WO2017105869A1

WO2017105869A1 - Methods for upgrading olefin-containing feeds

Info

Publication number: WO2017105869A1
Application number: PCT/US2016/064522
Authority: WO
Inventors: Mohsen N. Harandi; Rajagopalan SURIYANARAYANAN
Original assignee: Exxonmobil Research And Engineering Company
Priority date: 2015-12-16
Filing date: 2016-12-02
Publication date: 2017-06-22

Abstract

Methods are provided for upgrading olefin-containing feeds. An olefin-containing feed can be exposed to an acidic conversion catalyst under effective conversion conditions that include an olefin weight hourly space velocity of at least about 1 hr^-1 to produce an effluent comprising gasoline fraction boiling range compounds. The gasoline fraction boiling range compounds can include C5+ compounds in an amount of at least about 55 wt. % of the olefin- containing feed.

Description

METHODS FOR UPGRADING OLEFIN-CONTAINING FEEDS

FIELD

[0001] Methods are provided for the upgrading of olefin-containing feeds.

BACKGROUND

[0002] Olefin oligomerization processes provide a method for converting low molecular weight olefins to higher value fuel products, such as naphtha or diesel boiling range fractions. Unfortunately, the conditions for olefin oligomerization also typically lead to coke formation on the oligomerization catalyst. Partly due to this coke formation, olefin oligomerization processes are typically performed in a fluidized bed environment or other environment where catalyst can be withdrawn from the reaction environment for regeneration on an ongoing or continuous basis.

[0003] U.S. Patent No. 4,456,779 discloses a process for the catalytic conversion of olefins to higher hydrocarbons. The process includes combining a liquid olefinic feed with a liquid lower alkane stream (C3-C4) at a temperature of about 230°C. The combined stream is exposed to an acidic zeolite catalyst, and the effluent is cooled and then debutanized and fractionated.

[0004] U.S. Patent No. 5,482,617 discloses a process for desulfurization of hydrocarbon streams having at least 50 ppmw organic sulfur compounds, and C5+ hydrocarbons including benzene. The hydrocarbon stream is exposed to a fluidized bed of an acidic catalyst in the absence of added hydrogen at a pressure of 0.0 psig to 400 psig and a temperature of 400°F to 900°F.

SUMMARY

[0005] In various aspects, a method for upgrading an olefin-containing feed is provided, comprising: providing an olefin-containing feed comprising at least about 50 wt. % C1-C4 compounds and at least about 10 wt. % C2+ olefins; and exposing the olefin-containing feed to effective conversion conditions in one or more reaction vessels to produce an oligomerized olefin effluent comprising one or more naphtha boiling range compounds, wherein the effective conversion conditions comprise exposing at least a portion of the olefin-containing feed to an acidic conversion catalyst, a temperature of at least about 550°F, and an olefin weight hourly space velocity of at least about 0.8 hr¹.

BRIEF DESCRIPTION OF THE FIGURES

[0006] FIG. 1 shows results of processing an olefin-containing feed according to methods described herein.

DETAILED DESCRIPTION

Overview

[0007] In various aspects, systems and methods are provided for the catalytic upgrading of olefin-containing feeds. In one or more aspects, the olefin-containing feed can be exposed to an acidic conversion catalyst under conversion conditions that include an olefin WHSV of at least about 1 hr¹. In such aspects, these conditions can result in an improved yield of C5+ compounds while utilizing a reduced amount of catalyst, which leads to improved refinery economics.

[0008] Traditionally, olefin oligomerization processes have included a low total feed weight hourly space velocity in order to increase or maximize conversion and cycle length, particularly in fixed bed configurations. However, it has been unexpectedly discovered that using increased olefin weight hourly space velocities can lead to improved yields of C5+ compounds. For example, in certain aspects, a fluidized catalyst bed olefin oligomerization process that includes an increased olefin WHSV, such as above 1 hr¹, can increase the yield of C5+ compounds. Such an increase in the yield of C5+ compounds can have a positive effect on the olefin oligomerization process economics. Further, in one or more aspects, increasing the olefin WHSV above 1 hr^"1 also reduces the amount of catalyst being used compared to traditional olefin oligomerization processes, which also positively impacts olefin oligomerization process economics. In certain aspects, in order to further increase the yield of C5+ compounds, as the olefin WHSV is increased, the reaction temperature may be decreased.

[0009] In various aspects, the olefin oligomerization process described herein may include a series of small fixed catalyst beds, where the olefin-containing feed may be exposed to one or more of the small fixed catalyst beds in such a manner so as to minimize the contact of the olefin- containing feed with deactivated catalyst. In such aspects, an olefin oligomerization process utilizing a series of fixed catalyst beds as described herein may include an olefin WHSV greater than about 1 hr^"1, which may increase the yield of C5+ compounds. Further, in such aspects, since the olefin WHSV is increased, less catalyst is utilized relative to traditional olefin oligomerization processes, which can also increase olefin oligomerization process economics.

