WO2006083746A1 - Oligomerisation d'olefines - Google Patents

Oligomerisation d'olefines Download PDF

Info

Publication number
WO2006083746A1
WO2006083746A1 PCT/US2006/003108 US2006003108W WO2006083746A1 WO 2006083746 A1 WO2006083746 A1 WO 2006083746A1 US 2006003108 W US2006003108 W US 2006003108W WO 2006083746 A1 WO2006083746 A1 WO 2006083746A1
Authority
WO
WIPO (PCT)
Prior art keywords
stream
olefinic
olefin
recycle
feed
Prior art date
Application number
PCT/US2006/003108
Other languages
English (en)
Inventor
Stephen Brown
Keith H. Kuechler
Steven E. Silverberg
An Verberckmoes
Marc P. H PUTTEMANS
Original Assignee
Exxonmobil Chemical Patents Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Publication of WO2006083746A1 publication Critical patent/WO2006083746A1/fr

Links

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
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • This invention relates to an olefin oligomerization process for producing hydrocarbon compositions useful as fuels, such as jet fuel and diesel fuel.
  • Improved hydrocarbon compositions are needed to help meet the growing demand for middle distillate products, such as aviation turbine fuels, for example, JP-8 and diesel fuel.
  • Diesel fuel generally provides a higher energy efficiency in compression ignition engines than automotive gasoline provides in spark combustion engines, and has a higher rate of demand growth than automotive gasoline, especially outside the U.S.
  • improved fuel compositions are needed to meet the stringent quality specifications for aviation fuel and the ever tightening quality specifications for diesel fuel as established by industry requirements and governmental regulations.
  • One known route for producing hydrocarbon compositions useful as fuels is the oligomerization of olefins over various molecular sieve catalysts.
  • Exemplary patents relating to olefin oligomerization include U.S. Patents 4,444,988; 4,497,968; 4,482,772; 4,720,600 and 4,879,428.
  • feedstock olefins are mixed with an olefmic recycle material and contacted with a zeolite, particularly in a series of fixed bed reactors.
  • the oligomerized reaction product is then separated to provide a distillate stream, and typically a gasoline stream, and any number of olefmic recycle streams.
  • the processes employ, either directly or indirectly, a relatively large amount of olefinic recycle containing significant quantities of C 10 + material.
  • the relatively large recycle rate provides control over the exotherm of the oligomerization reaction in the preferred fixed bed, adiabatic reactor system, while the relatively heavy recycle composition enables the growth of heavier oligomers and thus higher molecular weight and denser distillate product.
  • a high rate of recycle requires much larger equipment to handle the increased volumetric flow rate, and uses more separation/fractionation energy, and hence more and larger associated energy conservation elements.
  • a high molecular weight oligomer product requires very high temperatures for the fractionation tower bottoms streams that may eliminate the use of simple steam reboilers and require more expensive and complicated fired heaters.
  • the dense distillate product is generally characterized by a relatively high specific gravity (in excess of 0.775) and a high viscosity, in part due to the composition comprising relatively high levels of aromatics and naphthenes.
  • U.S. Patent 4,720,600 discloses an oligomerization process for converting lower olefins to distillate hydrocarbons, especially useful as high quality jet or diesel fuels, wherein an olefmic feedstock is reacted over a shape selective acid zeolite, such as ZSM-5, to oligomerize feedstock olefins and further convert recycled hydrocarbons.
  • the reactor effluent is fractionated to recover a light-middle distillate range product stream and to obtain light and heavy hydrocarbon streams for recycle.
  • the middle distillate product has a boiling range of about 165°C to 29O 0 C and contains substantially linear C 9 to C 16 mono-olefinic hydrocarbons, whereas the major portion of the C 6 to C 8 hydrocarbon components are contained in the lower boiling recycle stream, and the major portion (e.g., 50 wt% to more than 90 wt%) of the C 16 + hydrocarbon components are contained in the heavy recycle fraction.
  • One embodiment of the present invention provides a process for producing a hydrocarbon composition that comprises: (a) contacting a feed stream and an olefmic recycle stream with a molecular sieve catalyst in a reaction zone under olefin oligomerization conditions to produce an oligomerization effluent stream, wherein said feed stream comprises at least one C 3 to C 8 olefin and said - A - olefinic recycle stream comprises a first olefmic recycle stream (or light olefinic recycle stream) and no more than 10 wt% of C 10 + non-normal olefins; (b) separating said oligomerization effluent stream to produce a first olefinic stream (or light olefinic stream) and a first hydrocarbon product stream, wherein said first hydrocarbon product stream comprises at least 1 wt% and no more than 30 wt% of C 9 non-normal olefin and said light olefinic stream has a weight
  • One embodiment of the present invention provides a process for producing a hydrocarbon composition that further comprises: (d) separating said first purge stream to produce a second purge stream and a second olefinic stream; and (e) splitting said second olefinic stream to produce a second olefinic recycle stream and a second hydrocarbon product stream, wherein said olefinic recycle stream further comprises at least 1 wt% and no more than 80 wt% of said second olefinic recycle stream based on the total weight of the olefinic recycle stream.
  • the term "olefinic recycle stream” refers to the single or combined individual recycle streams provided along with the feed stream for contacting (a).
  • Such individual streams may be combined in any manner, including as a mixture with the feed stream.
  • attributes of the "olefinic recycle stream” refer to that stream which would result if all individual recycle streams were combined excluding the feed stream, regardless of specifically how the individual streams are provided for contacting (a).
  • the feed stream comprises a mixture of C 3 to C 5 olefins comprising at least 5 wt% of C 4 olefin, which the mixture may comprise at least 40 wt% of C 4 olefin and at least 10 wt% of C 5 olefin.
  • the feed stream comprises no more than about 10 wt% C 9 + hydrocarbons.
  • the feed stream comprises less than 45 wt% saturates.
  • the feed stream comprises no greater than 10 wt% propane.
  • the feed stream comprises no more than 1.0 wt% C 2 hydrocarbons
  • the feed stream comprises a product stream from one or more of an oxygenates to olefins process, a steam cracking process, or a catalytic cracking process.
  • the feed stream contains C 4 olefin and the contacting (a) is conducted so as to convert about 80 wt% to about 99 wt% of the C 4 olefin in the feed.
  • the contacting (a) occurs in a boiling water reactor, also referred to as a heat exchanger reactor, hi one embodiment of the present invention, the contacting (a) occurs in at least 3 reactors.
  • the olefin oligomerization conditions in said contacting (a) has an olefinic recycle stream to feed stream weight ratio of from about 0.1 to about 3.0, alternatively from about 0.5 to about 2.0, alternatively from about 0.5 to about 1.3.
  • the contacting (a) is conducted at a WHSV of about 0.5 to about 6.0 based on the olefin in the feed stream.
  • the contacting (a) is conducted at a WHSV of about 0.7 to about 9.0 based on the olefin in the combined feed stream and olefinic recycle stream. In one embodiment of the present invention, the contacting (a) is conducted in a reaction zone, alternatively in a plurality of reaction zones in parallel, alternatively connected in series, and the difference between the highest and lowest temperatures within each reaction zone is 40°F (22°C) or less. In one embodiment of the present invention, the contacting (a) is conducted at a partial pressure of olefins of at least 400 psig. hi one embodiment of the present invention, the contacting (a) occurs in the presence of substantially no hydrogen.
  • the highest and lowest temperatures within any reaction zone are between about 150°C and about 350°C.
  • the molecular sieve comprises ZSM- 5, ZSM-Il, ZSM-12, ZSM-22, ZSM-57 and/or MCM-22.
  • the yield of butane and lighter saturates generated in contacting (a) is less than 2.0 wt%, alternatively less than 1.5 wt%, alternatively less than 1.0 wt%, alternatively less than 0.5 wt%.
  • the olefinic recycle stream comprises no more than 7 wt% of C 10 + non-normal olefins, and may have a final boiling point of no greater than 360°F (182 0 C). In one embodiment of the present invention, the olefinic recycle stream comprises no more than 30 wt% of Cg+ non- normal olefins, and may have a final boiling point of no greater than 310°F (154°C).
  • the olefinic recycle stream comprises at least about 1 wt% to about 50 wt% C 4 hydrocarbons, hi one embodiment of the present invention, the olefinic recycle stream comprises less than about 20 wt% C 3 - hydrocarbons.
  • the first hydrocarbon product stream comprises between about 2.0 wt% and about 25.0 wt% of C 9 non- normal olefin, hi one embodiment of the present invention, the first hydrocarbon product stream comprises between about 0.5 wt% and about 12 wt% of C 17 to C 20 hydrocarbons. In one embodiment of the present invention, the first hydrocarbon product stream has a final boiling point of less than about 350°F (177 0 C). hi one embodiment of the present invention, the first hydrocarbon product stream has an initial boiling point of at least 260 0 F (127°C).
