oligomerization reactor. 5. Method according to claim 1, and CHARACTERIZED by the fact that it includes removing C2-5 alkanes from the product olefin stream before distributing the product olefin stream to the oligomerization reactor. 6. Method according to claim 1, CHARACTERIZED by the fact that the C2-5 alkane feed stream includes less than 2% of alkenes and alkynes. 7. Method according to claim 1, CHARACTERIZED by the fact that the C2-5 alkane feed stream comprises 80 to 100% ethane and 0 to 20% propane. 8. Method according to claim 1, CHARACTERIZED by the fact that the C2-5 alkane feed stream comprises 100% ethane. 9. Method, according to claim 1, CHARACTERIZED by the fact that the oligomerization reactor operates without olefin hydrogenation. 10. Method for converting C2-5 alkanes into a feed stream in a range of C5-24 + fuel products, FEATURED by the fact that it comprises: olefining the alkanes in a feed stream rich in alkane in a thermal olefin reactor at an operable temperature, pressure and spatial speed to convert at least 80% of the alkanes to product olefins without the use of a dehydrogenation catalyst and without the use of steam, the alkane-rich feed stream containing at least 90% by weight of feeding alkanes having from two to five carbons; converting product olefins into combustible products by contacting product olefins with a zeolite catalyst in an oligomerization reactor at a temperature, pressure and spatial speed operable to break, oligomerize and cyclize product olefins to form; and recover fuel products. Hydrogen / Methane Purge (Reuse) Petition 870200157331, of 12/15/2020, p. 79/95 LG2F Process C2 Recycling Gas Separation + Yield from Rich Sources R1: R2: Catalyzed Acid Cooling Product in Olefination Alkane Σ (Oligomerize & Grade 1/17 Light C2 Gas + Thermal Cracking) I2FE Fuel / Reform Mixture Gasoline C4-C12 Cracking Processes OR Fractionation Diesel Blend C9-C24 Gas Processing LPG Processing Oil & Gas Extraction SUBSTITUTE SHEET (REGULATION 26) Propylene Ethane Methane Ethane SUBSTITUTE SHEET (REGULATION 26) SUBSTITUTE SHEET (REGULATION 26) Membrane Separation or LG2F Purgo Flash Drum - Example of Process Steps Extraction SUBSTITUTE SHEET (REGULATION 26) Non-Aromatic Product Distribution as a Function of Spatial Speed Arrows indicate the direction of speed Petition 870200157331, of 12/15/2020, p. 83/95 increased space Selectivity (%) 5/17 SUBSTITUTE SHEET (REGULATION 26) Non-Aromatic Carbon Number Impact of Selectivity of 30% mol / mol of Ethylene for Aliphatics at 0.75 WHSV & 0 PSIG in Variation Temperature Petition 870200157331, of 12/15/2020, p. 84/95 Selectivity (%) 6/17 SUBSTITUTE SHEET (REGULATION 26) Carbon Number Impact of Product Distribution as a Function of Spatial Speed Arrows indicate the direction of increased space speed Petition 870200157331, of 12/15/2020, p. 85/95 Selectivity (%) 7/17 SUBSTITUTE SHEET (REGULATION 26) Aromatic Carbon Number Impact of Selectivity of 30% mol / mol of Ethylene for Aliphatics at 0.75 WHSV & 0 PSIG in Variation Temperature Petition 870200157331, of 12/15/2020, p. 86/95 Selectivity (%) 8/17 Carbon Number SUBSTITUTE SHEET (REGULATION 26) Impact of aromatic n-paraffin iso-paraffin cycloparaffins Average Jet A Carbon Number % in large scale SUBSTITUTE SHEET (REGULATION 26) Typical Carbon Distribution - Diesel Fuel n-Paraffins, Iso-paraffins, Cycloparaffins, Aromatics Petition 870200157331, of 12/15/2020, p. 88/95% by Mass 10/17 Carbon # SUBSTITUTE SHEET (REGULATION 26) Purge H2 and CH4 Light Non-Reagent Gases Petition 870200157331, of 12/15/2020, p. 89/95 Recycle target cutoff Light Alkanes C2-C5 11/17 C3 + Liquids * Diesel Blend SUBSTITUTE SHEET (REGULATION 26) Rich in C2 + Alkane OR * Alternative Gasoline Blend Gasoline Blend I2FE & LG2F Combined R1: Thermal Olefination R2: Acid based: Petition 870200157331, 12/15/2020, p. 90/95 Feed Σ (Oligomerize & Crack) Reformed Thermal Slit Flow Separation Optional Light Gas Cracking Reaction C2 + Cool Low Severity Paraffin I2FE Optional: Hydrogen Yield Feed 12/17 Grade Liquid Product Fuel Gasoline Blend C4-C12 OR C9-C24 Diesel Blend SUBSTITUTE SHEET (REGULATION 26) Hydrogen / Methane Purge (Reuse) LG2F Process Petition 870200157331, 12/15/2020, p. 91/95 Separation Recycle C2 + R2-Alkane Gas: Catalyzed acid Yield of R1: Mixture Product Olefination Σ (Oligomerize & Cool Thermal Crack) of C6 Fuel Grade + C4-C12 Gasoline Mixture Alkenes OR 13/17 Light Gases C2 + Mixture of Diesel C9-C24 Cracking Any Source of Olefin Product of MTO SUBSTITUTE SHEET (REGULATION 26) Propylene Oligomerization at 45 PSIG & 3 WHSV Temperature (ºC) Hydrocarbon Light grandchildren Performance (%) SUBSTITUTE SHEET (REGULATION 26) Benzene Elimination Process - LG2F Petition 870200157331, of 12/15/2020, p. 93/95 Alken Feed Low Alkylbenzene Aroma Reaction Temperature 15/17 Food C7 + Benzene Gasoline Blends SUBSTITUTE SHEET (REGULATION 26)