[0010] In this discussion, unless otherwise specified, "hydrocarbon feed WHSV" refers to the ratio of the mass flow of hydrocarbon feed, or olefin-containing feed, (kg/hr) to the mass of the catalyst (kg), and has units of hr¹. In this discussion, unless otherwise specified, "olefin WHSV" refers to the ratio of the mass flow of olefins in the olefin-containing feed (kg/hr) to the mass of the catalyst (kg), and has units of hr^"1. In this discussion, unless otherwise specified, "naphtha boiling range" refers to an initial or T5 boiling point of at least about 50°F (10°C), and/or a final or T95 boiling point of less than about 450°F (232°C). In this discussion, unless otherwise specified, "naphtha boiling range compounds" refers to one or more compounds that exhibit the naphtha boiling range specified above. In this discussion, unless otherwise specified, "T5 boiling point" refers to a temperature at which 5 wt. % of the feed, effluent, product, stream, or composition of interest will boil. In this discussion, unless otherwise specified, "T95 boiling point" refers to a temperature at which 95 wt. % of the feed, effluent, product, stream, or composition of interest will boil.

Olefin-Containing Feed

[0011] The olefin-containing feed can be any hydrocarbon feed that contains olefins. In some aspects, at least a portion of the olefin-containing feed can include one or more low value refinery streams, such as refinery fuel gas. In such aspects, the one or more low value streams may be present in the olefin-containing feed in an amount of at least about 10 wt. %, at least about 20 wt. %, at least about 30 wt. %, at least about 40 wt. %, at least about 50 wt. %, or at least about 60 wt. %. In the same or alternative aspects, the one or more low value streams may be present in the olefin-containing feed in an amount of about 100 wt. % or less, about 99 wt. % or less, about 95 wt. % or less, about 90 wt. % or less, about 80 wt. % or less, or about 70 wt. % or less.

[0012] In various aspects, the olefin-containing feed can include at least about 10 wt. % olefins, at least about 20 wt. %, at least about 30 wt. %, at least about 40 wt. %, at least about 50 wt. %, or at least about 60 wt. %. In the same or alternative aspects, the olefin-containing feed can include less than about 100 wt. % olefins, less than about 90 wt. %, less than about 80 wt. %, or less than about 70 wt. %.

[0013] In various aspects, the olefin-containing feed can include at least about 5 wt. % C1-C3 (or C1-C4) hydrocarbon compounds, with a portion being C2-C3 (or C2-C4) olefins, such as the olefin amounts listed above, at least about 10 wt. %, at least about 20 wt. %, at least about 30 wt. %, at least about 40 wt. %, at least about 50 wt. %, at least about 60 wt. %, or at least about 70 wt. %. In the same or alternative aspects, the olefin-containing feed can include less than about 100 wt. % C1-C3 (or C1-C4) hydrocarbon compounds, with a portion being C2-C3 (or C2-C4) olefins, such as the olefin amounts listed above, less than about 90 wt. %, less than about 80 wt. %, or less than about 70 wt. %. In certain aspects, the olefin-containing feed can include C1-C3 (or C1-C4) hydrocarbon compounds, with a portion being C2-C3 (or C2-C4) olefins, such that the C1-C3 (or C1-C4) hydrocarbon compounds are at least about 10 wt. % greater than the amount (wt. %) of C2-C3 (or C2-C4) olefins, at least about 20 wt. % greater, at least about 30 wt. % greater, at least about 40 wt. % greater, at least about 50 wt. % greater, or at least about 60 wt. % greater.

[0014] In various aspects, the olefin-containing feed can have a sulfur content of at least about 30 wppm, or at least about 100 wppm, or at least about 500 wppm, or at least about 1000 wppm, or at least about 1500 wppm. In another aspect, the sulfur content can be about 7000 wppm or less, or about 6000 wppm or less, or about 5000 wppm or less, or about 3000 wppm or less. The sulfur may be present as organically bound sulfur. [0015] In one or more aspects, nitrogen can also be present in the olefin-containing feed. In an aspect, the amount of nitrogen can be at least about 5 wppm, or at least about 10 wppm, or at least about 20 wppm, or at least about 40 wppm. In another aspect, the nitrogen content can be about 250 wppm or less, or about 150 wppm or less, or about 100 wppm or less, or about 50 wppm or less.

[0016] It is appreciated that other olefin-containing feeds may be used in the processes disclosed herein and that the above-described feed properties are only exemplary.

