EP3814322A1 - Verfahren zur herstellung einer rohproduktzusammensetzung aus polysulfiden - Google Patents

Verfahren zur herstellung einer rohproduktzusammensetzung aus polysulfiden

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Publication number
EP3814322A1
EP3814322A1 EP19748992.5A EP19748992A EP3814322A1 EP 3814322 A1 EP3814322 A1 EP 3814322A1 EP 19748992 A EP19748992 A EP 19748992A EP 3814322 A1 EP3814322 A1 EP 3814322A1
Authority
EP
European Patent Office
Prior art keywords
alternatively
branched
represented
mercaptans
cio
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP19748992.5A
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English (en)
French (fr)
Inventor
Jason L. Kreider
R. Shawn Childress
Michael S. Matson
Jim D. Byers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron Phillips Chemical Co LP
Original Assignee
Chevron Phillips Chemical Co LP
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Filing date
Publication date
Priority claimed from US16/021,736 external-priority patent/US10294200B2/en
Application filed by Chevron Phillips Chemical Co LP filed Critical Chevron Phillips Chemical Co LP
Publication of EP3814322A1 publication Critical patent/EP3814322A1/de
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
    • C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/04—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by addition of hydrogen sulfide or its salts to unsaturated compounds

Definitions

  • Patent 9,738,601 which is a divisional of and claims priority to U.S. Patent Application No. 14/981,469 filed December 28, 2015, now U.S. Patent 9,512,071, and entitled“Mixed Decyl Mercaptans Compositions and Methods of Making Same,” each of which is incorporated by reference herein in its entirety.
  • U.S. Patent Application No. 15/669,097 is also a continuation-in-part application of U.S. Patent Application No. 15/463,867 filed March 20, 2017, now U.S. Patent 9,879, 102, which is a continuation of and claims priority to U.S. Patent Application No. 15/284,802 filed October 4, 2016, now U.S. Patent 9,631,039, which is a divisional of and claims priority to U.S. Patent Application No. 14/981,428 filed December 28, 2015, now U.S. Patent 9,512,248, and entitled“Mixed Decyl Mercaptans Compositions and Use Thereof as Chain Transfer Agents,” each of which is incorporated by reference herein in its entirety.
  • the present disclosure relates to compositions containing C20 + polysulfides and/or C20 + monosulfides and methods of making same. More specifically, the present disclosure relates to compositions containing mixed C20 + polysulfides and/or mixed C20 + monosulfides, and methods of making same.
  • Polysulfides of the type disclosed herein are individual organic molecules containing chains of multiple sulfur atoms. Polysulfides are used in diverse applications including lubricants for the mining industry; sealants for automotive, construction, and marine uses; and to some extent as flexibilizing hardeners for epoxy adhesives. Polysulfides are also used as sulfiding agents in synthetic chemistry processes. While processes for making polysulfides from mercaptans are available, preparing individual mercaptans can be costly due numerous purification steps required for the feedstock and/or mercaptan product. Some mercaptans can be used as precursors for agriculture chemicals or as natural gas additives. However, many applications may not require a single pure mercaptan compound, but could utilize mercaptan mixtures. Thus, there is a need to develop mercaptan compositions suitable for such applications, and methods of making same.
  • composition comprising polysulfides, wherein at least about 50 wt.% of the polysulfides are branched C20 to Obo polysulfides represented by general formula R 15 S 1 -[S] n -S 2 R 16 wherein R 15 and R 16 are each independently a branched C10 to C30 alkyl group and wherein n is an integer from 1 to 10.
  • Also disclosed herein is a process of producing a polysulfides crude product comprising one or more branched C20 to Obo polysulfides comprising: (A) reacting a feedstock comprising one or more branched C10 to C30 mercaptans and sulfur in the presence of a catalyst and (B) collecting the polysulfides crude product.
  • Also disclosed herein is a process of producing one or more branched C20 to Obo polysulfides comprising: (a) reacting hydrogen sulfide (H2S) and a feedstock comprising one or more branched C10 to C30 olefins in the presence of an initiating agent to produce a branched C10 + mercaptans crude composition;(b) recovering an intermediate reaction product comprising one or more branched C10 to C30 mercaptans from the branched C10 + mercaptans crude composition; (c) reacting sulfur and the intermediate reaction product comprising one or more branched C10 to C30 mercaptans in the presence of a catalyst; and (d) collecting a C20 + polysulfides crude product comprising the one or more branched C20 to Obo polysulfides.
  • H2S hydrogen sulfide
  • a feedstock comprising one or more branched C10 to C30 olefins in the presence of an initiating
  • compositions comprising: (A) at least about 25 wt.% branched C20 to Obo polysulfides represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 are each independently a branched C10 to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group; and (B) at least about 5 wt.% branched C20 to Obo monosulfides represented by general formula R 17 -S-R 18 , wherein R 17 and R 18 are each independently a branched Cio to
  • compositions comprising: (A) from at least about 50 wt.% to at least about 90 wt.% polysulfides, wherein at least about 50 wt.% of the polysulfides are branched C20 to C60 polysulfides represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 are each independently a branched Cio to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group; and (B) from at least about 10 wt.% to at least about 30 wt
  • compositions comprising: (A) at least about 25 wt.% branched C20 to C60 polysulfides represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 are each independently a branched C10 to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R' ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group; and (B) at least about 5 wt.% branched C20 to Obo monosulfides represented by general formula R 17 -S-R 18 , wherein R 17 and R 18 are each independently a branched C
  • Figure 1 displays a reaction schematic for addition of hydrogen sulfide (H2S) to an olefin
  • Figure 2 displays a GC trace of a crude product from an UV initiated reaction after removal of residual H 2 S;
  • Figure 3 displays a GC trace of a reaction product from an UV initiated reaction after removal of lights;
  • Figure 4 displays a GC trace of a crude product from an UV initiated reaction after removal of residual H 2 S;
  • Figure 5 displays a GC trace of a reaction product from an UV initiated reaction after removal of lights
  • Figure 6 displays a comparison of GC traces for a product obtained by UV initiation and a product obtained by acid catalysis.
  • the upper chromatogram is the UV-initiated Cio mercaptan product, and the lower chromatogram is the acid catalyzed Cio mercaptan product;
  • Figure 7 displays a comparison of GC traces for a Cio mercaptan fraction isolated from a product obtained by UV initiation and a Cio mercaptan fraction isolated from a product obtained by acid catalysis, and particularly, representative GC profiles of the purified Cio mercaptan reaction product.
  • the upper chromatogram is the acid catalyzed Cio mercaptan product
  • the lower chromatogram is the UV-initiated Cio mercaptan product
  • Figure 8 displays a GC trace of a crude product from a reaction catalyzed by a hydrodesulfurization catalyst after removal of residual FES.
  • Figure 9 displays a GC trace of a crude product from a reaction catalyzed by a polysulfidization catalyst.
  • Figure 10 displays a GC trace of a crude product from a reaction catalyzed by a polysulfidization catalyst after filtration through silica gel.
  • Groups of elements of the Periodic Table are indicated using the numbering scheme indicated in the version of the Periodic Table of elements published in Chemical and Engineering News, 63(5), 27, 1985.
  • a group of elements can be indicated using a common name assigned to the group; for example, alkali metals for Group 1 elements, alkaline earth metals (or alkaline metals) for Group 2 elements, transition metals for Groups 3-12 elements, and halogens for Group 17 elements.
  • transitional term“comprising”, which is synonymous with“including,”“containing,”“having,” or“characterized by,” is inclusive or open-ended and does not exclude additional, unrecited elements or method steps.
  • the transitional phrase“consisting of’ excludes any element, step, or ingredient not specified in the claim.
  • the transitional phrase“consisting of’ limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the present disclosure as claimed.
  • a feedstock consisting essentially of a material A can include impurities typically present in a commercially produced or commercially available sample of the recited compound or composition.
  • a claim includes different features and/or feature classes (for example, a method step, feedstock features, and/or product features, among other possibilities), the transitional terms comprising, consisting essentially of, and consisting of apply only to the feature class to which is utilized and it is possible to have different transitional terms or phrases utilized with different features within a claim.
  • a method can comprise several recited steps (and other non-recited steps), but utilize a catalyst system preparation consisting of specific steps, or alternatively, consisting essentially of specific steps, but utilize a catalyst system comprising recited components and other non-recited components.
  • compositions and methods are described in terms of“comprising” (or other broad term) various components and/or steps, the compositions and methods can also be described using narrower terms, such as “consist essentially of’ or“consist of’ the various components and/or steps.
  • a general reference to a compound includes all structural isomers, unless explicitly indicated otherwise; e.g., a general reference to pentane includes n-pentane, 2-methyl- butane, and 2,2-dimethylpropane, while a general reference to a butyl group includes an n-butyl group, a sec- butyl group, an iso-butyl group, and a tert-butyl group.
  • any general formula or name presented also encompasses all conformational isomers, regioisomers, and stereoisomers that can arise from a particular set of substituents.
  • a chemical“group” is described according to how that group is formally derived from a reference or “parent” compound, for example, by the number of hydrogen atoms formally removed from the parent compound to generate the group, even if that group is not literally synthesized in this manner.
  • an“alkyl group” can formally be derived by removing one hydrogen atom from an alkane
  • an “alkylene group” can formally be derived by removing two hydrogen atoms from an alkane.
  • a more general term can be used to encompass a variety of groups that formally are derived by removing any number (“one or more”) of hydrogen atoms from a parent compound, which in this example can be described as an “alkane group,” and which encompasses an“alkyl group,” an“alkylene group,” and materials having three or more hydrogens atoms, as necessary for the situation, removed from the alkane.
  • alkane group an “alkane group”
  • an“alkyl group” an“alkylene group”
  • materials having three or more hydrogens atoms as necessary for the situation, removed from the alkane.
  • substituent, ligand, or other chemical moiety that can constitute a particular“group” implies that the well- known rules of chemical structure and bonding are followed when that group is employed as described.
  • hydrocarbon whenever used in this specification and claims refers to a compound containing only carbon and hydrogen. Other identifiers can be utilized to indicate the presence of particular groups in the hydrocarbon (e.g., halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon).
  • hydrocarbyl group is used herein in accordance with the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from a hydrocarbon.
  • Non-limiting examples of hydrocarbyl groups include ethyl, phenyl, tolyl, propenyl, and the like.
  • a“hydrocarbylene group” refers to a group formed by removing two hydrogen atoms from a hydrocarbon, either two hydrogen atoms from one carbon atom or one hydrogen atom from each of two different carbon atoms. Therefore, in accordance with the terminology used herein, a“hydrocarbon group” refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group) from a hydrocarbon.
  • A“hydrocarbyl group,”“hydrocarbylene group,” and“hydrocarbon group” can be acyclic or cyclic groups, and/or can be linear or branched.
  • A“hydrocarbyl group,”“hydrocarbylene group,” and“hydrocarbon group” can include rings, ring systems, aromatic rings, and aromatic ring systems, which contain only carbon and hydrogen.
  • “Hydrocarbyl groups,”“hydrocarbylene groups,” and“hydrocarbon groups” include, by way of example, aryl, arylene, arene, alkyl, alkylene, alkane, cycloalkyl, cycloalkylene, cycloalkane, aralkyl, aralkylene, and aralkane groups, among other groups, as members.
  • alkane whenever used in this specification and claims refers to a saturated hydrocarbon compound. Other identifiers can be utilized to indicate the presence of particular groups in the alkane (e.g., halogenated alkane indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the alkane).
  • alkyl group is used herein in accordance with the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from an alkane.
  • an“alkylene group” refers to a group formed by removing two hydrogen atoms from an alkane (either two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms).
  • An“alkane group” is a general term that refers to a group formed by removing one or more hydrogen atoms (as necessary for the particular group) from an alkane.
  • An“alkyl group,”“alkylene group,” and“alkane group” can be acyclic or cyclic groups, and/or can be linear or branched unless otherwise specified.
  • Primary, secondary, and tertiary alkyl group are derived by removal of a hydrogen atom from a primary, secondary, and tertiary carbon atom, respectively, of an alkane.
  • the n-alkyl group can be derived by removal of a hydrogen atom from a terminal carbon atom of a linear alkane.
  • An aliphatic compound is an acyclic or cyclic, saturated or unsaturated carbon compound, excluding aromatic compounds.
  • an aliphatic compound is an acyclic or cyclic, saturated or unsaturated carbon compound, excluding aromatic compounds; that is, an aliphatic compound is a non-aromatic organic compound.
  • An“aliphatic group” is a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group) from a carbon atom of an aliphatic compound.
  • an aliphatic compound is an acyclic or cyclic, saturated or unsaturated carbon compound, excluding aromatic compounds. That is, an aliphatic compound is a non-aromatic organic compound.
  • Aliphatic compounds and therefore aliphatic groups can contain organic functional group(s) and/or atom(s) other than carbon and hydrogen.
  • substituted when used to describe a compound or group, for example, when referring to a substituted analog of a particular compound or group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in that group, and is intended to be non-limiting.
  • a group or groups can also be referred to herein as“unsubstituted” or by equivalent terms, such as“non-substituted,” which refers to the original group in which a non-hydrogen moiety does not replace a hydrogen within that group.
  • “Substituted” is intended to be nonlimiting and include inorganic substituents or organic substituents.
  • olefin whenever used in this specification and claims refers to hydrocarbons that have at least one carbon-carbon double bond that is not part of an aromatic ring or an aromatic ring system.
  • the term “olefin” includes aliphatic and aromatic, cyclic and acyclic, and/or linear and branched hydrocarbons having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system unless specifically stated otherwise. Olefins having only one, only two, only three, etc., carbon-carbon double bonds can be identified by use of the term“mono,”“di,”“tri,” etc., within the name of the olefin. The olefins can be further identified by the position of the carbon-carbon double bond(s).
  • alkene whenever used in this specification and claims refers to a linear or branched aliphatic hydrocarbon olefin that has one or more carbon-carbon double bonds. Alkenes having only one, only two, only three, etc., such multiple bonds can be identified by use of the term“mono,”“di,”“tri,” etc., within the name.
  • alkaminoenes, alkadienes, and alkatrienes refer to linear or branched acyclic hydrocarbon olefins having only one carbon-carbon double bond (acyclic having a general formula of C n Ffi n ), only two carbon- carbon double bonds (acyclic having a general formula of C 1 JT2 11 -2), and only three carbon-carbon double bonds (acyclic having a general formula of C n Fh n -4), respectively.
  • Alkenes can be further identified by the position of the carbon-carbon double bond(s). Other identifiers can be utilized to indicate the presence or absence of particular groups within an alkene.
  • a haloalkene refers to an alkene having one or more hydrogen atoms replaced with a halogen atom.
  • alpha olefin refers to an olefin that has a carbon- carbon double bond between the first and second carbon atoms of the longest contiguous chain of carbon atoms.
  • the term“alpha olefin” includes linear and branched alpha olefins unless expressly stated otherwise. In the case of branched alpha olefins, a branch can be at the 2 position (a vinylidene) and/or the 3 position or higher with respect to the olefin double bond.
  • normal alpha olefin whenever used in this specification and claims refers to a linear aliphatic mono-olefin having a carbon-carbon double bond between the first and second carbon atoms. It is noted that “normal alpha olefin” is not synonymous with“linear alpha olefin” as the term“linear alpha olefin” can include linear olefinic compounds having a double bond between the first and second carbon atoms.
  • C 9 - compounds that can be in the reaction product include C 9 - monoolefins (e.g., unreacted C 9 - monoolefins), C 9 - mercaptans, C 9 - alkanes, C 9 - alcohols, cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene, 2-ethyl- 1- hexanol, and the like, or combinations thereof.
  • C 9 - monoolefins e.g., unreacted C 9 - monoolefins
  • C 9 - mercaptans C 9 - alkanes
  • C 9 - alcohols cyclohexane, methylcyclopentane, methylcyclohexane
  • benzene toluene
  • ethylbenzene xylene
  • FbS can be removed from the reaction product via distillation, stripping, flashing, or other suitable means known to those of skill in the art without removing any substantial amounts of the“lights,”“light fraction,” or“light compounds” from the reaction product.
  • this definition of“lights,”“light fraction,” or“light compounds” includes any compounds with about nine or less carbon atoms present in the reaction product that can be detected, even in trace amounts.
  • the light fraction can also contain trace amounts of lower carbon number sulfides.
  • C 10-17 compounds include C 10 mercaptans (including both branched and non-branched C 10 mercaptans), C 12-17 mercaptan isomers, C 12 -C 17 sulfides, and the like, or combinations thereof.
  • this definition of“intermediates” or“intermediate fraction” includes any compounds with about ten to seventeen carbon atoms present in the reaction product that can be detected, even in trace amounts.
  • the intermediate fraction can also contain trace amounts of lower carbon number compounds, including sulfides.
  • a product can be recovered from the intermediate fraction (e.g., a Cio mercaptan fraction), and the remaining Cn to Cn compounds (e.g., C 12-16 mercaptans) can be referred to as the intermediate fraction.
  • the terms“heavies” or“heavy fraction” whenever used in this specification and claims refers to compounds with about eighteen or more carbon atoms (Ci 8+ ) per molecule.
  • Ci 8+ products include Cis sulfides, C20 sulfides, C24 sulfides, C28 sulfides, C32 sulfides, C 1 8 mercaptans. and the like, or combinations thereof.
  • the heavy fraction can also contain trace amounts of lower carbon number compounds, including mercaptans and sulfides.
  • These light, intermediate, and heavy fractions can be referred to as“rough-cuts,” in that they contain a plurality of compounds spread across a range of carbon atoms, i.e., a plurality of compounds having a different number of carbon atoms (e.g., a rough cut comprising C10, Cn, C12, C13, C14, C15, Ci6, C17, etc. compounds).
  • These rough cuts are in contrast to one or more“fine-cuts” that contain a fewer number of compounds than the rough-cuts, for example, a C10 fine cut (e.g., a C10 mercaptan fraction) derived from or otherwise recovered separately from the rough cut.
  • a rough cut can be comprised of a number of fine cuts, for example where a plurality of cuts are taken via distillation over a period of time and across a ramped temperature range, and referred to collectively as a rough cut or individually as fine cuts.
  • Those of ordinary skill in the art can produce a fine-cut fraction from a rough-cut fraction, for example via further distillation (e.g., a Cio splitter, a C20 splitter, etc.) or other purification technique.
  • the terms“room temperature” or“ambient temperature” are used herein to describe any temperature from 15 °C to 35 °C wherein no external heat or cooling source is directly applied to the reaction vessel. Accordingly, the terms“room temperature” and“ambient temperature” encompass the individual temperatures and any and all ranges, subranges, and combinations of subranges of temperatures from 15 °C to 35 °C wherein no external heating or cooling source is directly applied to the reaction vessel.
  • the term“atmospheric pressure” is used herein to describe an earth air pressure wherein no external pressure modifying means is utilized. Generally, unless practiced at extreme earth altitudes, “atmospheric pressure” is about 1 atmosphere (alternatively, about 14.7 psi or about 101 kPa).
  • references to substitution patterns are taken to indicate that the indicated group(s) is (are) located at the indicated position and that all other non-indicated positions are hydrogen.
  • reference to a 4-substituted phenyl group indicates that there is a non-hydrogen substituent located at the 4 position and hydrogens located at the 2, 3, 5, and 6 positions.
  • reference to a 3-substituted naphth-2-yl indicates that there is a non-hydrogen substituent located at the 3 position and hydrogens located at the 1, 4, 5, 6, 7, and 8 positions.
  • references to compounds or groups having substitutions at positions in addition to the indicated position will be referenced using comprising or some other alternative language.
  • a reference to a phenyl group comprising a substituent at the 4 position refers to a phenyl group having a non-hydrogen substituent group at the 4 position and hydrogen or any non-hydrogen group at the 2, 3, 5, and 6 positions.
  • any carbon-containing group for which the number of carbon atoms is not specified can have, according to proper chemical practice, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbon atoms, or any range or combination of ranges between these values.
  • any carbon-containing group can have from 1 to 30 carbon atoms, from 1 to 25 carbon atoms, from 1 to 20 carbon atoms, from 1 to 15 carbon atoms, from 1 to 10 carbon atoms, or from 1 to 5 carbon atoms.
  • other identifiers or qualifying terms can be utilized to indicate the presence or absence of a particular substituent, a particular regiochemistry and/or stereochemistry, or the presence or absence of a branched underlying structure or backbone.
  • Processes and/or methods described herein utilize steps, features, and compounds which are independently described herein.
  • the process and methods described herein may or may not utilize step identifiers (e.g., 1), 2), etc., a), b), etc., or i), ii), etc.), features (e.g., 1), 2), etc., a), b), etc., or i), ii), etc.), and/or compound identifiers (e.g., first, second, etc.).
  • step identifiers e.g., 1), 2), etc., a), b), etc., or i), ii), etc.
  • features e.g., 1), 2), etc., a), b), etc., or i), ii), etc.
  • compound identifiers e.g., first, second, etc.
  • processes and/or methods described herein can have multiple steps, features (e.g., reagent ratios, formation conditions
  • step or feature identifier e.g., 1), 2), etc., a), b), etc., or i), ii), etc.