  • the light olefinic stream contains no more than 7 wt% of C 10 + non-normal olefins, and may have a final boiling point of no greater than 360°F (182°C) and may have an initial boiling point of at least 260°F (127°C). In one embodiment of the present invention, the light olefinic stream comprises no more than 30 wt% C 9 + non-normal olefins, and may have a final boiling point of no greater than 310 0 F (154°C). In one embodiment of the present invention, the light olefinic stream comprises at least about 2 wt% to about 50 wt% C 4 hydrocarbons.
  • the light olefinic stream comprises no greater than about 20 wt% C 3 - hydrocarbons.
  • the separating (b) is conducted in one or more steps, such as in one or more of a flash drum, membrane, and fractional distillation tower. In one embodiment, the separating (b) is conducted in a fractionation tower.
  • At least 20 wt% of the light olefinic stream generated in splitting (c) is provided as said olefinic recycle stream in contacting (a), hi one embodiment of the present invention, at least 20 wt% of said olefinic recycle stream comprises said light olefinic recycle stream based on the total weight of said olefinic recycle stream.
  • the first hydrocarbon product stream is saturated with hydrogen to produce a saturated product which may comprise at least 80 wt% aliphatic hydrocarbons.
  • said first purge stream comprises from about 5 wt% to about 80 wt% of said light olefinic stream
  • said second purge stream is richer in C 4 - molecules than the first purge stream
  • said second purge stream comprises at least about 50 wt% C 4 - molecules.
  • the second purge stream comprises at least about 50 wt% C 4 - saturates, hi one embodiment of the present invention, the second purge stream comprises no greater than 30 wt% C 5 + molecules, hi one embodiment of the present invention, the second purge stream is in the vapor phase, hi one embodiment of the present invention, said second olefinic stream is richer in C 5 - C 8 molecules than the first purge stream, hi one embodiment of the present invention, the second olefinic stream comprises at least about 50 wt% C 5 - C 8 molecules, hi one embodiment of the present invention, the second olefinic stream comprises at least about 10 wt% to about 80 wt% C 5 - C 8 saturates, hi one embodiment of the present invention, the second olefinic stream comprises no greater than about 30 wt% C 4 - molecules, hi one embodiment of the present invention, the second olefinic stream comprises no greater than about 7.0 wt% C 10 + non-normal o
  • the second olefinic stream comprises no greater than about 30 wt% C 9 + non-normal olefins, and may have a final boiling point of no more than about 31O 0 F (154 0 C).
  • said splitting (e) is such that at least about 50 wt% of said second olefinic recycle stream is provided as said olefinic recycle stream in contacting (a).
  • the separating (d) of the first purge stream occurs in one or more steps.
  • Figure 1 is a flow diagram of a process for producing a hydrocarbon composition according to one embodiment of the invention.
  • C x hydrocarbon indicates hydrocarbon molecules having the number of carbon atoms represented by the subscript "x".
  • C x + hydrocarbons indicates those molecules noted above having the number of carbon atoms represented by the subscript "x” or greater.
  • C 10 + hydrocarbons would include C 10 , C 11 and higher carbon number hydrocarbons.
  • C x - hydrocarbons indicates those molecules noted above having the number of carbon atoms represented by the subscript "x” or fewer.
  • C 5 - C 8 means molecules having to 5 to 8 carbons.
  • Weight Hourly Space Velocity (WHSV) values cited herein are based on the amount of the molecular sieve contained in the olefin oligomerization catalysts without allowing for any binder or matrix that may also be present in the catalyst.
  • Distillation temperature values cited herein, including initial boiling point and final boiling point (or end point) refer to measurements made in accordance with ASTM Test Method D86, the entire contents of which are incorporated herein by reference.
  • normal olefin refers to any olefin that contains a single, unbranched chain of carbon atoms as defined in Hawley 's Condensed Chemical Dictionary, 14 th Edition. Therefore a "non-normal olefin,” as used herein, is an olefin that is not a “normal olefin,” and would, therefore, contain at least one branched chain of carbon atoms.
  • the present invention provides a process for oligomerizing a feed containing at least one C 3 to C 8 olefin together with an olefinic recycle stream containing no more than 10 wt% C 10 + non-normal olefins over a molecular sieve catalyst such that said olefinic recycle stream to fresh feed stream weight ratio is from about 0.1 to about 3.0, alternatively from about 0.5 to about 2.0, alternatively from about 0.5 to about 1.3, and the difference between the highest and lowest temperatures within the reactor is 40°F (22°C) or less.
  • the oligomerization effluent is then separated into a first hydrocarbon product stream and at least one light olefinic stream, also referred to as the first olefinic stream. At least part of the light olefinic stream(s) is recycled to the oligomerization process.
  • the hydrocarbon product streams are useful as fuel products or blending stocks to produce fuel products, such as Jet Fuel A and No. 1 and No. 2 Diesel. If desired, at least part of the hydrocarbon product streams can be hydrogenated to at least partially saturate the olefins contained therein, and similarly used as fuel products or blendstocks.
  • the fresh feed to the oligomerization process can include any single C 3 to C 8 olefin or any mixture thereof in any proportion.
  • Particularly suitable feeds include mixtures of propylene and butylenes having at least 5 wt%, such as at least 10 wt%, for example, at least 20 wt%, such as at least 30 wt% or at least 40 wt% C 4 olefin.
  • Also useful are mixtures of C 3 to C 5 olefins having at least 40 wt% C 4 olefin and at least 10 wt% C 5 olefin.
  • the feed should contain no more than about 1.0 wt%, or even no more than 0.1 wt% of C 2 - hydrocarbons, because ethylene is less reactive in the present process than other light olefin, and thus requires substantially more processing to obtain a good ultimate conversion. Further, ethylene and light saturates, such as ethane and methane, are highly volatile, and it will require much more work to recover them in the separation system, likely necessitating the use of expensive and complicated refrigeration systems.
  • C 9 + hydrocarbons of any kind, in the feed, to no more than about 10 wt%, or no more than 5 wt%, or even no more than 1 wt%, because C 9 + hydrocarbons are useful components of the first hydrocarbon product stream and so it is counter-productive to subject them to the oligomerization process of the invention.
  • the amount of non-olefins, especially saturates, in the feed should be less than 45 wt%, such as less than 35 wt%, for example, less than 25 wt%, typically less than 15 wt%, or less than 10 wt% or even less than 5 wt%.
  • the amount of non-olefins, especially saturates in the feed should be from about 5 wt% to about 45 wt%, from about 10 wt% to about 35 wt%, from about 15 wt% to about 25 wt%. More particularly, the amount of propane can be no greater than about 10 wt%, such as no more than 5 wt%, for example, no more than 1 wt%, or no more than 0.5 wt%. Even more particularly, the amount of propane can be no greater than about 0.5 wt% to about 10 wt% or about 1 wt% to about 5 wt%.
  • the olefmic feed is obtained by the conversion of an oxygenate, such as methanol, to olefins over a silicoaluminophosphate (SAPO) catalyst, according to the method of, for example, U.S. Patents 4,677,243 and 6,673,978; or an aluminosilicate catalyst, according to the method of, for example, WO04/18089; WO04/16572; EP 0 882 692; and U.S. Patent 4,025,575.
  • SAPO silicoaluminophosphate
  • the olefinic feed can be obtained by the catalytic cracking of relatively heavy petroleum fractions, or by the pyrolysis of various hydrocarbon streams, ranging from ethane to naphtha to heavy fuel oils, in admixture with steam, in a well understood process known as "steam cracking".
  • steam cracking a well understood process known as "steam cracking”.
  • the overall feed to the oligomerization process also contains an olefinic recycle stream containing no more than 10 wt% of C 10 + non- normal olefins.
  • the olefinic recycle stream should contain no greater than 7.0 wt%, for example, no greater than 5.0 wt%, such as no greater than 2.0 wt%, or no greater than 1.0 wt%, or even no greater than 0.1 wt% of C 10 + non- normal olefins.
  • the olefinic recycle stream should contain from about 0.1 wt% to about 10.0 wt%, or about 0.5 wt% to about 10.0 wt%, or about 1.0 wt% to about 7.0 wt% of C 1O + non-normal olefins.
  • the final boiling point temperature of the olefinic recycle stream should be no greater than 360°F (182°C), no greater than 34O 0 F (171°C), such as no greater than 32O 0 F (160 0 C), for example, no greater than 310 0 F (154°C), or even no greater than 305°F (152°C).
  • the final boiling point temperature of the olefinic recycle stream should be in the range of from 300°F (149°C) to 36O 0 F (182°C), from 305 0 F (152°C) to 340 0 F (171°C), or from 310 0 F (154°C) to 32O 0 F (160 0 C).
  • the olefinic recycle stream contains no greater than 30.0 wt%, such as, no greater than 25.0 wt%, for example, no greater than 20.0 wt%, or no greater than 15.0 wt%, or no greater than 10.0 wt% Of Cg+ non-normal olefins.
  • the olefinic recycle stream contains from about 5.0 wt% to about 30.0 wt%, or from about 10 wt% to about 25 wt%, or from about 15 wt% to about 20 wt% of C 9 + non-normal olefins.
  • the final boiling point temperature of the olefinic recycle stream should be no greater than 29O 0 F (143°C), such as no greater than 275 0 F (135°C), for example, no greater than 260 0 F (127°C).
  • the final boiling point temperature of the olefinic recycle stream should be in the range of from 260 0 F (127°C) to 310 0 F (154°C) or from 275 0 F (135°C) to 290 0 F (143°C).
