WO2020081210A1 - Oligomérisation d'oléfines - Google Patents

Oligomérisation d'oléfines Download PDF

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Publication number
WO2020081210A1
WO2020081210A1 PCT/US2019/053184 US2019053184W WO2020081210A1 WO 2020081210 A1 WO2020081210 A1 WO 2020081210A1 US 2019053184 W US2019053184 W US 2019053184W WO 2020081210 A1 WO2020081210 A1 WO 2020081210A1
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oligomer
olefin
catalyst
surfactant
less
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PCT/US2019/053184
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English (en)
Inventor
Shiwen Li
Alan A. Galuska
Jennifer A. CARVAJAL DIAZ
Mika L. SHIRAMIZU
Wenyih F. Lai
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Exxonmobil Chemical Patents Inc.
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Publication of WO2020081210A1 publication Critical patent/WO2020081210A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7096—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

Definitions

  • the present disclosure relates to olefin oligomerization.
  • the condensation reaction of an olefin or a mixture of olefins to form higher molecular weight products is widely known and practiced.
  • This type of condensation reaction is referred to herein as an oligomerization reaction or process, and the products are low molecular weight oligomers which are formed by the condensation of up to 12, typically 2, 3 or 4, but up to 5, 6, 7, or even 8 olefin molecules with each other.
  • “Oligomerization” refers to a process for the formation of oligomers and/or polymers.
  • Low molecular weight olefins such as, for example, ethylene, propene, 2-methylpropene, 1 -butene and 2-butenes, pentenes and hexenes
  • oligomerization over, for example, a solid phosphoric acid catalyst (commonly referred to as“sPa” catalyst) or a molecular sieve catalyst (e.g., a zeolite catalyst), to an oligomer product.
  • a solid phosphoric acid catalyst commonly referred to as“sPa” catalyst
  • a molecular sieve catalyst e.g., a zeolite catalyst
  • the products of olefin oligomerization are usually mixtures of, for example, olefin dimers, trimers, and higher oligomers. Further, each olefin oligomer is itself usually a mixture of isomers, both skeletal and in double bond location. Highly branched isomers are less reactive than linear or lightly branched materials in many of the downstream reactions for which the oligomers are used as feedstocks. This is also true of isomers in which access to the double bond is sterically hindered.
  • the olefin types of the oligomers are denominated according to the degree of substitution of the double bond, as follows:
  • Type I compounds are sometimes described as a- or vinyl olefins and Type III as vinylidene olefins.
  • Type IV is sometimes subdivided to provide a Type IVA, in which access to the double bond is less hindered, and Type IVB where it is more hindered.
  • the degree of branching and double bond Type distribution affect some properties and performance of the olefin derivatives, e.g. , the low temperature performance and volatility when converted to alcohols and subsequently to plasticizers.
  • the degree of branching and mixture of double bond types also affect the reactivity of the oligomer olefins to alkylation and, especially, oxonation.
  • Types I and II have excellent reactivity, Type III fair reactivity, Type IVA good reactivity, and types IVB and V poor reactivity.
  • alkylation reactivity is affected by the ease of protonation of the more readily approached, less hindered, double bonds of the preferred structures. Similar effects apply to the reactivity of the oligomer olefins to oxonation, the low branching and less hindered double bonds allowing the molecules to be converted to aldehydes and alcohols rather than being hydrogenated to paraffins.
  • Oligomer products are valuable components of high-octane gasoline blending stock that may be used or blended into a distillate type liquid fuel or as a lubricant, or as a starting material for the production of chemical intermediates and end-products.
  • chemical intermediates and end-products include high purity hydrocarbon fluids or solvents, alcohols, detergents/surfactants, and esters such as plasticizer esters and synthetic lubricants.
  • detergent products obtainable from the products of alkylation of the olefinic oligomer products would have numerous advantages in use. These include better hard water solubility, and better biodegradability resulting from the lower levels of quaternary carbons.
  • a number of catalysts may be used in such oligomerization processes.
  • industrial oligomerization reactions employing molecular sieve catalysts are generally performed in a plurality of tubular or chamber reactors, similar to those processes employing sPa catalysts.
  • sPa catalysts With sPa catalysts, the pressure drop over the catalyst bed(s) increases gradually over the duration of the run, due to coking and/or swelling of the catalyst pellets and the reactor run is typically terminated when a maximum allowable pressure drop over the reactor is reached.
  • Molecular sieve catalysts do not show pressure drop increases similar to sPa catalysts. Oligomerization reactors using molecular sieve catalysts are therefore characterized by longer reactor ran lengths and are typically decommissioned when the catalyst selectivity and activity has dropped to an unacceptably low level.
  • the present disclosure relates to olefin oligomerization. More specifically, the present invention relates to oligomerization processes that utilize a rare earth element impregnated ZSM-23 catalyst having no amine treatment, having a Si/Ak molar ratio of 20 to 60, and optionally including titania in the catalyst matrix. Such a catalyst demonstrates high selectivity to lightly branched olefins without the drawbacks of the amine treatment.
  • a first example embodiment of the present invention is a process for olefin oligomerization, the process comprising: contacting a feedstock comprising at least one C 3 to C20 olefin/paraffin under oligomerization conditions in the presence of a rare earth element impregnated Si/Al ZSM-23 catalyst having no amine treatment and a S i/A 1 molar ratio of 20 to 60 and/or a rare earth element impregnated Si/Al/T ZSM-23 catalyst having no amine treatment, a S i/A 1 molar ratio of 20 to 60, and a Ti/Al molar ratio of 0.1 to 3; and recovering an oligomeric product comprising dimers having a branching index (BI) of less than 2.1, or within a range from 0.5, or 1.0, or 1.1, or 1.2, or 1.3 to 1.6, or 1.8, or 2.0, or 2.1, trimers having a branching index of less than 2.1, or within a
  • Detergent formulations can be made from surfactants derived from the oligomer products described herein.
  • Detergent formulations comprise an aqueous fluid; and a reaction product of one or more oligomer products, the reaction product comprising a hydrophobic portion and a polar head group bonded to the hydrophobic portion; wherein an olefin moiety in the one or more oligomer products reacts to produce the hydrophobic portion; and wherein the one or more oligomer products have a Branch Index ranging from 0.5 and 2.1 and branching is retained in the hydrophobic portion of the reaction product; wherein the surfactant is present in the aqueous fluid at a concentration ranging from about 10 wt% to about 80 wt%.
  • a detergent formulation comprising: 0 wt% to 30 wt% Cs surfactant, 40 wt % to 85 wt % C10-13 surfactant, 0 wt % to 30 wt% C14-16 surfactant, and 0 wt% to 10 wt % C 17+ surfactant, based on the total weight of the detergent, wherein each surfactant has a branching index of less than 2.1, preferably 1.5 or less.
  • Yet another embodiment is a detergent formulation comprising: 0 wt% to 15 wt%
  • Ce surfactant 0 wt% to 15 wt% C9 surfactant, and 10 wt% to 70 wt% C12 + surfactant, wherein each surfactant has a branching index of less than 2.1, preferably 1.5 or less.