  • compound identifier e.g., first, second, etc.
  • step or feature identifiers can be added and/or modified to indicate individual different steps/features/compounds utilized within the process and/or methods without detracting from the general disclosure.
  • Embodiments disclosed herein can provide the materials listed as suitable for satisfying a particular feature of the embodiment delimited by the term“or.”
  • a particular feature of the disclosed subject matter can be disclosed as follows: Feature X can be A, B, or C. It is also contemplated that for each feature the statement can also be phrased as a listing of alternatives such that the statement“Feature X is A, alternatively B, or alternatively C” is also an embodiment of the present disclosure whether or not the statement is explicitly recited.
  • compositional aspects of the various compositions described herein can be determined by gas chromatography (GC), gas chromatography-mass spectroscopy (GC-MS), Raman spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, or any other suitable analytical method known to those of skill in the art.
  • GC gas chromatography
  • GC-MS gas chromatography-mass spectroscopy
  • Raman spectroscopy Raman spectroscopy
  • NMR nuclear magnetic resonance
  • the weight percent compositional aspects of the various compositions described herein can be determined using a gas chromatograph with a flame ionization detector (GC-FID) detector based on the total GC peak areas (as described herein) and reported as gas chromatography (GC) area percent (GC area %), which is a common analytical technique for compositions comprising sulfur-containing compounds. While not wishing to be bound by this theory, it is believed that the amount in area % is very similar to the amount in weight percent (wt.%), and these respective amounts need not be exactly equivalent or interchangeable in order to be understood by a person of ordinary skill.
  • GC-FID flame ionization detector
  • a process of the present disclosure comprises reacting, in a reactor, hydrogen sulfide (H2S) and a feedstock comprising one or more branched Cio monoolefms in the presence of an initiating agent to produce a crude composition (also referred to as a crude product); wherein the branched Cio monoolefms comprise 5-methyl- l-nonene, 3 -propyl- l-heptene, 4-ethyl- l-octene, 2-butyl- 1 -hexene, or combinations thereof; and wherein the crude composition comprises branched Cio mercaptans and branched C20 sulfides.
  • H2S hydrogen sulfide
  • a feedstock comprising one or more branched Cio monoolefms in the presence of an initiating agent
  • the branched Cio monoolefms comprise 5-methyl- l-nonene, 3 -propyl- l-hepten
  • the crude composition can be further processed, for example via distillation, to yield one or more products (also referred to as distilled, purified, refined, finished, or final products) selected from the group consisting of mercaptan compositions (e.g., a composition comprising one or more branched Cio mercaptans), sulfide compositions (e.g., a composition comprising one or more branched C20 sulfides); and compositions having both mercaptans (e.g., branched Cio mercaptans) and sulfides (e.g., branched C20 sulfides), referred to as mercaptan/sulfide compositions.
  • mercaptan compositions e.g., a composition comprising one or more branched Cio mercaptans
  • sulfide compositions e.g., a composition comprising one or more branched C20 sulfides
  • a mercaptan composition comprises branched Cio mercaptans selected from the group consisting of 5-methyl-l-mercapto-nonane, 3 -propyl- l-mercapto-heptane, 4-ethyl- l-mercapto-octane, 2- butyl- 1 -mercapto-hexane, 5 -methyl-2-mercapto-nonane, 3 -propyl-2-mercapto-heptane, 4-ethyl -2 -mercapto- octane, 5-methyl-5-mercapto-nonane, and combinations thereof.
  • Cio mercaptans selected from the group consisting of 5-methyl-l-mercapto-nonane, 3 -propyl- l-mercapto-heptane, 4-ethyl- l-mercapto-octane, 2- butyl- 1 -mercapto-hexane, 5 -methyl-2
  • a sulfide composition comprises branched C20 sulfides represented by the structure R'-S-R 2 .
  • R 1 and R 2 are each independently a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- l-nonene, 3-propyl-l-heptene, 4-ethyl- l-octene, 2-butyl- 1 -hexene, or combinations thereof.
  • a mercaptan/sulfide composition comprises (A) branched Cio mercaptans selected from the group consisting of 5-methyl-l-mercapto-nonane, 3 -propyl- l-mercapto-heptane, 4-ethyl- l-mercapto- octane, 2-butyl- 1 -mercapto-hexane, 5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane, 4-ethyl-2- mercapto-octane, 5-methyl-5-mercapto-nonane, and combinations thereof; and (B) branched C20 sulfides represented by the structure R'-S-R 2 .
  • R 1 and R 2 are each independently a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- l-nonene, 3 -propyl- l-heptene, 4-ethyl- l-octene, 2-butyl-l- hexene, or combinations thereof.
  • the mercaptan compositions, sulfide compositions, and mercaptan/sulfide compositions can be salable or otherwise used for a variety of end uses such as mining ore collector compositions and chain transfer agents.
  • compositions disclosed herein can be prepared by a process comprising reacting, in a reactor, hydrogen sulfide (ThS) and a feedstock comprising one or more branched Cio monoolefms in the presence of an initiating agent to produce a crude (reaction product) composition, wherein the branched Cio monoolefms comprise 5 -methyl- l-nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • ThS hydrogen sulfide
  • a feedstock comprising one or more branched Cio monoolefms in the presence of an initiating agent to produce a crude (reaction product) composition
  • the branched Cio monoolefms comprise 5 -methyl- l-nonene (represented by Structure I), 3 -
  • Any feedstock comprising one or more branched Cio monoolefms of the type described herein can be used, for example a feedstock obtained from a commercial petroleum refining or petrochemical process.
  • Such feedstocks can comprise other olefins in addition to the one or more branched Cio monoolefms of the type described herein, for example linear Cio monoolefms as well as olefins having more or less than 10 carbon atoms.
  • the feedstock comprises one or more branched Cio monoolefms and is obtained from a 1 -hexene production process effluent stream.
  • a feedstock obtained from a 1 -hexene production process effluent stream can comprise Cio monoolefms (e.g., branched and/or linear Cio monoolefms) as well as olefins having more or less than 10 carbon atoms.
  • Cio monoolefms e.g., branched and/or linear Cio monoolefms
  • olefins having more or less than 10 carbon atoms.
  • the feedstock can comprise (a) at least about 76 mol%, alternatively at least about 78 mol%, alternatively at least about 80 mol%, or alternatively at least about 82 mol% Cio monoolefms, and (b) at least about 1 mol%, alternatively at least about 2 mol%, alternatively at least about 3 mol%, or alternatively at least about 4 mol% C14 monoolefms.
  • the feedstock can comprise (a) from about 76 mol% to about 92 mol%, alternatively from about 78 mol% to about 90 mol%, alternatively from about 80 mol% to about 88 mol%, or alternatively from about 82 mol% to about 86 mol% Cio monoolefms; and (b) from about 1 mol% to about 12 mol%, alternatively from about 2 mol% to about 10 mol%, alternatively from about 3 mol% to about 8 mol%, or alternatively from about 4 mol% to about 7 mol% C14 monoolefms.
  • a feedstock comprising (a) at least about 76 mol% Cio monoolefms, and (b) at least about 1 mol% C14 monoolefms can also be referred to as a“first feedstock.”
  • the first feedstock is obtained from a 1 -hexene production process effluent stream, for example an effluent stream obtained from a 1 -hexene production process of the type disclosed in co-pending International Patent Application PCT/US2015/40433, which is incorporated by reference herein in its entirety.
  • the feedstock can comprise at least about 95 mol%, alternatively at least about 96 mol%, alternatively at least about 97 mol%, alternatively at least about 98 mol%, or alternatively at least about 99 mol% Cio monoolefms.
  • a feedstock comprising at least about 95 mol% Cio monoolefms can also be referred to as a“second feedstock.”
  • the second feedstock can be produced by purifying the first feedstock, such as for example by distillation of an effluent stream obtained from a 1 -hexene production process of the type disclosed in co-pending International Patent Application PCT/US2015/40433, which is incorporated by reference herein in its entirety.
  • the Cio monoolefms of any feedstock described herein can comprise, can consist essentially of, or can be, 2-butyl- 1 -hexene, 3-propyl- l-heptene, 4- ethyl-l-octene, and 5 -methyl- l-nonene.
  • the Cio monoolefms of any feedstock described herein can comprise i) at least about 3 mol%, alternatively at least about 4 mol%, alternatively at least about 5 mol%, alternatively at least about 6 mol%, alternatively at least about 7 mol%, or alternatively at least about 8 mol% 2-butyl- 1 -hexene (represented by Structure L), ii) at least about 8 mol%, alternatively at least about 9 mol%, alternatively at least about 10 mol%, alternatively at least about 11 mol%, alternatively at least about 12 mol%, or alternatively at least about 13 mol% 3 -propyl- l-heptene (represented by Structure J), iii) at least about 6 mol%, alternatively at least about 7 mol%, alternatively at least about 8 mol%, alternatively at least about 9 mol%, alternatively at least about 10 mol%, or alternatively at least about 11 mol% 4-ethyl- l-
  • the Cio monoolefms of any feedstock described herein can have a molar ratio of 2-butyl- 1 -hexene to 5 -methyl- l-nonene of at least about 2: 1, alternatively at least about 2.4: 1, alternatively at least about 2.6: 1, or alternatively at least about 2.8: 1.
  • the Cio monoolefms of any feedstock described herein can have a molar ratio of 3 -propyl- 1- heptene to 5 -methyl- l-nonene of at least about 1.2: 1, alternatively at least about 1.4: 1, alternatively at least about 1.6: 1, or alternatively at least about 1.8: 1.
  • the Cio monoolefms of any feedstock described herein can have a molar ratio of 4-ethyl- l-octene to 5-methyl- l-nonene of at least about 1.6: 1, alternatively at least about 1.7: 1, alternatively at least about 1.9: 1, or alternatively at least about 2.1: 1.
  • the Cio monoolefms of any feedstock described herein can have a molar ratio of 2-butyl- 1 -hexene to 5 -methyl- l-nonene of at least about 2: 1, alternatively at least about 2.4: 1, alternatively at least about 2.6: 1, or alternatively at least about 2.8: 1; a molar ratio of 3 -propyl- l-heptene to 5 -methyl- l-nonene of at least about 1.2: 1, alternatively at least about 1.4: 1, alternatively at least about 1.6: 1, or alternatively at least about 1.8: 1; and a molar ratio of 4-ethyl- l-octene to 5 -methyl- l-nonene of at least about 1.6: 1, alternatively at least about 1.7: 1, alternatively at least about 1.9: 1, or alternatively at least about 2.1: 1.
  • the Cio monoolefms of any feedstock described herein can comprise linear Cio monoolefms.
  • the linear Cio monoolefms can comprise, can consist essentially of, or can be, l-decene, 4-decene, 5-decene, or combinations thereof; alternatively, l-decene; alternatively, 4-decene and/or 5-decene; alternatively, 4-decene; or alternatively, 5- decene.
  • the Cio monoolefms of any feedstock described herein can comprise less than or equal to about 26 mol%, alternatively less than or equal to about 24 mol%, alternatively less than or equal to about 22 mol%, alternatively less than or equal to about 20 mol%, or alternatively less than or equal to about 18 mol% linear Cio monoolefms.
  • the Cio monoolefms of any feedstock described herein can comprise from about 1 mol% to about 16 mol%, alternatively from about 2 mol% to about 15 mol%, alternatively from about 3 mol% to about 14 mol%, alternatively from about 4 mol% to about 13 mol%, or alternatively from about 6 mol% to about 12 mol% 4-decene and/or 5-decene.
  • the Cio monoolefms of any feedstock described herein can comprise less than or equal to about 10 mol%, alternatively less than or equal to about 9 mol%, alternatively less than or equal to about 8 mol%, alternatively less than or equal to about 7 mol%, or alternatively less than or equal to about 6 mol% l-decene.
  • the Cio monoolefms of any feedstock described herein can comprise from about 0.5 mol% to about 9 mol%, alternatively from about 1 mol% to about 8 mol%, alternatively from about 1.5 mol% to about 7 mol%, or alternatively from about 2 mol% to about 6 mol% l-decene.
  • the first feedstock disclosed herein can further comprise C 9- monoolefms, Cn + monoolefms, or combinations thereof; alternatively, C 9 - monoolefms; or alternatively, Cn + monoolefms.
  • the C 9 - monoolefms can comprise, can consist essentially of, or can be, a C 7 monoolefin, a Cx monoolefin, a C 9 monoolefin, or combinations thereof; alternatively, a C 7 monoolefin; alternatively, a C monoolefin; or alternatively, a C 9 monoolefin.
  • the C 9 - monoolefms can comprise, can consist essentially of, or can be, a Cx monoolefin.
  • the Cn + monoolefms can comprise, can consist essentially of, or can be, a Cn monoolefin, a C 12 monoolefin, a C 13 monoolefin, a C 14 monoolefin, a C 15 monoolefin, a Ci 6 monoolefin, a Cn monoolefm, a Cis monoolefm, or combinations thereof; alternatively, a Cn monoolefm; alternatively, a C 12 monoolefm; alternatively, a C 13 monoolefm; alternatively, a C 14 monoolefm; alternatively, a C 15 monoolefm; alternatively, a Ci 6 monoolefm; alternatively, a Cn monoolefm; or alternatively, a Cis monoolefm.
  • the Cn + monoolefms can comprise, can consist essentially of, or can be, a C 12 monoolefm, a Ci 6 monoolefm, a Cis monoolefm, or combinations thereof; alternatively, a C 12 monoolefm; alternatively, a Ci 6 monoolefm; or alternatively, a Cis monoolefm.
  • the first feedstock disclosed herein can further comprise Cx monoolefms, C12 monoolefms, Ci 6 monoolefms, Cis monoolefms, or combinations thereof; alternatively, Cx monoolefms; alternatively, C12 monoolefms; alternatively, Ci 6 monoolefms and/or Cis monoolefms; alternatively, Ci 6 monoolefms; or alternatively, Cis monoolefms.
  • the Cx monoolefms can comprise l-octene.
  • the C12 monoolefms can comprise l-dodecene.
  • the first feedstock can further comprise from about 0.1 mol% to about 5 mol%, alternatively from about 0.25 mol% to about 4 mol%, or alternatively from about 0.5 mol% to about 3 mol% C12 monoolefms.
  • the C12 monoolefms can comprise from about 54 mol% to about 74 mol%, alternatively from about 56 mol% to about 72 mol%, alternatively from about 58 mol% to about 70 mol%, or alternatively from about 60 mol% to about 68 mol% l-dodecene.
  • the first feedstock can further comprise from about 0.1 mol% to about 5 mol%, alternatively from about 0.25 mol% to about 4 mol%, or alternatively from about 0.5 mol% to about 3 mol% Cx monoolefms.
  • the Cx monoolefms can comprise at least about 95 mol%, alternatively at least about 96 mol%, alternatively at least about 97 mol%, alternatively at least about 98 mol%, or alternatively at least about 99 mol% l-octene.
  • the first feedstock can further comprise from about 0.05 mol% to about 2 mol%, alternatively from about 0.04 mol%to about 1.5 mol%, alternatively from about 0.06 mol%to about 1.25 mol%, alternatively from about 0.08 mol% to about 1 mol%, or alternatively from about 0.1 mol% to about 0.75 mol% Ci 6 monoolefms and/or Cis monoolefms.
  • a feedstock comprising branched C10 monoolefms produced in a 1 -hexene process can be purified to produce a second feedstock of the type described herein, for example to improve olefin reactivity and resultant mercaptan and/or sulfide purity.
  • a light fraction, comprising C 9 -, can be removed from the feedstock and any C 10 olefin isomers can be collected overhead to obtain a high purity (>95%) C 10 monoolefm fraction as the second feedstock.
  • This high purity C10 monoolefm fraction i.e., second feedstock
  • the high purity C 10 olefin can be reacted with ThS to produce a crude composition.
  • Reaction conditions to produce a crude composition from the high purity C10 monoolefm fraction i.e., a second feedstock
  • the major difference between reacting a first feedstock and a second feedstock is the composition of the crude composition and any resulting purified or partially purified products (e.g., fractions or cuts taken from the crude composition).
  • the crude composition can comprise residual FfiS, unreacted Cio olefin, Cio mercaptan isomers, and C10H21-S-C10H21 sulfides and minimal other mercaptans or sulfides.
  • the resultant partially purified product will contain Cio mercaptan isomers and C20 sulfides, but will not contain any of the intermediate mercaptans and asymmetric sulfide components formed by reactions of olefins having less than or greater than 10 carbon atoms (because there were minimal, if any, such olefins having less than or greater than 10 carbon atoms in the purified feedstock). While not wishing to be bound by theory, it is believed that the intermediate mercaptans and asymmetric sulfide components can be produced from the reaction of Cio mercaptans with other non-Cio olefins.
  • l3 ⁇ 4S and a feedstock comprising one or more branched Cio monoolefins can be reacted at an l3 ⁇ 4S to olefin molar ratio of from about 1 : 1 to about 20: 1, alternatively from about 2: 1 to about 15 : 1 , or alternatively from about 3 : 1 to about 10: 1.
  • l3 ⁇ 4S and a feedstock comprising one or more branched Cio monoolefins can be reacted at a pressure of from about 30 psig (206 kPag) to about 1,500 psig (10,300 kPag), alternatively from about 100 psig (690 kPag) to about 1,250 psig (8,600 kPag), or alternatively from about 250 psig (1,700 kPag) to about 1,000 psig (6,900 kPag).
  • FfiS and a feedstock comprising one or more branched Cio monoolefins can be reacted to produce olefin conversion of equal to or greater than about 80%, alternatively equal to or greater than about 85%, or alternatively equal to or greater than about 90%.
  • an olefin conversion refers to the mol% of olefins that have reacted during the reaction between FfiS and a feedstock in a reactor, with respect to the amount of olefins introduced into the reactor during the same time period.
  • the process can comprise reacting FfiS and a feedstock (e.g., a first or second feedstock as described herein) comprising one or more branched Cio monoolefins in the presence of an initiating agent to produce a crude composition; wherein the initiating agent comprises ultraviolet (UV) radiation.
  • the UV radiation can be any UV radiation capable of initiating the reaction of the olefins present in the feedstock and FfiS.
  • the UV radiation can be generated by a medium pressure mercury lamp.
  • UV radiation can be the initiating agent, other suitable types of light sources can be used.
  • FfiS and a feedstock comprising one or more branched Cio monoolefins can be reacted in the presence of an initiating agent comprising UV radiation in a batch reactor or a continuous reactor.
  • continuous reactors suitable for use in the present disclosure include continuous flow reactors, continuous stirred reactors, fixed bed reactors, and the like, or combinations thereof.
  • batch reactors suitable for use in the present disclosure include UV batch reactors.
  • any other suitable type of batch and continuous reactors can be used for reacting ThS and a feedstock comprising one or more branched Cio monoolefms in the presence of UV radiation.
  • UV reactors and conditions suitable for reacting TfiS and a feedstock comprising one or more branched Cio monoolefms in the presence of UV radiation are described in more detail in U.S. Patent No. 7,989,655, and U.S. Publication No. 20140221692 Al, each of which is incorporated by reference herein in its entirety.
  • the continuous reactor can be sized and configured to the desired continuous production rate. That is, a person skilled in the art will be able to select an appropriate reaction vessel size, geometry and material (e.g., a transparent material for sidewalls, windows, or internal chambers); along with an appropriate number of UV sources; and arrange the sources and reactor vessel (e.g., place UV sources adjacent a transparent exterior portion of the reaction vessel and/or disposed in transparent chambers within the reactor vessel) to yield a desired continuous production rate.
  • an appropriate reaction vessel size, geometry and material e.g., a transparent material for sidewalls, windows, or internal chambers
  • the sources and reactor vessel e.g., place UV sources adjacent a transparent exterior portion of the reaction vessel and/or disposed in transparent chambers within the reactor vessel
  • the batch reactor can be characterized by a reaction time of from about 1 minute to about 4 hours, alternatively from about 10 minutes to about 2 hours, or alternatively from about 30 minutes to about 1.5 hours.
  • TbS and a feedstock comprising one or more branched Cio monoolefms can be reacted in the presence of UV radiation at a temperature of from about 0 °C to about 100 °C, alternatively from about 10 °C to about 70 °C, or alternatively from about 15 °C to about 35 °C.
  • TfiS and a feedstock comprising one or more branched Cio monoolefms can be reacted in the presence of UV radiation at a TbS to olefin molar ratio of from about 1 : 1 to about 15: 1, alternatively from about 2: 1 to about 12.5: 1, or alternatively from about 5: 1 to about 10: 1.
  • the process can comprise reacting TfiS and a feedstock comprising one or more branched Cio monoolefms in the presence of an initiating agent to produce a crude composition; wherein the initiating agent comprises ultraviolet (UV) radiation, and wherein the initiating agent further comprises a phosphite promoter, a photoinitiator, or both.
  • an initiating agent comprises ultraviolet (UV) radiation
  • UV ultraviolet
  • the initiating agent further comprises a phosphite promoter, a photoinitiator, or both.