  • the olefinic recycle stream contains at least 1 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt%, or at least 20 wt% C 4 hydrocarbons of any species. In one embodiment, the olefinic recycle stream contains no greater than 50 wt%, no greater than 40 wt%, no greater than 30 wt%, or no greater than 25 wt%, or no greater than 20 wt%, or no greater than 10 wt%, or no greater than 5 wt% C 4 hydrocarbons (of any species).
  • the olefinic recycle stream contains from about 1 wt% to about 50 wt%, or from about 5 wt% to about 40 wt%, or from about 10 wt% to about 30 wt%, or from about 20 wt% to about 25 wt% C 4 hydrocarbons (of any species). Additionally, the olefinic recycle stream may contain no greater than 20 wt%, no greater than 10 wt%, no greater than 5 wt%, or no greater than 2 wt% C 3 - hydrocarbons, such as propylene or propane.
  • the olefinic recycle stream may contain from about 0.1 wt% to about 20 wt%, or from about 0.5 wt% to about 10 wt%, or from about 1.0 wt% to about 5 wt%, or from about 1.5 wt% to about 2 wt% C 3 - hydrocarbons, such as propylene or propane.
  • This can be achieved by, for example, employing an additional separation of all or a portion of the olefinic recycle stream generated by a separation device into one stream comprising C 4 - with only a small amount of C 5 + hydrocarbons, and a second debutanized stream as all or a portion of the olefinic recycle stream provided to the oligomerization reactor.
  • the amount of olefinic recycle stream fed to the oligomerization process is such that said olefinic recycle stream to fresh feed stream weight ratio is from about 0.1 to about 3.0, alternatively from about 0.5 to about 2.0, alternatively from about 0.5 to about 1.3. More particularly, the weight ratio of olefinic recycle stream to fresh olefmic feedstock can be at least 0.1, or at least 0.3, or at least 0.5, or at least 0.7 or at least 0.9, but generally is no greater than 3.0, or no greater than 2.5, or no greater than 2.0, or no greater than 1.8, or no greater than 1.5 or no greater than 1.3.
  • the weight ratio of olefinic recycle stream to fresh olefinic feedstock can be from about 0.1 to about 3.0, or from about 0.3 to about 2.5, or from about 0.5 to about 2.0, or from about 0.7 to about 1.8, or from about 0.9 to about 1.5, or from about 1.0 to about 1.3.
  • the olefinic recycle stream is comprised of one or more substituent recycle streams obtained through various separations described herein, such as light olefinic recycle stream (also referred to as first olefinic recycle stream), or second olefinic recycle stream, or both in combination, or including others derived therefrom.
  • the oligomerization process of the invention comprises contacting the C 3 to C 8 olefin feed and the olefinic recycle stream with a molecular sieve catalyst under conditions such that the olefins are oligomerized to produce a hydrocarbon composition conveniently comprising at least 90 wt% of C 9 to C 20 non-normal olefin, non-normal saturates or combinations thereof.
  • a hydrocarbon composition conveniently comprising at least 90 wt% of C 9 to C 20 non-normal olefin, non-normal saturates or combinations thereof.
  • the hydrocarbon composition comprises less than 15 wt% of C 17 + non-normal olefins, and generally less than 15 wt% of C 17 + hydrocarbons.
  • the catalyst used in the oligomerization process can include any crystalline molecular sieve which is active in olefin oligomerization reactions.
  • the catalyst includes a medium pore size molecular sieve having a Constraint Index of about 1 to about 12. Constraint Index and a method of its determination are described in U.S. Patent 4,016,218, which is incorporated herein by reference.
  • suitable medium pore size molecular sieves are those having 10-membered ring pore openings and include those of the TON framework type (for example, ZSM-22, ISI-I, Theta-1, Nu-10, and KZ-2), those of the MTT framework type (for example, ZSM-23 and KZ-I), of the MFI structure type (for example, ZSM-5), of the MFS framework type (for example, ZSM-57), of the MEL framework type (for example, ZSM-Il), of the MTW framework type (for example, ZSM-12), of the EUO framework type (for example, EU-I) and members of the ferrierite family (for example, ZSM-35).
  • TON framework type for example, ZSM-22, ISI-I, Theta-1, Nu-10, and KZ-2
  • MTT framework type for example, ZSM-23 and KZ-I
  • MFI structure type for example, ZSM-5
  • MFS framework type for example, ZSM-57
  • MEL framework type for example,
  • Suitable molecular sieves include those having 12- membered pore openings, such as ZSM-18, zeolite beta, faujasites, zeolite L, mordenites, as well as members of the MCM-22 family of molecular sieves (including, for example, MCM-22, PSH-3, SSZ-25, ERB-I, ITQ-I, ITQ-2, MCM- 36, MCM-49 and MCM-56).
  • Other 10- and 12-member pore ring structure aluminosilicates and their SAPO analogs will also function.
  • the molecular sieve catalyst comprises ZSM-5 having a homogeneous crystal size of ⁇ 0.05 micron and a relatively high activity (alumina content) characterized by a SiO 2 / Al 2 O 3 molar ratio of around 50:1.
  • the molecular sieve may be supported or unsupported, for example, in powder form, or used as an extrudate with an appropriate binder.
  • the binder is conveniently a metal oxide, such as alumina, and is present in an amount such that the oligomerization catalyst contains between about 2 and about 80 wt% of the molecular sieve.
  • the oligomerization reaction should be conducted at sufficiently high WHSV of fresh feed to the reactor to ensure the desired low level of C 17 + oligomers in the reaction product.
  • WHSV is based on the weight of the entire catalyst in the reaction zone, for a catalyst that is 65 wt% active molecular sieve and 35 wt% inert binder/filler. (One can thus determine WHSV based on weight of active material in the reaction zone through dividing the values provided herein by 0.65, allowing one to determine the appropriate WHSV for a catalyst comprising any amount of active material used in the present invention.
  • WHSV of 1.0 stated herein would, for a catalyst having 32.5 wt% active material and 67.5 wt% inert binder/filler, be equivalent to a WHSV of 0.5).
  • the reaction should occur at a WHSV of no less than 0.5 or no less than 0.7, or no less than 1.0, or no less than 1.2, or no less than 1.4, or no less than 1.6, or no less than 1.8, or no less than 2.0, or no less than 2.5, or no less than 3.0, or no less than 3.5, or no less than 4.0 based on olefin in the fresh feed to the reactor.
  • the upper level of WHSV is not narrowly defined, but is generally not more than 6.0 or 5.0 based on olefin in the fresh feed to the reactor. Increasing the WHSV beyond these levels may significantly decrease the catalyst/reactor cycle length between regenerations, especially at higher levels of C 4 conversion.
  • the reaction should occur at a WHSV of from 0.5 to about 6.0, or from about 0.7 to about 5.0, or from about 1.0 to about 4.0 based on olefin in the fresh feed to the reactor.
  • the WHSV should be no less than about 0.7, or no less than about 1.0, or no less than about 1.5, or no less than about 1.8, or no less than about 2.2, or no less than about 2.5, or no less than about 3.0 or no less than about 3.5 based on the olefin contained in the combined feed stream and olefinic recycle stream(s) to the reactor.
  • the WHSV for the combined fresh olefin feed and recycle to the reactor should be no more than about 9.0, about 8.0, about 7.0, or about 6.0 based on the olefin contained in the combined feed stream and olefinic recycle stream(s) to the reactor.
  • the WHSV should be from about 0.7 to about 9.0, or from about 1.0 to about 8.0, or from about 1.5 to about 7.0, or from about 1.8 to about 6.0.
  • the oligomerization process can be conducted over a wide range of temperatures, although generally the highest and lowest temperatures within the oligomerization reaction zone should be between about 150°C and about 35O 0 C, such as between about 180 0 C and about 330 0 C, for example, between about 210 0 C and 310 0 C.
  • the difference between the highest and lowest temperatures within the reactor should be maintained at about 4O 0 F (22 0 C) or less, such as about 30 0 F (17°C) or less, for example, about 2O 0 F (H 0 C) or less, conveniently about 10°F (6 0 C) or less, or even about 5 0 F (3 0 C) or less.
  • the difference between the highest and lowest temperatures within the reactor should be maintained from about 1°F (0.6 0 C) to about 40 0 F (22°C), or from about 5 0 F (3°C) to about 30 0 F (17°C), or from about 1O 0 F (6°C) to about 20 0 F (11°C).
  • the oligomerization process can be conducted over a wide range of olefin partial pressures, although higher olefin partial pressures are preferred since low pressures tend to promote cyclization and cracking reactions, and are thermodynamically less favorable to the preferred oligomerization reaction.
  • Typical olefin partial pressures of olefins in the combined feed stream and olefinic recycle stream as total charge to the reactor comprise at least about 400 psig (2860 kPa), such as at least about 500 psig (3550 kPa), for example, at least about 600 psig (4240 kPa), or at least about 700 psig (4930 kPa), or at least about 800 psig (5620 kPa), or even about 900 psig (6310 kPa).
  • Typical olefin partial pressures of olefins in the combined feed stream and olefinic recycle stream as total charge to the reactor are in the range of from about 400 psig (2860 kPa) to about 2000 psig (13,782 kPa), or from about 500 psig (3550 kPa) to about 1500 psig (10,337 kPa), or from about 600 psig (4240 kPa) to about 1200 psig (8269 kPa). It will, of course, be appreciated that the olefin partial pressure will be lower at the exit to the reactor as fewer moles of olefins exist due to the oligomerization reaction.