Conditions for Upgrading an Olefin-Containing Feed

[0017] In various aspects, the olefin-containing feed can be exposed to an acidic catalyst (such as a zeolite) under effective conversion conditions for olefinic oligomerization and/or sulfur removal. Optionally, the zeolite or other acidic catalyst can also include a hydrogenation functionality, such as a Group VIII metal or other suitable metal that can activate hydrogenation / dehydrogenation reactions. The olefin-containing feed can be exposed to the acidic catalyst without providing substantial additional hydrogen to the reaction environment. Added hydrogen refers to hydrogen introduced as an input flow to the process, as opposed to any hydrogen that might be generated in-situ during processing. Exposing the feed to an acidic catalyst without providing substantial added hydrogen is defined herein as exposing the feed to the catalyst in the presence of a) less than about 100 SCF/bbl of added hydrogen, or less than about 50 SCF/bbl; b) a partial pressure of less than about 50 psig (350 kPag), or less than about 15 psig (100 kPag) of hydrogen; or c) a combination thereof.

[0018] The acidic catalyst used in the processes described herein can be a zeolite-based catalyst, that is, it can comprise an acidic zeolite in combination with a binder or matrix material such as alumina, silica, or silica-alumina, and optionally further in combination with a hydrogenation metal. More generally, the acidic catalyst can correspond to a molecular sieve (such as a zeolite) in combination with a binder, and optionally a hydrogenation metal. Molecular sieves for use in the catalysts can be medium pore size zeolites, such as those having the framework structure of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, or MCM-22. Such molecular sieves can have a 10-member ring as the largest ring size in the framework structure. The medium pore size zeolites are a well-recognized class of zeolites and can be characterized as having a Constraint Index of 1 to 12. Constraint Index is determined as described in U.S. Pat. No. 4,016,218 incorporated herein by reference. Catalysts of this type are described in U.S. Pat. Nos. 4,827,069 and 4,992,067 which are incorporated herein by reference and to which reference is made for further details of such catalysts, zeolites and binder or matrix materials. [0019] Additionally or alternately, catalysts based on large pore size framework structures (12- member rings) such as the synthetic faujasites, especially zeolite Y, such as in the form of zeolite USY. Zeolite beta may also be used as the zeolite component. Other materials of acidic functionality which may be used in the catalyst include the materials identified as MCM-36 and MCM-49. Still other materials can include other types of molecular sieves having suitable framework structures, such as silicoaluminophosphates (SAPOs), aluminosilicates having other heteroatoms in the framework structure, such as Ga, Sn, or Zn, or silicoaluminophosphates having other heteroatoms in the framework structure. Mordenite or other solid acid catalysts can also be used as the catalyst.

[0020] In various aspects, the exposure of the olefin-containing feed to the acidic catalyst can be performed in any convenient manner, such as exposing the olefin-containing feed to the acidic catalyst under fluidized bed conditions, moving bed conditions, and/or in a riser reactor. In some aspects, the particle size of the catalyst can be selected in accordance with the fluidization regime which is used in the process. Particle size distribution can be important for maintaining turbulent fluid bed conditions as described in U.S. Pat. No. 4,827,069 and incorporated herein by reference. Suitable particle sizes and distributions for operation of dense fluid bed and transport bed reaction zones are described in U.S. Pat. Nos. 4,827,069 and 4,992,607 both incorporated herein by reference. Particle sizes in both cases will normally be in the range of 10 to 300 microns, typically from 20 to 100 microns.

[0021] Acidic zeolite catalysts suitable for use as described herein can be those exhibiting high hydrogen transfer activity and having a zeolite structure of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, MCM-22, MCM-36, MCM-49, zeolite Y, and zeolite beta. Such catalysts can be capable of oligomerizing olefins from the olefin-containing feed. For example, such catalysts can convert C2-C4 olefins, such as those present in a refinery fuel gas, to C5+ olefins. Such catalysts can also be capable of converting organic sulfur compounds such as mercaptans to hydrogen sulfide without added hydrogen by utilizing hydrogen present in the hydrocarbon feed. Group VIII metals such as nickel may be used as desulfurization promoters. A fluid-bed reactor/regenerator can assist with maintaining catalyst activity in comparison with a fixed-bed system. Further, the hydrogen sulfide produced in accordance with the processes described herein can be removed using conventional amine based absorption processes.

[0022] ZSM-5 crystalline structure is readily recognized by its X-ray diffraction pattern, which is described in U.S. Pat. No. 3,702,866. ZSM-11 is disclosed in U.S. Pat. No. 3,709,979, ZSM-12 is disclosed in U.S. Pat. No. 3,832,449, ZSM-22 is disclosed in U.S. Pat. No. 4,810,357, ZSM-23 is disclosed in U.S. Pat. Nos. 4,076,842 and 4,104,151, ZSM-35 is disclosed in U.S. Pat. No.4,016,245, ZSM-48 is disclosed in U.S. Pat. No.4,375,573 and MCM-22 is disclosed in U.S. Pat. No. 4,954,325. The U.S. Patents identified in this paragraph are incorporated herein by reference.