  • the phosphite promoter can be used in an amount of from about 0.01 wt.% to about 5 wt.%, alternatively from about 0.1 wt.% to about 4 wt.%, or alternatively from about 1 wt.% to about 2.5 wt.%, based on a weight of olefins.
  • the phosphite promoter can be characterized by formula P(OR 5 ) 3 , wherein each R 5 can independently be a Ci-Cis hydrocarbyl group, alternatively Ci-Cio hydrocarbyl group, alternatively C1-C5 hydrocarbyl group; alternatively a C1-C18 alkyl group, alternatively C1-C10 alkyl group, alternatively C1-C5 alkyl group; alternatively, a C6-C18 aryl group, or alternatively, a C6-C10 aryl group.
  • each R 5 can independently be a Ci-Cis hydrocarbyl group, alternatively Ci-Cio hydrocarbyl group, alternatively C1-C5 hydrocarbyl group; alternatively a C1-C18 alkyl group, alternatively C1-C10 alkyl group, alternatively C1-C5 alkyl group; alternatively, a C6-C18 aryl group, or alternatively, a C6-C10 aryl group.
  • R 5 groups suitable for use in the present disclosure in the phosphite promoter include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group; a phenyl group, a tolyl group, a xylyl group, a naphthyl group; and the like, or combinations thereof.
  • Nonlimiting examples of phosphite promoters suitable for use in the present disclosure include a trialkylphosphite, trimethylphosphite, triethylphosphite, tributylphosphite; a triarylphosphite, triphenylphosphite; and the like, or combinations thereof.
  • the photoinitiator can be used in an amount of from about 0.05 wt.% to about 5 wt.%, alternatively from about 0.1 wt.% to about 4 wt.%, or alternatively from about 1 wt.% to about 2.5 wt.%, based on the weight of olefins present in the feed mixture.
  • Nonlimiting examples of photoinitiators suitable for use in the present disclosure include 1 -hydroxy- cyclohexyl -phenyl -ketone, benzophenone, Bis-(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 2-hydroxy- 1 - ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl ⁇ -2-methy-l -propan- 1 -one, 2-hydroxy-2 -methyl- 1 - phenyl- l-propanone, and the like, or combinations thereof.
  • the process can comprise reacting FfiS and a feedstock comprising one or more branched Cio monoolefins in the presence of UV radiation to produce a crude composition (wherein the crude composition comprises from 50-100 wt.% Cio mercaptans, alternatively from 50-90 wt.% Cio mercaptans, alternatively from 75-85 wt.% Cio mercaptans); wherein the Cio mercaptans present in the crude composition further comprise from about 70 wt.% to about 100 wt.%, alternatively from about 70 wt.% to about 95 wt.%, alternatively from about 80 wt.% to about 90 wt.%, or alternatively from about 79 wt.% to about 85 wt.% Cio primary mercaptans; from about 0 wt.% to about 30 wt.%, alternatively from about 0 wt.% to about 20 wt.%, alternatively from
  • a primary mercaptan is a mercaptan that has the thiol group (-SH) attached to a primary carbon (e.g., a carbon atom that is attached to one and only one other carbon atom).
  • a secondary mercaptan is a mercaptan that has the thiol group (-SH) attached to a secondary carbon (e.g., a carbon atom that is attached to two and only two other carbon atoms).
  • a tertiary mercaptan is a mercaptan that has the thiol group (-SH) attached to a tertiary carbon (e.g., a carbon atom that is attached to three and only three other carbon atoms).
  • a tertiary carbon e.g., a carbon atom that is attached to three and only three other carbon atoms.
  • each of the primary, secondary, and tertiary mercaptans will depend on the make-up of the feedstock, as well as on the reaction conditions.
  • the Cio primary mercaptans can comprise 5 -methyl- l-mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto-heptane (represented by Structure B), 4-ethyl- l-mercapto-octane (represented by Structure C), 2-butyl- l-mercapto-hexane (represented by Structure D), l-mercapto-decane (represented by Structure M), or combinations thereof.
  • the Cio secondary mercaptans can comprise 4-mercapto-decane (represented by Structure N), 5-mercapto-decane (represented by Structure O), 5-methyl-2-mercapto-nonane (represented by Structure E), 3-propyl-2-mercapto-heptane (represented by Structure F), 4-ethyl-2-mercapto-octane (represented by Structure G), 2-mercapto-decane (represented by Structure P), or combinations thereof.
  • the Cio tertiary mercaptans can comprise equal to or greater than about 90 wt.%, alternatively equal to or greater than about 95 wt.%, or alternatively equal to or greater than about 99 wt.% 5- methyl-5-mercapto-nonane (represented by Structure H).
  • the process can comprise reacting FfS and a feedstock (e.g., a first or second feedstock as described herein) comprising one or more branched Cio monoolefms in the presence of an initiating agent (e.g., catalyst) to produce a crude composition; wherein the initiating agent comprises an acid catalyst.
  • a feedstock e.g., a first or second feedstock as described herein
  • an initiating agent e.g., catalyst
  • Nonlimiting examples of acid catalysts suitable for use in the present disclosure include acid washed clays (such as, but not limited to, Filtrol ® 24 or Filtrol ® 24X); acid washed bentonite; a tetrafluoroethylene polymer resin modified with perfluorovinyl ether groups terminated with sulfonate groups; a macroreticular, sulfonated, crosslinked copolymer of styrene and divinyl benzene; and the like, or combinations thereof.
  • acid washed clays such as, but not limited to, Filtrol ® 24 or Filtrol ® 24X
  • acid washed bentonite a tetrafluoroethylene polymer resin modified with perfluorovinyl ether groups terminated with sulfonate groups
  • a macroreticular, sulfonated, crosslinked copolymer of styrene and divinyl benzene and the like, or combinations thereof.
  • FfS and a feedstock comprising one or more branched Cio monoolefms can be reacted in the presence of an acid catalyst in a continuous reactor, such as for example continuous flow reactor, continuous stirred reactors, fixed bed reactors, packed bed reactors, and the like, or combinations thereof.
  • the continuous reactor can be characterized by a weight hourly space velocity (WHSV) of from about 0.1 h 1 to about 5 h 1 , alternatively from about 0.5 h 1 to about 4 h 1 , or alternatively from about 1 h 1 to about 3 h 1 , based on mass of olefin per mass of catalyst per hour.
  • WHSV weight hourly space velocity
  • FfS and a feedstock comprising one or more branched Cio monoolefms can be reacted in the presence of an acid catalyst at a temperature of from about 100 °C to about 300 °C, alternatively from about 120 °C to about 220 °C, or alternatively from about 180 °C to about 200 °C.
  • FfS and a feedstock comprising one or more branched Cio monoolefms can be reacted in the presence of an acid catalyst at a FfS to olefin molar ratio of from about 1 : 1 to about 10: 1, alternatively from about 2: 1 to about 7.5: 1, or alternatively from about 2.5: 1 to about 5: 1.
  • the process can comprise reacting FfS and a feedstock comprising one or more branched Cio monoolefms in the presence of an acid catalyst to produce a crude composition (wherein the crude composition comprises from 50-100 wt.% Cio mercaptans, alternatively from 50-90 wt.% Cio mercaptans, alternatively from 75-85 wt.% Cio mercaptans); wherein the Cio mercaptans comprise from about 0 wt.% to about 5 wt.% alternatively from about 0.1 wt.% to about 4 wt.%, or alternatively from about 0.5 wt.% to about 2.5 wt.% Cio primary mercaptans; from about 80 wt.% to about 95 wt.%, alternatively from about 82.5 wt.% to about 92.5 wt.%, or alternatively from about 85 wt.% to about 90 wt.% Cio secondary mercaptans
  • the process can comprise reacting 3 ⁇ 4S and a feedstock (e.g., a first or second feedstock as described herein) comprising one or more branched Cio monoolefms in the presence of an initiating agent to produce a crude composition; wherein the initiating agent comprises a hydrodesulfurization (HDS) catalyst.
  • a feedstock e.g., a first or second feedstock as described herein
  • the initiating agent comprises a hydrodesulfurization (HDS) catalyst.
  • HDS hydrodesulfurization
  • the HDS catalyst comprises a comprises a metal, a transition metal, Ru, Co, Mo, Ni, W, sulfides thereof, disulfides thereof, and the like, or combinations thereof.
  • the HDS catalyst can be Haldor Topsoe TK-554 or TK-570, and the like, or combinations thereof.
  • the HDS catalyst can further comprise a support, such as for example alumina, silica, and the like, or combinations thereof.
  • 3 ⁇ 4S and a feedstock comprising one or more branched Cio monoolefms can be reacted in the presence of an HDS catalyst in a continuous reactor, such as for example continuous flow reactor, continuous stirred reactors, fixed bed reactors, packed bed reactors, and the like, or combinations thereof.
  • the continuous reactor can be characterized by a WHSV of from about 0.1 h 1 to about 5 h 1 , alternatively from about 0.5 h 1 to about 4 h 1 , or alternatively from about 1 h 1 to about 3 h 1 , based on mass of olefin per mass of catalyst per hour.
  • 3 ⁇ 4S and a feedstock comprising one or more branched Cio monoolefms can be reacted in the presence of an HDS catalyst at a temperature of from about 100 °C to about 300 °C, alternatively from about 120 °C to about 220 °C, or alternatively from about 180 °C to about 200 °C.
  • 3 ⁇ 4S and a feedstock comprising one or more branched Cio monoolefms can be reacted in the presence of an HDS catalyst at a 3 ⁇ 4S to olefin molar ratio of from about 1 : 1 to about 10: 1, alternatively from about 2: 1 to about 7.5: 1, or alternatively from about 2.5: 1 to about 5: 1.
  • the process can comprise reacting 3 ⁇ 4S and a feedstock comprising one or more branched Cio monoolefms in the presence of an HDS catalyst to produce a crude composition (wherein the crude composition comprises from 50-100 wt.% Cio mercaptans, alternatively from 50-90 wt.% Cio mercaptans, alternatively from 75-85 wt.% Cio mercaptans); wherein the Cio mercaptans comprise from about 5 wt.% to about 30 wt.% alternatively from about 10 wt.% to about 25 wt.%, or alternatively from about 15 wt.% to about 20 wt.% Cio primary mercaptans; from about 60 wt.% to about 75 wt.%, alternatively from about 62.5 wt.% to about 72.5 wt.%, or alternatively from about 65 wt.% to about 70 wt.% Cio secondary mercaptans;
  • any such feedstocks comprising one or more branched Cio monoolefms can be reacted with hydrogen sulfide (H 2 S) in the presence of an initiating agent to produce a crude composition, and the crude composition can be further refined (e.g., distilled or otherwise separated into one or more fractions such as lights, intermediate, and heavies) to yield the various compositions described herein.
  • H 2 S hydrogen sulfide
  • the type and/or amounts of the constituent components that form the crude composition can vary depending upon the feedstock (e.g., the amount and types of olefins therein), the reaction conditions, the catalysts employed, etc., and one skilled in the art can tailor the post reactor processing of the crude composition to account for the specific compounds present in a given crude composition to yield various desired products and compositions of the types described herein.
  • a reactor effluent can be recovered from the reactor and H 2 S removed therefrom to yield a crude composition.
  • the term“crude composition” or“crude product” refers to an unrefined effluent stream recovered from the reactor after removal of H 2 S, and in particular to an FUS-free effluent stream that has not undergone any additional post-reactor processing such as flashing, distillation, or other separation techniques or processes to remove any components from the effluent stream other than the initial removal of H 2 S.
  • ITS Hydrogen sulfide
  • Bulk FTS can be removed under conditions of reduced pressure, and residual FTS can be removed at reduced temperature and pressure without removing any substantial quantities of the lights.
  • ITS can also be removed by sparging inert gas into the liquid phase.
  • there are other methods for removing ITS i.e., absorption, stripping, etc. that are known to those of skill in the art.
  • a reactor effluent can be treated to remove essentially all of any excess and/or unreacted hydrogen sulfide (H 2 S).
  • the crude composition comprises branched Cio mercaptans and branched C 2 o sulfides formed by the reaction of H 2 S and the one or more branched Cio monoolefms, and the structures of these branched Cio mercaptans and branched C 2 o sulfides are described in more detail herein.
  • the crude composition can comprise a number of other compounds such as unreacted olefins, inert compounds (e.g., alkanes), non-branched Cio mercaptans, non-branched C 2 o sulfides, non-Cio mercaptans, non-C 2 o sulfides, and other impurities.
  • the constituent components contained within the crude composition can vary depending upon the composition of the feedstock (e.g., an unpurified first feedstock as compared to a purified second feedstock as described herein) as well as reaction conditions, catalyst, etc.
  • a crude composition can comprise light, intermediate, and heavy fractions as described herein.
  • the crude compositions can contain a variety of other non-Cio mercaptan and non-C 2 o sulfides components (e.g., impurities) such as Cx mercaptans; C 12 mercaptans; C 14 mercaptans; Ci 6 mercaptans; Cis mercaptans; Cie- 36 sulfides represented by the structure R 3 -S-R 4 , wherein R 3 and R 4 are each independently a functional group derived from an olefin selected from the group consisting of Cx monoolefins, C 10 monoolefins, C 12 monoolefins, C 14 monoolefins, Ci 6 monoolefins, and Cis monoolefins, wherein R 3 and R 4 are not both branched Cio monoolefins; unreacted Cx-ix monoolefins; non-olefin impurities selected from the group consisting of C
  • a crude composition comprising branched Cio mercaptans and branched C 20 sulfides can be separated by any process or unit operation known in the art.
  • a crude composition can be processed (e.g., distilled) to remove a fraction of light compounds.
  • a crude composition can be processed to recover both a lights fraction and an intermediates fraction (e.g., a rough cut), followed by further processing to obtain one or more fine cuts.
  • a crude composition can be processed to recover a heavies fraction (e.g., a C 20 sulfide fraction).
  • a crude composition can be processed to separate out any combination of a lights fraction, an intermediates fraction (e.g., comprising Cio mercaptans, including branched Cio mercaptans), and a heavies fraction (e.g., comprising C 20 sulfides, including branched C 20 sulfides).
  • a light, intermediate or heavy fraction e.g., a rough cut
  • a desired fine cuts e.g., a Cio mercaptan fraction.
  • a crude composition can be separated to produce a high-purity Cio mercaptan stream and/or a high-purity C 20 sulfide stream (e.g., to obtain a desired fine cut or fraction such as a Cio mercaptan fraction). Further, these separated streams can be blended in any combination of ratios to produce a mixture with specific concentrations of one of more components (e.g., desired blend ratios of branched Cio mercaptans and/or branched C 20 sulfides, for example to aid in a particular end use).
  • the unit operations/processes used for these separations are known to one of skill and the art and include, but are not limited to, distillation, fractionation, flashing, stripping, and absorption, and others.
  • the unit operation conditions such as for example, temperature, pressure, flow rates, and others at which these unit operations produce one or more of the desired fractions can easily be determined by one of ordinary skill in the art.
  • a lights fraction is removed from the crude composition, for example by flashing, distillation, fractionation, stripping, absorption, etc.
  • the lights fraction can comprise at least about 90 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, alternatively at least about 96 wt.%, alternatively at least about 97 wt.%, alternatively at least about 98 wt.%, alternatively at least about 99 wt.% C 9 - compounds, based on the total weight of the lights fraction.
  • Nonlimiting examples of C9- compounds include C9- monoolefms (e.g., unreacted C9- monoolefms), C9- mercaptans, C9- alkanes, cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene, C9- alcohols, 2-ethyl- l-hexanol, and the like, or combinations thereof.
  • C9- monoolefms e.g., unreacted C9- monoolefms
  • C9-mercaptans C9- alkanes
  • cyclohexane methylcyclopentane
  • methylcyclohexane benzene
  • benzene toluene
  • ethylbenzene xylene
  • mesitylene C9- alcohols
  • the lights fraction can comprise less than about 10 wt.%, alternatively less than about 5 wt.%, alternatively less than about 4 wt.%, alternatively at less than about 3 wt.%, alternatively less than about 2 wt.%, alternatively less than about 1 wt.% C10+ compounds, based on the total weight of the lights fraction.
  • the C9- monoolefms can comprise, can consist essentially of, or can be, a C7 monoolefm, a Cx monoolefm, a C9 monoolefm, or combinations thereof; alternatively, a C7 monoolefm; alternatively, a Cx monoolefm; or alternatively, a C9 monoolefm.
  • the C9- monoolefms can comprise, can consist essentially of, or can be, a Cs monoolefm (e.g., l-octene).
  • the C9- mercaptans can comprise, can consist essentially of, or can be, a C7 mercaptan, a Cx mercaptan, a C9 mercaptan, or combinations thereof; alternatively, a C7 mercaptan; alternatively, a Cx mercaptan; or alternatively, a C9 mercaptan.
  • the C9- mercaptans can comprise, can consist essentially of, or can be, a Cs mercaptan.
  • a combined intermediate and heavy fraction i.e., C10+ compounds sometimes referred to as a kettle product in the Examples
  • the combined intermediate and heavy fraction can be used“as is” or can be further processed, for example separated or split into separate intermediate and heavy fractions (and said separate intermediate and heavy fractions can be subsequently recombined in various blends and associated blend ratios), as described in more detail herein.
  • a combined intermediate and heavy fraction (i.e., C10+ compounds) formed by removal of the lights fraction from the crude composition can comprise less than about 15 wt.%, alternatively less than about 10 wt.%, alternatively less than about 9 wt.%, alternatively less than about 8 wt.%, alternatively less than about 7 wt.%, alternatively less than about 6 wt.%, alternatively less than about 5 wt.%, alternatively less than about 4 wt.%, alternatively less than about 3 wt.%, alternatively less than about 2 wt.%, alternatively less than about 1 wt.% C9- products, based on the total weight of the combined intermediate and heavy fraction (i.e., C10+ compounds).
  • a combined intermediate and heavy fraction can comprise (A) at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% mercaptans; wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the mercaptans can be branched Cio mercaptans selected from the group consisting of 5 -methyl- l-mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto- h
  • both R 1 and R 2 can each independently be a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- l-nonene (represented by Structure I), 3-propyl-l- heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • the crude composition can be flashed to remove a lights fraction as described herein to produce a combined intermediate and heavy fraction (i.e., C 10+ compounds) comprising: (A) at least about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt.% Cio branched mercaptans selected from the group consisting of 5 -methyl- l-mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto-heptane (represented by Structure B), 4-ethyl- l-mercapto-octane (represented by Structure C), 2-butyl- l-mercapto- hexane (represented by Structure D), 5 -methyl -2 -mercapto-nonane (represented by Structure E), 3-propyl-2- mercapto-heptane (represented by Structure F), 4-ethyl -2 -mercapto-octane
  • both R 1 and R 2 can each independently be a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- l-nonene (represented by Structure I), 3-propyl-l- heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • the crude composition can be flashed to remove a lights fraction as described herein to produce a combined intermediate and heavy fraction (i.e., C 10+ compounds) comprising: (A) from at least about 50 wt.% to at least about 90 wt.%, alternatively from at least about 55 wt.% to at least about 85 wt.%, or alternatively from at least about 60 wt.% to at least about 80 wt.% mercaptans, wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the mercaptans can be branched Cio mercaptans selected from the group consisting of 5 -methyl- l-mercapto-nonane (represented by Structure A), 3 -propyl- l-
  • both R 1 and R 2 can each independently be a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- l-nonene (represented by Structure I), 3-propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • the crude composition can be flashed to remove a lights fraction and subsequently further separated to produce an intermediate fraction and a heavies fraction.
  • the intermediate fraction and the heavies fractions can then be optionally further processed (e.g., polished) and mixed in any appropriate ratio to produce a blended composition comprising: (A) at least about 25 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 90 wt.% C10 mercaptans (e.g., branched C10 mercaptans) selected from the group consisting of 5 -methyl- 1 -mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto- heptane (represented by Structure B), 4-ethyl- l-mercapto-octane (represented
  • R 1 and R 2 can each independently be a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- l-nonene (represented by Structure I), 3-propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof; and one or more of the following components (C) - (I): (C) less than about 5 wt.%, alternatively less than about 4 wt.%, alternatively less than about 3 wt.%, alternatively less than about 2 wt.%, or alternatively less than about 1 wt.% Cx mercaptans; (D) less than about 15 wt.%, alternatively less than about 10 wt.%, or alternatively less than about 5 wt.% C12 mercaptans; (E) less than about 15 wt.%,
  • the blended composition can comprise varying amounts of each of components (C)-(I), and the presence of each component (C)-(I) and the amount thereof can be independently formulated and/or controlled.
  • the blended composition can comprise an amount of one or more components (C)-(I) that is greater than zero (i.e., above a detection limit associated with the component) and less than the upper range endpoint set forth above (e.g., component (C) is present in the composition in an amount greater than zero and less than about 5 wt.%, and so forth as set forth above).