  • the conditions of the oligomerization process are controlled so as ensure that the conversion of C 4 olefins in the feed is at least about 80 wt%, or at least about 85 wt% or at least about 90 wt%, or at least about 92 wt%, but no greater than about 99%, or no greater than about 98 wt%, or no greater than about 96 wt%, or no greater than about 94 wt%.
  • the conditions of the oligomerization process are controlled so as to ensure that the conversion of C 4 olefins in the feed is in the range of from about 80 wt% to about 99 wt%, or from about 85 wt% to about 98 wt%, or from about 90 wt% to about 96 wt%, or from about 92 wt% to about 94 wt%.
  • the catalyst will lose activity due to the accumulation of carbonaceous deposits and hence the C 4 olefin conversion will tend, to decline with time.
  • the temperature at which the oligomerization reaction is conducted is continually raised until some limit, discussed above, is reached.
  • the catalyst is generally regenerated, either in situ or ex situ, by combustion of the coke deposits with oxygen/air using methods and conditions that are well known in the art.
  • the regenerated catalyst may then be used again in the oligomerization reaction at some initial temperature, with the continually increasing temperature cycle being repeated.
  • the catalyst and the reactor conditions may be selected to achieve a low yield of butane and lighter saturates from the oligomerization reaction, such as no greater than about 2.0 wt%, or no greater than about 1.5 wt%, or no greater than about 1.0 wt% butanes and lighter saturates.
  • the catalyst and the reactor conditions may be selected to achieve a low yield of butane and lighter saturates from the oligomerization reaction in the range of from about 0.1 wt% to about 2.0 wt%, or from about 0.2 wt% to about 1.5 wt% butanes and lighter saturates.
  • the oligomerization process is conducted in a plurality of serial adiabatic reactors with interstage cooling, such as is disclosed in U.S. Patent 4,560,536, the entire contents of which is incorporated herein by reference.
  • the reactors employed are boiling water reactors, sometimes called heat exchanger reactors, e.g., such as is discussed in U.S. Patents 4,263,141 and 4,369,255 (for methanol production), and "Petroleum Processing, Principles and Applications," RJ. Hengstebeck, McGraw-Hill, 1959, pages 208-218 (specifically for olefin oligomerization, using solid phosphoric acid).
  • hydrogen is added to the reactor or is present in detectable amounts in the feed stream, there can be no greater than about 0.60 wt%, no greater than about 0.50 wt%, no greater than about 0.40 wt%, no greater than about 0.30 wt%, no greater than about 0.20 wt%, no greater than about 0.10 wt%, no greater than about 0.05 wt%, no greater than about 0.01 wt%, or no greater than about 0.005 wt%, based on the total feed stream to the reactor.
  • hydrogen is added to the reactor or is present in detectable amounts in the feed stream, there can be a range of from about 0.001 wt% to about 0.60 wt%, or from about 0.005 wt% to about 0.50 wt%, or from about 0.01 wt% to about 0.40 wt%, or from about 0.05 wt% to about 0.30 wt%, or from about 0.10 wt% to about 0.20 wt%, based on the total feed stream to the reactor.
  • hydrogen is added to the reactor or is present in detectable amounts in the feed stream, and therefore present in the olefinic recycle streams, there can be no greater than about 0.20 wt%, no greater than about 0.18 wt%, no greater than about 0.15 wt%, no greater than about 0.10 wt%, no greater than about 0.05 wt%, no greater than about 0.01 wt%, or no greater than about 0.005 wt%, based on the total feed stream and the olefinic recycle streams to the reactor.
  • hydrogen is added to the reactor or is present in detectable amounts in the feed stream, and therefore present in the olefinic recycle streams, there can be a range of from about 0.001 wt% to about 0.20 wt%, or from about 0.005 wt% to about 0.18 wt%, or from about 0.01 wt% to about 0.15 wt%, or from about 0.05 wt% to about 0.10 wt%, based on the total feed stream and the olefinic recycle streams to the reactor.
  • the separation may be conducted in one or more steps, e.g., a series of flash drums, membranes, or fractional distillation towers, whose appropriate products, either singly or in combination, meet the requirement of having no greater than 10 wt% C 10 + non-normal olefins to be provided as part of the olefinic recycle to the reactor.
  • steps e.g., a series of flash drums, membranes, or fractional distillation towers, whose appropriate products, either singly or in combination, meet the requirement of having no greater than 10 wt% C 10 + non-normal olefins to be provided as part of the olefinic recycle to the reactor.
  • One configuration of the present invention will have the oligomerization product provided directly to a fractionation tower to conduct the separation.
  • directly is meant that no other appreciable separation of components in the oligomerization product is conducted that results in a stream provided to the reactor for recycle prior to the oligomerization product being introduced to the fractionation tower, e.g., the oligomerization product may be provided to a flash drum, to reliably let down the pressure of the stream and provide a separate vapor and liquid stream to different parts of a fractionation tower, where the appropriate separation to produce a light olefinic stream, also referred to as first olefinic stream, is conducted; this would still be "direct.”
  • the light olefin stream, or first olefin stream, overhead which may be a large portion of the overall olefinic recycle stream(s), and the hydrocarbon product bottoms, which is suitable for use without further processing
  • Conditions can be selected, with regard to the feedstock saturates level, the proportion of light olefinic stream, or first olefinic stream, utilized as olefinic recycle stream and the overhead pressure of the fractionation tower, to allow the overhead product of the fractionation tower receiving the oligomerization product to be totally condensed at a temperature (that is, have a "bubble point temperature") of at least about 80°F (27°C), or about 9O 0 F (32°C), or about 100 0 F (38°C), or about 110 0 F (43 0 C), or even about 12O 0 F (49°C).
  • At least 80 or 90 wt% of the overhead product can be condensed at a temperature of at least about 80 0 F (27 0 C), or about 90 0 F (32°C), or about 100 0 F (38°C), or about 110 0 F (43°C), or even about 120° F (49°C).
  • This uses what is called a mixed condenser, where both a vapor and liquid stream are generated as overhead products. Controlling features are the same as for total condensation.
  • an overhead pressure of no greater than about 80 psig (550 kPa), or about 60 psig (413 kPa), or about 40 psig (276 kPa), or about 25 psig (172 kPa), or about 10 psig (69 kPa) is suitable.
  • the fractionation tower separating the oligomerization product can be operated at an overhead pressure of from about 1 psig (7 kPa) to about 80 psig (550 kPa), or from about 3 psig (21 kPa) to about 60 psig (413 kPa).
  • the weight ratio of C 4 molecules to C 5 - C 8 molecules in the light olefinic stream can be at least about 0.85, or about 0.90, or about 0.95 times and no greater than about 1.05, or about 1.10, or about 1.15 times the weight ratio of C 4 - molecules to C 5 - C 8 molecules in the oligomerization effluent stream.
  • the weight ratio of C 4 - molecules to C 5 - C 8 molecules in the light olefinic stream can be in the range of from about 0.85 to about 1.15, or from about 0.90 to about 1.10, or from about 0.95 to about 1.05 times the weight ratio of C 4- molecules to C 5 - C 8 molecules in the oligomerization effluent stream.
  • the light olefinic stream can also contain no greater than about 7.0 wt%, about 5.0 wt%, about 2.0 wt%, about 1.0 wt%, or even about 0.1 wt% C 10 + non-normal olefins.
  • the light olefinic stream can also contain a range of from about 0.1 wt% to about 7.0 wt%, or from about 0.5 wt% to about 5.0 wt%, or from about 1.0 wt% to about 2.0 wt% C 10 + non-normal olefins.
  • the final boiling point temperature of the light olefinic stream can be no greater than about 360°F (182°C), about 340 0 F (17O 0 C), about 32O 0 F (160 0 C), about 310°F (155 0 C), or even about 305 0 F (152°C), according to ASTM Test Method D86.
  • the initial boiling point of the distillate product can be at least about 26O 0 F (127°C), about 280°F (138°C), about 300 0 F (149°C), about 320°F (160 0 C), about 34O 0 F (171 0 C), or about 360 0 F (182°C), according to ASTM Test Method D86.
  • the final boiling point temperature of the light olefinic stream can be in the range of from about 300 0 F (149°C) to about 360 0 F (182 0 C), or from about 305 0 F (152 0 C) to about 340 0 F (171°C), or from about 310 0 F (155 0 C) to about 320 0 F (160 0 C), according to ASTM Test Method D86.
  • the initial boiling point of the distillate product can be in the range of from about 260 0 F (127°C) to about 360 0 F (182 0 C), or from about 280 0 F (138°C) to about 340 0 F (171°C), or from about 300 0 F (149 0 C) to about 320 0 F (16O 0 C), according to ASTM Test Method D86.
  • the light olefinic stream can also contain no greater than about 30.0 wt%, about 25.0 wt%, about 20.0 wt%, about 15.0 wt%, or about 10.0 wt% C 9 + non-normal olefins.
  • the light olefinic stream can also contain in the range of from about 5.0 wt% to about 30.0 wt%, or from about 10.0 wt% to about 25.0 wt%, or from about 15.0 wt% to about 20.0 wt% C 9 + non-normal olefins.
  • the final boiling point temperature of the light olefinic stream can be no greater than about 290°F (143°C), about 275°F (135°C), or about 26O 0 F (127°C), according to ASTM Test Method D86.
  • the final boiling point temperature of the light olefinic stream can be in the range of from about 260°F (127 0 C) to about 310°F (155°C), or from about 275°F (135 0 C) to about 29O 0 F (143°C), according to ASTM Test Method D86.
  • the light olefinic stream can have at least about 2 wt%, or about 5 wt%, or about 10 wt%, or about 20 wt%, or about 25 wt% C 4 hydrocarbons of any species.