  • Another embodiment is a detergent formulation comprising: 0 wt% to 30 wt% Ce surfactant, 0 wt% to 30 wt% C9 surfactant, 40 wt% to 85 wt% C12 surfactant, wherein each surfactant has a branching index of less than 2.1, preferably 1.5 or less.
  • Yet another embodiment is a detergent formulation comprising: 10 wt% to 70 wt% C 10 surfactant, 0 wt% to 15 wt% C 15 surfactant, and 0 wt% to 15 wt% C 20+ surfactant, wherein each surfactant has a branching index of less than 1.8, preferably 1.5 or less.
  • Another embodiment is a detergent formulation comprising: 40 wt% to 85 wt% C 10 surfactant, 0 wt% to 30 wt% C 15 surfactant, 0 wt% to 30 wt% C 20 surfactant, and 0 wt% to 10 wt% C 25+ surfactant, wherein each surfactant has a branching index of less than 1.8, preferably 1.5 or less.
  • FIG. 1 illustrates a first example oligomerization process 100 of the present invention.
  • FIG. 2 illustrates a second example oligomerization process 210 of the present invention.
  • FIG. 3 is a flow diagram of a process of oligomerization, predominantly directed to production and recovery of a dimer product.
  • FIG. 4 is a flow diagram of a process of oligomerization, predominantly directed to production and recovery of a trimer product.
  • the present disclosure relates to olefin oligomerization. More specifically, the present invention relates to oligomerization processes that utilize a rare earth element impregnated ZSM-23 catalyst having no amine treatment, having a S1/AI 2 molar ratio of 20 to 60, and optionally including titania in the catalyst matrix. Such a catalyst demonstrates high selectivity to lightly branched olefins without the drawbacks of the amine treatment.
  • FIG. 1 illustrates a first example oligomerization process 100 of the present invention.
  • a feedstock 102 is fed into a reactor 104 that contains oligomerization catalyst.
  • the reactor 104 is maintained at oligomerization conditions (described further herein) to facilitate catalyzed oligomerization of the feedstock 102 to produce an oligomer product 106.
  • the feedstock 102 comprises primarily C n and C2 n olefins/paraffins and the oligomer product 106 comprises C3 n oligomers.
  • Other example feedstocks and oligomer products are described herein.
  • FIG. 2 illustrates a second example oligomerization process 210 of the present invention.
  • a feedstock 212 is fed into a reactor 214 that contains oligomerization catalyst.
  • the reactor 214 is maintained at oligomerization conditions (described further herein) to facilitate catalyzed oligomerization of the feedstock 212 to produce an oligomer product 216.
  • the oligomer product is then separated (e.g., in a distiller 218) to produce a recycle stream 220 and a product stream 222.
  • the recycle stream 220 is fed back into the reactor 214. As illustrated, it is entrained with the feedstock 212.
  • the feedstock 102 comprises primarily C n and C 2n olefins/paraffins
  • the oligomer product 106 comprises a mixture of C n , C2 n , and C3 n
  • the recycle stream comprises C n and C2 n
  • the product stream comprises C3 n ⁇
  • Other example feedstocks and oligomer products are described herein.
  • recycle stream could be fed to a second reactor containing oligomerization catalyst and maintained at oligomerization conditions (described further herein).
  • FIGS. 3 and 4 Two specific examples of reactor and separation embodiments are provided in FIGS. 3 and 4. These examples may be adapted by those skilled in the art to accommodate other reaction and separation needs.
  • a C 4 , Cs, or mixed olefins/paraffins feedstock containing at least one of C 4 and Cs olefins 330 is fed in via heat-exchangers 332 to reactors 334a, 334b, in parallel and subsequently to reactors 336, 338 in series.
  • the product from reactor 338 is fed to the product recovery tower 340 via de-butanizer tower 342.
  • Cx dimer from butene
  • the de-butanizer tower overheads may optionally be recycled to the reactors 334a and 334b via line 346.
  • a C 4 , C5, or mixed olefins/paraffins feedstock containing at least one of C 4 and C5 olefins 450 is fed in via heat-exchangers 452 to reactors 454a, 454b, in parallel and subsequently to reactors 456, 458 in series.
  • the product from reactor 458 is fed to the C 8 product recovery tower 460 via de-butanizer tower 462.
  • Cx dimer from butene
  • the de-butanizer tower overheads may optionally be recycled to the reactors 454a and 454b via line 466.
  • the bottoms product from tower 460 is fed to the Ci 2 product recovery tower 468, C12 product being taken off as overhead, with optional recycles via line 470 if the Ci 6+ product is to be maximized.
  • the bottoms product from tower 468 is fed to product recovery tower 472, where C12 to C14 product is taken off as overheads with C 1 ⁇ 2 to C20 product being taken off as bottoms product.
  • the at least one feedstock or feedstream comprises olefins, paraffins, and other components.
  • feedstock(s) and feedstream(s) may be used interchangeably.
  • the at least one feedstream may comprise olefins having from 2 to 15 carbon atoms, such as, for example, from 3 to 6 carbon atoms and one or more paraffins.
  • olefins refers to any of the unsaturated hydrocarbons (e.g., compounds consisting essential of hydrogen and carbon atoms) having the formula C n F n , wherein n is an integer from 1 to 25, typically, from 1 to 15, preferably, from 3 to 6.
  • paraffins refers to any of the saturated hydrocarbons having the formula C n H2 n+ 2, wherein n is an integer from 1 to 25, typically, from 1 to 15, preferably, from 3 to 6. Additionally, the feedstream may comprise an oligomer, such as, for example, a dimer, for example, one provided by recycling a part of a product stream. As used herein, the terms “olefin/paraffin” and“olefins/paraffins” refers to a composition comprising at least one olefin and, optionally, further containing or at least one paraffin.
  • the feedstream may comprise olefins/paraffins having the same or different number of carbon atoms.
  • the feedstream may comprise one or more of propene, butenes, pentenes, hexenes, their isomers, paraffins having the same or different carbon numbers, and mixtures thereof.
  • the process is especially useful for the oligomerization of feedstreams comprising propene, butenes, pentenes, their isomers, other components, and mixtures thereof.
  • “oligomer(s)” or“oligomer product” refers to a polymer molecule (or a mixture of polymer molecules) made from a few monomer units such as, for example, a dimer, a trimer, a tetramer, and mixtures thereof.
  • “Oligomer(s)” refers to a polymer molecule (or a mixture of polymer molecules) having 20 carbon atoms or less, alternatively, 15 carbon atoms or less, alternatively, 10 carbon atoms or less, alternatively, 9 carbon atoms or less, and alternatively, 8 carbon atoms or less.
  • “oligomerization process” refers to any process of catalytically joining monomer units to form the oligomer(s) as defined above.
  • the oligomerization process is used synonymously herein with“polymerization process.”