[0023] While suitable zeolites having a coordinated metal oxide to silica molar ratio of 20: 1 to 200: 1 or higher may be used, it can be advantageous to employ aluminosilicate ZSM-5 having a silica: alumina molar ratio of about 25: 1 to 70: 1, suitably modified. A typical zeolite catalyst component having Bronsted acid sites can comprises, consist essentially of, or consist of crystalline aluminosilicate having the structure of ZSM-5 zeolite with 5 to 95 wt. % silica, clay and/or alumina binder.

[0024] These siliceous zeolites can be employed in their acid forms, ion-exchanged or impregnated with one or more suitable metals, such as Ga, Pd, Zn, Ni, Co, Mo, P, and/or other metals of Periodic Groups III to VIII. The zeolite may include other components, generally one or more metals of group IB, IIB, IIIB, VA, VIA or VIIIA of the Periodic Table (IUPAC).

[0025] Useful hydrogenation components can include the noble metals of Group VIIIA, such as platinum, but other noble metals, such as palladium, gold, silver, rhenium or rhodium, may also be used. Base metal hydrogenation components may also be used, such as nickel, cobalt, molybdenum, tungsten, copper or zinc.

[0026] The catalyst materials may include two or more catalytic components which components may be present in admixture or combined in a unitary multifunctional solid particle.

[0027] In addition to the preferred aluminosilicates, the gallosilicate, ferrosilicate and "silicalite" materials may be employed. ZSM-5 zeolites can be useful in the process because of their regenerability, long life and stability under the extreme conditions of operation. Usually the zeolite crystals have a crystal size from about 0.01 to over 2 microns or more, such as 0.02-1 micron.

[0028] In various aspects, the catalyst particles can contain about 25 wt. % to about 40 wt. % H-ZSM-5 zeolite, based on total catalyst weight, contained within a silica-alumina matrix. Typical Alpha values for the catalyst can be about 100 or less. Sulfur conversion to hydrogen sulfide can increase as the alpha value increases.

[0029] The Alpha Test is described in U.S. Pat. 3,354,078, and in the Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p. 395 (1980), each incorporated herein by reference as to that description.

[0030] In various aspects, the olefin-containing feed may be exposed to the acidic catalyst by using a moving or fluid catalyst bed reactor. In such aspects, the catalyst may be regenerated, such via continuous oxidative regeneration. The extent of coke loading on the catalyst can then be continuously controlled by varying the severity and/or the frequency of regeneration. In a turbulent fluidized catalyst bed the conversion reactions are conducted in a vertical reactor column by passing hot reactant vapor upwardly through the reaction zone and/or reaction vessel at a velocity greater than dense bed transition velocity and less than transport velocity for the average catalyst particle. A continuous process is operated by withdrawing a portion of coked catalyst from the reaction zone and/or reaction vessel, oxidatively regenerating the withdrawn catalyst and returning regenerated catalyst to the reaction zone at a rate to control catalyst activity and reaction severity to affect feedstock conversion. Preferred fluid bed reactor systems are described in Avidan et al U.S. Pat. No. 4,547,616; Harandi & Owen U.S. Pat. No. 4,751,338; and in Tabak et al U.S. Pat. No. 4,579,999, incorporated herein by reference. In other aspects, other types of reactors can be used, such as fixed bed reactors, riser reactors, fluid bed reactors, and/or moving bed reactors.

[0031] In one or more aspects, effective conversion conditions for exposing the olefin- containing feed to an acidic catalyst can include a temperature of about 300°F (149°C) to about 900°F (482°C), or about 350°F (177°C) to about 850°F (454°C), or about 350°F (177°C) to about 800°F (427°C), or about 350°F (177°C) to about 750°F (399°C), or about 350°F (177°C) to about 700°F (371°C), or a temperature of at least about 400°F (204°C), or at least about 500°F (260°C), or at least about 550°F (288°C), or at least about 600°F (316°C); a pressure of about 50 psig (0.34 MPag) to about HOOpsig (7.6MPag), or a pressure of about 100 psig (0.69 MPag) to about 1000 psig (6.9 MPag), or about 150 psig (1.0 MPag) to about 975 psig (6.7 MPag), or about 200 psig (1.4 MPag) to about 950 psig (6.6 MPag), or about 250 psig (1.7 MPag) to about 900 psig (6.2 MPag), or about 300 psig (4.1 MPag) to about 850 psig (5.9 MPag), or about 300 psig (4.1 MPag) to about 800 psig (5.5 MPag), or a pressure of at least about 50 psig (0.34 MPag), or a pressure of at least about 100 psig (0.69 MPag), or a pressure of at least about 150 psig (1.0 MPag), or a pressure of at least about 200 psig (1.4 MPag), or a pressure of at least about 250 psig (1.7 MPag), or a pressure of at least about 300 psig (4.1 MPag), or a pressure of at least about 350 psig (2.4 MPag); and a total feed WHSV of about 0.05 hr¹ to about 40 hr¹, or about 0.05 to about 30 hr¹, or about 0.1 to about 20 hr¹, or about 0.1 to about 10 hr¹. Optionally, the total feed WHSV can be about 1 hr¹ to about 40 hr¹ to improve C5+ yield.