  • the light olefinic stream can have a range of from about 2 wt% to about 25 wt%, or from about 5 wt% to about 20 wt%, or from about 10 wt% to about 15 wt% C 4 hydrocarbons of any species.
  • the light olefinic stream can work with no greater than about 60 wt% , or about 50 wt%, or about 40 wt%, or about 30 wt%, or about 25 wt%, or about 20 wt%, or about 10 wt%, or about 5 wt% C 4 hydrocarbons of any species, hi addition, the light olefinic stream can work with no greater than about 20 wt%, or about 10 wt%, or about 5 wt%, or about 2 wt%, or about 1 wt% of C 3 - hydrocarbons of any species.
  • the light olefinic stream can work with a range of from about 0.1 wt% to about 20 wt%, or from about 0.1 wt% to about 10 wt%, or from about 1 wt% to about 5 wt% C 3 - hydrocarbons of any species.
  • the light olefinic stream can work with no greater than about 50 wt%, or about 40 wt%, or about 30 wt%, or about 25 wt%, or about 20 wt%, or about 10 wt%, or about 5 wt% C 4 hydrocarbons (of any species),
  • the light olefinic stream can work with a range of from about 5 wt% to about 50 wt%, or from about 10 wt% to about 40 wt%, or from about 20 wt% to about 35 wt%, or from about 25 wt% to about 30 wt% C 4 hydrocarbons (of any species).
  • the light olefinic stream can work with no greater than about 20 wt%, or about 10 wt%, or about 5 wt%, or about 2 wt% of C 3 - hydrocarbons of any species.
  • the light olefinic stream can work with a range of from about 2 wt% to about 20 wt%, or from about 5 wt% to about 10 wt% of C 3 - hydrocarbons of any species.
  • the light olefinic stream is split into compositionally equivalent streams to form the light olefinic recycle stream, or first olefinic recycle stream, and the first purge stream.
  • Compositionally equivalent as used herein, is intended to mean merely a physical separation into two or more streams, and not a temperature or chemical separation, such as distillation, fractionation, or other well known means in the art.
  • the separations of the oligomerization effluent stream into the first olefinic stream and the first hydrocarbon product stream, and the first purge stream into the second purge stream and the second olefinic stream result in two streams that are compositionally distinct.
  • the first purge stream at least about 5 wt%, or about 10 wt%, or about 20 wt%, or about 35 wt%, or about 50 wt% of the light olefinic stream can be the first purge stream. No greater than about 80 wt% or about 60 wt% of the light olefinic stream can be first purge stream.
  • From about 5 wt% to about 80 wt%, or from about 10 wt% to about 60 wt%, or from about 20 wt% to about 50 wt%, or from about 30 wt% to about 35 wt% of the light (first) olefinic stream can be the first purge stream.
  • the second purge stream can contain at least about 50 wt%, or about 60 wt%, or about 70 wt%, or about 80 wt%, or about 90 wt%, or about 95 wt% C 4 - molecules.
  • the second purge stream can contain at least about 50 wt%, or about 60 wt%, or about 70 wt%, or about 80 wt%, or about 90 wt%, or about 95 wt% C 4 - saturates.
  • the second purge stream can contain no greater than about 30 wt%, or about 20 wt%, or about 10 wt%, or about 5 wt%, or about 1 wt% C 5 + molecules.
  • the second purge stream can contain a range of from about 50 wt% to about 95 wt%, or from about 60 wt% to about 90 wt%, or from about 70 wt% to about 80 wt% C 4 - molecules.
  • the second purge stream can contain a range of from about 50 wt% to about 95 wt%, or from about 60 wt% to about 90 wt%, or from about 70 wt% to about 80 wt% C 4 - saturates.
  • the second purge stream can contain a range of from about 1 wt% to about 30 wt%, or from about 5 wt% to about 20 wt%, or from about 10 wt% to about 15 wt% C 5 + molecules.
  • the second purge stream can be in the vapor phase, and can be utilized as a fuel gas.
  • the second olefinic stream can contain at least about 50 wt%, or about 60 wt%, or about 70 wt%, or about 80 wt%, or about 90 wt%, or about 95 wt% C 5 - C 8 molecules.
  • the second olefinic stream can contain at least about 10 wt%, or about 20 wt%, or about 30 wt% C 5 — C 8 saturates.
  • the second olefinic stream can contain no greater than about 80 wt%, or about 70 wt%, or about 60 wt%, or about 50 wt% C 5 - C 8 saturates.
  • the second olefinic stream can contain no greater than about 30 wt%, or about 20 wt%, or about 10 wt%, or about 5 wt%, or about 1 wt% C 4 - molecules.
  • the second olefinic stream can contain in the range of from about 50 wt% to about 95 wt%, or from about 60 wt% to about 90 wt%, or from about 70 wt% to about 80 wt% C 5 - C 8 molecules.
  • the second olefinic stream can contain in the range of from about 10 wt% to about 80 wt%, or from about 15 wt% to about 70 wt%, or from about 20 wt% to about 60 wt%, or from about 30 wt% to about 50 wt% C 5 - C 8 saturates.
  • the second olefinic stream can contain in the range of from about 1 wt% to about 30 wt%, or from about 5 wt% to about 20 wt%, or from about 10 wt% to about 15 wt% C 4 - molecules.
  • the second olefinic stream can also contain no greater than about 7.0 wt%, about 5.0 wt%, about 2.0 wt%, about 1.0 wt%, or even about 0.1 wt% C 1 O+ non-normal olefins.
  • the second olefinic stream can also contain in the range of from about 0.1 wt% to about 7.0 wt%, or from about 0.5 wt% to about 5.0 wt%, or from about 1.0 wt% to about 2.0 wt% C 10 + non-normal olefins.
  • the final boiling point temperature of the second olefinic stream can be no greater than about 360°F (182°C), about 34O 0 F (17O 0 C), about 320 0 F (160 0 C), about 310 0 F (155°C), or even about 305 0 F (152°C), according to ASTM Test Method D86.
  • the final boiling point temperature of the second olefinic stream can be in the range of from about 300 0 F (149 0 C) to about 360 0 F (182°C), or from about 305 0 F (152°C) to about 34O 0 F (171°C), or from about 310 0 F (155°C) to about 320 0 F (160 0 C), according to ASTM Test Method D86.
  • the second olefinic stream can also contain no greater than about 30.0 wt%, about 25.0 wt%, about 20.0 wt%, about 15.0 wt%, or about 10.0 wt% Cg+ non-normal olefins.
  • the second olefinic stream can also contain a range of from about 5.0 wt% to about 30.0 wt%, or from about 10.0 wt% to about 25.0 wt%, or from about 15.0 wt% to about 20.0 wt% C 9 + non-normal olefins.
  • the final boiling point temperature of the second olefinic stream can be no greater than about 290 0 F (143°C), about 275 0 F (135°C), or about 260 0 F (127°C), according to ASTM Test Method D86.
  • the final boiling point temperature of the second olefinic stream can be in the range of from about 260 0 F (127°C) to about 31O 0 F (155°C), or from about 275 0 F (135 0 C) to about 290 0 F (143 0 C), according to ASTM Test Method D86.
  • the second olefinic stream is split into compositionally equivalent streams to form the second olefinic recycle stream and the second hydrocarbon product stream.
  • compositionally equivalent as used herein, is intended to mean merely a physical separation into two or more streams, and not a temperature or chemical separation, such as distillation, fractionation, or other well known means in the art. Therefore, the description of the second olefinic stream is also the description of the second hydrocarbon product stream.
  • the separation may be conducted in one or more steps, e.g., a series of flash drums, membranes, or fractional distillation towers, whose appropriate products, either singly or in combination, meet the requirement of providing a stream richer in C 4 - molecules than the first purge stream, and a stream richer in C 5 — C 8 molecules than the first purge stream.
  • steps e.g., a series of flash drums, membranes, or fractional distillation towers, whose appropriate products, either singly or in combination, meet the requirement of providing a stream richer in C 4 - molecules than the first purge stream, and a stream richer in C 5 — C 8 molecules than the first purge stream.
  • One configuration will have the first purge stream provided directly to a fractionation tower to conduct the separation.
  • the first purge stream may be provided to a refrigerated condensor drum to provide a separate vapor and liquid stream to different parts of a fractionation tower, where the appropriate separation to produce a stream richer in C 4 - molecules than the first purge stream and a stream richer in C 5 - C 8 molecules than the first purge stream is conducted; this would still be "direct.”
  • the stream richer in C 4 - molecules separated from the first purge stream can be in the vapor phase, in an operation known as a partial condenser.
  • Conditions can be selected, with regard to the feedstock saturates level, the proportion of light olefinic stream utilized as olefinic recycle stream and the overhead pressure of the fractionation tower, to allow at least about 50 wt%, or about 60 wt%, or about 70 wt%, or about 80 wt%, or about 90 wt% of the overhead product to be condensed at a temperature of at least about 80°F (27°C), or about 90°F (32 0 C) 5 or about 100°F (38°C), or about 110°F (43°C), or even about 120°F (49 0 C).
  • fractionation tower In a partial condenser operation, no liquid product is withdrawn, rather all liquid is recycled to the top of the fractionation tower as reflux.
  • fractionation tower can be operated at a wide range of pressures, an overhead pressure of no greater than about 100 psig (689 kPa) or about 80 psig (551 kPa), and an overhead pressure of at least about 20 psig (138 kPa) or about 40 psig (276 kPa), is suitable.
  • a typical plant fuel gas system to which the vapor stream richer in C 4 - molecules may be directed, operates at around 50 - 70 psig (345 - 482 kPa).
  • the light olefinic stream is split into compositionally equivalent streams to form the light olefinic recycle stream, or first olefinic recycle stream, and the first purge stream.
  • At least about 20 wt%, or about 40 wt%, or about 60 wt%, or about 80 wt%, or about 90 wt% of the light olefinic stream can be provided to the reaction zone as olefinic recycle stream.