  • the term“oligomerization conditions” refers to any and all those variations of equipment, conditions (e.g. , temperatures, pressures, and flow rates), materials, and reactor schemes that are suitable to conduct the oligomerization process to produce the oligomer(s) as known and applied in the art and discussed more below.
  • the olefins to be oligomerized may be one or more of C3-C15 olefins or mixtures thereof including one or more paraffins having the same or different carbon number, alternatively, C3-C6 olefins or mixtures thereof, including one or more paraffins having the same or different carbon number, and preferably, C3-C5 olefins or mixtures thereof including one or more paraffins having the same or different carbon number.
  • the feedstream may comprise 45 wt% or more olefins, alternatively, 50 wt% or more olefins, alternatively, 60 wt% or more olefins, alternatively, 70 wt% or more olefins, and preferably, 80 wt% or more olefins, based upon the total weight of the feedstreams(s).
  • the at least one feedstream may comprise 45 wt% or more olefins/paraffins, alternatively 60 wt% or more olefins/paraffins, alternatively 75 wt% or more olefins/paraffins, alternatively, 80 wt% or more olefins/paraffins, alternatively, 85 wt% or more olefins/paraffins, alternatively, 90 wt% or more olefins/paraffins, and alternatively, 95 wt% or more olefins/paraffins, based upon the total weight of the feedstream(s).
  • the olefins/paraffins may have the same or different carbon number or may be a mixture of olefins/paraffins that have the same and different carbon numbers.
  • the at least one feedstream comprises the ranges stated above of propylene and propane but may also have other smaller amounts of other olefins/paraffins having different carbon numbers, such as, for example, butanes and butenes, ethanes and ethylenes, and the like.
  • the at least one feedstream may comprise 60 wt% or more combined C3 olefins/paraffins, alternatively, 70 wt% or more combined C3 olefins/paraffins, alternatively, 80 wt% or more combined C3 olefins/paraffins, alternatively, 85 wt% or more combined C3 olefins/paraffins, alternatively, 90 wt% or more combined C3 olefins/paraffins, and alternatively, 95 wt% or more combined C3 olefins/paraffins, based upon the total weight of the feedstream(s).
  • the at least one feedstream may comprise 60 wt% or more combined C 4 olefins/paraffins, alternatively, 70 wt% or more combined C3 olefins/paraffins, alternatively, 80 wt% or more combined C 4 olefins/paraffins, alternatively, 85 wt% or more combined C 4 olefins/paraffins, alternatively, 90 wt % or more combined C 4 olefins/paraffins, and alternatively, 95 wt % or more combined C 4 olefins/paraffins, based upon the total weight of the feedstream(s).
  • the at least one feedstream may comprise 60 wt% or more combined
  • C olefins/paraffins alternatively, 70 wt% or more combined C olefins/paraffins, alternatively, 80 wt% or more combined C 3 olefins/paraffins, alternatively, 85 wt% or more combined C olefins/paraffins, alternatively, 90 wt% or more combined C 5 olefins/paraffins, and alternatively, 95 wt% or more combined C olefins/paraffins, based upon the total weight of the feedstream(s).
  • the feedstream may be free of aromatic hydrocarbon compounds that consist solely of hydrogen and carbon or be substantially free of aromatic hydrocarbon compounds that consist solely of hydrogen and carbon.
  • substantially free refers to 25 wt% or less of the aromatic hydrocarbon compound present in the feedstream(s), alternatively, 15 wt% or less, alternatively, 10 wt% or less, alternatively, 5 wt% or less, and preferably, 1 wt% or less, based upon the total weight of the feedstream(s).
  • the feedstream may comprise isomers of any of the constituents found therein.
  • “isomer” refers to compounds having the same molecular formula but different structural formula. Examples may be structural isomers, stereoisomers, enantiomers, geometrical isomers, and the like.
  • the feedstream may comprise at least one isomer of the olefins/paraffins) or other constituents in the feedstream.
  • the feedstream may also comprise contaminants or compounds that may hinder catalyst life or productivity. These may include nitrogen, sulfur, chlorine, oxygen containing compounds, and mixtures thereof. Examples of nitrogen containing compounds include nitriles ( ⁇ ?.g. , acetonitrile, propionitrile, and the like), ammonia, amides, amines, pyridines, imides, cyanates, pyrroles, pyrrolidones, and mixtures thereof.
  • nitrogen containing compounds include nitriles ( ⁇ ?.g. , acetonitrile, propionitrile, and the like), ammonia, amides, amines, pyridines, imides, cyanates, pyrroles, pyrrolidones, and mixtures thereof.
  • the feedstream may also comprise other compounds that may hinder catalyst life or productivity. These may include linear and cyclic dienes such as butadiene, pentadiene, cyclo pentadiene, and mixtures thereof.
  • Suitable feedstream s include untreated refinery streams such as
  • Fluidized Catalytic Cracking FCC
  • coker coker
  • pygas streams as well as aromatics-containing streams, such as, for example, reformates.
  • Raffinate-l RAF-l
  • Raffinate-2 RAF-2
  • Raffinate-3 Raffinate-3
  • Raffinate-l, Raffinate-2, and Raffinate-3 may be regarded as stages in the processing of crude, generally, C 4 streams.
  • Raffinate products that can be used as feedstreams can be found in US 7,759,533, which is incorporated herein by reference. These streams are usually from olefin steam crackers but may also come from refinery cat-crackers, Butane Dehydrogenation Units, or Gas to Olefin (GTO) Units, or Fisher-Tropsch Units in which case they generally contain the same components but in different proportions with some variation understood by a skilled artisan.
  • GTO Gas to Olefin
  • the first stage of the process is to remove, by generally solvent extraction or hydrogenation (for example, in a Selective Butadiene Hydrogenation unit) the butadiene which may be as much as 40 wt% to 45 wt% of the stream.
  • the butadiene content is substantially reduced in the C 4 stream to, for example, 10000 wt ppm or less diene content, alternatively, 5000 wt ppm or less diene content, alternatively, 1000 wt ppm or less diene content, alternatively, 200 wt ppm or less diene content, and alternatively, 10 wt ppm or less diene content, based upon the total weight of the feedstream(s), the remaining product is Raffinate- 1.
  • isobutylene the two normal isomers, butene- 1 and butene-2, and smaller quantities of butanes and other compounds.
  • Raffinate 3 (RAF-3) is less common but may also be used. Raffinate 3 may be obtained after separation of 1 -butene from Raffinate 2 with a residual 1 -butene content of 1%.
  • Examples of suitable C 3 olefin/paraffin containing feedstreams include untreated
  • C 3 rich refinery streams such as“dilute” or“refinery grade” propylene from a Fluidized Catalytic Cracker (FCC), C 3 rich stream from a steam cracker, C 3 rich streams from the production of“chemical grade” or“polymer grade” propylene, C 3 rich streams from refinery gas recovery units, C 3 rich streams from Propane Dehydrogenation Units, C 3 rich streams from Gas to Olefin (GTO) Units, or Fisher-Tropsch Units, and C 3 rich return streams from polypropylene producing units.
