Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
  • C10G57/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with polymerisation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/20—Organic compounds not containing metal atoms
  • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
  • C10G57/005—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with alkylation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1088—Olefins
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1096—Aromatics or polyaromatics
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/301—Boiling range
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/307—Cetane number, cetane index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/02—Gasoline
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/04—Diesel oil
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/08—Jet fuel

Definitions

• the present invention relates to processes and systems that provide for the conversion of olefins to diesel and/or other distillate products.
• Light olefins are produced in typical hydrocarbon refining operations that also produce mogas and distillate products. There is a desire to obtain higher amounts of mogas and diesel end products per unit volume of crude oil extracted upstream. To supplement obtaining diesel from newly-extracted crude oil, and to meet the rising demand for diesel and other distillates, it is desirable to make use of light olefins to yield additional diesel and other distillate products.
• One aspect of the present invention provides a process for producing a hydrocarbon fuel composition that includes introducing an olefin feed composition including light olefins (e.g., C 2 to C 6 olefins) to an oligomerization catalyst to yield an intermediate composition including olefins having at least four carbon atoms, introducing the intermediate composition and a second feed of aromatic compounds (e.g., a feed containing from 2 to 99.9% alkylatable aromatics) to an aromatic alkylation catalyst to yield a hydrocarbon fuel composition.
• an olefin feed composition including light olefins e.g., C 2 to C 6 olefins
• an oligomerization catalyst e.g., C 2 to C 6 olefins
• Another aspect of the present invention provides a system for producing a hydrocarbon fuel composition that includes an olefin feed including light olefins (e.g., C 2 to C 6 olefins), a first reaction vessel containing an oligomerization catalyst in fluid communication with the first feed to yield an intermediate composition including olefins having at least four carbon atoms, a second reaction vessel containing an aromatic alkylation catalyst in fluid communication with a second feed of aromatic compounds and the intermediate composition to yield a hydrocarbon fuel composition, and a collection assembly in fluid communication with the second reaction vessel to recover the hydrocarbon fuel composition from the stream exiting the reaction vessel containing the aromatic alkylation catalyst.
• an olefin feed including light olefins (e.g., C 2 to C 6 olefins)
• a first reaction vessel containing an oligomerization catalyst in fluid communication with the first feed to yield an intermediate composition including olefins having at least four carbon atoms
• Figure 1 is a conceptual process flow diagram demonstrating conversion of a C 2 -C 6 olefin feed to a diesel and gasoline fuel composition, and a C 2 -C 6 paraffmic composition.
• Figure 2 is a conceptual process flow diagram depicting reformate alkylation within a diesel reactor system.
• Figure 3 is a conceptual process flow diagram for a FCC naptha and scanfmate alkylation process in accordance with a single feed embodiment of the present invention.
• Figure 4 is a plot demonstrating the conversion of benzene, 1-hexene and toluene as described in Example 1.
• Figure 5 is a plot based on the GC analysis of the feed and product, as described in Example 1.
• Figure 6 depicts an ASTM D86 test method analysis of the aromatic feed and alkylated product after reaction with hexene, as described in
• Figure 7 depicts an ASTM D86 test method analysis of an alkylated product after reaction with propylene and an alkylated aromatic product after reaction with hexane.
• Figure 8 is a second GC analysis of the feed and product of
• the term "produced in an industrial scale” refers to a production scheme in which gasoline and/or distillate end products are produced on a continuous basis (with the exception of necessary outages for plant maintenance) over an extended period of time (e.g., over at least a week, or a month, or a year) with the expectation of generating revenues from the sale or distribution of the gas and/or distillate.
• Production at an industrial scale is distinguished from laboratory or pilot plant settings which are typically maintained only for the limited period of the experiment or investigation, and are conducted for research purposes and not with the expectation of generating revenue from the sale or distribution of the gasoline or distillate produced thereby.
• gasoline boiling range components refers to a composition containing at least predominantly C 5 -Ci 2 hydrocarbons.
• gasoline or gasoline boiling range components is further defined to refer to a composition containing at least predominantly C 5 -Ci 2 hydrocarbons and further having a boiling range of from about 100°F to about 360°F.
• gasoline or gasoline boiling range components is defined to refer to a composition containing at least predominantly C 5 -Ci 2 hydrocarbons, having a boiling range of from about 100°F to about 360°F, and further defined to meet ASTM standard [0018]
• distillate or distillate boiling range components refers to a composition containing predominately Cio-C 40 hydrocarbons.