  • a mercaptan/sulfide composition of the type disclosed herein can be prepared by combining at least a portion of a first mercaptan/sulfide composition (wherein only a lights fraction has been removed from the crude product to yield a combined intermediate and heavy fraction, e.g., C10 + compounds) with at least a portion of a heavies fraction comprising a sulfide composition to yield a second mercaptan/sulfide composition, wherein a sulfide content of the second mercaptan/sulfide composition is greater than a sulfide content of the first mercaptan/sulfide composition.
  • the crude can be separated into light, intermediate, and heavy fractions by distillation, for example in a single distillation column having a light fraction recovered as an overhead stream, an intermediate fraction (e.g., comprising branched Cio mercaptans) recovered as a side stream, and a heavy fraction (e.g., comprising branched C20 sulfides) recovered as a bottom stream.
  • a light fraction recovered as an overhead stream
  • an intermediate fraction e.g., comprising branched Cio mercaptans
  • a heavy fraction e.g., comprising branched C20 sulfides
  • the separation can be in sequential steps such as removal of the lights fraction in a first distillation column, followed by separation of the intermediate fraction (e.g., comprising branched Cio mercaptans) as an overhead stream in a second distillation column and the heavy fraction (e.g., comprising Cn + compounds, including branched C20 sulfides) as a bottom stream of the second distillation column.
  • the intermediate fraction e.g., comprising branched Cio mercaptans
  • the heavy fraction e.g., comprising Cn + compounds, including branched C20 sulfides
  • These“rough-cut” light, intermediate, and heavy streams can be used“as is” or they can be further processed (e.g., further refined or polished, for example by additional distillation or other separation techniques to produce“fine-cuts”) and/or blended to obtain a variety of products that are salable or otherwise available for a variety of end uses such as mining ore collector compositions or chain transfer agents.
  • a variety of mercaptan compositions, sulfide compositions, and mixed mercaptan/sulfide compositions can be produced of the type disclosed in more detail herein.
  • an intermediate fraction can comprise at least about 25 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.% branched C10 mercaptans, alternatively at least about 75 wt.% branched C10 mercaptans, or alternatively at least about 85 wt.% branched C10 mercaptans.
  • the branched C10 mercaptans can be selected from the group consisting of 5 -methyl- l-mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto-heptane (represented by Structure B), 4-ethyl- l-mercapto-octane (represented by Structure C), 2-butyl- l-mercapto- hexane (represented by Structure D), 5-methyl-2-mercapto-nonane (represented by Structure E), 3-propyl-2- mercapto-heptane (represented by Structure F), 4-ethyl-2-mercapto-octane (represented by Structure G), 5- methyl-5-mercapto-nonane (represented by Structure H), and combinations thereof.
  • 5 -methyl- l-mercapto-nonane represented by Structure A
  • 3 -propyl- l-mercapto-heptane represented by Structure B
  • the heavy fraction can comprise at least about 5, 10, 15, 20, 25, 30, 35, 40,
  • branched C20 sulfides represented by structure R'-S-R 2 .
  • R 1 and R 2 are each independently a branched C10 alkyl group derived from the branched C10 monoolefm, and wherein the branched C10 alkyl group is selected from the group consisting of
  • a mercaptan composition can comprise mercaptans, wherein at least a portion of the mercaptans comprise Cio mercaptans, and wherein at least a portion of the Cio mercaptans comprise branched Cio mercaptans.
  • the branched Cio mercaptans can comprise 5-methyl-l- mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto-heptane (represented by Structure B), 4- ethyl- l-mercapto-octane (represented by Structure C), 2-butyl- l-mercapto-hexane (represented by Structure D), 5-methyl-2-mercapto-nonane (represented by Structure E), 3-propyl-2-mercapto-heptane (represented by Structure F), 4-ethyl-2-mercapto-octane (represented by Structure G), 5 -methyl-5 -mercapto-nonane (represented by Structure H), or combinations thereof.
  • branched Cio mercaptans refer to mercaptans (or thiols) that are characterized by the general formula R-SH, wherein R is a branched alkyl group (as opposed to a linear alkyl group), i.e., an alkyl group substituted with alkyl substituents; and wherein R has a total of 10 carbon atoms.
  • a composition comprising mercaptans, wherein at least a portion of the mercaptans are branched Cio mercaptans (e.g., 5 -methyl- l-mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto-heptane (represented by Structure B), 4-ethyl- l-mercapto-octane (represented by Structure C), 2-butyl- l-mercapto-hexane (represented by Structure D), 5-methyl-2-mercapto-nonane (represented by Structure E), 3-propyl-2-mercapto-heptane (represented by Structure F), 4-ethyl-2-mercapto- octane (represented by Structure G), 5 -methyl-5 -mercapto-nonane (represented by Structure H), or combinations thereof), can also be referred to as a“branched Cio mercaptan composition.”
  • Cio mercaptans e.g
  • the Cio mercaptans can further comprise non-branched Cio mercaptans, such as for example l-mercapto-decane (represented by Structure M), 4-mercapto-decane (represented by Structure N), 5-mercapto-decane (represented by Structure O), 2-mercapto-decane (represented by Structure P), or combinations thereof.
  • non-branched Cio mercaptans such as for example l-mercapto-decane (represented by Structure M), 4-mercapto-decane (represented by Structure N), 5-mercapto-decane (represented by Structure O), 2-mercapto-decane (represented by Structure P), or combinations thereof.
  • a mercaptan composition can comprise mercaptans, wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% of the mercaptans can be branched Cio mercaptans selected from the group consisting of 5- methyl-l-mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto-heptane (represented by Structure B), 4-ethyl- l-mercapto-octane (represented by Structure C), 2-butyl- l-mercapto-hexane (represented by Structure D), 5 -methyl-2 -mercapto-nonane (represented by Structure E), 3-propyl-2-mercapto
  • a mercaptan composition can comprise at least about 1 wt.%, alternatively at least about 5 wt.%, alternatively at least about 10 wt.%, alternatively at least about 20 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% mercaptans, wherein at least a portion of the mercaptans can be branched Cio mercaptans selected from the group consisting of 5 -methyl- l-mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto-heptane (represented by Structure A), 3 -propy
  • a mercaptan composition can comprise at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% mercaptans; wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least 85wt.% of the mercaptans can be branched Cio mercaptans selected from the group consisting of 5 -methyl- l-mercapto- nonane (represented by Structure A), 3 -propyl- l-mercapto-heptane (represented by Structure B), 4-ethyl-
  • a mercaptan composition can comprise at least about 50, 55, 60, 65,
  • Cio mercaptans selected from the group consisting of 5 -methyl- l-mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto-heptane (represented by Structure B), 4-ethyl- l-mercapto-octane (represented by Structure C), 2-butyl- l-mercapto-hexane (represented by Structure D), 5 -methyl -2 -mercapto-nonane (represented by Structure E), 3 -propyl-2 -mercapto-heptane (represented by Structure F), 4-ethyl-2-mercapto-octane (represented by Structure G), 5-methyl-5-mer
  • a mercaptan composition can comprise from at least about 50 wt.% to at least about 90 wt.%, alternatively from at least about 55 wt.% to at least about 85 wt.%, or alternatively from at least about 60 wt.% to at least about 80 wt.% mercaptans, wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the mercaptans can be branched Cio mercaptans selected from the group consisting of 5 -methyl- l-mercapto-nonane (represented by Structure A), 3-propyl- l-mercapto-heptane (represented by Structure B), 4-ethyl- l-mercapto-octane (
  • a mercaptan composition can consist of or consist essentially of branched Cio mercaptans selected from the group consisting of 5 -methyl- 1 -mercapto-nonane (represented by Structure A), 3 -propyl- 1 -mercapto-heptane (represented by Structure B), 4-ethyl- l-mercapto-octane (represented by Structure C), 2-butyl- l-mercapto-hexane (represented by Structure D), 5 -methyl -2 -mercapto- nonane (represented by Structure E), 3 -propyl -2 -mercapto-heptane (represented by Structure F), 4-ethyl-2- mercapto-octane (represented by Structure G), 5 -methyl-5 -mercapto-nonane (represented by Structure H), and combinations thereof.
  • Cio mercaptans selected from the group consisting of 5 -methyl- 1 -mercapto-nonane (represented by Structure
  • a mercaptan composition can comprise at least about 1, 5, 10,
  • Cio mercaptans selected from the group consisting of 5 -methyl- 1 -mercapto-nonane (represented by Structure A), 3 -propyl- 1 -mercapto- heptane (represented by Structure B), 4-ethyl- l-mercapto-octane (represented by Structure C), 2-butyl- 1- mercapto-hexane (represented by Structure D), 5-methyl-2-mercapto-nonane (represented by Structure E), 3- propyl-2 -mercapto-heptane (represented by Structure F), 4-ethyl-2-mercapto-octane (represented by Structure G), 5 -methyl-5 -mercapto-nonane (represented by Structure H), and combinations thereof.
  • a composition can comprise mercaptans, wherein at least about
  • Cio mercaptans selected from the group consisting of 5 -methyl- 1 -mercapto-nonane (represented by Structure A), 3 -propyl- 1 -mercapto- heptane (represented by Structure B), 4-ethyl- l-mercapto-octane (represented by Structure C), 2-butyl- 1- mercapto-hexane (represented by Structure D), 5-methyl-2-mercapto-nonane (represented by Structure E), 3- propyl-2 -mercapto-heptane (represented by Structure F), 4-ethyl-2-mercapto-octane (represented by Structure G), 5 -methyl-5 -mercapto-nonane (represented by Structure H), and combinations thereof.
  • a sulfide composition can comprise sulfides, wherein at least a portion of the sulfides comprise C 20 sulfides, and wherein at least a portion of the C 20 sulfides comprise branched C 20 sulfides represented by structure R'-S-R 2 . wherein R 1 and R 2 can each independently be an alkyl group, and wherein at least a portion of the alkyl groups comprises a branched Cio alkyl group.
  • the alkyl group (e.g., a branched Cio alkyl group as R 1 , R 2 ) can comprise a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- l-nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • the olefin comprises 5 -methyl- l-nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • a sulfide will be referred to by the total number of carbon atoms (as opposed to the number of carbons of only one of the alkyl groups present in a dialkyl sulfide).
  • a H 21 C 10 -S-C 10 H 21 sulfide will be referred to as a C 20 sulfide (rather than a C 10 sulfide).
  • branched C 20 sulfides refer to sulfides (or thioethers) that are characterized by the general formula R'-S-R 2 .
  • both R 1 and R 2 are each independently a branched C 10 alkyl group (as opposed to a linear alkyl group), i.e., an alkyl group substituted with alkyl substituents.
  • branched C 20 sulfides refer to sulfides wherein both R 1 and R 2 are branched C 10 alkyl groups, wherein R 1 and R 2 can be the same or different.
  • a composition comprising sulfides, wherein at least a portion of the sulfides are branched C 20 sulfides represented by structure R'-S-R 2 .
  • both R 1 and R 2 are each independently an alkyl group, wherein at least a portion of the alkyl group comprises a branched C 10 alkyl group (e.g., a functional group derived from an olefin, and wherein the olefin comprises 5-methyl-l- nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof), can also be referred to as a“branched C 20 sulfide composition.”
  • the sulfide composition can comprise any suitable amount of branched C 20 sulfides.
  • a sulfide composition can comprise sulfides, wherein at least a portion of the sulfides comprise C 20 sulfides, and wherein at least a portion of the C 20 sulfides comprise branched C 20 sulfides represented by structure R'-S-R 2 . wherein both R 1 and R 2 can each independently be a branched C 10 alkyl group derived from a branched C 10 monoolefm, and wherein the branched C 10 alkyl group is selected from the group consisting of
  • the branched C 10 monoolefm can comprises 5 -methyl- l-nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • a monoolefm is a linear or branched aliphatic hydrocarbon olefin that has one and only one carbon-carbon double bond.
  • a C n monoolefm is a linear or branched aliphatic hydrocarbon olefin that has n and only n carbon atoms, and one and only one carbon-carbon double bond.
  • a C 10 monoolefm is a linear or branched aliphatic hydrocarbon olefin that has ten and only ten carbon atoms, and one and only one carbon-carbon double bond.
  • a branched C 10 monoolefm is a branched aliphatic hydrocarbon olefin that has ten and only ten carbon atoms, and one and only one carbon-carbon double bond.
  • the C20 sulfides can further comprise non-branched C20 sulfides and/or partially branched C20 sulfides represented by structure R'-S-R 2 .
  • R 1 and R 2 in the case of non- branched C20 sulfides
  • one of the R 1 and R 2 in the case of partially-branched C20 sulfides
  • R 1 and R 2 can be a linear C10 alkyl group derived from a linear C10 monoolefm, such as for example 4-decene (represented by Structure Q), 5-decene (represented by Structure R), l-decene (represented by Structure S), or combinations thereof.
  • the non-branched C20 sulfides represented by structure R'-S-R 2 are the sulfides wherein both R 1 and R 2 are each independently a linear C10 alkyl group derived from a linear C10 monoolefin.
  • the partially branched C20 sulfides represented by structure R'-S-R 2 are the sulfides wherein one of the R 1 and R 2 is a linear C10 alkyl group derived from a linear C10 monoolefm, while the other one of the R 1 and R 2 is a branched C10 alkyl group derived from a branched C10 monoolefm as described herein.
  • a sulfide composition can comprise sulfides, wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% of the sulfides can be branched C20 sulfides represented by structure R'-S-R 2 .
  • both R 1 and R 2 can each independently be a functional group derived from an olefin, wherein the olefin comprises 5-methyl-l- nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • a sulfide composition can comprise at least about 1 wt.%, alternatively at least about 5 wt.%, alternatively at least about 10 wt.%, alternatively at least about 20 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% sulfides, wherein at least a portion of the sulfides can be branched C20 sulfides represented by structure R'-S-R 2 .
  • both R 1 and R 2 can each independently be a functional group derived from an olefin, wherein the olefin comprises 5- methyl-l-nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • a sulfide composition can comprise at least about 1, 5, 10, 15, 20, 25,
  • sulfides wherein at least about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.%, sulfides, wherein at least about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of the sulfides can be branched C20 sulfides represented by structure R'-S-R 2 .
  • both R 1 and R 2 can each independently be a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- l-nonene (represented by Structure I), 3-propyl-l- heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • a sulfide composition can comprise at least about 10 wt.%, alternatively at least about 15 wt.%, alternatively at least about 20 wt.%, or alternatively at least about 25 wt.% sulfides; wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the sulfides can be branched C20 sulfides represented by structure R'-S-R 2 .
  • both R 1 and R 2 can each independently be a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- 1- nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • a sulfide composition can comprise from at least about 10 wt.% to at least about 30 wt.%, alternatively from at least about 12.5 wt.% to at least about 22.5 wt.%, or alternatively from at least about 15 wt.% to at least about 20 wt.% sulfides; wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the sulfides can be branched C20 sulfides represented by structure R'-S-R 2 .
  • both R 1 and R 2 can each independently be a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- l-nonene (represented by Structure I), 3-propyl-l- heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • a sulfide composition can consist of or consist essentially of branched C20 sulfides represented by structure R'-S-R 2 .
  • R 1 and R 2 can each independently be a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- l-nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2- butyl-l -hexene (represented by Structure L), or combinations thereof.
  • a sulfide composition can comprise at least about 5 wt.%, alternatively at least about 10 wt.%, alternatively at least about 15 wt.%, or alternatively at least about 20 wt.% C20 sulfides (e.g., branched C20 sulfides) represented by structure R'-S-R 2 .
  • C20 sulfides e.g., branched C20 sulfides
  • both R 1 and R 2 can each independently be a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- l-nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • a sulfide composition comprises at least about 1, 5, 10, 15, 20,
  • R 1 and R 2 are each independently a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- l-nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • a mercaptan/sulfide composition can comprise one or more mercaptans and one or more sulfides of the type disclosed herein.
  • a composition comprising (i) mercaptans, wherein at least a portion of the mercaptans are branched C10 mercaptans, and (ii) sulfides, wherein at least a portion of the sulfides are branched C20 sulfides, can also be referred to as a“branched C10 mercaptan/C2o sulfide composition.”
  • the mercaptan/sulfide composition can comprise any suitable amount of branched C10 mercaptans, and any suitable amount of branched C20 sulfides.
  • a mercaptan/sulfide composition can comprise (A) at least about 1 wt.%, alternatively at least about 5 wt.%, alternatively at least about 10 wt.%, alternatively at least about 20 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% mercaptans, wherein at least a portion of the mercaptans can be branched C10 mercaptans selected from the group consisting of 5 -methyl- l-mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto-
  • both R 1 and R 2 can each independently be a functional group derived from an olefin, wherein the olefin comprises 5 -methyl- l-nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • a mercaptan/sulfide composition can comprise Cio mercaptans represented by the general formula R-SH and/or C20 sulfides represented by structure R'-S-R 2 that are formed by reacting an olefin feedstock comprising olefins with H2S as described in more detail herein, wherein the olefins present in the olefin feedstock provide the alkyl group represented by R, R 1 , and R 2 .
  • the R group of the Cio mercaptans and/or the R 1 and R 2 groups of the C20 sulfides are provided by or derived from the counterpart R, R 1 , and R 2 groups present in the olefins in the olefin feedstock.
  • R, R 1 and R 2 can each independently be an alkyl group, wherein at least a portion of the alkyl groups can comprise a functional group derived from an olefin, wherein the olefin is present in a feedstock (e.g., a first feedstock as described herein) comprising a) at least about 76 mol%, alternatively at least about 78 mol%, alternatively at least about 80 mol%, or alternatively at least about 82 mol% Cio monoolefins; and b) at least about 1 mol%, alternatively at least about 2 mol%, alternatively at least about 3 mol%, or alternatively at least about 4 mol% C14 monoolefins.
  • a feedstock e.g., a first feedstock as described herein
  • the Cio monoolefins can comprise i) at least about 3 mol%, alternatively at least about 4 mol%, alternatively at least about 5 mol%, alternatively at least about 6 mol%, alternatively at least about 7 mol%, or alternatively at least about 8 mol% 2-butyl- 1 -hexene (represented by Structure L), ii) at least about 8 mol%, alternatively at least about 9 mol%, alternatively at least about 10 mol%, alternatively at least about 11 mol%, alternatively at least about 12 mol%, or alternatively at least about 13 mol% 3 -propyl- l-heptene (represented by Structure J), iii) at least about 6 mol%, alternatively at least about 7 mol%, alternatively at least about 8 mol%, alternatively at least about 9 mol%, alternatively at least about 10 mol%, or alternatively at least about 11 mol% 4-ethyl- l-octene (represented by Structure L)
  • the Cio monoolefins can comprise from about 1 mol% to about 16 mol%, alternatively from about 2 mol% to about 15 mol%, alternatively from about 3 mol% to about 14 mol%, alternatively from about 4 mol% to about 13 mol%, or alternatively from about 6 mol% to about 12 mol% 4-decene and/or 5-decene.
  • the Cio monoolefins can comprise from about 0.5 mol% to about 9 mol%, alternatively from about 1 mol% to about 8 mol%, alternatively from about 1.5 mol% to about 7 mol%, or alternatively from about 2 mol% to about 6 mol% l-decene.
  • the olefin (e.g., corresponding to R, R 1 or R 2 ) present in the olefin feedstock
  • a first feedstock as described herein can further comprise from about 0.1 mol% to about 5 mol%, alternatively from about 0.25 mol% to about 4 mol%, or alternatively from about 0.5 mol% to about 3 mol% C12 monoolefins.
  • the C12 monoolefins can comprise from about 54 mol% to about 74 mol%, alternatively from about 56 mol% to about 72 mol%, alternatively from about 58 mol% to about 70 mol%, or alternatively from about 60 mol% to about 68 mol% l-dodecene.
  • the olefin (e.g., corresponding to R, R 1 or R 2 ) present in the olefin feedstock
  • a first feedstock as described herein can further comprise from about 0.1 mol% to about 5 mol%, alternatively from about 0.25 mol% to about 4 mol%, or alternatively from about 0.5 mol% to about 3 mol% Cx monoolefins.
  • the Cx monoolefms can comprise at least about 95 mol%, alternatively at least about 96 mol%, alternatively at least about 97 mol%, alternatively at least about 98 mol%, or alternatively at least about 99 mol% l-octene.
  • the olefin (e.g., corresponding to R, R 1 or R 2 ) present in the olefin feedstock
  • a first feedstock as described herein can further comprise from about 0.05 mol% to about 2 mol%, alternatively from about 0.04 mol%to about 1.5 mol%, alternatively from about 0.06 mol%to about 1.25 mol%, alternatively from about 0.08 mol% to about 1 mol%, or alternatively from about 0.1 mol% to about 0.75 mol% Ci6 monoolefms and/or Cix monoolefms.
  • the resultant mercaptan/sulfide composition can be a crude composition that can be further separated and refined into other compositions as described herein.
  • mercaptan compositions, sulfide compositions, and/or mercaptan/sulfide compositions as disclosed herein advantageously display improvements in one or more composition characteristics when compared to otherwise similar compositions lacking branched Cio mercaptans.
  • a mercaptan composition and/or a mercaptan/sulfide composition comprising equal to or greater than about 25 wt.%
  • Cio branched mercaptans as disclosed herein can advantageously have an odor less unpleasant and less offensive than an odor of an otherwise similar composition comprising equal to or greater than about 25 wt.% n-decyl mercaptan, as perceived by equal to or greater than about 51% of human subjects exposed to the odor of each composition.