[0032] In addition to a total feed WHSV, a WHSV can also be specified for just the olefin compounds in the feed. In other words, an olefin WHSV represents a space velocity defined by just the weight of olefins in a feed relative to the weight of catalyst. In one or more aspects, the effective conversion conditions can include an olefin WHSV of at least about 0.8 hr¹, or at least about 1.0 hr¹, or at least about 2.0 hr¹, or at least about 3.0 hr¹, or at least about 4.0 hr¹, or at least about 5.0 hr¹, or at least about 8.0 hr¹, or at least about 10 hr¹, or at least about 15 hr¹. In the same or alternative aspects, the effective conversion conditions can include an olefin WHSV of about 40 hr¹ or less, or about 30 hr¹ or less, or about 20 hr¹ or less. In certain aspects, the effective conversion conditions can include an olefin WHSV of about 0.8 hr¹ to about 30 hr¹, or about 0.8 hr¹ to about 20 hr¹, or about 0.8 hr¹ to about 15 hr¹, or about 0.8 hr¹ to about 10 hr¹, or about 0.8 hr¹ to about 7 hr¹, or about 0.8 hr¹ to about 5 hr¹, or about 1.0 hr^"1 to about 30 hr¹, or about 1.0 hr¹ to about 20 hr¹, or about 1.0 hr¹ to about 15 hr¹, or about 1.0 hr¹ to about 10 hr¹, or about 1.0 hr¹ to about 7 hr¹, or about 1.0 hr¹ to about 5 hr¹, or about 2.0 hr^"1 to about 30 hr¹, or about 2.0 hr¹ to about 20 hr¹, or about 2.0 hr¹ to about 15 hr¹, or about 2.0 hr¹ to about 10 hr¹, or about 2.0 hr^"1 to about 7 hr^"1, or about 2.0 hr^"1 to about 5 hr^"1, about 4.0 hr^"1 to about 30 hr^"1, or about 4.0 hr^"1 to about 20 hr^"1, or about 4.0 hr^"1 to about 15 hr^"1, or about 4.0 hr^"1 to about 10 hr^"1, or about 4.0 hr^"1 to about 7 hr^"1. An olefin WHSV of about 1 hr^"1 to about 40 hr^"1 can be beneficial for increasing the C5+ yield.

[0033] In various aspects, decreasing the temperature when the olefin WHSV is increased, e.g., when the olefin WHSV is increased above 1 hr^"1, may improve product yield. For example, in such aspects, temperatures of about 600°F (316°C) to about 800°F (427°C), or about 650°F (343°C) to about 750°F (399°C) may aid in increasing product yield, such as the yield of C5+ compounds, when the olefin WHSV is increased above 1 hr¹.

[0034] In various aspects, exposing an olefin-containing feed to the conversion conditions discussed above can produce an oligomerized olefin effluent that includes naphtha boiling range compounds. In such aspects, the naphtha boiling range compounds in the oligomerized olefin effluent can include compounds with 5 or more carbon atoms (C5+ compounds) in an amount of at least about 20 wt. %, at least about 30 wt. %, at least about 40 wt. %, at least about 50 wt. %, at least about 65 wt. %, at least about 70 wt. %, or at least about 75 wt. %. In one or more aspects, the naphtha boiling range compounds in the oligomerized effluent can include C5+ compounds in an amount of at least about 50 wt. % of the olefin-containing feed, at least about 55 wt. %, at least about 60 wt. %, at least about 65 wt. %, at least about 70 wt. %, or at least about 75 wt. %. In various aspects, the naphtha boiling range compounds in the oligomerized effluent can have an aromatic content of less than about 25 wt. %, less than about 15 wt. %, less than about 10 wt. %, or less than about 5 wt. %. In one or more aspects, the naphtha boiling range compounds in the oligomerized effluent can have a reduced sulfur content compared to the olefin-containing feed. In such aspects, the sulfur content of naphtha boiling range compounds in the oligomerized olefin effluent can be about 100 wppm or less, or about 75 wppm or less, or about 50 wppm or less, or about 30 wppm or less, or about 20 wppm or less, or about 10 wppm or less. Modified Hydroprocessing Strategy - Consecutive Bed / Reactor Exposure

[0035] In certain aspects, the olefin-containing feed may be exposed to the acidic catalyst by using one or more fixed catalyst beds. Conventionally, increasing the total space velocity was viewed as not favorable in fixed bed operation of olefin oligomerization, due to a resulting decrease in cycle length for the reaction. This difficulty can be overcome by using an alternative type of fixed bed configuration.