  • FCC Fluidized Catalytic Cracker
  • the feedstream may comprise a mixed C 3 /C 4 FCC light olefin/paraffin stream that typically comprises ethane, ethylene, propane, propylene, isobutane, n-butane, butenes, pentanes, and other optional components.
  • a specific example of such a feedstream is provided in Table 1.
  • the feedstream may comprise a C3 rich FCC stream that typically comprises ethane, ethylene, propane, propylene, isobutane, isobutene, and other optional components.
  • a specific example of such a feedstream is provided in Table 2.
  • the feedstream comprises a C3 rich olefin/paraffin containing stream that is a mixture of refinery C3 rich streams and diluent stream(s) that typically comprises ethane, ethylene, propane, propylene, isobutane, isobutene, and other optional components.
  • diluent stream(s) typically comprises ethane, ethylene, propane, propylene, isobutane, isobutene, and other optional components.
  • Table 3 A specific example of such a feedstream is provided in Table 3.
  • the feedstream comprises a C 4 rich olefin/paraffin containing stream.
  • a specific example of such a feedstream is provided in Table 4.
  • the feedstream comprises a C 4 ric olefin/paraffin containing stream.
  • a specific example of such a feedstream is provided in Table 5.
  • the feedstream(s) may comprise a diluent.
  • the diluent may comprise any suitable hydrocarbon such as alkanes or a mixture comprising at least one alkane.
  • the alkanes may be represented the general formula: CnH2n+2, wherein n is a number from 1 to 20, alternatively, from 1 to 10, alternatively, from 1 to 5, and alternatively, from 3 to 4. Examples may include methane, ethane, propane, butane, pentane, and mixtures thereof.
  • the feedstream(s) may comprise at least 10%, at least 25%, at least 30%, at least 35%, or at least 40% of the diluent, for example, the alkane such as propane and/or butane, based upon the total volume of the feedstream.
  • the diluent may be present in the feedstream in the range from 10% to 40%, alternatively, from 10% to 35%, and alternatively, from 20% to 35% based upon the total volume of the feedstream.
  • the diluent may also be delivered to the reactor(s) through separate feedstream s.
  • the diluent may be fed in amounts to be equivalent to the embodiments wherein the diluent is co-fed with the feedstream. These amounts may not necessarily be the same as the ranges stated above given that more or less of the diluent may be necessary when fed separately to provide an equivalent.
  • the diluent, when present, may improve reactor continuity.
  • the reaction system may include one or more of a fixed bed reactor, a packed bed reactor, a tubular reactor, a fluidized bed reactor, a slurry reactor, a continuous catalyst regeneration reactor, and any combination thereof.
  • the reactor(s) may be operated in any combination such as, for example, in series and/or parallel sequence.
  • the reactor(s) may be operated in semi-continuous (i.e., continuous but down for routine maintenance), continuous, and/or batch mode.
  • the oligomerization conditions may include operating temperatures from 200°C to 350°C. More typically, the reaction temperature is from 2lO°C to 300°C, and alternatively, from 220°C to 260°C. Close to and above the upper end of the range, deoligomerization rates increase and may predominate over the oligomerization reaction providing an upper limit to practical operation. To mitigate this, the weight hourly space velocity (WHSV) may be increased. As used herein,“Weight Hour Space Velocity” (WHSV) is a measure of the weight of feedstream flowing per unit weight of the catalyst per hour, weight of the catalyst may be that of molecular sieve or that of formulated molecular sieve extrudates
  • the olefin/paraffin WHSV may be in the range of from 0.1 hr 1 to 30 hr 1 , alternatively 0.5 hr 1 to 15 hr 1 , alternatively 1 hr 1 to 10 hr 1 , and alternatively 1 hr 1 to 5 hr
  • the pressure may be in the range of from 400 psig to 4000 psig (2860 kPa to 27680 kPa), and alternatively, from 500 psig to 1500 psig (3550 kPa to 10440 kPa).
  • the process is conducted at a temperature of 200°C to 250°C; an olefin/paraffin WHSV of 0.1 hr 1 to 10 hr 1 ; and a pressure of 2860-27680 kPa.
  • the process is conducted at a temperature of 250°C to 300°C; an olefin/paraffin WHSV of 2 hr 1 to 15 hr 1 ; and a pressure of 2860-27680 kPa.
  • the process is conducted at a temperature of 300°C to 350°C; an olefin/paraffin WHSV of 5 hr 1 to 30 hr 1 ; and a pressure of 2860-27680 kPa.
  • the catalyst can be a rare earth impregnated Si/Al ZSM-23 catalyst having no amine treatment and a Si/Ah molar ratio of 20 to 60, alternatively 25 to 55, alternatively 30 to 50, and preferably 30 to 45.
  • Si/Al ZSM-23 catalysts can be prepared using the recipe described in US 4,076,842 and US 5,332,566.
  • the catalyst can be a Si/Al/Ti ZSM-23 catalyst having no amine treatment and a Si/Ah molar ratio of 20 to 60, alternatively 25 to 55, alternatively 30 to 50 and a Ti/Al molar ratio of 0.1 to 3, alternatively 0.2 to 2, alternatively 0.3 to 1.
  • Si/Al/Ti ZSM-23 catalysts can be prepared using the recipe described in US 4,076,842 and US 5,332,566. A combination of the two catalysts can be used.
  • ZSM-23 catalyst is used generally to refer to Si/Al ZSM-23 catalyst, Si/Al/Ti ZSM-23 catalyst, or a combination of Si/Al ZSM-23 catalyst and Si/Al/Ti ZSM-23 catalysts
  • the rare earth impregnated ZSM-23 catalysts can be prepared from extrudates (1 wt% to 90 wt% binder and 10 wt% to 100 wt% zeolite) or from ZSM-23 crystal seeds.
  • binders include silica, alumina, zirconia, titania, and the like, and mixtures thereof ZSM-23 catalysts that are crystals can have an aspect ratio of 1 to 5, alternatively 2-4, with a width of less than 0.1 microns and a length of less than 0.3 microns.
  • the rare earth impregnated ZSM-23 catalysts can be calcined in air at 425°C to 650°C for 1 hour to overnight.
  • the rare earth impregnated ZSM-23 catalysts after calcining can be treated. Suitable treatments include, but are not limited to, steaming, acid washing, depositing coke, and any combination thereof.
  • Steaming can be performed by exposing the ZSM-23 catalysts to steam at 200°C to 550°C, alternatively 225°C to 400°C, for 1 hour to 24 hours, alternatively 5 hours to 6 hours, alternatively 1 hour to 4 hours.
  • Acid washing can be performed by exposing the ZSM-23 catalysts to an aqueous acid solution at 20°C to l00°C, alternatively 25 °C to 50°C, for 1 hour to 24 hours, alternatively 5 hours to 6 hours, alternatively 1 hour to 4 hours.
  • Suitable acids include, but are not limited to, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, tartaric acid, and the like, and mixtures thereof.