  • a mercaptan composition and/or a mercaptan/sulfide composition comprising equal to or greater than about 25 wt.%
  • Cio branched mercaptans as disclosed herein can advantageously have an odor less unpleasant than an odor of an otherwise similar composition comprising equal to or greater than about 25 wt.% n-dodecyl mercaptan and/or tert-dodecyl mercaptan, as perceived by equal to or greater than about 51% of human subjects exposed to the odor of each composition. Additional advantages of the mercaptan compositions, sulfide compositions, and/or mercaptan/sulfide compositions and processes of producing same as disclosed herein can be apparent to one of skill in the art viewing this disclosure.
  • a process of the present disclosure comprises reacting, in a reactor, a sulfur source
  • a crude composition also referred to as a crude product
  • the crude composition comprises Cn + mercaptans and C 22+ sulfides.
  • a process of the present disclosure comprises reacting, in a reactor, a sulfur source
  • Cn + monoolefms comprise Cn and C12 internal monoolefms, C13 and C14 internal monoolefms, C14 and Ci 6 linear alpha monoolefms, and the like, or combinations thereof.
  • a process of the present disclosure comprises reacting, in a reactor, a sulfur source
  • a feedstock comprising one or more Cn + monoolefms in the presence of an initiating agent, as previously described herein for the branched Cio monoolefms, to produce a Cn + mercaptans crude composition; wherein the one or more Cn + monoolefms is selected from the group consisting of Cn and C 12 internal monoolefms, C 13 and C 14 internal monoolefms, C 14 and Ci 6 linear alpha monoolefms, and combinations thereof.
  • a process of the present disclosure comprises reacting, in a reactor, a sulfur source
  • a feedstock comprising one or more Cn + monoolefms in the presence of an initiating agent, as previously described herein for the branched Cio monoolefms, to produce a C 11+ mercaptans crude composition; wherein the one or more Cn + monoolefms is selected from the group consisting of Cn and C 12 internal monoolefms, C 13 and C 14 internal monoolefms, and Ci 4 and Ci 6 linear alpha monoolefms.
  • the sulfur source can be any sulfur source suitable to provide sulfur for the conversion of olefins
  • the sulfur source can comprise H 2 S, thioacetic acid, and the like, or combinations thereof. In some aspects, the sulfur source can comprise H 2 S, as previously described herein.
  • the feedstock can comprise Cn and C12 internal monoolefms.
  • Any feedstock comprising Cn and C12 internal monoolefms of the type described herein can be used, for example a feedstock obtained from a commercial petroleum refining or petrochemical process.
  • Such feedstocks can comprise other olefins in addition to the Cn and C12 internal monoolefms of the type described herein, for example Cio- monoolefins, as well as C 13+ monoolefms.
  • Cn and C12 internal monoolefms feedstock suitable for use in the present disclosure include NEODENE 1112 IO higher olefins, which contains a combination of Cn and C12 internal olefins that is commercially available from Shell Chemicals.
  • NEODENE 1112 IO higher olefins A typical composition of NEODENE 1112 IO higher olefins is given in the table below:
  • the feedstock can comprise at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, alternatively at least about 85 wt.%, alternatively at least about 90 wt.%, or alternatively at least about 95 wt.% Cn and C 12 internal monoolefins, based on the total weight of the feedstock.
  • the feedstock can comprise (a) less than about 10 wt.%, alternatively less than about 5 wt.%, or alternatively less than about 1.5 wt.% C 10 - monoolefms; and (b) less than about 10 wt.%, alternatively less than about 5 wt.%, or alternatively less than about 2 wt.% C 13+ monoolefms; based on the total weight of the feedstock.
  • a feedstock comprising at least about 70 wt.% Cn and C 12 internal monoolefms, based on the total weight of the feedstock can also be referred to as a“first Cn and C 12 feedstock.”
  • the feedstock can comprise at least about 95 wt.%, alternatively at least about
  • a feedstock comprising at least about 95 wt.% Cn and C 12 internal monoolefms, based on the total weight of the feedstock can also be referred to as a“second Cn and C 12 feedstock.”
  • the second Cn and C 12 feedstock can be produced by purifying the first Cn and C 12 feedstock, such as for example by distillation of the first Cn and C 12 feedstock.
  • the Cn internal monoolefms and C 12 internal monoolefms of any feedstock described herein can comprise linear Cn internal monoolefms and linear C 12 internal monoolefms, respectively.
  • the Cn internal monoolefms and C 12 internal monoolefms of any feedstock described herein can comprise branched Cn internal monoolefms and branched C 12 internal monoolefms, respectively.
  • the branched Cn internal monoolefms can comprise methyl branches.
  • the branched C 12 internal monoolefms can comprise methyl branches.
  • the Cn and C 12 internal monoolefms can comprise linear Cn internal monoolefms, linear C 12 internal monoolefms, branched Cn internal monoolefms, branched C 12 internal monoolefms, or combinations thereof.
  • the feedstock can comprise (A) at least about 30 wt.%, alternatively at least about 35 wt.%, or alternatively at least about 40 wt.% Cn internal monoolefms, and (B) at least about 40 wt.%, alternatively at least about 45 wt.%, alternatively at least about 50 wt.% C 12 internal monoolefms, based on the total weight of the feedstock.
  • the feedstock can comprise C 13 and C 14 internal monoolefins.
  • feedstock comprising C 13 and C 14 internal monoolefms of the type described herein can be used, for example a feedstock obtained from a commercial petroleum refining or petrochemical process.
  • feedstocks can comprise other olefins in addition to the C 13 and Ci 4 internal monoolefms of the type described herein, for example C 12- monoolefms, as well as C 15+ monoolefms.
  • C 13 and C 14 internal monoolefms feedstock suitable for use in the present disclosure include NEODENE 1314 IO higher olefins (also known as NEODENE 134 IO higher olefins), which contains a combination of C 13 and C 14 internal olefins that is commercially available from Shell Chemicals.
  • NEODENE 1314 IO higher olefins also known as NEODENE 134 IO higher olefins
  • a typical composition of NEODENE 1314 IO higher olefins is given in the table below:
  • the feedstock can comprise at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, alternatively at least about 85 wt.%, alternatively at least about 90 wt.%, or alternatively at least about 95 wt.% C13 and C14 internal monoolefms, based on the total weight of the feedstock.
  • the feedstock can comprise (a) less than about 10 wt.%, alternatively less than about 5 wt.%, or alternatively less than about 2 wt.% C 12- monoolefms; and (b) less than about 10 wt.%, alternatively less than about 5 wt.%, or alternatively less than about 2.5 wt.% C15+ monoolefms; based on the total weight of the feedstock.
  • a feedstock comprising at least about 70 wt.% C13 and C 14 internal monoolefms, based on the total weight of the feedstock can also be referred to as a“first C13 and C14 feedstock.”
  • the feedstock can comprise at least about 95 wt.%, alternatively at least about 96 wt.%, alternatively at least about 97 wt.%, alternatively at least about 98 wt.%, or alternatively at least about
  • a feedstock comprising at least about 95 wt.% C 13 and C 14 internal monoolefms, based on the total weight of the feedstock can also be referred to as a“second C13 and C 14 feedstock.”
  • the second C 13 and C14 feedstock can be produced by purifying the first C13 and C14 feedstock, such as for example by distillation of the first C 13 and C i 4 feedstock.
  • the C 13 internal monoolefins and C 14 internal monoolefins of any feedstock described herein can comprise linear C 13 internal monoolefins and linear C 14 internal monoolefins, respectively.
  • the C13 internal monoolefins and C 14 internal monoolefins of any feedstock described herein can comprise branched C13 internal monoolefins and branched C 14 internal monoolefins, respectively.
  • the branched C 13 internal monoolefins can comprise methyl branches.
  • the branched C 14 internal monoolefins can comprise methyl branches.
  • the C 13 and C14 internal monoolefins can comprise linear C 13 internal monoolefins, linear C 14 internal monoolefins, branched C13 internal monoolefins, branched C 14 internal monoolefins, or combinations thereof.
  • the feedstock can comprise (A) at least about 35 wt.%, alternatively at least about 40 wt.%, or alternatively at least about 45 wt.% C 13 internal monoolefins, and (B) at least about 35 wt.%, alternatively at least about 40 wt.%, alternatively at least about 45 wt.% Ci 4 internal monoolefins; based on the total weight of the feedstock.
  • the feedstock can comprise Ci 4 and Ci 6 alpha monoolefins, such as Ci 4 and Ci 6 linear alpha monoolefins.
  • Ci 4 and Ci 6 alpha monoolefins such as Ci 4 and Ci 6 linear alpha monoolefins.
  • the terms“alpha olefin (monoolefin)” and “terminal olefin (monoolefin)” can be used interchangeably.
  • Any feedstock comprising C 14 and Ci 6 alpha monoolefins of the type described herein can be used, for example a feedstock obtained from a commercial petroleum refining or petrochemical process.
  • Such feedstocks can comprise other olefins in addition to the Ci 4 and Ci 6 alpha monoolefins of the type described herein, for example C 13- monoolefins, as well as C 17+ monoolefins.
  • a feedstock comprising Ci 4 and Ci 6 alpha monoolefins can further comprise C 15 monoolefins, such as C15 alpha monoolefin, C 15 linear alpha monoolefin, etc.
  • a feedstock comprising linear olefins can further comprise a minor amount of branched monoolefins; or alternatively can exclude branched monoolefins.
  • the feedstock comprising Ci 4 and Ci 6 linear alpha monoolefins comprises less than 1 wt.%, alternatively less than 0.1 wt.%, alternatively less than 0.01 wt.%, alternatively less than 0.001 wt.%, or alternatively less than 0.0001 wt.% branched monoolefins, based on the total weight of the feedstock.
  • the feedstock comprising Ci 4 and Ci 6 linear alpha monoolefins is substantially free of branched monoolefins.
  • C14 and Ci 6 alpha monoolefms feedstock suitable for use in the present disclosure include NEODENE 14/16 higher olefins, which contains a combination of C14 and Ci 6 alpha olefins (2: 1 blend of a high purity l-tetradecene (C14) and l-hexadecene (Ci 6 ) made by the Shell Higher Olefins Process (SHOP) by the oligomerization of ethylene) that is commercially available from Shell Chemicals.
  • SHOP Shell Higher Olefins Process
  • the feedstock can comprise at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, alternatively at least about 85 wt.%, alternatively at least about 90 wt.%, or alternatively at least about 95 wt.% C14 and Ci6 linear alpha monoolefins, based on the total weight of the feedstock.
  • the feedstock can comprise (a) less than about 10 wt.%, alternatively less than about 5 wt.%, or alternatively less than about 2 wt.% C 12- monoolefms; and (b) less than about 10 wt.%, alternatively less than about 5 wt.%, or alternatively less than about 2 wt.% Ci8 + monoolefms; based on the total weight of the feedstock.
  • a feedstock comprising at least about 70 wt.% C14 and Ci6 linear alpha monoolefms, based on the total weight of the feedstock, can also be referred to as a “first C 14 and Ci6 feedstock.”
  • the feedstock can comprise at least about 95 wt.%, alternatively at least about
  • a feedstock comprising at least about 95 wt.% C14 and Ci 6 linear alpha monoolefms, based on the total weight of the feedstock can also be referred to as a“second C14 and Ci 6 feedstock.”
  • the second C14 and Ci6 feedstock can be produced by purifying the first C14 and Ci 6 feedstock, such as for example by distillation of the first C14 and Ci 6 feedstock.
  • the feedstock comprising C14 and Ci 6 linear alpha monoolefin (e.g., a first C14 and Ci 6 feedstock or a second C14 and Ci6 feedstock) can comprise less than less than about 10 wt.%, alternatively less than about 7.5 wt.%, or alternatively less than about 4.5 wt.% branched olefins, based on the total weight of the feedstock.
  • the feedstock can comprise (A) at least about 50 wt.%, alternatively at least about 55 wt.%, or alternatively at least about 60 wt.% l-tetradecene, and (B) at least about 20 wt.%, alternatively at least about 25 wt.%, alternatively at least about 30 wt.% l-hexadecene, based on the total weight of the feedstock.
  • a sulfur source e.g., FfiS
  • a feedstock comprising one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci6 linear alpha monoolefms)
  • a sulfur source to olefin molar ratio of from about 1 : 1 to about 20: 1, alternatively from about 2: 1 to about 15: 1, or alternatively from about 3: 1 to about 10: 1; as previously described herein for the branched C10 monoolefms.
  • a sulfur source e.g., H 2 S
  • a feedstock comprising one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms)
  • Cn + monoolefms e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms
  • a pressure of from about 30 psig (206 kPag) to about 1,500 psig (10,300 kPag), alternatively from about 100 psig (690 kPag) to about 1,250 psig (8,600 kPag), or alternatively from about 250 psig (1,700 kPag) to about 1,000 psig (6,900 kPag); as previously described herein for the branched C 10 monoo
  • a sulfur source e.g., FfiS
  • a feedstock comprising one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms)
  • Cn + monoolefms e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms
  • olefin conversion of equal to or greater than about 70%, alternatively equal to or greater than about 75%, or alternatively equal to or greater than about 80%, alternatively equal to or greater than about 85%, or alternatively equal to or greater than about 90%.
  • a sulfur source e.g., FfiS
  • a feedstock comprising one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci6 linear alpha monoolefms)
  • an initiating agent e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci6 linear alpha monoolefms
  • the initiating agent comprises ultraviolet (UV) radiation; as previously described herein for the branched C io monoolefms .
  • the initiating agent can further comprise a phosphite promoter, a photoinitiator, a sulfur scavenger, an antioxidant, and the like, or combinations thereof.
  • a sulfur source e.g., TfiS
  • a feedstock comprising one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms)
  • Cn + monoolefms e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms
  • the initiating agent comprises a acid catalyst; as previously described herein for the branched C10 monoolefms.
  • a sulfur source e.g., H2S
  • a feedstock comprising one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms)
  • Cn + monoolefms e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms
  • an initiating agent comprises a hydrodesulfurization (HDS) catalyst
  • any suitable feedstocks comprising one or more Cn + monoolefms (e.g.,
  • Cn and C 12 internal monoolefms; C 13 and C14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms can be reacted with a sulfur source (e.g., TfiS) in the presence of an initiating agent to produce a Cn + mercaptans crude composition, and the Cn + mercaptans crude composition can be further refined (e.g., distilled or otherwise separated into one or more fractions such as lights, intermediate, and heavies) to yield various compositions described herein.
  • a sulfur source e.g., TfiS
  • the type and/or amounts of the constituent components that form the Cn + mercaptans crude composition can vary depending upon the feedstock (e.g., the amount and types of olefins therein), the reaction conditions, the catalysts employed, etc., and one skilled in the art can tailor the post reactor processing of the Cn + mercaptans crude composition to account for the specific compounds present in a given Cn + mercaptans crude composition to yield various desired products and compositions of the types described herein.
  • a reactor effluent can be recovered from the reactor and H2S removed therefrom to yield a C n+ mercaptans crude composition.
  • C 11+ mercaptans crude composition or “C11+ mercaptans crude product” refers to an unrefined effluent stream recovered from the reactor after removal of the sulfur source (e.g., TfiS), and in particular to a sulfur source-free effluent stream that has not undergone any additional post-reactor processing such as flashing, distillation, or other separation techniques or processes to remove any components from the effluent stream other than the initial removal of the sulfur source.
  • the sulfur source e.g., TfiS
  • the Ci 1+ mercaptans crude composition comprises Cn + mercaptans and C22+ sulfides formed by the reaction of the sulfur source (e.g., TfiS) and the one or more C11+ monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C14 internal monoolefms; or Cn and Cn linear alpha monoolefms), wherein the structures of these Cn + mercaptans and C 22+ sulfides are consistent with (e.g., derived from) the structures of the corresponding Cn + monoolefms.
  • the sulfur source e.g., TfiS
  • C11+ monoolefms e.g., Cn and C 12 internal monoolefms; C 13 and C14 internal monoolefms; or Cn and Cn linear alpha monoolefms
  • the resulting Cn+ mercaptans can be characterized by the following structures that are consistent with (e.g., derived from) the structures of the corresponding l-tetradecene and l-hexadecene:
  • C28 sulfides, C30 sulfides, and C32 sulfides can be characterized by the following structures that are consistent with (e.g., derived from) the structures of the corresponding l-tetradecene and l-hexadecene:
  • the Cn + mercaptans are characterized by structure R 6 -SH, wherein R 6 is a functional group (e.g., alkyl group) derived from the one or more C 11+ monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms) disclosed herein.
  • R 6 is a functional group (e.g., alkyl group) derived from the one or more C 11+ monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms) disclosed herein.
  • the C 22+ sulfides are characterized by structure R 7 -S-R 8 , wherein both R 7 and R 8 can each independently be a functional group derived from the one or more C 11+ monoolefms (e.g., Cn and C 12 internal monoolefins; C 13 and C 14 internal monoolefins; or C 14 and Ci 6 linear alpha monoolefms) disclosed herein.
  • R 7 and R 8 can be the same or different, e.g., R 7 and R 8 can have the same structure; R 7 and R 8 can have different structures; R 7 and R 8 can have the same chain length; R 7 and R 8 can have different chain length; etc.
  • the one or more Cn + monoolefms e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms
  • the resulting Cn + mercaptans and C 22+ sulfides would also contain methyl branches consistent with (e.g., derived from) the structures of the corresponding Cn + monoolefms.
  • the Cn + mercaptans crude composition can comprise a number of other compounds such as unreacted olefins, inert compounds (e.g., alkanes), Cio- mercaptans, C 21 - sulfides, and other impurities.
  • the constituent components contained within the C 11+ mercaptans crude composition can vary depending upon the composition of the feedstock (e.g., an unpurified feedstock as compared to a purified feedstock as described herein) as well as reaction conditions, catalyst, etc.
  • a Cn + mercaptans crude composition can comprise light, intermediate, and heavy fractions as described herein.
  • the Cn + mercaptans crude composition can comprise less than about 10 wt.%, alternatively less than about 5 wt.%, alternatively less than about 4 wt.%, alternatively at less than about 3 wt.%, alternatively less than about 2 wt.%, or alternatively less than about 1 wt.% C 22+ sulfides, based on the total weight of the crude composition, wherein the C 22+ sulfides are characterized by structure R 7 -S-R 8 , wherein both R 7 and R 8 can each independently be a functional group derived from the one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms) disclosed herein.
  • Cn + monoolefms e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolef
  • a process of the present disclosure can further comprise recovering a reaction product from the C11 + mercaptans crude composition; wherein the reaction product can comprises C11 + mercaptans and/or C 22+ sulfides, wherein the Cn + mercaptans are characterized by structure R 6 -SH, wherein R 6 is a functional group (e.g., alkyl group) derived from the one or more C 11+ monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and Ci 4 internal monoolefms; or Ci 4 and Ci 6 linear alpha monoolefms) disclosed herein; and wherein the C 22+ sulfides are characterized by structure R 7 -S-R 8 , wherein both R 7 and R 8 can each independently be a functional group derived from the one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and Ci
  • the reaction product can comprise a Cn + mercaptans composition (intermediate fraction), a C22 + sulfides composition (heavy fraction), a Cn + mercaptans/C22 + sulfides composition (intermediate and heavy fractions), or combinations thereof.
  • a Cn + mercaptans crude composition as disclosed herein can be separated into two or more fractions (e.g., light fraction, intermediate fraction, heavy fraction, etc.) by any process or unit operation known in the art.
  • a Cn + mercaptans crude composition can be processed (e.g., distilled) to remove a fraction of light compounds.
  • a Cn + mercaptans crude composition can be processed to recover both a light fraction and an intermediate fraction (e.g., a rough cut), followed by further processing to obtain one or more fine cuts.
  • a Cn + mercaptans crude composition can be processed to recover a heavy fraction (e.g., a C 22+ sulfide fraction).
  • a Cn + mercaptans crude composition can be processed to separate out any combination of a light fraction, an intermediate fraction (e.g., comprising C 11+ mercaptans), and a heavy fraction (e.g., comprising C 22+ sulfides).
  • a light, intermediate or heavy fraction e.g., a rough cut
  • one or more desired fine cuts e.g., a Cn + mercaptan fraction
  • a Cn + mercaptans crude composition can be separated to produce a high-purity Cn + mercaptan stream and/or a high-purity C 22+ sulfide stream (e.g., to obtain a desired fine cut or fraction such as a C 11+ mercaptan fraction).
  • these separated streams can be blended in any combination of ratios to produce a mixture with specific concentrations of one of more components (e.g., desired blend ratios of Cn + mercaptans and/or C 22+ sulfides, for example to aid in a particular end use).
  • the unit operations/processes used for these separations are known to one of skill and the art and include, but are not limited to, distillation, fractionation, flashing, stripping, and absorption, and others.