  • the light olefinic stream can be provided to the reaction zone as olefinic recycle stream in the range of from about 20 wt% to about 90 wt%, or from about 40 wt% to about 80 wt%, or from about 50 wt% to about 60 wt% of the light olefinic stream.
  • the light olefinic recycle stream can be at least about 20 wt%, or about 40 wt%, or about 60 wt%, or about 80 wt%, or about 90 wt% of the total olefinic recycle stream(s) provided to the reaction zone.
  • the light olefinic recycle stream can be in the range of from about 20 wt% to about 90 wt%, or from about 40 wt% to about 80 wt%, or from about 50 wt% to about 60 wt% of the total olefinic recycle stream(s) provided to the reaction zone. In fact, it may comprise the entire (100%, i.e., the only) olefinic recycle stream provided to the reaction zone.
  • the light olefinic recycle stream can be mixed with the olefinic feed stream, e.g., in a drum, with the combined stream from the drum then pumped up to the reaction pressure for introduction to the reaction zone.
  • a portion of the second olefinic stream can be provided to the oligomerization reaction zone as part of the olefinic recycle stream, separately or combined with another substituent stream (e.g., a light olefinic stream), as the second olefinic recycle stream, with the remainder purged from the system as a second hydrocarbon product stream.
  • another substituent stream e.g., a light olefinic stream
  • the second olefinic recycle stream provided to the oligomerization reaction zone as part of the olefinic recycle stream can be at least about 50 wt%, or about 60 wt%, or about 70 wt%, or about 80 wt%, or about 90 wt% of the total second olefinic stream.
  • the second olefinic recycle stream provided to the oligomerization reaction zone as part of the olefinic recycle stream can be in the range of from about 50 wt% to about 90 wt%, or from about 60 wt% to about 80 wt%, or from about 65 wt% to about 70 wt% of the total second olefinic stream.
  • the hydrocarbon composition recovered as the first hydrocarbon product stream in the process of the invention comprises at least about 1.0 wt%, such as at least about 2.0 wt%, such as at least about 3.0 wt%, for example, at least about 4.0 wt%, conveniently at least about 5.0 wt%, or even at least about 10.0 wt% of C 9 non-normal olefin.
  • the hydrocarbon composition recovered as the first hydrocarbon product stream in the process of the invention comprises in the range of from about 1.0 wt% to about 10.0 wt%, or from about 2.0 wt% to about 5.0 wt%, or from about 3.0 wt% to about 4.0 wt% of C 9 non-normal olefin.
  • the first hydrocarbon product stream comprises no greater than about 30 wt%, for example, no greater than about 25 wt%, conveniently no greater than about 20 wt%, or no greater than about 15 wt% of Cg non-normal olefin.
  • the hydrocarbon composition recovered as the first hydrocarbon product stream in the process of the invention comprises in the range of from about 1.0 wt% to about 30 wt%, or from about 2.0 wt% to about 25.0 wt%, or from about 3.0 wt% to about 20.0 wt% of Cg non-normal olefin.
  • the first hydrocarbon product stream contains at least about 90 wt%, for example, at least about 92 wt%, such as at least about 95 wt%, or even at least about 97 wt% of C 9 to C 20 non-normal olefins, non-normal saturates or combinations thereof.
  • the first hydrocarbon product stream contains in the range of from about 90 wt% to about 97 wt%, or from about 92 wt% to about 95 wt% of C 9 to C 20 non-normal olefins, non-normal saturates or combinations thereof.
  • the first hydrocarbon product stream generally contains at least about 0.5 wt%, or at least about 1.0 wt%, or at least about 2.0 wt%, or even at least about 3.0 wt%, or at least about 5.0 wt% of C 17 to C 20 non-normal olefins, but typically no greater than about 12.0 wt%, or no greater than about 10.0 wt%, or no greater than about 8.0 wt%, or no greater than about 6.0 wt%, or even no greater than about 4.0 wt%, or even no greater than about 2.0 wt% of C 17 to C 20 non-normal olefins.
  • the first hydrocarbon product stream generally contains in the range of from about 0.5 wt% to about 12.0 wt%, or from about 1.0 wt% to about 10.0 wt%, or from about 2.0 wt% to about 8.0 wt%, or from about 3.0 wt% to about 6.0 wt%, or from about 4.0 wt% to about 5.0 wt% of C 17 to C 20 non- normal olefins.
  • C 21 + hydrocarbons, such as non-normal olefins may also be present, though typically the content is very low or even undetectable.
  • the initial boiling point of the first hydrocarbon product stream is typically at least about 260°F (127 0 C), such as at least about 280°F (138 0 C), including at least about 300°F (149 0 C), for example, at least about 32O 0 F (16O 0 C), or even at least about 340°F (171 0 C), or even at least about 36O 0 F (182 0 C).
  • the initial boiling point of the first hydrocarbon product stream is typically in the range of from about 26O 0 F (127 0 C) to about 36O 0 F (182 0 C), or from about 28O 0 F (138 0 C) to about 340 0 F (171 0 C), or from about 300 0 F (149 0 C) to about 32O 0 F (160 0 C).
  • the final boiling point of the first hydrocarbon product stream is typically no greater than about 35O 0 C, such as no greater than about 33O 0 C, for example, no greater than about 310 0 C or even no greater than about 300 0 C.
  • the final boiling point of the first hydrocarbon product stream is typically in the range of from about 260°C to about 350°C, or from about 280°C to about 330°C.
  • the first hydrocarbon product stream produced by the process of the invention can be used directly as a blending stock to produce jet or diesel fuel.
  • the first hydrocarbon product stream can be hydrogenated, e.g., according to the method of U.S. Patents 4,211,640 and 6,548,721, the entire contents of which are incorporated herein by reference, to saturate at least part of the olefins therein and produce a saturated product.
  • the saturated product can contain at least about 80 wt%, or at least about 85 wt%, or at least about 90 wt%, or at least about 95 wt% or at least about 99 wt% aliphatic hydrocarbons.
  • the saturated product can contain in the range of from about 80 wt% to about 99 wt%, or from about 85 wt% to about 95 wt%, or from about 87 wt% to about 90 wt% aliphatic hydrocarbons. All other characteristics of the saturated distillate product in terms of carbon number distribution, non-normal proportions and boiling point ranges will remain largely unchanged from the olefinic product.
  • FIG. 1 there is shown one example of an oligomerization process for producing a hydrocarbon composition according to the invention.
  • the process shown in Figure 1 employs an oligomerization system 10, comprising heat exchanger reactor and feed system 12 and separation system 14.
  • Heat exchanger reactor and feed system 10 includes heat exchanger reactor 26 and feed mixing drum 22.
  • Ancillary elements of heat exchanger reactor and feed system 12 that may exist in practical application of the system according to the present invention, within the knowledge of the skilled artisan, have been omitted for the sake of clarity of the present inventive concept.
  • a pump on the suction of feed mixing drum 22 providing pressurized material to heat exchanger reactor 26, heat exchangers for preheating the pressurized material or cooling the oligomerization effluent stream from heat exchanger reactor 26, and various control valves and instrumentation.
  • Separation system 14 includes a first fractional distillation column 38 and a second fractional distillation column 46, and again, ancillary elements of separation system 14 that may exist in practical application of the system according to the present invention, within the knowledge of the skilled artisan, have been omitted for the sake of clarity of the present inventive concept.
  • ancillary elements would include, for example, overhead condensers, reflux drums and reflux pumps, water removal means associated with the reflux drum bottoms reboilers, product pumps, heat exchangers for cooling product and achieving improved efficiency by preheating pressurized material provided to heat exchanger reactor 26, and various control valves and instrumentation.
  • a feed stream containing at least one C 3 to C 8 olefin is provided in line 16 to feed mixing drum 22.
  • a portion of the light olefinic recycle stream is provided via line 18 as one olefinic recycle stream to feed mixing drum 22, along with the second olefinic recycle stream in line 20.
  • the combined feed stream and olefinic recycle streams are provided as a common stream in line 24 to heat exchanger reactor 26.
  • Oligomerization catalyst is present within the tubes 28 of heat exhanger reactor 26. Conditions are provided, for example, the pressure and temperature of the combined feed stream and olefinic recycle streams in line 24, the pressure and temperature within heat exchanger reactor 26, and WHSV, among others, such that the oligomerization reaction occurs within tubes 28.
  • the oligomerization reaction generates heat, and the heat passes through tubes 28 to be absorbed by boiling water flowing around the outside of the tubes in shell side 30.
  • the boiling water in shell side 30 is a mixture of steam and liquid water that passes through line 34.
  • Make-up liquid boiler feed water conveniently at its bubble point at the desired pressure within shell side 30, is provided in line 32.
  • the steam generated in the heat exchanger reactor 26 may be used, for example, to provide heat in fractionation tower reboilers or to make electricity in turbogenerators.
  • a quite pure component such as water
  • the temperature of the boiling fluid in shell side 30 must be kept lower than the desired oligomerization reaction temperature within tubes 28, conveniently at least 5°C lower, such as at least 10 0 C lower, including at least 15°C lower and even at least 20 0 C lower, but typically not exceeding 40°C lower.