  • the acid may be at any suitable concentration, for example, 1 molar to 4 molar, alternatively 1 molar to 2 molar, alternatively 2 molar to 4 molar.
  • Depositing coke on the ZSM-23 catalysts can be achieved by exposing the ZSM-23 catalysts to a carbon feedstock under coking conditions.
  • the ZSM-23 catalysts can be exposed to hydrocarbons at 200°C to 400°C at 50 bar to 100 bar to deposit coke on the surface of the ZSM-23 catalysts.
  • hydrocarbons include the feedstocks described herein.
  • rare earth elements suitable for use with the ZSM-23 catalyst include, but are not limited to, yttrium, tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, lanthanum, lanthanides, or a noble metal such as platinum or palladium. Combinations of the foregoing metals may also be used. Impregnation of the ZSM-23 catalyst with the rare earth element can be performed according to US 7,759,533, which is incorporated herein by reference.
  • the rare earth element can comprise 0.5 wt% to 2.5 wt% of the ZSM-23 catalyst, alternatively 0.75 wt% to 2 wt%, or alternatively 1.5 wt% to 2.5 wt%.
  • the oligomer product may comprise dimers, trimers, tetramers, pentamers, and higher oligomers of the feedstock components.
  • the feedstock components that compose the oligomers may be the same or different.
  • a dimer of C 3 and C 4 components results in a C-7 oligomer.
  • a dimer of C 3 components results in a Ce oligomer
  • the oligomer product may comprise one or more Ce to Ceo oligomers, alternatively one or more Ce to C20 oligomers, alternatively one or more Ce to C12 oligomers, and alternatively one or more Cx to C 1 ⁇ 2 oligomers.
  • the catalyst and oligomerization conditions favor the formation of linear and lightly branched oligomers.
  • the degree of branching of the oligomer product as a whole or for individual components is referred to as the“branching index” or“BI.”
  • the branching index is an indication of the average number of branches per monomer unit.
  • Product carbon number distribution and branching index can be measured using an HP-5890 GC equipped by a 30 meter DB-l column (O.lmm id) and 0.2 pm film thickness with an H2-GC.
  • the product branching index is calculated following similar method used in US 7,759,533. That is, for C 8 , C 12 , and/or Ci6 olefins.
  • the oligomer product as a whole may have a branching index of less than 1.8, preferably 1.5 or less (e.g., 1.0 to 1.5).
  • An individual component of the oligomer product e.g., the C 12 component or the Ci6 component
  • the conversion percentage of feedstock to oligomer may be 20% or greater, alternatively 40% or greater, alternatively 60% or greater, or alternatively 80% or greater.
  • the concentration of dimers may be 25 wt% to 75 wt%, alternatively 25 wt% to 50 wt%, alternatively 40 wt% to 65 wt%, or alternatively 50 wt% to 75 wt%, based on the weight of the oligomer product.
  • the concentration of trimer may be 25 wt% to 50 wt%, alternatively 30 wt% to 45 wt%, or alternatively 25 wt% to 35 wt%.
  • the concentration of tetramer may be 0 wt % to 25 wt %, alternatively 5 wt% to 15 wt%, or alternatively 0 wt% to 10 wt%.
  • the concentration of pentamer and higher oligomers cumulatively may be 0 wt% to 10 wt%, alternatively 0 wt% to 5 wt%, or alternatively 0 wt% to 2 wt%.
  • an oligomer product derived from a C 4 feedstock may comprise 25 wt% to 75 wt% Cx oligomer, 25 wt% to 50 wt% Ci 2 oligomer, and 0 wt% to 25 wt% Ci 6 oligomer, based on the weight of the feedstpcl.
  • an oligomer product derived from a C 4 feedstock may comprise 35 wt% to 75 wt% Cx oligomer, 25 wt% to 45 wt% Ci 2 oligomer, and 5 wt% to 15 wt% Ci 6 oligomer.
  • an oligomer product derived from a C 4 feedstock (e.g., Table 4) may comprise 50 wt% to 75 wt% C8 oligomer, 25 wt% to 35 wt% C12 oligomer, and 0 wt% to 10 wt% Ci6 oligomer. Any of the foregoing examples can have a branching index of less than 2.1, preferably 1.5 or less.
  • an oligomer product derived from a C3 feedstock may comprise 25 wt% to 75 wt% Ce oligomer, 25 wt% to 50 wt% C9 oligomer, and 0 wt% to 25 wt% C12 oligomer.
  • an oligomer product derived from a C3 feedstock may comprise 35 wt% to 75 wt% Ce oligomer, 25 wt% to 45 wt% C9 oligomer, and 5 wt% to 15 wt% C12 oligomer.
  • an oligomer product derived from a C3 feedstock may comprise 50 wt% to 75 wt% Ce oligomer, 25 wt% to 35 wt% C9 oligomer, and 0 wt% to 10 wt% C12 oligomer.
  • Any of the foregoing examples can have a branching index of less than 2.1, preferably 1.8 or less, and more preferably 1.5 or less.
  • an oligomer product derived from a C5 feedstock may comprise 25 wt% to 75 wt% C10 oligomer, 25 wt% to 50 wt% C15 oligomer, and 0 wt% to 25 wt% C20 oligomer.
  • an oligomer product derived from a C5 feedstock may comprise 35 wt% to 75 wt% C10 oligomer, 25 wt% to 45 wt% C15 oligomer, and 5 wt% to 15 wt% C20 oligomer.
  • an oligomer product derived from a C5 feedstock may comprise 50 wt% to 75 wt% C10 oligomer, 25 wt% to 35 wt% C15 oligomer, and 0 wt% to 10 wt% C20 oligomer.
  • Any of the foregoing examples can have a branching index of less than 2.1, preferably 1.8 or less, and more preferably 1.5 or less.
  • the oligomer product can be used as feedstock and passed over the catalyst again.
  • the catalyst can be in a different reactor.
  • the same catalyst can be used where the oligomer product is passed back through the reactor optionally diluted with original feedstock.
  • recycling the feedstock allows for monomers to react with dimer and dimers to react with dimers to produce higher concentrations of trimers and tetramers. Because the catalyst described herein also produces light branching, the oligomer product after a second pass will have light branching also.
  • a first oligomer product derived from a C 4 feedstock may comprise 50 wt% to 75 wt% Cx oligomer, 25 wt% to 35 wt% Ci 2 oligomer, and 0 wt% to 10 wt% Ci 6 oligomer, based on the weight of the feedstock.
  • the second oligomer product may comprise 0 wt% to 30 wt% C 8 oligomer, 45 wt% to 85 wt% Ci 2 oligomer, 5 wt% to 55 wt% C 1 ⁇ 2 oligomer, and 0 wt% to 10 wt% C20 + oligomer.
  • the first oligomer product can be distilled where only a portion of the first oligomer product is in the second pass.