• distillate or distillate boiling range components is further defined to refer to a composition containing at least predominately Ci 0 -C 4 o hydrocarbons and further having a boiling range of from about 300°F to about 1 100°F. Examples of distillates or distillate boiling range components include, but are not limited to, naphtha, jet fuel, diesel, kerosene, aviation gas, fuel oil, and blends thereof.
• diesel refers to middle distillate fuels containing at least predominantly Ci 2 -C 2 5 hydrocarbons.
• diesel is further defined to refer to a composition containing at least predominantly Ci 2 -C 25 hydrocarbons, and further having a boiling range of from about 330°F to about 700°F.
• diesel is as defined above to refer to a composition containing at least predominantly Ci 2 -C 25 hydrocarbons, having a boiling range of from about 330°F to about 700°F, and further defined to meet ASTM standard D975.
• the cetane value for the recovered diesel can vary.
• the recovered diesel has a cetane number of at least 35, or alternatively has a cetane value of at least 40, or still alternatively has a cetane value of at least 45.
• a feed is rich in a certain component if it contains at least 50 wt% of that component. In certain embodiments, a feed is rich in a certain component contains at least 75 wt%, or at least 90 wt%, at least 95 wt% or at least 99 wt% of that component.
• a SPA-type catalyst refers to a catalyst which contains as one of its principal raw ingredients an acid of phosphorus such as ortho-, pyro- or tetraphosphoric acid.
• a MWW-type catalyst is a catalyst having the MWW framework topology, as classified by the Structure Commission of the
• alkylatable aromatics refers to aromatic compounds that can be alkylated under suitable alkylation conditions. While benzene is the prototypical alkylatable aromatic, it is understood that alkylatable aromatics can also include - in addition to benzene - toluene, xylenes and lower alkyl benzenes (e.g., ethylbenzene). It should also be understood that reference to benzene in this application in the context of alkylation reactions also encompasses other alkylatable aromatics in addition to benzene, such as those compounds described above.
• One aspect of the present invention provides a process for producing a hydrocarbon fuel composition (e.g., diesel or other distillate) that includes introducing an olefin feed composition including light olefins (e.g., a
• composition containing C 2 to C 6 olefins) to an oligomerization catalyst e.g., a MCM-22, ZSM-22 or ZSM-57 catalyst
• an intermediate composition including olefins having at least four carbon atoms e.g., a composition that includes at least 1 wt%, or at least 5 wt%, or at least 10 wt%, or at least 25 wt%, or at least 50 wt% C 5 -Ci 6 olefin oligomers
• aromatic compounds e.g., a feed including from 2 to 99.9% of alkylatable aromatics
• aromatic alkylation catalyst e.g., a MCM-22 type catalyst
• the olefin feed composition can be obtained utilizing existing process streams within a hydrocarbon refining plant, from chemical grade olefin sources, or a mixture thereof.
• the olefin feed composition is obtained from fuel gas, chemical grade propylene, refinery grade propylene, polymer grade propylene, liquefied petroleum gas (LPG), light cracked naptha (LCN) process streams, scafmate (hydroprocessed LCN) process streams, de- hydrogenated LVN process streams (light virgin naptha), and butylene or butylene-containing process streams (e.g., an alkylation feed).
• the olefin feed composition is obtained from a FCC coking operation, such as a FCC off-gas or coker off-gas stream, or from a steam cracking operation.
• the olefin oligomer content in the intermediate stream can vary depending on the olefin content in the olefin feed stream, which in turn may vary depending on the source of the olefin feed stream. While the intermediate stream in some embodiments of the presently disclosed subject matter contains at least 50wt% olefins oligomers (e.g., at least 50 wt% C 5 -Ci 6 olefin oligomers), other embodiments that employ a more dilute olefin feed stream will provide an intermediate with a lower concentration of olefins oligomers (e.g., at least 5 wt%, or at leastlO wt%, or at least 25 wt% C 5 -Ci 6 olefin oligomers).
• the feed of aromatic compounds can be obtained from existing process streams within a hydrocarbon refining plant. In one
• the aromatic compounds are obtained from light reformate, a benzene heart-cut reformate, heavy reformate, full reformate or catalytic cracked naptha (cat naphtha), virgin naptha, or hydrocracked naptha process streams.
• the oligomerization catalyst can be a solid phosphoric acid (SPA) catalyst, a MWW type catalysts or a ZSM-type catalyst.