  • the unit operation conditions such as for example, temperature, pressure, flow rates, and others at which these unit operations produce one or more of the desired fractions can easily be determined by one of ordinary skill in the art.
  • a light fraction is removed from the C 11+ mercaptans crude composition, for example by flashing, distillation, fractionation, stripping, absorption, etc.
  • the light fraction removed from the C + mercaptans crude composition can comprise at least about 90 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, alternatively at least about 96 wt.%, alternatively at least about 97 wt.%, alternatively at least about 98 wt.%, alternatively at least about 99 wt.% C 10 - compounds, based on the total weight of the light fraction.
  • Nonlimiting examples of C 10 - compounds include C 10 - monoolefins (e.g., unreacted C 10 - monoolefins), C 10 - mercaptans, C 10 - alkanes, C 10 - alcohols, and the like, or combinations thereof.
  • the light fraction removed from the C 11+ mercaptans crude composition can comprise less than about 10 wt.%, alternatively less than about 5 wt.%, alternatively less than about 4 wt.%, alternatively at less than about 3 wt.%, alternatively less than about 2 wt.%, or alternatively less than about 1 wt.% Cn + compounds, based on the total weight of the light fraction.
  • a combined intermediate and heavy fraction i.e., Cn + compounds sometimes referred to as a kettle product in the Examples
  • the combined intermediate and heavy fraction can be used“as is” or can be further processed, for example separated or split into separate intermediate and heavy fractions (and said separate intermediate and heavy fractions can be subsequently recombined in various blends and associated blend ratios), as described in more detail herein.
  • a combined intermediate and heavy fraction (i.e., Cn + compounds) formed by removal of the light fraction from the Cn + mercaptans crude composition can comprise less than about 15 wt.%, alternatively less than about 10 wt.%, alternatively less than about 9 wt.%, alternatively less than about 8 wt.%, alternatively less than about 7 wt.%, alternatively less than about 6 wt.%, alternatively less than about 5 wt.%, alternatively less than about 4 wt.%, alternatively less than about 3 wt.%, alternatively less than about 2 wt.%, alternatively less than about 1 wt.% Cio- products, based on the total weight of the combined intermediate and heavy fraction (i.e., Cn + compounds).
  • a combined intermediate and heavy fraction (i.e., Cn + compounds) recovered from the from the Cn + mercaptans crude composition can comprise (A) at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% Cn + mercaptans, based on the total weight of the combined fraction, wherein the Cn + mercaptans are characterized by structure R 6 -SH, wherein R 6 is a functional group (e.g., alkyl group) derived from the one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms) disclosed
  • the Cn + mercaptans crude composition can be flashed to remove a lights fraction as described herein to produce a combined intermediate and heavy fraction (i.e., Cn + compounds) comprising: (A) from at least about 50 wt.% to at least about 99 wt.%, alternatively from at least about 50 wt.% to at least about 95 wt.%, alternatively from at least about 55 wt.% to at least about 85 wt.%, or alternatively from at least about 60 wt.% to at least about 80 wt.% Cn + mercaptans, wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the Cn + mercaptans can be Cn + mercaptans characterized by structure
  • the Cn + mercaptans crude composition can be flashed to remove a light fraction and subsequently further separated to produce an intermediate fraction and a heavy fraction (i.e., Cn + compounds).
  • the intermediate fraction and the heavy fractions recovered from the Cn + mercaptans crude composition can then be optionally further processed (e.g., polished) and mixed in any appropriate ratio to produce blended compositions, as previously described herein for crude compositions derived from branched Cio monoolefms.
  • an intermediate fraction recovered from the Cn + mercaptans crude composition can comprise at least about 25 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.%, alternatively at least about 75 wt.%, or alternatively at least about 85 wt.% Cn + mercaptans, based on the total weight of the intermediate fraction, wherein the Cn + mercaptans are characterized by structure R 6 -SH, wherein R 6 is a functional group (e.g., alkyl group) derived from the one or more Cn+ monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci6 linear alpha monoolefms) disclosed herein.
  • R 6 -SH wherein R 6 is a functional group (e.g., alkyl group) derived from the one or more Cn
  • the heavy fraction recovered from the Cn + mercaptans crude composition can comprise at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt.%, C 22+ sulfides, based on the total weight of the heavy fraction, wherein the C 22+ sulfides are characterized by structure R 7 -S-R 8 , wherein both R 7 and R 8 can each independently be a functional group derived from the one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms) disclosed herein.
  • Cn + monoolefms e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms
  • a Cn + mercaptans composition can comprise Cn + mercaptans, wherein at least a portion of the Cn + mercaptans are characterized by structure R 6 -SH, wherein R 6 is a functional group (e.g., alkyl group) derived from the one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci6 linear alpha monoolefms) disclosed herein.
  • the Cn + mercaptans composition can comprise any suitable amount of Cn + mercaptans as disclosed herein.
  • a Cn + mercaptans composition can comprise at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% C 11+ mercaptans, based on the total weight of the Cn + mercaptans composition; wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least 85 wt.% of the Cn + mercaptans can be Cn + mercaptans characterized by structure R 6 -SH, wherein R 6 is a functional group (e.g., alkyl group) derived from the
  • a Cn + mercaptans composition can consist of or consist essentially of Cm mercaptans characterized by structure R 6 -SH, wherein R 6 is a functional group (e.g., alkyl group) derived from the one or more Cn + monoolefins (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms) disclosed herein.
  • R 6 is a functional group (e.g., alkyl group) derived from the one or more Cn + monoolefins (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms) disclosed herein.
  • a Cn + mercaptans composition can comprise at least about 1, 5, 10, 15, 20,
  • C 11+ mercaptans characterized by structure R 6 -SH, wherein R 6 is a functional group (e.g., alkyl group) derived from the one or more C 11+ monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms) disclosed herein.
  • R 6 is a functional group (e.g., alkyl group) derived from the one or more C 11+ monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms) disclosed herein.
  • a C 22+ sulfides composition can comprise C 22+ sulfides, wherein at least a portion of the C 22+ sulfides are characterized by structure R 7 -S-R 8 , wherein both R 7 and R 8 can each independently be a functional group derived from the one or more C 11+ monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms) disclosed herein.
  • the C 22+ sulfides composition can comprise any suitable amount of C 22+ sulfides as disclosed herein.
  • a C 22+ sulfides composition can comprise C 22+ sulfides, wherein at least about
  • C 22+ sulfides can be C 22+ sulfides characterized by structure R 7 -S-R 8 , wherein both R 7 and R 8 can each independently be a functional group derived from the one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms) disclosed herein.
  • Cn + monoolefms e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or C 14 and Ci 6 linear alpha monoolefms
  • a C 22+ sulfides composition can consist of or consist essentially of C 22+ sulfides characterized by structure R 7 -S-R 8 , wherein both R 7 and R 8 can each independently be a functional group derived from the one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or Cn and Ci 6 linear alpha monoolefms) disclosed herein.
  • Cn + monoolefms e.g., Cn and C 12 internal monoolefms; C 13 and C 14 internal monoolefms; or Cn and Ci 6 linear alpha monoolefms
  • a C 22+ sulfides composition comprises at least about 1, 5, 10, 15, 20, 25,
  • R 7 -S- R 8 can each independently be a functional group derived from the one or more Cn + monoolefms (e.g., Cn and C 12 internal monoolefms; C 13 and Cn internal monoolefms; or Cn and Cn linear alpha monoolefms) disclosed herein.
  • Cn + monoolefms e.g., Cn and C 12 internal monoolefms; C 13 and Cn internal monoolefms; or Cn and Cn linear alpha monoolefms
  • a Cn + mercaptans/C22 + sulfides composition can comprise one or more Cn + mercaptans and one or more C22 + sulfides of the type disclosed herein.
  • the Cn + mercaptans/C22 + sulfides composition can comprise any suitable amount of Cn + mercaptans, and any suitable amount of C22 + sulfides.
  • a Cn + mercaptans/C22 + sulfides composition can comprise (A) at least about 1 wt.%, alternatively at least about 5 wt.%, alternatively at least about 10 wt.%, alternatively at least about 15 wt.%, alternatively at least about 20 wt.%, alternatively at least about 25 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% Cn + mercaptans, based on the total weight of the Cn + mercaptans/C 22+ sulfides composition, wherein at least a portion
  • a Cn + mercaptans/C 22+ sulfides composition can comprise Cn + mercaptans represented by structure R 6 -SH and/or C 22+ sulfides represented by structure R 7 -S-R 8 that are formed by reacting an olefin feedstock comprising Cn + monoolefms with H2S as disclosed herein, wherein the Cn + monoolefms present in the olefin feedstock provide the alkyl group represented by R 6 , R 7 , and R 8 .
  • the R 6 group of the Cn + mercaptans and/or the R 7 and R 8 groups of the C 22+ sulfides are provided by or derived from the counterpart R 6 , R 7 , and R 8 groups present in the Cn + monoolefms in the olefin feedstock.
  • the C 11+ mercaptans compositions, C 22+ sulfides compositions, and Cn+ mercaptans/C 22+ sulfides compositions can be salable or otherwise used for a variety of end uses such as mining ore collector compositions and chain transfer agents.
  • the Cn + mercaptans as disclosed herein can be further converted to multi-sulfur containing compounds, which could then be used for any suitable applications, such as adhesives, epoxy adhesives, chain transfer agents, catalyst sulfurization, lubricants, mining collectors, etc.
  • the C + mercaptans as disclosed herein can be further converted to polysulfides, which could then be used for epoxy adhesives.
  • the Cn + mercaptans as disclosed herein can be further converted to trithiocarbonates, which could then be used as chain transfer agents.
  • a Cn + mercaptans composition and/or a Cn + mercaptans/C 22+ sulfides composition comprising equal to or greater than about 25 wt.% Cn + mercaptans as disclosed herein can advantageously have an odor less unpleasant than an odor of an otherwise similar composition comprising equal to or greater than about 25 wt.% n-dodecyl mercaptan and/or tert-dodecyl mercaptan, as perceived by equal to or greater than about 51% of human subjects exposed to the odor of each composition.
  • a process of the present disclosure comprises reacting, in a reactor, a sulfur source
  • a crude composition also referred to as a crude product
  • the crude composition comprises branched C 10+ mercaptans and branched C 20+ sulfides.
  • a process of the present disclosure comprises reacting, in a reactor, a sulfur source
  • branched C 10+ monoolefms comprise C 10 to C 30 monoolefms, alternatively Cn to C 30 monoolefms, alternatively C 12 to C 30 monoolefms, alternatively C 14 to C 30 monoolefms, alternatively Ci 6 to C 28 monoolefms, or alternatively Cis to C 26 monoolefms; and wherein the branched C 10+ mercaptans crude composition comprises branched C 10+ mercaptans and branched C 20+ sulfides.
  • the sulfur source can be any sulfur source suitable to provide sulfur for the conversion of olefins
  • the sulfur source can comprise TfiS, thioacetic acid, and the like, or combinations thereof.
  • the sulfur source can comprise ThS, as previously described herein.
  • the branched C 10+ mercaptans crude composition can be further processed, for example via distillation, as previously described herein for the branched C 10 monoolefms, to yield one or more products (also referred to as distilled, purified, refined, finished, or final products) selected from the group consisting of mercaptan compositions (e.g., a composition comprising one or more branched C 10+ mercaptans), sulfide compositions (e.g., a composition comprising one or more branched C 20+ sulfides); and compositions having both mercaptans (e.g., branched C 10+ mercaptans) and sulfides (e.g., branched C 20+ sulfides), referred to as mercaptan/sulfide compositions.
  • mercaptan compositions e.g., a composition comprising one or more branched C 10+ mercaptans
  • a C 10+ mercaptans composition comprises one or more branched C 10+ mercaptans, wherein the branched C 10+ mercaptans comprise C 10 to C 30 mercaptans, alternatively Cn to C 30 mercaptans, alternatively C 12 to C30 mercaptans, alternatively C 14 to C30 mercaptans, alternatively Ci6 to C 28 mercaptans, or alternatively Cis to C 26 mercaptans.
  • a C 20+ sulfides composition comprises one or more branched C 20+ sulfides represented by the structure R 10 -S-R u , wherein R 10 and R 11 are each independently a functional group derived from an olefin, wherein the olefin comprises a branched Cio + monoolefm as disclosed herein.
  • the branched C20+ sulfides comprise C20 to Obo sulfides, alternatively C21 to Obo sulfides, alternatively C22 to Obo sulfides, alternatively C24 to Obo sulfides, alternatively C28 to Obo sulfides, alternatively C32 to C56 sulfides, or alternatively C36 to C52 sulfides.
  • a C10 + mercaptans/C2o + sulfides composition comprises (A) one or more branched
  • the C 10 + mercaptans compositions, C20 + sulfides compositions, and C10 + mercaptans/C2o + sulfides compositions can be salable or otherwise used for a variety of end uses such as mining ore collector compositions and chain transfer agents.
  • compositions disclosed herein can be prepared by a process comprising reacting, in a reactor, a sulfur source (e.g., TLS) and a feedstock comprising one or more branched C 10+ monoolefms in the presence of an initiating agent to produce a branched C10+ mercaptans crude (reaction product) composition, wherein the branched C 10+ monoolefms comprise a branched C 10+ monoolefm represented by Structure 1-1, a branched C 10+ monoolefm represented by Structure J-l, a branched C 10+ monoolefm represented by Structure K-l, a branched C 10+ monoolefm represented by Structure L-l, or combinations thereof; wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5 to C21 alkyl group,
  • the R 9 can be a linear Ci to C21 alkyl group or a branched Ci to C21 alkyl group.
  • the C 10+ monoolefms comprising the R 9 alkyl group are branched monoolefms, regardless of whether R 9 is linear or branched, owing to a branched sub-structure that is linked to the R 9 alkyl group, as it can be seen in Structures I- 1, J-l, K-l, and L-l.
  • R 9 can be selected from the group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a henicosyl group, and combinations thereof.
  • the branched C10 + monoolefins comprise one or more branched Cio monoolefms, as previously disclosed herein.
  • the branched Cio monoolefms can comprise 5- methyl-l-nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2-butyl- 1 -hexene (represented by Structure L), or combinations thereof.
  • Any feedstock comprising one or more branched C10 + monoolefms of the type described herein can be used, for example a feedstock obtained from a commercial petroleum refining or petrochemical process.
  • feedstocks can comprise other olefins in addition to the one or more branched C10 + monoolefms of the type described herein, for example linear C10 + monoolefms as well as olefins having less than 10 carbon atoms.
  • the feedstock can comprise one or more branched Cio to C30 monoolefms.
  • Any feedstock comprising branched Cio to C30 monoolefms of the type described herein can be used, for example a feedstock obtained from a commercial petroleum refining or petrochemical process.
  • Such feedstocks can comprise other olefins in addition to the branched Cio to C30 monoolefms of the type described herein, for example C9- monoolefms, C31 + monoolefms, as well as linear Cio to C30 monoolefms.
  • the feedstock can comprise at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, alternatively at least about 85 wt.%, alternatively at least about 90 wt.%, or alternatively at least about 95 wt.% branched Cio to C30 monoolefms, based on the total weight of the feedstock.
  • the feedstock can comprise (a) less than about 15 wt.%, alternatively less than about 10 wt.%, alternatively less than about 5 wt.%, or alternatively less than about 1 wt.% C9- monoolefms; and (b) less than about 15 wt.%, alternatively less than about 10 wt.%, alternatively less than about 5 wt.%, or alternatively less than about 1 wt.% C31 + monoolefms; based on the total weight of the feedstock.
  • a feedstock comprising at least about 70 wt.% branched Cio to C30 monoolefms, based on the total weight of the feedstock, can also be referred to as a“first Cio to C30 feedstock.”
  • the feedstock can comprise at least about 95 wt.%, alternatively at least about
  • a feedstock comprising at least about 95 wt.% branched Cio to C 30 monoolefins, based on the total weight of the feedstock can also be referred to as a“second Cio to C 30 feedstock.”
  • the second Cio to C 30 feedstock can be produced by purifying the first Cio to C 30 feedstock, such as for example by distillation of the first Cio to C 30 feedstock.
  • the Cio to C30 monoolefins of any feedstock described herein e.g., a first Cio to
  • C30 feedstock or a second Cio to C30 feedstock can comprise, can consist essentially of, or can be, a branched C10 + monoolefin represented by Structure 1-1, a branched C10 + monoolefin represented by Structure J-l, a branched C10 + monoolefin represented by Structure K-l, and a branched C10 + monoolefin represented by Structure L-l; wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5 to C21 alkyl group, alternatively a C7 to C19 alkyl group, or alternatively a C9 to C17 alkyl group.
  • the Cio to C30 monoolefins of any feedstock described herein e.g., a first Cio to
  • Cio to C30 feedstock or a second Cio to C30 feedstock can comprise linear Cio to C30 monoolefins.
  • the Cio to C30 monoolefins of any feedstock described herein can comprise less than or equal to about 26 mol%, alternatively less than or equal to about 24 mol%, alternatively less than or equal to about 22 mol%, alternatively less than or equal to about 20 mol%, or alternatively less than or equal to about 18 mol% linear Cio to C30 monoolefins.
  • the Cio to C30 monoolefins of any feedstock described herein can comprise from about 0.1 mol% to about 26 mol%, alternatively from about 0.5 mol% to about 24 mol%, alternatively from about 1 mol% to about 22 mol%, alternatively from about 1.5 mol% to about 20 mol%, or alternatively from about 2.5 mol% to about 18 mol% linear Cio to C30 monoolefins.
  • the first Cio to C 30 feedstock disclosed herein can further comprise C 9- monoolefins,
  • the C 9- monoolefins can comprise, can consist essentially of, or can be, a C 7 monoolefin, a Cx monoolefin, a C 9 monoolefin, or combinations thereof; alternatively, a C 7 monoolefin; alternatively, a Cx monoolefin; or alternatively, a C 9 monoolefin.
  • the C 9- monoolefins can comprise, can consist essentially of, or can be, a Cx monoolefin.
  • the C 31+ monoolefins can comprise, can consist essentially of, or can be, a C 31 monoolefin, a C 32 monoolefin, a C 33 monoolefin, a C 34 monoolefin, a C 35 monoolefin, a C 36 monoolefin, a C 37 monoolefin, a C 38 monoolefin, or combinations thereof; alternatively, a C 31 monoolefin; alternatively, a C 32 monoolefin; alternatively, a C 33 monoolefin; alternatively, a C 34 monoolefin; alternatively, a C 35 monoolefin; alternatively, a C 36 monoolefin; alternatively, a C 37 monoolefin; or alternatively, a C 38 monoolefin.
  • the C 31+ monoolefins can comprise, can consist essentially of, or can be, a C 32 monoolefin, a C 36 monoolefin, a C 38 monoolefin, or combinations thereof; alternatively, a C 32 monoolefin; alternatively, a C36 monoolefin; or alternatively, a C38 monoolefin.
  • the first Cio to C 30 feedstock can further comprise from about 0.1 mol% to about
  • the Cx monoolefins can comprise at least about 95 mol%, alternatively at least about 96 mol%, alternatively at least about 97 mol%, alternatively at least about 98 mol%, or alternatively at least about 99 mol% l-octene.
  • a sulfur source e.g., ffiS
  • a feedstock comprising one or more branched Cio to C30 monoolefms
  • a sulfur source to olefin molar ratio of from about 1 : 1 to about 20: 1, alternatively from about 2: 1 to about 15: 1, or alternatively from about 3: 1 to about 10: 1; as previously described herein for the branched Cio monoolefms.
  • a sulfur source e.g., H 2 S
  • a feedstock comprising one or more branched Cio to C 30 monoolefms can be reacted at a pressure of from about 30 psig (206 kPag) to about 1,500 psig (10,300 kPag), alternatively from about 100 psig (690 kPag) to about 1,250 psig (8,600 kPag), or alternatively from about 250 psig (1,700 kPag) to about 1,000 psig (6,900 kPag); as previously described herein for the branched Cio monoolefms.
  • a sulfur source e.g., l3 ⁇ 4S
  • a feedstock comprising one or more branched Cio to C30 monoolefms
  • olefin conversion of equal to or greater than about 70%, alternatively equal to or greater than about 75%, or alternatively equal to or greater than about 80%, alternatively equal to or greater than about 85%, or alternatively equal to or greater than about 90%.
  • a sulfur source e.g., l3 ⁇ 4S
  • a feedstock comprising one or more branched Cio to C30 monoolefms
  • an initiating agent comprises ultraviolet (UV) radiation; as previously described herein for the branched Cio monoolefms.
  • the initiating agent can further comprise a phosphite promoter, a photoinitiator, a sulfur scavenger, an antioxidant, and the like, or combinations thereof.
  • PfiS and a feedstock comprising one or more branched Cio to C30 monoolefms can be reacted in the presence of UV radiation at a l3 ⁇ 4S to olefin molar ratio of from about 1 : 1 to about 15: 1, alternatively from about 2: 1 to about 12.5: 1, or alternatively from about 5: 1 to about 10: 1; as previously described herein for the branched Cio monoolefms.