[0036] As an alternative to a conventional strategy, in various aspects a reactor or reactors can include multiple beds of olefin oligomerization catalyst. In such aspects, the feed is not initially exposed to all catalyst beds (and/or reactors) of the olefin oligomerization catalyst. Instead, the feed can be introduced upstream from a final one or more catalyst beds (and/or reactors), thus bypassing the remaining catalyst beds. An alternative way of describing this situation can be that the feed is introduced at a first position that is upstream from one or more catalyst beds but downstream from one or more additional catalyst beds. The feed can then be oligomerized under higher space velocity conditions over the final one or more catalyst beds. However, because only the final one or more beds are exposed to the feed, the reaction system does not need to be shut down after the catalyst deactivates. Instead, after the final one or more beds deactivate, the entry point for the feed can be switched to an upstream location. The feed can then be exposed to the additional group of one or more beds. The feed can optionally also pass through the final one or more beds of deactivated catalyst. This strategy can be repeated until all available beds have been used as fresh catalyst for processing of the feed. This type of strategy can lead to high cycle length for a reactor while also providing an increased yield of C5+ compounds.

[0037] It is noted that the above strategy can more generally be applied in any situation where desirable processing conditions for a feed are in conflict with conditions that extend the run length of a catalyst. Thus, the above strategy can be used with naphtha feeds, distillate feed, lubricating base oil feed, or any other convenient type of feed. Similarly, the above strategy can be used with any type of oligomerization catalyst, hydrotreating catalyst, a dewaxing catalyst, a hydrocracking catalyst, an aromatic saturation catalyst, or a combination thereof. This type of strategy for consecutively using the beds and/or reactors in a reaction system can be employed with any convenient number of reaction zones, such as 2 to 30 reaction zones.

Example - Yield of Cs+ Compounds in Olefin Oligomerization Processes

[0038] It has been discovered that the yield of C5+ compounds obtained by exposing an olefin- containing feed to an acid conversion catalyst can be impacted by the olefin WHSV. In particular, increasing the olefin WHSV can lead to increased yield of C5+ compounds. [0039] FIG. 1 shows examples of data obtained from the processing of an olefin-containing feed in a fluidized bed reactor. Particularly, the chart in FIG. 1 displays data on the relationship between the olefin WHSV and the yield of C5+ compounds for a fluidized bed olefin oligomerization process. As shown in FIG. 1, the data relating to running a fluidized bed reactor at 800°F (427°C) has been grouped into three subgroups: A, B, and C. The group A data corresponds to running the olefin oligomerization process with an olefin WHSV close to 0.2 hr¹, where the yield of C5+ compounds is about 53-54 wt. % of the olefin-containing feed. The group B data corresponds to running the olefin oligomerization process with an olefin WHSV close to 0.35-0.4 hr¹, where the yield of C5+ compounds is about 57-61 wt. % of the olefin-containing feed. The group C data corresponds to running the olefin oligomerization process with an olefin WHSV close to about 0.7-0.75 hr¹, where the yield of C5+ compounds is about 62-64 wt. % of the olefin- containing feed.

[0040] The data in groups A, B, and C appear to show that by increasing the olefin WHSV the yield of C5+ compounds increases. Specifically, the data of groups A, B, and C appear to show that by roughly doubling the olefin WHSV the yield of C5+ compounds increases by about 4 wt. % (compare the data from groups A and B, and compare the data from groups B and C). It is noted that the increase in conversion versus olefin WHSV can gradually slow as higher yields are achieved.

[0041] The chart in FIG. 1 also includes data relating to running a fluidized bed olefin oligomerization process at 700°F (371° C) and at 750°F (399°C). While the data for each temperature (700°F and 750°F) only includes data for one olefin WHSV, the data appears to provide some insight into how temperature affects the yield of C5+ compounds. For example, the 700°F fluidized bed reactor was run with an olefin WHSV of about 0.375-0.4 hr¹ and resulted in a yield of C5+ compounds of about 66-67 wt. % of the olefin-containing feed, while the 800°F fluidized bed reactor run at a comparable olefin WHSV (close to 0.35-0.4 hr¹) results in a yield of C5+ compounds of about 57-61 wt. % of the olefin-containing feed. This comparison appears to show that by decreasing the temperature the yield of C5+ compounds can be increased. This trend is also observed when comparing the data from the 750°F fluidized bed olefin oligomerization process (run at an olefin WHSV of about 0.75-0.8 hr¹), which produced a yield of C5+ compounds of about 66 to about 68 wt.% of the olefin-containing feed, to the olefin oligomerization data from the 800°F fluidized bed olefin oligomerization process run at a comparable olefin WHSV (close to about 0.7-0.75 hr¹), which produced a yield of C5+ compounds is about 62-64 wt. % of the olefin- containing feed. It is also noted that although the 750°F data is at a higher temperature than the 700°F data, the yield at 750°F is comparable due to the higher olefin WHSV. This demonstrates the significance of the increase in yield due to increased olefin WHSV as compared with changes in yield due to temperature variations. In this example, doubling the olefin WHSV offset the yield impact of 50°F temperature rise.