• the oligomerization catalyst can be selected from, for example, a MCM-22 catalyst, a ZSM-22 catalyst or a ZSM-57 catalyst, or a combination thereof.
• the aromatic catalyst is a MCM-22 catalyst.
• Other solid acid catalysts can be employed and optimized to provide desired product properties.
• the oligomerization catalyst can be contained in a reaction vessel.
• the reaction vessel containing the oligomerization catalyst is a fixed bed reaction vessel.
• the fixed bed reaction vessel can be of a chamber design or a tubular design.
• the reaction vessel containing the oligomerization catalyst is maintained at a pressure of from about 200 psig to about 1500 psig and/or at a temperature of from about 100°F to about 600 °F.
• the aromatic alkylation catalyst can also be contained in a reaction vessel.
• the vessel containing the aromatic alkylation catalyst is a fixed bed reaction vessel.
• the fixed bed reaction vessel can be of a chamber design or a tubular design.
• the vessel containing the aromatic alkylation catalyst is maintained at a pressure from about 50 or 100 psig to about 1000 or 1500 psig and at a temperature of from about 80 or 100°F to about 600 °F.
• Another aspect of the present invention provides a system for producing a hydrocarbon fuel composition that includes an olefin feed including C 2 to C 6 olefins, a first reaction vessel containing an oligomerization catalyst in fluid communication with the olefin feed to yield an intermediate composition including olefins having at least four carbon atoms, a second reaction vessel containing an aromatic alkylation catalyst in fluid communication with a second feed of aromatic compounds and the intermediate composition to yield a hydrocarbon fuel composition, and a collection assembly in fluid communication with the second reaction vessel to recover the hydrocarbon fuel composition from the stream exiting the reaction vessel containing the aromatic alkylation catalyst.
• An exemplary process flow diagram (100) is shown in Figure 1.
• An olefin feed composition (101) containing C 2 to C 6 olefins is introduced to an oligomerization reaction zone (102), which can include an oligomerization catalyst housed in a reaction vessel (e.g., a fixed bed reactor containing an oligomerization catalyst).
• a reaction vessel e.g., a fixed bed reactor containing an oligomerization catalyst.
• the olefin feed composition can also contain paraffins, hydrogen, and/or other inert compounds.
• an intermediate composition (103), containing C 9 -Ci 6 olefins is combined with a benzene containing feed (104), and the combined stream is introduced to an benzyl (or aromatic) reaction zone (105), which can include an aromatic alkylation catalyst housed in a reaction vessel (e.g., a fixed bed reaction vessel).
• the product (106) of the benzyl (or aromatic) reaction zone is then introduced to a fractionation operation (107), in which a C 2 -C 6 paraffmic composition (108), a gasoline boiling range material (109) and a diesel boiling range material (110) is provided as end products.
• the fractionation operation can include fractionation columns or stills, which can be operated under reaction conditions known to those of ordinary skill in the art.
• FIG. 2 provides another exemplary embodiment of the present invention, in which a conceptual process configuration (200) is shown which produces diesel end-product with a cetane rating of 45-55+.
• a feed (201) is provided which can be rich in C 3 olefins, or rich in C 4 olefins, or alternatively can contain a mixture of C 3 and C 4 olefins.
• the feed is introduced to a fixed bed reaction vessel (202) containing an oligomerization catalyst.
• the vessel (202) is maintained a temperature of about 150-200°C and a pressure of about 500 to about 1200 psig.
• the LHSV is from about 0.1 to lOhr "1 , preferably about 1 hr -1 , based on the total amount of olefin feed.
• the oligomerized olefin stream exiting the reaction vessel (202) is combined with a reformate stream or feed (203) of benzene, toluene, and xylenes, and the combined stream (204) is introduced to fixed bed reaction vessel (205) containing a aromatic alkylation catalyst.
• the vessel (205) is maintained at a temperature of about 200°C and a pressure of from about 250 psig to about 500 psig.
• the LHSV is about 1 hr "1 , based on the amount of olefin feed.
• the product (206) leaving the reaction vessel will contain alkylated aromatic compounds that can be recovered to obtain a diesel fuel composition with a cetane rating of 45-55+.
• the end product can contain n-nonylbenzene and/or n-dodecylbenzene, which have cetane ratings of 49-51 and 55-68 respectively. It is expected that different product isomers will be formed having a range of cetane numbers.
• the heat generated by reaction vessels (202) and (205) can be managed by interstage cooling or by recycle streams. Reaction vessels 202 and 205 can exist as two physical reactors, or alternatively they can be combined into a single vessel.