  • the first oligomer product derived from a C 4 feedstock may comprise 50 wt% to 85 wt% Cx oligomer, 25 wt% to 35 wt% C12 oligomer, and 0 wt% to 10 wt% C 1 ⁇ 2 oligomer. Then, the first oligomer product can be distilled and the unreacted C 4 feedstock and the produced Cx oligomer can be removed from the first oligomer product by distillation. The resultant C 4 /Cx mixture can then be all or a portion of the feedstock in the second pass that produced the second oligomer product.
  • an oligomer product derived from a C 4 /Cx feedstock may comprise 0 wt% to 30 wt% Cx oligomer, 45 wt% to 85 wt% C12 oligomer, 5 wt% to 55 wt% C 1 ⁇ 2 oligomer, and 0 wt% to 10 wt% C20 + oligomer.
  • an oligomer product derived from a C 4 /Cx feedstock may comprise 5 wt% to 25 wt% C 8 oligomer, 50 wt% to 85 wt% C12 oligomer, 10 wt% to 30 wt% C 1 ⁇ 2 oligomer, and 0 wt% to 10 wt% C20 + oligomer.
  • an oligomer product derived from a C 4 /Cs feedstock may comprise 5 wt% to 25 wt% C8 oligomer, 60 wt% to 85 wt% C12 oligomer, 8 wt% to 20 wt% Ci6 oligomer, and 0 wt% to 5 wt% C20 + oligomer.
  • Any of the foregoing examples can have a branching index of less than 2.1, preferably 1.8 or less, and more preferably 1.5 or less.
  • oligomer product encompasses oligomer product from a feedstock having not been exposed to the catalyst and oligomer product from a feedstock having been exposed to the catalyst (i.e., recycled oligomer product).
  • the oligomer product described herein can be used as a chemical intermediate in the production of high purity hydrocarbon fluids or solvents, alcohols, detergents/surfactants, esters such as plasticizer esters and synthetic lubricants, and the like.
  • Common classes of surfactants include not limited to, for example, alkylbenzene sulfonates, alcohol sulfates, carboxylates, alcohol ethoxylates and alkylphenol ethoxylates, having low branching indexes of hydrophobe are particular useful as they have better hard water solubility and better biodegradability resulting from the lower levels of quaternary carbons.
  • the oligomer product can be used as a feed for a hydroformylation reaction for the production of aldehydes and alcohols.
  • the aldehydes may be oxidized to produce acids or hydrogenated to produce alcohols.
  • the alcohols may then be used in the production of synthetic esters such as plasticizer esters or synthetic lubricants or in the production of surfactants, for example, alkylbenzene sulfonates, alcohol sulfates, carboxylates, alcohol ethoxylates and alkylphenol ethoxylates.
  • the oligomer product may be hydroformylated by, for example, the processes described in PCT Publication WO 2005/058787. It is preferred to use high pressure hydroformylation technology which is typically cobalt catalyzed, but rhodium may also be used as the catalyst.
  • the olefin oligomers of the present invention are particularly useful as feedstocks that are hydroformylated in the manner described in PCT Publication WO 2005/058787 where the low level of antioxidant enables improved hydroformylation reactions.
  • aldehydes produced by this method are hydrogenated, this may readily be accomplished by the method described in PCT Publication WO 2005/058782.
  • An example alcohol composition using an oligomer composition derived from a C 4 feedstock may comprise 25 wt% to 75 wt% Cx alcohol, 25 wt% to 50 wt% Ci 2 alcohol, and 0 wt% to 25 wt% Ci 6 alcohol, based on the weight of the feedstock.
  • Another example alcohol composition using an oligomer composition derived from a C 4 feedstock may comprise 35 wt% to 75 wt% C8 alcohol, 25 wt% to 45 wt% C12 alcohol, and 5 wt% to 15 wt% Ci6 alcohol.
  • Yet another example alcohol composition using an oligomer composition derived from a C 4 feedstock may comprise 50 wt% to 75 wt% Cx alcohol, 25 wt% to 35 wt% C12 alcohol, and 0 wt% to 10 wt% Ci 6 alcohol.
  • Any of the foregoing examples can have a branching index of less than 2.1, preferably 1.8 or less, and more preferably 1.5 or less.
  • An example alcohol composition using an oligomer composition derived from a C 4 /C 8 feedstock may comprise 0 wt% to 30 wt% Cx alcohol, 45 wt% to 85 wt% C12 alcohol, 5 wt% to 55 wt% C 1 ⁇ 2 alcohol, and 0 wt% to 10 wt% C20+ alcohol.
  • Another example alcohol composition using an oligomer composition derived from a C 4 /Cx feedstock e.g.
  • Table 5 or a recycled oligomer product distilled or as is may comprise 5 wt% to 25 wt% Cs alcohol, 50 wt% to 85 wt% C12 alcohol, 10 wt% to 30 wt% Ci6 alcohol, and 0 wt% to 10 wt% C20+ alcohol.
  • Yet another example alcohol composition using an oligomer composition derived from a C 4 /Cs feedstock e.g.
  • Table 5 or a recycled oligomer product distilled or as is may comprise 5 wt% to 25 wt% Cs alcohol, 60 wt% to 85 wt% C12 alcohol, 8 wt% to 20 wt% Ci6 alcohol, and 0 wt% to 5 wt% C20+ alcohol.
  • Any of the foregoing examples can have a branching index of less than 2.1, preferably 1.8 or less, and more preferably 1.5 or less.
  • An example alcohol composition using an oligomer composition derived from a C3 feedstock may comprise 25 wt% to 75 wt% Ce alcohol, 25 wt% to 50 wt% C9 alcohol, and 0 wt% to 25 wt% C12 alcohol, based on the weight of the feedstock.
  • Another example alcohol composition using an oligomer composition derived from a C3 feedstock may comprise 35 wt% to 75 wt% Ce alcohol, 25 wt% to 45 wt% C9 alcohol, and 5 wt% to 15 wt% C12 alcohol.
  • Yet another example alcohol composition using an oligomer composition derived from a C3 feedstock may comprise 50 wt% to 75 wt% Ce alcohol, 25 wt% to 35 wt% C9 alcohol, and 0 wt% to 10 wt% C12 alcohol.
  • Any of the foregoing examples can have a branching index of less than 2.1, preferably 1.8 or less, and more preferably 1.5 or less.
  • An example alcohol composition using an oligomer composition derived from a C5 feedstock may comprise 25 wt% to 75 wt% C10 alcohol, 25 wt% to 50 wt% C15 alcohol, and 0 wt% to 25 wt% C20 alcohol.
  • Another example alcohol composition using an oligomer composition derived from a C5 feedstock may comprise 35 wt% to 75 wt% C10 alcohol, 25 wt% to 45 wt% C15 alcohol, and 5 wt% to 15 wt% C20 alcohol.
  • Yet another example alcohol composition using an oligomer composition derived from a C5 feedstock may comprise 50 wt% to 75 wt% C10 alcohol, 25 wt% to 35 wt% C15 alcohol, and 0 wt% to 10 wt% C20 alcohol.