  • the tubes 28, have a small diameter, for example, an outside diameter of less than about 3 inches, conveniently less than about 2 inches, such as less than about 1.7 inches, and an inside diameter commensurate with the desired pressure rating for the inside of the tubes 28.
  • Tubes 28, also may have a relatively long length, such as greater than about 5 meters, including greater than about 7 meters, conveniently greater than about 9 meters.
  • the oligomerization effluent stream exits heat exchanger reactor 26 through line 36, having a first weight ratio of C 4 - molecules to C 5 - C 8 molecules, and is provided to first fractional distillation column 38, comprising a feed tray and a number of trays above and below the feed tray sufficient to enable separation of components in the oligomerization reaction product.
  • First fractional distillation column 38 serves to separate the oligomerized effluent stream in line 36 into a light olefinic stream as an overhead product in line 42, and a first hydrocarbon product stream as a bottoms product in line 40.
  • First fractional distillation column 38 is operated such that the light olefinic stream in line 42 has a composition including a second weight ratio of C 4 - molecules to C 5 - C 8 molecules that is at least 0.80 and no greater than 1.20 times the weight ratio of C 4 - molecules to C 5 - C 8 molecules found in the oligomerization effluent stream. Further, the light olefinic stream in line 42 contains no greater than 10 wt% C 10 + olefinic hydrocarbon molecules, and the first hydrocarbon product stream in line 40 contains at least 1 and no greater than 30 wt% C 9 non-normal hydrocarbons. Such a separation is readily effected through proper selection of, for example, the number of trays, the reboiler duty, the condensor duty and rate of reflux, in first fractional distillation column 38.
  • the light olefinic stream in line 42 is split into two streams.
  • a first portion of the light olefinic stream is provided in line 18, as the light olefinic recycle stream, to feed mixing drum 22, and is then provided to heat exchange reactor 26.
  • a second portion of the light olefinic stream, a first purge stream, is provided in line 44 to second fractional distillation tower 46.
  • Second fractional distillation column 46 serves to separate the first purge stream in line 44 into a stream richer in C 4 - molecules than the light olefinic stream (and the first purge stream) as a second purge stream in line 48, and a stream richer in C 5 - C 8 molecules than the light olefinic stream (and the first purge stream) as a second olefinic stream in line 50.
  • Such a separation is readily effected through proper selection of, for example, the number of trays, the reboiler duty, the condensor duty and rate of reflux, in second fractional distillation column 46.
  • the stream richer in C 5 - C 8 molecules than the light olefinic stream, the second olefinic stream, in line 50 is split into two streams.
  • a first portion of the second olefinic stream is provided via line 20 as a second olefinic recycle stream to feed mixing drum 22, and is then provided to heat exchanger reactor 26.
  • a second portion of the second olefinic stream, the second hydrocarbon product stream, is purged from the system via line 52, and may be subjected to further processing to create valuable chemicals or utilized as fuel.
  • Olefinic feedstock and recycle materials were prepared as shown in Table 1 and were oligomerized over a catalyst comprising 65 wt% of 0.02 to 0.05 micron crystals of ZSM- 5 having a SiO 2 / Al 2 O 3 molar ratio of 50:1, and 35 wt% of an alumina binder.
  • the catalyst was in the form of 1/16 inch extrudates and about 90 cc of catalyst was blended with about 202 cc of inert, silicon carbide beads to reduce the heat generation per unit volume of reaction and placed in the reaction bed of a tubular reactor equipped with a heat management system that allowed the oligomerization reaction to proceed under near isothermal conditions.
  • thermocouples were available, positioned evenly through the reaction bed in the reactor, with one very near the first point where the charge and catalyst come into contact, and one very near the outlet of the reaction bed. The difference between the highest and lowest temperatures within the reactor was from 2 to 7°C.
  • the reaction product was analyzed with a gas chromatograph, and the composition of the products is provided in Table 2. No products having a carbon number greater than 21 were detected.
  • Example 3 The same apparatus and procedure as Example 1 was utilized for a second, extended experimental run with a fresh batch of catalyst and another set of charge compositions as shown in Table 3.
  • the olefmic feedstocks shown in Table 3 were produced by reacting methanol over a SAPO-34 catalyst generally according to the method of U.S. Patent 6,673,978, with separation of the methanol reaction products to provide a C 4 + olefin composition.
  • Over 90 wt% of the olefins in each feed composition were normal in atomic configuration, and the feed composition further contained about 1000 wppm oxygenates, such as methanol and acetone (not shown in Table 3), and 1000 ppm dienes.
  • the olefmic recycle compositions shown in Table 3 were produced by taking accumulated batches of the reaction products from the first and this second experimental run and periodically providing those batches to a fractionation tower to separate a distillate product from a light olefmic recycle material, collecting those fractionated materials, and using the fractionated light olefmic recycle material for subsequent experiments. Over 90 wt% of the olefins in each recycle composition were non-normal in atomic configuration. Some minor adjustments of some components in the recycle compositions were made via addition of reagent grade materials to account for unavoidable losses in the fractionation step and test certain other aspects of the operation.
  • Example 3 The batches of distillate materials obtained in Example 3 were hydrogenated in discrete batches by reacting them with hydrogen over a hydrogenation catalyst. Distillates 1 and 2 were hydrogenated over a nickel- containing catalyst while Distillate 3 was hydrogenated over a palladium- containing catalyst, each according to operations and conditions well known.
  • the carbon number distribution of the distillates are provided in Table 5 and in Table 5A. Hydrogenation did not significantly change the non-normal character of distillate compositions although, following hydrogenation, the distillate materials were almost completely aliphatic. No products having a carbon number greater than 21 were detected. Table 5 provides the carbon number distribution according to the Linear Paraffin GC method, which defines carbon number between two adjacent linear paraffins and integrates each normal peak separately.
  • Table 6 provides composition and other physical and fuel performance properties of the hydro genated distillate materials.
  • An oligomerization system is operated according to the method of the present invention as embodied in Figure 1.
  • Table 7, below, provides the material flows of key streams in the system.
  • Olefinic feed stream in line 16 is provided from a methanol to olefins reaction, using a SAPO-34 catalyst, and associated olefin recovery system.
  • Such a source will leave a small amount of oxygenates in the olefinic feed stream.
  • Oxygen from the oxygenates is almost completely converted to water in the oligomerization reaction, and will exit with the oligomerization effluent stream in line 36.
  • the remaining carbon and hydrogen in the oxygenates almost completely incorporates into the hydrocarbons in the oligomerization effluent stream exiting in line 36.
  • the overhead pressure of first fractionation tower 38 is 23.2 psia, and the overhead temperature is 131 0 F, which is approximately the bubble point temperature of the light olefinic stream in line 42 (having the composition in lines 18 and 44); the location of these conditions would be in the reflux drum after the overhead condenser of first fractionation tower 38 (neither of which are shown).
  • the overhead pressure of the second fractionation tower 46 is 89.2 psia, and the overhead temperature is 131 0 F, conditions at which the second purge stream in line 48 will be a vapor product, but still providing a liquid to utilize as tower reflux; the location of these conditions would be in the reflux drum after the overhead condenser of second fractionation tower 46 (neither of which are shown), in a partial condensor operation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'une composition d'hydrocarbures consistant à : mettre en contact un flux d'alimentation, comprenant au moins une oléfine C3 à C8, et un flux de recyclage oléfinique, comprenant un premier flux de recyclage oléfinique et pas plus de 10 % en poids d'oléfines non normales C10+, en présence d'un catalyseur à tamis moléculaire dans une zone de réaction dans des conditions d'oligomérisation d'oléfines de façon à produire un flux effluent d'oligomérisation ; séparer ce flux effluent d'oligomérisation pour produire un premier flux oléfinique, qui possède un rapport pondéral de molécules C4-/(C5 - C8) correspondant à environ 0,8 à 1,2 fois le rapport pondéral de molécules C4-/(C5 - C8) observé dans le flux effluent d'oligomérisation, et un premier flux de produits hydrocarbonés, qui comprend au moins 1 % en poids et pas plus de 30 % en poids d'oléfine non normale C9 ; et diviser le premier flux oléfinique pour produire le premier flux de recyclage oléfinique et un premier flux de purge.
PCT/US2006/003108 2005-01-31 2006-01-27 Oligomerisation d'olefines WO2006083746A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US64849705P 2005-01-31 2005-01-31
US64893805P 2005-01-31 2005-01-31
US60/648,497 2005-01-31
US60/648,938 2005-01-31
US72756305P 2005-10-17 2005-10-17
US60/727,563 2005-10-17