• Olefin feeds containing rich in near linear olefins with a minimum of five carbon atoms are, in certain embodiments, preferred in order to provide a diesel fuel composition with higher cetane ratings.
• Benzene rings with an n- alkyl substituent from 6 to 9 carbon atoms have a cetane rating between about 40 and 50.
• an olefin feed composition is introduced to an oligomerization catalyst to provide an intermediate composition that includes oligomerized olefins.
• the oligomerization catalyst will be contained within a vessel (e.g., a reactor), which is referred to herein as the first reaction vessel.
• a vessel e.g., a reactor
• the first reaction vessel e.g., a reactor
• a person of ordinary skill in the art can determine the proper reaction conditions, and thus the proper conditions for the first reaction vessel, in order to convert a feed containing, for example, C 2 -C 6 olefins to yield an intermediate composition containing at least four carbon atoms (e.g., a composition containing C4-C16 olefins).
• the vessel containing the oligomerization catalyst (i.e. the first reaction vessel) is maintained at a temperature ranging from about 100°F to about 600°F more preferably from about 200 to 400°F. In certain embodiments, the vessel containing the oligomerization catalyst is maintained at a pressure ranging from about 200 psig to about 1500 psig, more preferably from about 400 to about 1100 psig. [0043] In certain embodiments, the conversion of the olefin feed
• composition after being contacted with the oligomerization catalyst ranges from about 50 to 100%, or from about 70 to 99%, or from about 80 to 95%.
• the process can be operated at a lower conversion if necessary, for example if the refinery were economically balancing the production of LPG.
• a person of ordinary skill in the art can adjust the flow rate and operating temperature of the olefin feed composition in order to operate at the desired oligomerization conversion.
• the olefin feed can be operated over a range of 0.1 to 10 LHSV and over a temperature range of 200-400°F.
• Suitable oligomerization reaction conditions are also disclosed in U.S. Published Patent Application No. 2007/0173676, which is hereby incorporated by reference in its entirety.
• the ultimate product distribution can change based on the olefin feed composition entering the oligomerization reaction zone. If the olefin feed composition is rich in C 3 olefins, the first reactor will yield an intermediate composition rich in C 6 -Ci 2 + olefins. Alternatively, if the olefin feed
• composition is rich in C 4 , olefins
• the product produced in the largest quantity will be C 8 -Ci6+ olefins. If the feed contains a mixture of C 3 and C 4 olefins, the product produced in the largest quantity will be C 6 -Ci 6 olefins.
• higher oligomers are preferred such that they produce molecules within the distillate boiling range as these higher oligomers tend to produce alkylaromatics with higher cetane values. It is preferred to select an oligomerization catalyst that provided near linear oligomers as increasing linearity of the oligomer corresponds to increasing cetane of the resulting alkylaromatic.
• one embodiment includes selecting a feed rich in C 3 olefins for use in the process of the present invention, as described anywhere in this application, in order to obtain a hydrocarbon fuel composition rich in C 6 - Ci 2 + olefins.
• An alternative embodiment includes selecting a feed rich in C 4 olefins for use in the process of the present invention, as described anywhere in this application, in order to obtain a hydrocarbon fuel composition rich in C 8 - Ci 6 + olefins.
• the intermediate composition obtained from the oligomerization reaction zone, and a second feed of aromatic compounds is introduced to an aromatic alkylation catalyst to provide a hydrocarbon fuel composition.
• the intermediate composition can be combined with the second feed of aromatic compounds upstream from the aromatic alkylation catalyst such that one feed containing both the intermediate composition and aromatic compounds is introduced to the aromatic alkylation catalyst.
• the intermediate composition and the second feed of aromatic compounds can be introduced separately to the aromatic alkylation catalyst.
• the aromatic alkylation catalyst will be contained within a vessel (e.g., a reactor), which is referred to herein as the second reaction vessel.
• a person of ordinary skill in the art can determine the proper reaction conditions, and thus the proper conditions for the second reaction vessel, in order to convert a feed that includes, for example, an intermediate composition (e.g., a feed containing C 9 -Ci 6 olefins) and a second feed of aromatic compounds (e.g., a feed containing 2-99.9% benzene and other alkylatable aromatics) to yield a composition which includes a hydrocarbon fuel composition.
• the hydrocarbon fuel composition can be recovered (i.e., further isolated) using refining and separation techniques known to those of ordinary skill in the art.