  • the process can comprise reacting H2S and a feedstock comprising one or more branched Cio to C30 monoolefms in the presence of UV radiation to produce a branched C10 + mercaptans crude composition
  • the branched C10 + mercaptans crude composition comprises from 50-100 wt.% Cio to C30 mercaptans, alternatively from 50-90 wt.% Cio to C30 mercaptans, or alternatively from 75-85 wt.% Cio to C30 mercaptans
  • the Cio to C30 mercaptans present in the crude composition further comprise from about 70 wt.% to about 100 wt.%, alternatively from about 70 wt.% to about 95 wt.%, alternatively from about 80 wt.% to about 90 wt.%, or alternatively from about 79 wt.% to about 85 wt.% Cio to C30 primary mercaptans;
  • the make-up of the branched C10 + mercaptans crude composition in terms of primary, secondary, and tertiary mercaptans, will depend on the make-up of the feedstock, as well as on the reaction conditions. Further, as will be appreciated by one of skill in the art, and with the help of this disclosure, the make-up of each of the primary, secondary, and tertiary mercaptans will depend on the make-up of the feedstock, as well as on the reaction conditions.
  • the Cio to C30 primary mercaptans can comprise a branched C10 + mercaptan represented by Structure A-l, a branched C10 + mercaptan represented by Structure B-l, a branched C10 + mercaptan represented by Structure C-l, a branched C10 + mercaptan represented by Structure D-l, or combinations thereof; wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5 to C21 alkyl group, alternatively a C7 to C19 alkyl group, or alternatively a C9 to C17 alkyl group.
  • Cio to C30 pnmary mercaptans can further comprise a linear C10 + mercaptan represented by
  • R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5 to C21 alkyl group, alternatively a C7 to C19 alkyl group, or alternatively a C9 to C 17 alkyl group.
  • the C10 to C30 primary mercaptans comprise one or more branched primary C10 mercaptans, as previously disclosed herein.
  • the branched primary C10 mercaptans can comprise 5 -methyl- l-mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto-heptane (represented by Structure B), 4-ethyl- l-mercapto-octane (represented by Structure C), 2-butyl- l-mercapto-hexane (represented by Structure D), or combinations thereof.
  • Primary C10 mercaptans can further comprise 1- mercapto-decane (represented by Structure M), as disclosed herein.
  • the C 10 to C30 secondary mercaptans can comprise a branched C 10+ mercaptan represented by Structure E-l, a branched C 10+ mercaptan represented by Structure F-l, a branched C 10+ mercaptan represented by Structure G-l, or combinations thereof; wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5 to C21 alkyl group, alternatively a C7 to C 19 alkyl group, or alternatively a C9 to C 17 alkyl group.
  • the Cio to C 30 secondary mercaptans can further comprise a linear C 10+ mercaptan represented by Structure N-l, a linear C 10+ mercaptan represented by Structure O-l, a linear C 10+ mercaptan represented by Structure P-l, or combinations thereof; wherein R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively a C 3 to C 21 alkyl group, alternatively a C 5 to C 21 alkyl group, alternatively a C 7 to C 19 alkyl group, or alternatively a C 9 to C 17 alkyl group.
  • the Cio to C 30 secondary mercaptans comprise one or more branched secondary Cio mercaptans, as previously disclosed herein.
  • the branched secondary Cio mercaptans can comprise 5-methyl-2-mercapto-nonane (represented by Structure E), 3-propyl-2-mercapto- heptane (represented by Structure F), 4-ethyl-2-mercapto-octane (represented by Structure G), or combinations thereof.
  • Secondary Cio mercaptans can further comprise 4-mercapto-decane (represented by Structure N), 5- mercapto-decane (represented by Structure O), 2-mercapto-decane (represented by Structure P), or combinations thereof; as disclosed herein.
  • the Cio to C 30 tertiary mercaptans can comprise equal to or greater than about 90 wt.%, alternatively equal to or greater than about 95 wt.%, or alternatively equal to or greater than about 99 wt.% of a branched C 10+ mercaptan represented by Structure H-l; wherein R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively a C 3 to C 21 alkyl group, alternatively a C 5 to C 21 alkyl group, alternatively a C 7 to C 19 alkyl group, or alternatively a C 9 to C 17 alkyl group.
  • the Cio to C30 tertiary mercaptans comprise one or more branched tertiary Cio mercaptans, as previously disclosed herein.
  • the branched tertiary Cio mercaptans can comprise 5 -methyl-5 -mercapto-nonane (represented by Structure H), as disclosed herein.
  • a sulfur source e.g., H2S
  • a feedstock comprising one or more branched Cio to C30 monoolefms
  • an initiating agent e.g., H2S
  • the initiating agent comprises an acid catalyst
  • 3 ⁇ 4S and a feedstock comprising one or more branched Cio to C30 monoolefms can be reacted in the presence of an acid catalyst at a 3 ⁇ 4S to olefin molar ratio of from about 1 : 1 to about 10: 1, alternatively from about 2 : 1 to about 7.5 : 1 , or alternatively from about 2.5 : 1 to about 5 : 1 ; as previously described herein for the branched Cio monoolefms.
  • the process can comprise reacting TfiS and a feedstock comprising one or more branched Cio to C30 monoolefms in the presence of an acid catalyst to produce a branched C 10+ mercaptans crude composition (wherein the branched C10+ mercaptans crude composition comprises from 50-100 wt.% Cio to C30 mercaptans, alternatively from 50-90 wt.% Cio to C30 mercaptans, or alternatively from 75-85 wt.% Cio to C30 mercaptans); wherein the Cio to C30 mercaptans comprise from about 0 wt.% to about 5 wt.% alternatively from about 0.1 wt.% to about 4 wt.%, or alternatively from about 0.5 wt.% to about 2.5 wt.% Cio to C30 primary mercaptans; from about 80 wt.% to about 95 wt.%, alternatively from about 8
  • a sulfur source e.g., H2S
  • a feedstock comprising one or more branched Cio to C30 monoolefms
  • an initiating agent comprises a hydrodesulfurization (HDS) catalyst; as previously described herein for the branched Cio monoolefms.
  • HDS hydrodesulfurization
  • TfiS and a feedstock comprising one or more branched Cio to C30 monoolefms can be reacted in the presence of an HDS catalyst at a 3 ⁇ 4S to olefin molar ratio of from about 1 : 1 to about 10: 1, alternatively from about 2 : 1 to about 7.5 : 1 , or alternatively from about 2.5 : 1 to about 5 : 1 ; as previously described herein for the branched Cio monoolefms.
  • the process can comprise reacting 3 ⁇ 4S and a feedstock comprising one or more branched Cio to C30 monoolefms in the presence of an HDS catalyst to produce a branched C10+ mercaptans crude composition (wherein the branched C 10+ mercaptans crude composition comprises from 50-100 wt.% Cio to C30 mercaptans, alternatively from 50-90 wt.% Cio to C30 mercaptans, or alternatively from 75-85 wt.% Cio to C30 mercaptans); wherein the Cio to C30 mercaptans comprise from about 5 wt.% to about 30 wt.% alternatively from about 10 wt.% to about 25 wt.%, or alternatively from about 15 wt.% to about 20 wt.% Cio to C30 primary mercaptans; from about 60 wt.% to about 75 wt.%, alternatively from about 62.5 w
  • any suitable feedstocks comprising one or more branched Cio to C 30 monoolefms can be reacted with a sulfur source (e.g., H2S) in the presence of an initiating agent to produce a branched C1 0 + mercaptans crude composition, and the branched C1 0 + mercaptans crude composition can be further refined (e.g., distilled or otherwise separated into one or more fractions such as lights, intermediate, and heavies) to yield various compositions described herein.
  • a sulfur source e.g., H2S
  • an initiating agent e.g., a branched C1 0 + mercaptans crude composition
  • the branched C1 0 + mercaptans crude composition can be further refined (e.g., distilled or otherwise separated into one or more fractions such as lights, intermediate, and heavies) to yield various compositions described herein.
  • the type and/or amounts of the constituent components that form the branched C1 0 + mercaptans crude composition can vary depending upon the feedstock (e.g., the amount and types of olefins therein), the reaction conditions, the catalysts employed, etc., and one skilled in the art can tailor the post reactor processing of the branched C1 0 + mercaptans crude composition to account for the specific compounds present in a given branched C1 0 + mercaptans crude composition to yield various desired products and compositions of the types described herein.
  • a reactor effluent can be recovered from the reactor and sulfur source (e.g., H2S) removed therefrom to yield a branched C1 0 + mercaptans crude composition; as previously described herein for the branched Cio monoolefms.
  • a sulfur source e.g., H2S
  • branched C1 0 + mercaptans crude composition or“branched C1 0 + mercaptans crude product” refers to an unrefined effluent stream recovered from the reactor after removal of the sulfur source (e.g., TfiS), and in particular to a sulfur source-free effluent stream that has not undergone any additional post-reactor processing such as flashing, distillation, or other separation techniques or processes to remove any components from the effluent stream other than the initial removal of the sulfur source.
  • the sulfur source e.g., TfiS
  • the branched C 10+ mercaptans crude composition comprises branched Cio to C 30 mercaptans and branched C 20 to G,o sulfides formed by the reaction of TfiS and the one or more branched Cio to C 30 monoolefms, and the structures of these branched Cio to C 30 mercaptans and branched C 20 to C 60 sulfides are described in more detail herein.
  • the branched C 10+ mercaptans crude composition can comprise a number of other compounds such as unreacted olefins, inert compounds (e.g., alkanes), non-branched Cio to C 30 mercaptans, non-branched C 20 to C 60 sulfides, non-Cio to C30 mercaptans (e.g., C9- mercaptans), non-C 2 o to C60 sulfides (e.g., C 19 - sulfides), and other impurities.
  • inert compounds e.g., alkanes
  • non-branched Cio to C 30 mercaptans non-branched C 20 to C 60 sulfides
  • non-Cio to C30 mercaptans e.g., C9- mercaptans
  • non-C 2 o to C60 sulfides e.g., C 19 - sulfides
  • the constituent components contained within the branched C 10+ mercaptans crude composition can vary depending upon the composition of the feedstock (e.g., an unpurified first Cio to C 30 feedstock as compared to a purified second Cio to C 30 feedstock as described herein) as well as reaction conditions, catalyst, etc.
  • a branched C 10+ mercaptans crude composition can comprise light, intermediate, and heavy fractions as described herein.
  • the branched Cio + mercaptans crude composition can contain a variety of other non-Cio to C30 mercaptans and non-C 2 o to G,o sulfides components (e.g., impurities) such as Cx mercaptans; Ci 6 to C 19 sulfides represented by the structure R 12 -S-R 13 , wherein R 12 and R 13 are each independently a functional group derived from a Cx- monoolefm, wherein R 12 and R 13 are not both derived from a branched C 10+ monoolefm; unreacted Cx- monoolefms; non-olefin impurities selected from the group consisting of Cx- 14 alkanes, cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene, hexa
  • a process of the present disclosure can further comprise recovering a reaction product from the branched C 10+ mercaptans crude composition; wherein the reaction product can comprise branched C 10+ mercaptans and/or branched C 20+ sulfides, wherein the branched C 10+ mercaptans comprise branched C 10 to C30 mercaptans; and wherein the branched C 20+ sulfides comprise branched C 20 to Obo sulfides represented by the structure R 10 -S-R u , wherein R 10 and R 11 are each independently a functional group derived from an olefin, wherein the olefin comprises a branched C 10+ monoolefm as disclosed herein.
  • reaction product can comprise a branched O' in— mercaptans composition
  • a branched C 10+ mercaptans crude composition comprising branched C 10+ mercaptans and branched C 20+ sulfides as disclosed herein can be separated into two or more fractions (e.g., light fraction, intermediate fraction, heavy fraction, etc.) by any process or unit operation known in the art.
  • a branched C 10+ mercaptans crude composition can be processed (e.g., distilled) to remove a fraction of light compounds.
  • a branched C 10+ mercaptans crude composition can be processed to recover both a light fraction and an intermediate fraction (e.g., a rough cut), followed by further processing to obtain one or more fine cuts.
  • a branched C 10+ mercaptans crude composition can be processed to recover a heavy fraction (e.g., a C 20+ sulfides fraction).
  • a branched C 10+ mercaptans crude composition can be processed to separate out any combination of a light fraction, an intermediate fraction (e.g., comprising C 10+ mercaptans, including branched C 10+ mercaptans), and a heavy fraction (e.g., comprising C 20+ sulfides, including branched C 20+ sulfides).
  • a light, intermediate or heavy fraction e.g., a rough cut
  • one or more desired fine cuts e.g., a C 10 to C 30 mercaptan fraction
  • a branched C 10+ mercaptans crude composition can be separated to produce a high-purity C 10+ mercaptan stream and/or a high-purity C 20+ sulfide stream (e.g., to obtain a desired fine cut or fraction such as a C 10 to C 30 mercaptan fraction).
  • these separated streams can be blended in any combination of ratios to produce a mixture with specific concentrations of one of more components (e.g., desired blend ratios of branched C 10+ mercaptans and/or branched C 20+ sulfides, for example to aid in a particular end use).
  • the unit operations/processes used for these separations are known to one of skill and the art and include, but are not limited to, distillation, fractionation, flashing, stripping, and absorption, and others.
  • the unit operation conditions such as for example, temperature, pressure, flow rates, and others at which these unit operations produce one or more of the desired fractions can easily be determined by one of ordinary skill in the art.
  • a light fraction is removed from the branched Cio + mercaptans crude composition, for example by flashing, distillation, fractionation, stripping, absorption, etc.
  • the light fraction removed from the branched Cio + mercaptans crude composition can comprise at least about 90 wt.%, alternatively at least about 92 wt.%, alternatively at least about 95 wt.%, alternatively at least about 96 wt.%, alternatively at least about 97 wt.%, alternatively at least about 98 wt.%, alternatively at least about 99 wt.% C9- compounds, based on the total weight of the light fraction.
  • Nonlimiting examples of C9- compounds include C9- monoolefms (e.g., unreacted C9- monoolefms), C9- mercaptans, C9- alkanes, cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene, C9- alcohols, 2-ethyl- l-hexanol, and the like, or combinations thereof.
  • C9- monoolefms e.g., unreacted C9- monoolefms
  • C9-mercaptans C9- alkanes
  • cyclohexane methylcyclopentane
  • methylcyclohexane benzene
  • benzene toluene
  • ethylbenzene xylene
  • mesitylene C9- alcohols
  • the light fraction removed from the branched C10 + mercaptans crude composition can comprise less than about 10 wt.%, alternatively less than about 5 wt.%, alternatively less than about 4 wt.%, alternatively at less than about 3 wt.%, alternatively less than about 2 wt.%, alternatively less than about 1 wt.% C10 + compounds, based on the total weight of the light fraction.
  • a combined intermediate and heavy fraction i.e., C 10+ compounds sometimes referred to as a kettle product in the Examples
  • the combined intermediate and heavy fraction can be used“as is” or can be further processed, for example separated or split into separate intermediate and heavy fractions (and said separate intermediate and heavy fractions can be subsequently recombined in various blends and associated blend ratios), as described in more detail herein.
  • a combined intermediate and heavy fraction (i.e., C10+ compounds) formed by removal of the light fraction from the branched C10+ mercaptans crude composition can comprise less than about 15 wt.%, alternatively less than about 10 wt.%, alternatively less than about 9 wt.%, alternatively less than about 8 wt.%, alternatively less than about 7 wt.%, alternatively less than about 6 wt.%, alternatively less than about 5 wt.%, alternatively less than about 4 wt.%, alternatively less than about 3 wt.%, alternatively less than about 2 wt.%, or alternatively less than about 1 wt.% C9- products, based on the total weight of the combined intermediate and heavy fraction (i.e., C 10+ compounds).
  • a combined intermediate and heavy fraction (i.e., C10 + compounds) recovered from the branched C10 + mercaptans crude composition can comprise (A) at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% mercaptans, based on the total weight of the combined fraction; wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the mercaptans can be branched Cio to C30 mercaptans selected from the group consisting of a branched Cio
  • the branched C10+ mercaptans crude composition can be flashed to remove a light fraction as described herein to produce a combined intermediate and heavy fraction (i.e., C10+ compounds) comprising: (A) at least about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt.% C10+ branched mercaptans selected from the group consisting of a branched Cio to C30 mercaptan represented by Structure A-l, a branched Cio to C30 mercaptan represented by Structure B-l, a branched Cio to C30 mercaptan represented by Structure C- 1, a branched Cio to C30 mercaptan represented by Structure D-l, a branched Cio to C30 mercaptan represented by Structure E-l, a branched Cio to C30 mercaptan represented by Structure F-l, a branched Cio to C30
  • the branched C10 + mercaptans crude composition can be flashed to remove a lights fraction as described herein to produce a combined intermediate and heavy fraction (i.e., C10 + compounds) comprising: (A) from at least about 50 wt.% to at least about 90 wt.%, alternatively from at least about 55 wt.% to at least about 85 wt.%, or alternatively from at least about 60 wt.% to at least about 80 wt.% mercaptans, wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the mercaptans can be branched Cio to C30 mercaptans selected from the group consisting of a branched C10 to C30 mercaptan represented by
  • the branched C10 + mercaptans crude composition can be flashed to remove a light fraction and subsequently further separated to produce an intermediate fraction and a heavy fraction (i.e., C10 + compounds).
  • the intermediate fraction and the heavy fractions recovered from the branched C10 + mercaptans crude composition can then be optionally further processed (e.g., polished) and mixed in any appropriate ratio to produce blended compositions, as previously described herein for crude compositions derived from branched Cio monoolefins.
  • an intermediate fraction recovered from the branched C10 + mercaptans crude composition can comprise at least about 25 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.%, alternatively at least about 75 wt.%, or alternatively at least about 85 wt.% C10 + mercaptans, based on the total weight of the intermediate fraction, wherein the C10 + mercaptans are branched Cio to C30 mercaptans as disclosed herein.
  • the heavy fraction recovered from the branched C10 + mercaptans crude composition can comprise at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt.%, C20 + sulfides, based on the total weight of the heavy fraction, wherein the C20 + sulfides are branched C20 to C60 sulfides as disclosed herein.
  • the branched Cio + mercaptans crude composition can be separated into light, intermediate, and heavy fractions by distillation, for example in a single distillation column having a light fraction recovered as an overhead stream, an intermediate fraction (e.g., comprising Cio + compounds, including branched Cio + mercaptans) recovered as a side stream, and a heavy fraction (e.g., comprising C20 + compounds, including branched C20 + sulfides) recovered as a bottom stream.
  • an intermediate fraction e.g., comprising Cio + compounds, including branched Cio + mercaptans
  • a heavy fraction e.g., comprising C20 + compounds, including branched C20 + sulfides
  • the separation can be in sequential steps such as removal of the lights fraction in a first distillation column, followed by separation of the intermediate fraction (e.g., comprising C10 + compounds, including branched C10 + mercaptans) as an overhead stream in a second distillation column and the heavy fraction (e.g., comprising C20 + compounds, including branched C20 + sulfides) as a bottom stream of the second distillation column.
  • the intermediate fraction e.g., comprising C10 + compounds, including branched C10 + mercaptans
  • the heavy fraction e.g., comprising C20 + compounds, including branched C20 + sulfides
  • These “rough-cut” light, intermediate, and heavy streams can be used“as is” or they can be further processed (e.g., further refined or polished, for example by additional distillation or other separation techniques to produce“fine-cuts”) and/or blended to obtain a variety of products that are salable or otherwise available for a variety of end uses such as mining ore collector compositions or chain transfer agents.
  • a variety of C10 + mercaptans compositions, C20 + sulfides compositions, and mixed C10 + mercaptans/C2o + sulfides compositions can be produced of the type disclosed in more detail herein.
  • olefin feedstock e.g., olefin feedstock reacted with a sulfur source (e.g.,
  • H2S in the presence of an initiating agent to produce the branched C10+ mercaptans crude composition
  • the intermediate fraction comprises C 10 to C 19 mercaptans
  • the heavy fraction comprises C20 to C38 sulfides.
  • olefin feedstock e.g., olefin feedstock reacted with a sulfur source (e.g.,
  • FfiS in the presence of an initiating agent to produce the branched C10+ mercaptans crude composition
  • the intermediate fraction comprises C20 to C30 mercaptans
  • the heavy fraction comprises C40 to G,o sulfides.
  • olefin feedstock e.g., olefin feedstock reacted with a sulfur source (e.g.,
  • FfiS in the presence of an initiating agent to produce the branched C10+ mercaptans crude composition
  • the intermediate and heavy fractions recovered by distillation can comprise mercaptans and sulfides as follows.
  • the intermediate fraction can comprise C10 to C 19 mercaptans
  • the heavy fraction can comprise C20 to C30 mercaptans and C20 to Obo sulfides.
  • intermediate fraction can comprise C10 to C30 mercaptans and C20 to C30 sulfides
  • the heavy fraction can comprise C31 to Obo sulfides.
  • a first intermediate fraction can comprise C10 to C 19 mercaptans
  • a second intermediate fraction can comprise C20 to C30 mercaptans and C20 to C30 sulfides
  • the heavy fraction can comprise C31 to G,o sulfides.