Additional Embodiments

[0042] Embodiment 1. A method for upgrading an olefin-containing feed, comprising: providing an olefin-containing feed comprising at least about 50 wt. % C1-C4 compounds and at least about 10 wt. % C2+ olefins; and exposing the olefin-containing feed to effective conversion conditions in one or more reaction vessels to produce an oligomerized olefin effluent comprising one or more naphtha boiling range compounds, wherein the effective conversion conditions comprise exposing at least a portion of the olefin-containing feed to an acidic conversion catalyst, a temperature of at least about 550°F, and an olefin weight hourly space velocity of at least about 0.8 hr¹.

[0043] Embodiment 2. The method of Embodiment 1, wherein the one or more naphtha boiling range compounds comprise C5+ olefins, the C5+ olefins optionally being present in an amount of at least about 55 wt. % of the C2+ olefins from the olefin-containing feed, or at least about 60 wt. %, or at least about 65 wt. %, or at least about 70 wt. %.

[0044] Embodiment 3. The method of any of the above embodiments, wherein the oligomerized olefin effluent comprises at least about 60 wt% of C5+ olefins.

[0045] Embodiment 4. The method of any of the above embodiments, wherein the effective conversion conditions comprise exposing the at least a portion of the olefin-containing feed to a fluidized bed of the acidic conversion catalyst.

[0046] Embodiment 5. The method of any of Embodiments 1 - 3, wherein the effective conversion conditions comprise exposing the at least a portion of the olefin-containing feed to the acidic conversion catalyst in a moving bed, in a riser reactor, in a fluidized bed, or a combination thereof.

[0047] Embodiment 6. The method of any of Embodiments 1 - 3, wherein the effective conversion conditions comprise exposing the at least a portion of the olefin-containing feed to at least one fixed bed of the acidic conversion catalyst.

[0048] Embodiment 7. The method of Embodiment 6, wherein exposing the at least a portion of the olefin-containing feed to at least one fixed bed of the acidic conversion catalyst comprises: exposing the at least a portion of the olefin-containing feed to one or more beds of the acidic conversion catalyst, the one or more beds of the acidic conversion catalyst being located downstream from a first location in a reaction system, an additional one or more beds of the acidic conversion catalyst being located upstream from the first location, the at least a portion of the olefin-containing feed being introduced into the reaction system at a position downstream from the first location; modifying a position for introducing the at least a portion of the separated higher boiling fraction to a second location, the second location being upstream from the additional one or more beds of the acidic conversion catalyst; and exposing the at least a portion of the olefin- containing feed to the additional one or more beds of the acidic conversion catalyst.

[0049] Embodiment 8. The method of Embodiment 7, wherein exposing the at least a portion of the olefin-containing feed to the additional one or more beds of the acidic conversion catalyst further comprises exposing the at least a portion of the olefin-containing feed to the one or more beds of the acidic conversion catalyst located downstream from the first location after said exposing to the additional one or more beds of the acidic conversion catalyst.

[0050] Embodiment 9. The method of any of the above embodiments, wherein the oligomerized olefin effluent comprises aromatic compounds in an amount of less than about 25 wt. %, or less than about 15 wt%, or less than about 10 wt. %, or less than about 5 wt. %.

[0051] Embodiment 10. The method of any of the above embodiments, wherein the oligomerized olefin effluent has a sulfur content of about 100 wppm or less.

[0052] Embodiment 1 1. The method of any of the above embodiments, wherein the olefin weight hourly space velocity is about 1 hr¹ to about 30 hr¹, or about 1 hr¹ to about 20 hr¹, or about 1 hr^"1 to about 15 hr^"1, or about 1 hr^"1 to about 10 hr^"1, or about 1 hr^"1 to about 5 hr^"1.

[0053] Embodiment 12. The method of Embodiment 11 , wherein the olefin weight hourly space velocity is at least about 1.5 hr^"1, or at least about 2 hr^"1, or at least about 4 hr^"1, or at least about 8 hr¹.