• the amount of alkylatable aromatics in the second feed of aromatic compounds can vary.
• the second feed of aromatic compounds can include at least 1 wt%, or at least 5 wt%, or at least 10 wt% of alkylatable aromatics, based on the total weight of the second feed of aromatic compounds.
• the vessel containing the aromatic alkylation catalyst (i.e., the second reaction vessel) is maintained at a temperature ranging from about 80°F to about 600°F, or from about 100°F to about 400°F. In certain embodiments, the vessel containing the aromatic alkylation catalyst is
• the conversion of aromatic compounds can vary. In one embodiment, the conversion of aromatic compounds ranges from about 50% to about 100%. Higher aromatic conversions are preferred to maximize the amount of distillate produced.
• composition to the aromatic alkylation reaction zone can also vary. It is desirable to operate with a molar ratio of Olefin: Aromatic of 0.5 to 3, more preferably about 1.
• the oligomerization catalyst and aromatic alkylation catalyst are housed in separate vessels.
• the oligomerization catalyst and aromatic alkylation catalyst are housed in separate vessels.
• oligomerization catalyst and aromatic alkylation catalyst can be housed in the same vessel.
• reaction conditions for the respective vessels refer to reaction conditions for that portion of the vessel that contains the oligomerization catalyst, or aromatic alkylation catalyst, as appropriate.
• the pre- oligomerization step is eliminated and a composition containing olefins having at least three carbon atoms is combined with an aromatic feed, and the combined stream is introduced to an aromatic alkylation catalyst (e.g., a MCM-22 type catalyst) to yield a hydrocarbon fuel composition.
• an aromatic alkylation catalyst e.g., a MCM-22 type catalyst
• existing streams within a hydrocarbon refinery that contain both olefins and aromatics can be introduced to an aromatic alkylation catalyst to yield diesel fuel.
• FIG. 3 An exemplary single feed embodiment is shown in Figure 3.
• a FCC Naptha stream (401) is combined with a scanfmate stream (402), and the combined stream (403) is introduced to a fixed bed reactor (404) containing MCM-22 catalyst.
• nitrogen and sulphur containing compounds Prior to being introduced to the catalyst, nitrogen and sulphur containing compounds are removed from the FCC Naptha stream, since these components cause detrimental effects on the catalyst.
• the FCC Naphtha stream (401) contains about 20-30% linear olefins (as a percentage of total olefin content), with the balance being primarily mono-branched olefins.
• the resulting product stream (405) contains a diesel fuel composition. Oligomerization Catalysts
• zeolites are classified by the Structure Commission of the International Zeolite Association according to the rules of the IUPAC Commission on Zeolite Nomenclature.
• a framework-type describes the topology and connectivity of the tetrahedrally coordinated atoms constituting the framework and makes an abstraction of the specific properties for those materials.
• Molecular sieves for which a structure has been established are assigned a three letter code and are described in the Atlas of Zeolite Framework Types, 5 th edition, Elsevier, London, England (2001), which is hereby incorporated by reference in its entirety.
• the oligomerization catalysts of the present invention is without limitation so long as it facilitates the
• the oligomerization catalyst is selected from a solid phosphoric acid catalyst (SPA), a MWW type catalyst and a ZSM-type catalyst.
• Solid phosphoric acid (SPA) catalysts are known in the art and are commercially available, for example, from UOP LLC (Des Plaines, IL). Further details regarding the composition and production of SPA catalysts can be obtained from U.S. Patent Nos. 3,050,472; 3,050,473; and 3,132,109, which are each hereby incorporated by reference in their entirety.
• the SPA catalyst can be provided with a carrier, such as a naturally occurring porous silica-containing materials (e.g., kieselguhr, kaolin, infusorial earth and diatomaceous earth).
• a carrier such as a naturally occurring porous silica-containing materials (e.g., kieselguhr, kaolin, infusorial earth and diatomaceous earth).
• the SPA catalyst can also be employed in conjunction with crystalline molecular sieve catalysts, such as, for example, ZSM-22, ZSM-23, SAPO-11 , ZSM-48 or other molecular sieve catalysts described herein or otherwise known in the art.
• MWW type catalysts are also known in the art and can be
• the MWW family of zeolite materials has achieved recognition as having a characteristic framework structure which presents unique and interesting catalytic properties.
• the MWW topology consists of two independent pore systems: a sinusoidal ten-member ring [10 MR] two dimensional channel separated from each other by a second, two dimensional pore system comprised of 12 MR super cages connected to each other through 10 MR windows.