Publications (1)

Publication Number Publication Date
WO2006083746A1 true WO2006083746A1 (fr) 2006-08-10

Family

ID=36499173

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2006/003108 WO2006083746A1 (fr) 2005-01-31 2006-01-27 Oligomerisation d'olefines

Country Status (1)

Country Link
WO (1) WO2006083746A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8753503B2 (en) 2008-07-24 2014-06-17 Uop Llc Process and apparatus for producing a reformate by introducing isopentane

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5059744A (en) * 1988-03-03 1991-10-22 Mobil Oil Corporation Reactor and recovery system for upgrading lower olefins
US5177279A (en) * 1990-10-23 1993-01-05 Mobil Oil Corporation Integrated process for converting methanol to gasoline and distillates

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5059744A (en) * 1988-03-03 1991-10-22 Mobil Oil Corporation Reactor and recovery system for upgrading lower olefins
US5177279A (en) * 1990-10-23 1993-01-05 Mobil Oil Corporation Integrated process for converting methanol to gasoline and distillates

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8753503B2 (en) 2008-07-24 2014-06-17 Uop Llc Process and apparatus for producing a reformate by introducing isopentane

Similar Documents

Publication Publication Date Title
US7678953B2 (en) Olefin oligomerization
US7692049B2 (en) Hydrocarbon compositions useful for producing fuels and methods of producing the same
US7741526B2 (en) Feedstock preparation of olefins for oligomerization to produce fuels
US7678954B2 (en) Olefin oligomerization to produce hydrocarbon compositions useful as fuels
CA1252122A (fr) Procede pour ameliorer les olefines de la synthese fischer-tropsch
US8318994B2 (en) Olefin oligomerization and biodegradable compositions therefrom
US8536392B2 (en) Series catalyst beds
EP0145234A2 (fr) Procédé en plusieurs étapes et appareil de conversion de composés contenant de l'oxygène en hydrocarbures
CA2816141C (fr) Production de combustible a etapes multiples a boucle unique
US8481796B2 (en) Olefin oligomerization and compositions therefrom
KR20120002586A (ko) 높은 벤젠 전환율로 벤젠을 알킬화시킴으로써 감소된 벤젠 함량을 갖는 고옥테인 가솔린을 제조하는 방법
US20110147263A1 (en) Process and system to convert olefins to diesel and other distillates
TW200800852A (en) Paraffin alkylation process
US4520215A (en) Catalytic conversion of olefinic Fischer-Tropsch light oil to heavier hydrocarbons
US20160264492A1 (en) Integrated process for converting light paraffins to gasoline and distillate
WO2006083746A1 (fr) Oligomerisation d'olefines
WO2006083699A2 (fr) Oligomerisation d'olefines et compositions resultantes
US20240034699A1 (en) Flexible Benzene Production Via Selective-Higher-Olefin Oligomerization of Ethylene

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06734018

Country of ref document: EP

Kind code of ref document: A1