[0054] Embodiment 13. A conversion product from upgrading an olefin-containing feed, comprising a naphtha boiling range fraction including at least about 65 wt. % of Cs+ olefins and about 10 wt. % or less of aromatic compounds.

[0055] Embodiment 14. The conversion product of Embodiment 13, wherein the naphtha boiling range fraction comprises at least about 70 wt. % C5+ olefins.

[0056] Embodiment 15. The conversion product of Embodiment 13 or 14, wherein the naphtha boiling range fraction comprises about 5 wt. % or less of aromatic compounds.

[0057] Although the present invention has been described in terms of specific embodiments, it is not so limited. Suitable alterations/modifications for operation under specific conditions should be apparent to those skilled in the art. It is therefore intended that the following claims be interpreted as covering all such alterations/modifications as fall within the true spirit/scope of the invention.

Claims

CLAIMS;

1. A method for upgrading an olefin-containing feed, comprising:

providing an olefin-containing feed comprising at least about 50 wt. % C1-C4 compounds and at least about 10 wt. % C2+ olefins; and

exposing the olefin-containing feed to effective conversion conditions in one or more reaction vessels to produce an oligomerized olefin effluent comprising one or more naphtha boiling range compounds, wherein the effective conversion conditions comprise exposing at least a portion of the olefin-containing feed to an acidic conversion catalyst, a temperature of at least about 550°F, and an olefin weight hourly space velocity of at least about 0.8 hr¹.

2. The method of claim 1, wherein the one or more naphtha boiling range compounds comprise C5+ olefins.

3. The method of claim 2, wherein the C5+ olefins are present in an amount of at least about 55 wt. % of the C2+ olefins from the olefin-containing feed.

4. The method of claim 2, wherein the C5+ olefins are present in an amount of at least about 60 wt. % of the C2+ olefins from the olefin-containing feed.

5. The method of claim 1, wherein the oligomerized olefin effluent comprises at least about 60 wt% of C₅+ olefins.

6. The method of claim 1, wherein the effective conversion conditions comprise exposing the at least a portion of the olefin-containing feed to a fluidized bed of the acidic conversion catalyst.

7. The method of claim 1, wherein the effective conversion conditions comprise exposing the at least a portion of the olefin-containing feed to the acidic conversion catalyst in a moving bed, in a riser reactor, in a fluidized bed, or a combination thereof.

8. The method of claim 1, wherein the effective conversion conditions comprise exposing the at least a portion of the olefin-containing feed to at least one fixed bed of the acidic conversion catalyst.

9. The method of claim 8, wherein exposing the at least a portion of the olefin-containing feed to at least one fixed bed of the acidic conversion catalyst comprises:

exposing the at least a portion of the olefin-containing feed to one or more beds of the acidic conversion catalyst, the one or more beds of the acidic conversion catalyst being located downstream from a first location in a reaction system, an additional one or more beds of the acidic conversion catalyst being located upstream from the first location, the at least a portion of the olefin-containing feed being introduced into the reaction system at a position downstream from the first location; modifying a position for introducing the at least a portion of the separated higher boiling fraction to a second location, the second location being upstream from the additional one or more beds of the acidic conversion catalyst; and

exposing the at least a portion of the olefin-containing feed to the additional one or more beds of the acidic conversion catalyst.

10. The method of claim 9, wherein exposing the at least a portion of the olefin-containing feed to the additional one or more beds of the acidic conversion catalyst further comprises exposing the at least a portion of the olefin-containing feed to the one or more beds of the acidic conversion catalyst located downstream from the first location after said exposing to the additional one or more beds of the acidic conversion catalyst.

11. The method of claim 1, wherein the oligomerized olefin effluent comprises aromatic compounds in an amount of less than about 25 wt. %.

12. The method of claim 1, wherein the oligomerized olefin effluent comprises aromatic compounds in an amount of less than about 10 wt. %.

13. The method of claim 1, wherein the oligomerized olefin effluent has a sulfur content of about 100 wppm or less.

14. The method of claim 1, wherein the olefin weight hourly space velocity is about 1 hr¹ to about 30 hr¹.

15. The method of claim 1, wherein the olefin weight hourly space velocity is about 1.5 hr¹ to about 20 hr¹.

16. The method of claim 1, wherein the olefin weight hourly space velocity is at least about 2 hr¹.

17. The method of claim 1, wherein the olefin weight hourly space velocity is at least about 4 hr¹.

18. A conversion product from upgrading an olefin-containing feed, comprising a naphtha boiling range fraction including at least about 65 wt. % of C5+ olefins and about 10 wt. % or less of aromatic compounds.

19. The conversion product of claim 18, wherein the naphtha boiling range fraction comprises at least about 70 wt. % C5+ olefins.

20. The conversion product of claim 18, wherein the naphtha boiling range fraction comprises about 5 wt. % or less of aromatic compounds.