• MWW-type catalysts that can be used in connection with the presently disclosed subject matter include, but are not limited to, PSH-3, MCM-22, MCM-36, MCM-49, MCM-56, SSZ-25, ERB-1 , EMM-1, EMM-2, and ITQ-1 catalysts.
• the MWW type catalyst is selected from a MCM catalyst (e.g., MCM-22, MCM-36, MCM-49, and MCM-56 catalyst).
• MCM catalysts are known in the art, and can be obtained from, for example from ExxonMobil Catalyst Technologies LLC (Baytown, TX). MCM type catalysts, including synthesis details, are described in, for example, U.S. Patent Nos.
• the MWW type catalyst is a MCM-22 catalyst.
• MCM-22 is described in U.S. Pat. No. 4,954,325 as well as in U.S. Pat. Nos. 5,250,777; 5,284,643 and 5,382,742.
• MCM-49 is described in U.S. Pat. No. 5,236,575; MCM-36 in U.S. Pat. No. 5,229,341 and MCM-56 in U.S. Pat. No. 5,362,697. Each of these patents are hereby incorporated by reference in their entirety.
• the oligomerization catalyst is a EMM catalyst (e.g., EMM-1 or EMM-2 catalyst).
• EMM catalysts are known in the art and are preferably obtained from ExxonMobil Catalyst Technologies LLC (Baytown, TX). Synthesis details regarding EMM catalysts can be found, for example, in U.S. Patent Nos. 7,255,849 and 6,787,124 and U.S. Published Application Nos. 2006/0079723, 2009/0163753, each of which are hereby incorporated by reference in its entirety.
• the oligomerization catalyst is a ZSM-type catalyst.
• ZSM Zerolite Socony Mobil
• ZSM-type catalysts are known in the art and can be commercially obtained or synthesized.
• Commercially available ZSM-type catalysts can be obtained from, for example, Zeolyst International Corporation (Valley Forge, PA), BASF Catalysts LLC (Iselin, NJ), Sud-Chemie Incorporated (Louisville, KY), and, preferably, from ExxonMobil Catalyst Technologies LLC (Baytown, TX).
• ZSM catalysts, including synthesis details, are generally described, for example, in U.S. Patent Nos.
• the oligomerization catalyst is a ZSM-type catalyst selected from ZSM-5, ZSM-1 1, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57 catalysts.
• the ZSM-type catalyst is selected from ZSM-23 and ZSM-57, or a combination thereof.
• the oligomerization catalyst is a combination of a ZSM-23 and ZSM-57 catalyst, since this combination yields a high amount of linear olefins.
• the oligomerization catalyst is an ITQ type catalysts.
• ITQ type catalysts including synthesis details, are described in, for example, U.S. Patent Nos. 7,449,169; 7,081,556; 6,709,572; and 6,469,226, as well as published U.S. Application No. 2008/0021253. Each of these references are hereby incorporated by reference in their entirety.
• the ITQ type catalyst is ITQ-13.
• ITQ- 13 structure is 10x10x9 -member rings.
• Pore sizes of the ITQ-13 are 4.8 x 5.3 A; 4.8 x 5.1 A; 4.0 x 4.8 A (9-member ring).
• the aromatic alkylation catalysts of the present invention is without limitation so long as it facilitates the aromatic alkylation of an intermediate olefin composition.
• the aromatic alkylation catalyst is a MWW framework type catalyst, including the MWW type catalyst described above.
• the MWW type catalyst is a MCM-22 catalyst. It is also contemplated that zeolites beta catalyst and USY catalysts may be used.
• a feed including 30.8 wt% 1-hexene, 17.0 wt% benzene, 3.4 wt% toluene and the additional components identified below in Table 1 was prepared.
• the feed was passed over a MCM-49 catalyst containing a 80/20 zeolite :binder ratio and 1/20 11 quadrulube in a fixed bed reactor about 1" in diameter. 177g/hr of feed was passed over 63g of the catalyst at around 400°F and 600 psig.
• ASTM D86 analysis of feed and typical product is shown in Figures 6 and 7.
• ASTM D86 is a standard test method known to those skilled in the art. There, the movement in MW of the feed from the mogas boiling range to the distillate boiling range can be seen.
• the y-axis represents the boiling point in degrees F and the x-axis represents the liquid volume % off the sample at each corresponding boiling point temperature.

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