  • Any of the foregoing examples can have a branching index of less than 2.1, preferably 1.8 or less, and more preferably 1.5 or less.
  • surfactants can be performed on the oligomer products and alcohols produced from the oligomer product described herein.
  • the surfactants would have a tail group mixture corresponding to the oligomer product and a head group that can be anionic, cationic, amphoteric, or nonionic.
  • anionic head groups include, but are not limited to, phosphates, sulfonates, benzyl sulfonates, sulfates, benzyl sulfates carboxylates, and the like.
  • cationic head groups include, but are not limited to, quaternary ammonium salts and the like.
  • amphoteric head groups include, but are not limited to, aminopropionic acid, iminodipropionate, betaine, and the like.
  • nonionic head groups include, but are not limited to, polyethylene oxide, polyethylene glycol, polypropylene oxide, polypropylene glycol, and the like.
  • detergent formulations can be made from surfactants derived from the oligomer products described herein.
  • Detergent formulations comprise an aqueous fluid; and a reaction product of one or more oligomer product, the reaction product comprising a hydrophobic portion and a polar head group bonded to the hydrophobic portion; wherein an olefin moiety in the one or more oligomer product reacts to produce the hydrophobic portion; and wherein the one or more oligomer product have a Branch Index ranging from 0.5 and 2.1 and branching is retained in the hydrophobic portion of the reaction product; wherein the surfactant is present in the aqueous fluid at a concentration ranging from about 10 wt% to about 80 wt%.
  • Cx surfactant refers to an oligomer having‘x’ carbon number that is used to make the surfactant, thus, a C8 surfactant is a surfactant produced from a C8 oligomer through hydroformylation and/or some other means. Also, as used herein, when referring to a “Cx alcohol”, the alcohol has a carbon number of x+l.
  • the surfactant used in a detergent formulation may comprise any number of surfactants having different chain lengths and thus form a surfactant composition.
  • An example surfactant composition using an oligomer composition derived from a C 4 feedstock may comprise 0 wt% to 15 wt% Cx surfactant, 10 wt% to 70 wt% Ci 2 surfactant, and 0 wt% to 15 wt% Ci 6+ surfactant, based on the weight of the surfactant composition.
  • Another example surfactant composition using an oligomer composition derived from a C 4 feedstock may comprise 0 wt% to 30 wt% Cx surfactant, 40 wt% to 85 wt% Ci 2 surfactant, and 0 wt% to 30 wt% Ci 6+ surfactant.
  • Yet another example surfactant composition using an oligomer composition derived from a C 4 feedstock may comprise 0 wt% to 10 wt% Cx surfactant, 80 wt% to 100 wt% C 12 surfactant, and 0 wt% to 10 wt% Ci 6+ surfactant.
  • Any of the foregoing examples can have a branching index of less than 2.1, preferably 1.8 or less, and more preferably 1.5 or less.
  • An example surfactant composition using an oligomer composition derived from a C /C 8 feedstock may comprise
  • Another example surfactant composition using an oligomer composition derived from a C 4 /Cx feedstock may comprise 0 wt% to 30 wt% Cx surfactant, 40 wt% to 85 wt% Ci 2 surfactant, and 0 wt% to 30 wt% Ci 6+ surfactant.
  • Yet another example surfactant composition using an oligomer composition derived from a C 4 /Cs feedstock may comprise 0 wt % to 10 wt % Cs surfactant, and 80 wt % to 100 wt % C12 + surfactant.
  • Any of the foregoing examples can have a branching index of less than 2.1, preferably 1.8 or less, and more preferably 1.5 or less.
  • An example surfactant composition using an oligomer composition derived from a C3 feedstock may comprise 0 wt % to 15 wt% Ce surfactant, 0 wt% to 15 wt% C9 surfactant, and 10 wt% to 70 wt% C12 + surfactant.
  • Another example surfactant composition using an oligomer composition derived from a C3 feedstock may comprise 0 wt% to 30 wt% Ce surfactant, 0 wt% to 30 wt% C9 surfactant, and 40 wt% to 85 wt% C12 + surfactant.
  • Yet another example surfactant composition using an oligomer composition derived from a C3 feedstock may comprise 0 wt% to 10 wt% Ce surfactant, 0 wt% to 10 wt% C9 surfactant, and 80 wt% to 100 wt% C 12 + surfactant.
  • Any of the foregoing examples can have a branching index of less than 2.1, preferably 1.8 or less, and more preferably 1.5 or less.
  • C5 feedstock may comprise 0 wt% to 15 wt% C10 surfactant, 10 wt% to 70 wt% C15 surfactant, and 0 wt% to 15 wt% C20 + surfactant.
  • Another example surfactant composition using an oligomer composition derived from a C5 feedstock may comprise 0 wt% to 30 wt% C10 surfactant, 40 wt% to 85 wt% C15 surfactant, and 0 wt% to 30 wt% C20 + surfactant.
  • Yet another example surfactant composition using an oligomer composition derived from a C5 feedstock may comprise 80 wt% to 100 wt% C10 surfactant, 0 wt% to 10 wt% C15 surfactant, and 0 wt% to 10 wt% C20 + surfactant.
  • Any of the foregoing examples can have a branching index of less than 2.1, preferably 1.8 or less, and more preferably 1.5 or less.
  • a first example embodiment of the present invention is a process for olefin oligomerization, the process comprising: contacting a feedstock comprising at least one C 3 to C20 olefin/paraffin under oligomerization conditions in the presence of a rare earth element impregnated Si/Al ZSM-23 catalyst having no amine treatment and a S1/AI2 molar ratio of 20 to 60 and/or a rare earth element impregnated Si/Al/T ZSM-23 catalyst having no amine treatment, a S1/AI2 molar ratio of 20 to 60, and a Ti/Al molar ratio of 0.1 to 3; and recovering an oligomeric product comprising dimers having a branching index of less than 2.1, trimers having a branching index of less than 2.1, and tetramers having a branching index of less than 2.1; or in any one or more of these, a BI within a range from 0.5, or 1.0, or 1.1, or 1.2
  • Element 1 wherein the at least one C 3 to C20 olefin/paraffin comprises at least one C3 to C5 olefin/paraffin at a concentration of at least 40 wt% of the at least one C3 to C20 olefin/paraffin
  • Element 2 wherein the at least one C3 to C20 olefin/paraffin comprises C3 olefins/paraffins at a concentration of at least 40 wt% of the at least one C3 to C20 olefin/paraffin
  • Element 3 wherein the oligomeric product comprises 25 wt% to 75 wt% Ce oligomer, 25 wt% to 50 wt% C9 oligomer, and 0 wt% to 25 wt% C12 oligomer
  • Element 4 wherein the at least one C3 to C20 olefin/paraffin comprises C 4 olefins/paraffins
  • combinations include, but are not limited to, Elements 2 and 3 in combination optionally in further combination with Element 11 or 12; Elements 4 and 5 in combination optionally in further combination with Element 11 or 12; Elements 6 and 7 in combination optionally in further combination with Element 11 or 12; Elements 13 and 14 in combination optionally in further combination with Element 11 or 12; Elements 15 and 16 in combination optionally in further combination with Element 11 or 12; Elements 17 and 18 in combination optionally in further combination with Element 11 or 12; Element 1 and one or Elements 8-10 in combination optionally in further combination with Element 11 or 12; any of the foregoing combinations in combination with one or more of Elements 19-39; and two or more of Elements 36-39 in combination.
  • Another embodiment is a detergent comprising the surfactants produced by the first embodiment with Element 32 and optionally one or more of Elements 1-30 and 33-36.
  • Yet another embodiment is a detergent formulation comprising: 0 wt% to 15 wt%
  • each surfactant has a branching index of less than 1.8, preferably 1.5 or less.
  • Another embodiment is a detergent formulation comprising: 0 wt% to 30 wt% Cx surfactant, 40 wt% to 85 wt% C12 surfactant, 0 wt% to 30 wt% Ci 6+ surfactant, wherein each surfactant has a branching index of less than 1.8, preferably 1.5 or less.
  • Yet another embodiment is a detergent formulation comprising: 0 wt% to 15 wt% Ce surfactant, 0 wt% to 15 wt% C9 surfactant, and 10 wt% to 70 wt% C12 surfactant, wherein each surfactant has a branching index of less than 1.8, preferably 1.5 or less.
  • Another embodiment is a detergent formulation comprising: 0 wt% to 30 wt% Ce surfactant, 0 wt% to 30 wt% C9 surfactant, 40 wt% to 85 wt% C12 + surfactant, wherein each surfactant has a branching index of less than 1.8, preferably 1.5 or less.
  • Yet another embodiment is a detergent formulation comprising: 40 wt% to 85 wt% Cio surfactant, 0 wt % to 30 wt % Cis surfactant, and 0 wt % to 30 wt % C20 surfactant, wherein each surfactant has a branching index of less than 1.8, preferably 1.5 or less.
  • Another embodiment is a detergent formulation comprising: 10 wt% to 70 wt% Cio surfactant, 0 wt% to 15 wt% C15 surfactant, 0 wt% to 15 wt% C20 + surfactant, wherein each surfactant has a branching index of less than 1.8, preferably 1.5 or less.
  • Each of the foregoing detergent embodiments and each surfactant independently may have one of the following head groups: phosphates, sulfonates, benzyl sulfonates, sulfates, benzyl sulfates carboxylates, quaternary ammonium salt, aminopropionic acid, iminodipropionate, betaine, polyethylene oxide, polyethylene glycol, polypropylene oxide, and polypropylene glycol. Further, each of the foregoing detergent embodiments may include two or more surfactants having different head groups.
  • compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methods can also“consist essentially of’ or“consist of’ the various components and steps.
  • Si/Al ZSM-23 catalysts were prepared using the recipe described in US 4,076,842 and US 5,332,566 to have a Si/Ah molar ratio of 40.
  • Si/Al/Ti ZSM-23 catalysts were prepared using the recipe described in US 4,076,842 and US 5,332,566 to have a Si/Ah molar ratio of 40 and a Ti/Al molar ratio of 0.4.
  • Si/Al ZSM-23 catalysts and Si/Al/Ti ZSM-23 were impregnated with 0.1-5 wt% yttrium according to US 7,759,533.
  • the oligomerization reaction was carried out in fixed bed reactor with internal diameter 7mm. 0.5-2 grams of catalyst particles with size 0.3-0.6mm diluted with SiC was loaded into reactor. Prior to the reaction, the catalyst was dried at l50°C under N 2 for 5 hours The reaction was operated in down flow mode. Mass flow controllers delivered the hydrocarbon feed to the catalyst. Product carbon number distribution and branching index was detected by HP-5890 GC equipped by a 30 meter DB-l column (O.lmm id and 0.2 pm film thickness with an H2-GC. The reaction conditions were at a temperature l50°C to 250°C, a WHSV of 2 hr 1 to 20 hr 1 , and a pressure of 70 bar. The exact temperature and WHSV for each reaction is provided in the details below.
  • the feedstock was 1 -butene: butane: isobutane at relative wt% of 50: 40:10.
  • the isobutane was used as an internal standard.
  • Example 1 The Y impregnated Si/Al ZSM-23 and Y impregnated Si/Al/Ti ZSM- 23 catalysts reacted with feedstock at l90°C. Table 7 provides the reaction product details.
  • Example 2 The Y passivated ZSM-23 and Al/Ti ZSM-23 catalyst was reacted with the feedstock at 2lO°C. Table 8 provides the reaction product details.

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Abstract

La présente invention concerne un procédé d'oligomérisation d'oléfine qui peut comprendre : la mise en contact d'une charge d'alimentation comprenant au moins une oléfine/paraffine en C3 à C20 dans des conditions d'oligomérisation en présence d'un élément des terres rares imprégné d'un catalyseur Si/Al ZSM-23 sans traitement d'amine et un rapport molaire Si/Ah de 20 à 60 et/ou un élément des terres rares imprégné d'un catalyseur Si/Al/T ZSM-23 sans traitement d'amine, un rapport molaire Si/Ah de 20 à 60, et un rapport molaire Ti/Al de 0,1 à 3 ; et la récupération d'un produit oligomère comprenant des dimères ayant un indice de ramification inférieur à 2,1, des chronorégulateurs ayant un indice de ramification inférieur à 2,1, et des tétramères ayant un indice de ramification inférieur à 2,1.
PCT/US2019/053184 2018-10-17 2019-09-26 Oligomérisation d'oléfines WO2020081210A1 (fr)

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WO2022233878A1 (fr) 2021-05-07 2022-11-10 Exxonmobil Chemical Patents Inc. Fonctionnalisation d'oligomères oléfiniques légèrement ramifiés
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WO2022233875A1 (fr) 2021-05-07 2022-11-10 Exxonmobil Chemical Patents Inc. Production améliorée d'oligomères oléfiniques légèrement ramifiés par oligomérisation d'oléfines
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US11905227B2 (en) 2018-10-17 2024-02-20 Exxonmobil Chemical Patents Inc. Oligomerization of olefins
WO2022233878A1 (fr) 2021-05-07 2022-11-10 Exxonmobil Chemical Patents Inc. Fonctionnalisation d'oligomères oléfiniques légèrement ramifiés
WO2022233876A1 (fr) 2021-05-07 2022-11-10 Exxonmobil Chemical Patents Inc. Production améliorée d'oligomères d'oléfine légèrement ramifiés par oligomérisation d'oléfines
WO2022233875A1 (fr) 2021-05-07 2022-11-10 Exxonmobil Chemical Patents Inc. Production améliorée d'oligomères oléfiniques légèrement ramifiés par oligomérisation d'oléfines
WO2022233879A1 (fr) 2021-05-07 2022-11-10 Exxonmobil Chemical Patents Inc. Fonctionnalisation d'oligomères oléfiniques légèrement ramifiés

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