  • Intermediate and heavy fractions comprising both mercaptans and sulfides could be used as recovered (e.g., mixed mercaptans/sulfides compositions), or can be further processed to separate and recover further mercaptan compositions and sulfide compositions.
  • an intermediate fraction can comprise at least about 25 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.%, alternatively at least about 75 wt.%, or alternatively at least about 85 wt.% branched Cio + mercaptans.
  • the branched Cio + mercaptans can be selected from the group consisting of a branched Cio to C30 mercaptan represented by Structure A-l, a branched Cio to C30 mercaptan represented by Structure B-l, a branched Cio to C30 mercaptan represented by Structure C-l, a branched Cio to C30 mercaptan represented by Structure D-l, a branched Cio to C30 mercaptan represented by Structure E-l, a branched Cio to C30 mercaptan represented by Structure F-l, a branched Cio to C30 mercaptan represented by Structure G-l, a branched Cio to C30 mercaptan represented by Structure H-l, and combinations thereof; wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5
  • the heavy fraction can comprise at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50,
  • branched C20+ sulfides represented by structure R 10 -S-R u , wherein both R 10 and R 11 can each independently be a branched Cio to C30 alkyl group derived from a branched Cio to C30 monoolefm, and wherein the branched Cio to C30 alkyl group is selected from the group consisting of
  • R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively a C 3 to C 21 alkyl group, alternatively a C 5 to C 21 alkyl group, alternatively a C 7 to C 19 alkyl group, or alternatively a C 9 to C 17 alkyl group.
  • a C 10+ mercaptans composition can comprise C 10+ mercaptans, wherein at least a portion of the C 10+ mercaptans comprise branched Cio to C 30 mercaptans.
  • the branched Cio to C 30 mercaptans can comprise a branched Cio to C 30 mercaptan represented by Structure A-l, a branched Cio to C 30 mercaptan represented by Structure B-l, a branched Cio to C 30 mercaptan represented by Structure C-l, a branched Cio to C 30 mercaptan represented by Structure D-l, a branched Cio to C 30 mercaptan represented by Structure E-l, a branched Cio to C 30 mercaptan represented by Structure F-l, a branched Cio to C 30 mercaptan represented by Structure G-l, a branched Cio to C 30 mercaptan represented by Structure
  • branched C 10+ mercaptans refer to mercaptans (or thiols) that are characterized by the general formula R 14 -SH, wherein R 14 is a branched alkyl group (as opposed to a linear alkyl group), i.e., an alkyl group substituted with alkyl substituents; and wherein R 14 has from 10 to 30 carbon atoms, alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.
  • a composition comprising mercaptans, wherein at least a portion of the mercaptans are branched C 10+ mercaptans (e.g., branched Cio to C 30 mercaptans as disclosed herein), can also be referred to as a“branched C 10+ mercaptans composition.”
  • the C 10+ mercaptans composition can comprise any suitable amount of branched Cio to C 30 mercaptans.
  • the C 10+ mercaptans can further comprise non-branched C 10+ mercaptans, such as for example a linear Cio to C 30 mercaptan represented by Structure M-l, a linear Cio to C 30 mercaptan represented by Structure N-l, a linear Cio to C 30 mercaptan represented by Structure O-l, a linear Cio to C 30 mercaptan represented by Structure P-l, or combinations thereof; wherein R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively a C 3 to C 21 alkyl group, alternatively a C 5 to C 21 alkyl group, alternatively a C 7 to C 19 alkyl group, or alternatively a C 9 to C 17 alkyl group.
  • non-branched C 10+ mercaptans such as for example a linear Cio to C 30 mercaptan represented by Structure M-l, a linear Cio to C 30 mercaptan represented by Structure
  • the C 10+ mercaptans can further comprise non-branched
  • Cio mercaptans as previously disclosed herein.
  • the non-branched Cio mercaptans can comprise l-mercapto- decane (represented by Structure M), 4-mercapto-decane (represented by Structure N), 5-mercapto-decane (represented by Structure O), 2-mercapto-decane (represented by Structure P), or combinations thereof.
  • a C 10+ mercaptans composition can comprise at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% C 10+ mercaptans, based on the total weight of the C 10+ mercaptans composition; wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least 85 wt.% of the Cio + mercaptans can be branched Cio to C30 mercaptans characterized by the general formula R 14 -SH, wherein R 14 is a branched alkyl group; and
  • the branched Cio to C30 mercaptans characterized by the general formula R 14 -SH can be selected from the group consisting of a branched Cio to C30 mercaptan represented by Structure A-l, a branched Cio to C30 mercaptan represented by Structure B-l, a branched Cio to C30 mercaptan represented by Structure C-l, a branched Cio to C30 mercaptan represented by Structure D-l, a branched Cio to C30 mercaptan represented by Structure E-l, a branched Cio to C30 mercaptan represented by Structure F-l, a branched Cio to C30 mercaptan represented by Structure G-l, a branched Cio to C30 mercaptan represented by Structure H-l, and combinations thereof; wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to
  • a C10+ mercaptans composition can comprise at least about 1 wt.%, alternatively at least about 5 wt.%, alternatively at least about 10 wt.%, alternatively at least about 20 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% mercaptans, wherein at least a portion of the mercaptans can be branched Cio to C30 mercaptans characterized by the general formula R 14 -SH, wherein R 14 is a branched alkyl group; and wherein R 14 has from 10 to 30 carbon atoms, alternatively
  • the branched Cio to C30 mercaptans characterized by the general formula R 14 -SH can be selected from the group consisting of a branched Cio to C30 mercaptan represented by Structure A-l, a branched Cio to C30 mercaptan represented by Structure B-l, a branched Cio to C30 mercaptan represented by Structure C-l, a branched Cio to C30 mercaptan represented by Structure D-l, a branched Cio to C30 mercaptan represented by Structure E-l, a branched Cio to C30 mercaptan represented by Structure F-l, a branched Cio to C30 mercaptan represented by Structure G-l, a branched Cio to C30 mercaptan represented by Structure H-l, and combinations thereof; wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to
  • a C10 + mercaptans composition can comprise at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% mercaptans; wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least 85wt.% of the mercaptans can be branched Cio to C30 mercaptans characterized by the general formula R 14 -SH, wherein R 14 is a branched alkyl group; and wherein R 14 has from 10 to 30 carbon atoms, alternatively from 11 to 30 carbon atoms
  • the branched Cio to C30 mercaptans characterized by the general formula R 14 -SH can be selected from the group consisting of a branched Cio to C30 mercaptan represented by Structure A-l, a branched Cio to C30 mercaptan represented by Structure B-l, a branched Cio to C30 mercaptan represented by Structure C-l, a branched Cio to C30 mercaptan represented by Structure D-l, a branched Cio to C30 mercaptan represented by Structure E-l, a branched Cio to C30 mercaptan represented by Structure F-l, a branched Cio to C30 mercaptan represented by Structure G-l, a branched Cio to C30 mercaptan represented by Structure H-l, and combinations thereof; wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to
  • a C 10+ mercaptans composition can comprise at least about 50, 55, 60,
  • mercaptans can be branched Cio to C30 mercaptans characterized by the general formula R 14 -SH, wherein R 14 is a branched alkyl group; and wherein R 14 has from 10 to 30 carbon atoms, alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.
  • the branched Cio to C30 mercaptans characterized by the general formula R 14 -SH can be selected from the group consisting of a branched Cio to C30 mercaptan represented by Structure A-l, a branched Cio to C30 mercaptan represented by Structure B-l, a branched Cio to C30 mercaptan represented by Structure C-l, a branched Cio to C30 mercaptan represented by Structure D-l, a branched Cio to C30 mercaptan represented by Structure E-l, a branched Cio to C30 mercaptan represented by Structure F-l, a branched Cio to C30 mercaptan represented by Structure G-l, a branched Cio to C30 mercaptan represented by Structure H-l, and combinations thereof; wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to
  • a C10 + mercaptans composition can comprise from at least about 50 wt.% to at least about 90 wt.%, alternatively from at least about 55 wt.% to at least about 85 wt.%, or alternatively from at least about 60 wt.% to at least about 80 wt.% mercaptans, wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the mercaptans can be branched Cio to C30 mercaptans characterized by the general formula R 14 -SH, wherein R 14 is a branched alkyl group; and wherein R 14 has from 10 to 30 carbon atoms, alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30 carbon atoms,
  • the branched Cio to C30 mercaptans characterized by the general formula R 14 -SH can be selected from the group consisting of a branched Cio to C30 mercaptan represented by Structure A-l, a branched Cio to C30 mercaptan represented by Structure B-l, a branched Cio to C30 mercaptan represented by Structure C-l, a branched Cio to C30 mercaptan represented by Structure D-l, a branched Cio to C30 mercaptan represented by Structure E-l, a branched Cio to C30 mercaptan represented by Structure F-l, a branched Cio to C30 mercaptan represented by Structure G-l, a branched Cio to C30 mercaptan represented by Structure H-l, and combinations thereof; wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to
  • a C 10+ mercaptans composition can consist of or consist essentially of branched Cio to C30 mercaptans characterized by the general formula R 14 -SH, wherein R 14 is a branched alkyl group; and wherein R 14 has from 10 to 30 carbon atoms, alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.
  • the branched Cio to C30 mercaptans characterized by the general formula R 14 -SH can be selected from the group consisting of a branched Cio to C30 mercaptan represented by Structure A-l, a branched Cio to C30 mercaptan represented by Structure B-l, a branched Cio to C30 mercaptan represented by Structure C-l, a branched Cio to C30 mercaptan represented by Structure D-l, a branched Cio to C30 mercaptan represented by Structure E-l, a branched Cio to C30 mercaptan represented by Structure F-l, a branched Cio to C30 mercaptan represented by Structure G-l, a branched Cio to C30 mercaptan represented by Structure H-l, and combinations thereof; wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to
  • a C 10+ mercaptans composition can comprise at least about 1, 5, 10,
  • Cio to C30 mercaptans characterized by the general formula R 14 -SH, wherein R 14 is a branched alkyl group; and wherein R 14 has from 10 to 30 carbon atoms, alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.
  • the branched Cio to C30 mercaptans characterized by the general formula R 14 -SH can be selected from the group consisting of a branched Cio to C30 mercaptan represented by Structure A-l, a branched Cio to C30 mercaptan represented by Structure B-l, a branched Cio to C30 mercaptan represented by Structure C- 1, a branched Cio to C30 mercaptan represented by Structure D- 1, a branched Cio to C30 mercaptan represented by Structure E-l, a branched Cio to C30 mercaptan represented by Structure F-l, a branched Cio to C30 mercaptan represented by Structure G-l, a branched Cio to C30 mercaptan represented by Structure H-l, and combinations thereof; wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21
  • a Cio + mercaptans composition can comprise mercaptans, wherein at least about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of the mercaptans are branched Cio to C30 mercaptans characterized by the general formula R 14 -SH, wherein R 14 is a branched alkyl group; and wherein R 14 has from 10 to 30 carbon atoms, alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.
  • the branched Cio to C30 mercaptans characterized by the general formula R 14 -SH can be selected from the group consisting of a branched Cio to C30 mercaptan represented by Structure A-l, a branched Cio to C30 mercaptan represented by Structure B-l, a branched Cio to C30 mercaptan represented by Structure C- 1, a branched Cio to C30 mercaptan represented by Structure D- 1, a branched Cio to C30 mercaptan represented by Structure E-l, a branched Cio to C30 mercaptan represented by Structure F-l, a branched Cio to C30 mercaptan represented by Structure G-l, a branched Cio to C30 mercaptan represented by Structure H-l, and combinations thereof; wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21
  • a C 20+ sulfides composition can comprise sulfides, wherein at least a portion of the sulfides comprise C 20+ sulfides, and wherein at least a portion of the C 20+ sulfides comprise branched C 20 to C 60 sulfides represented by structure R 10 -S-R u , wherein both R 10 and R 11 can each independently be an alkyl group, and wherein at least a portion of the alkyl groups comprises a branched Cio to C 30 alkyl group, alternatively a branched Cn to C 30 alkyl group, alternatively a branched C 12 to C 30 alkyl group, alternatively a branched C 14 to C 30 alkyl group, alternatively a branched Ci 6 to C 28 alkyl group, or alternatively a branched Cis to C 26 alkyl group.
  • the alkyl group (e.g., a branched Cio to C 30 alkyl group as R 10 , R 11 ) can comprise a functional group derived from an olefin, wherein the olefin comprises a branched Cio to C 30 monoolefin represented by Structure 1-1, a branched Cio to C 30 monoolefin represented by Structure J-l, a branched Cio to C 30 monoolefin represented by Structure K-l, a branched Cio to C 30 monoolefin represented by Structure L-l, or combinations thereof; wherein R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively a C 3 to C 21 alkyl group, alternatively a C 5 to C 21 alkyl group, alternatively a C 7 to C 19 alkyl group, or alternatively a C 9 to Cn alkyl group.
  • the olefin comprises a branched Cio to
  • a sulfide e.g., a branched C 20 to C 60 sulfide
  • the total number of carbon atoms as opposed to the number of carbons of only one of the alkyl groups present in a dialkyl sulfide.
  • a H 21 C 10 -S-C 10 H 21 sulfide will be referred to as a C 20 sulfide (rather than a Cio sulfide);
  • a H 25 C 12 -S-C 14 H 29 sulfide will be referred to as a C 26 sulfide (rather than a C 12 sulfide or a C 14 sulfide);
  • a H 45 C 22 -S-C 22 H 45 sulfide will be referred to as a C 44 sulfide (rather than a C 22 sulfide); etc.
  • branched C 20 to Cgo sulfides refer to sulfides (or thioethers) that are characterized by the general formula R 10 -S-R u , wherein both R 10 and R 11 are each independently a branched Cio to C 30 alkyl group, alternatively a branched Cn to C 30 alkyl group, alternatively a branched C 12 to C 30 alkyl group, alternatively a branched C 14 to C 30 alkyl group, alternatively a branched Ci 6 to C 28 alkyl group, or alternatively a branched Cis to C 26 alkyl group (as opposed to a linear alkyl group), i.e., an alkyl group substituted with alkyl substituents.
  • branched C 20 to Obo sulfides refer to sulfides wherein both R 10 and R 11 are branched C 10 to C 30 alkyl groups, wherein R 10 and R 11 can be the same or different.
  • a composition comprising sulfides, wherein at least a portion of the sulfides are branched C 20 to Obo sulfides represented by structure R 10 -S-R u , wherein both R 10 and R 11 are each independently an alkyl group, wherein the alkyl group comprises a branched C 10 to C 30 alkyl group (e.g., a functional group derived from an olefin, and wherein the olefin comprises a branched C 10 to C 30 monoolefin as disclosed herein), can also be referred to as a“branched C 20+ sulfides composition.”
  • the C 20+ sulfides composition can comprise any suitable amount of
  • a C 20+ sulfides composition can comprise sulfides, wherein at least a portion of the sulfides comprise C 20+ sulfides, and wherein at least a portion of the C 20+ sulfides comprise branched C 20 to Obo sulfides represented by structure R 10 -S-R u , wherein both R 10 and R 11 can each independently be a branched C 10 to C 30 alkyl group derived from a branched C 10 to C 30 monoolefin, and wherein the branched C 10 to C 30 alkyl group is selected from the group consisting of
  • R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively a C 3 to C 21 alkyl group, alternatively a C 5 to C 21 alkyl group, alternatively a C 7 to C 19 alkyl group, or alternatively a C 9 to C 17 alkyl group.
  • the branched C 10 to Go monoolefm can comprise a branched Go to Go monoolefm represented by Structure I- 1, a branched Go to Go monoolefm represented by Structure J-l, a branched Go to Go monoolefm represented by Structure K-l, a branched Go to Go monoolefm represented by Structure L-l, or combinations thereof.
  • the Go to Go sulfides can further comprise non-branched Go to Go sulfides and/or partially branched Go to Go sulfides represented by structure R 10 -S-R u , wherein both R 10 and R 1 1 (in the case of non-branched Go to Go sulfides) or one of the R 10 and R 1 1 (in the case of partially-branched Go to Go sulfides) can be a linear Go to Go alkyl group derived from a linear Go to Go monoolefm, such as for example a linear Go to Go monoolefm represented by Structure Q-l, a linear Go to Go monoolefm represented by Structure R-l, a linear Go to Go monoolefm represented by Structure S-l, or combinations thereof; wherein R 9 is a Ci to Gi alkyl group, alternatively a G to Gi alkyl group, alternatively a G to Gi alkyl group, alternatively a G to Gi alkyl group, alternatively a G to
  • the non-branched C 20 to Go sulfides represented by structure R 10 -S-R u are the sulfides wherein both R 10 and R 1 1 are each independently a linear C 10 to C 30 alkyl group derived from a linear C 10 to C 30 monoolefin.
  • the partially branched C 20 to G,o sulfides represented by structure R 10 -S-R u are the sulfides wherein one of the R 10 and R 1 1 is a linear C 10 to C 30 alkyl group derived from a linear C 10 to C 30 monoolefm, while the other one of the R 10 and R 1 1 is a branched C 10 to C 30 alkyl group derived from a branched C 10 to C 30 monoolefm as described herein.
  • the linear C 10 to C 30 monoolefm can further comprise linear C 10 monoolefms, as previously disclosed herein.
  • the linear C 10 monoolefms can comprise 4-decene (represented by Structure Q), 5-decene (represented by Structure R), l-decene (represented by Structure S), or combinations thereof.
  • a C20+ sulfides composition can comprise sulfides, wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% of the sulfides can be branched C20 to Obo sulfides represented by structure R 10 -S-R u , wherein both R 10 and R 11 can each independently be a functional group derived from an olefin, and wherein the olefin comprises a branched C 10 to C30 monoolefin, alternatively a branched Cn to C30 monoolefin, alternatively a branched C 12 to C30 monoolefin, alternatively a branched C14 to C30 monoolefin, alternative
  • the olefin can comprise a branched C 10 to C30 monoolefin represented by Structure 1-1, a branched C10 to C30 monoolefin represented by Structure J-l, a branched C 10 to C30 monoolefin represented by Structure K-l, a branched C 10 to C30 monoolefin represented by Structure L-l, or combinations thereof.
  • a C20+ sulfides composition can comprise at least about 1 wt.%, alternatively at least about 5 wt.%, alternatively at least about 10 wt.%, alternatively at least about 20 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% sulfides, wherein at least a portion of the sulfides can be branched C20 to Obo sulfides represented by structure R 10 -S-R u , wherein both R 10 and R 11 can each independently be a functional group derived from an olefin, and wherein the
  • the olefin can comprise a branched C 10 to C30 monoolefin represented by Structure 1-1, a branched C10 to C30 monoolefin represented by Structure J-l, a branched C 10 to C30 monoolefin represented by Structure K-l, a branched C 10 to C30 monoolefin represented by Structure L-l, or combinations thereof.
  • a C20+ sulfides composition can comprise at least about 1, 5, 10, 15, 20, 25, 30,
  • sulfides wherein at least about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.%, sulfides, wherein at least about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of the sulfides can be branched C20 to Ceo sulfides represented by structure R 10 -S-R u , wherein both R 10 and R 11 can each independently be a functional group derived from an olefin, and wherein the olefin comprises a branched C10 to C30 monoolefin, alternatively a branched Cn to C30 monoolefin, alternatively a branched C 12 to C30 monoolefin, alternatively a branched Ci 4 to C30 monoolefin, alternatively a branched Ci6 to
  • the olefin can comprise a branched C 10 to C30 monoolefin represented by Structure 1-1, a branched C10 to C30 monoolefin represented by Structure J-l, a branched C10 to C30 monoolefin represented by Structure K-l, a branched Cio to C30 monoolefin represented by Structure L-l, or combinations thereof.
  • a C 20+ sulfides composition can comprise at least about 10 wt.%, alternatively at least about 15 wt.%, alternatively at least about 20 wt.%, or alternatively at least about 25 wt.% sulfides; wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the sulfides can be branched C 20 to Obo sulfides represented by structure R 10 -S-R u , wherein both R 10 and R 11 can each independently be a functional group derived from an olefin, and wherein the olefin comprises a branched C 10 to C 30 monoolefin, alternatively a branched Cn to C 30 monoolefin, alternatively
  • the olefin can comprise a branched C 10 to C 30 monoolefin represented by Structure 1-1, a branched C 10 to C 30 monoolefin represented by Structure J-l, a branched Cio to C 30 monoolefin represented by Structure K-l, a branched Cio to C 30 monoolefin represented by Structure L-l, or combinations thereof.
  • a C 20+ sulfides composition can comprise from at least about 10 wt.% to at least about 30 wt.%, alternatively from at least about 12.5 wt.% to at least about 22.5 wt.%, or alternatively from at least about 15 wt.% to at least about 20 wt.% sulfides; wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the sulfides can be branched C 20 to Obo sulfides represented by structure R 10 -S-R u , wherein both R 10 and R 11 can each independently be a functional group derived from an olefin, and wherein the olefin comprises a branched Cio to C 30 monoo
  • the olefin can comprise a branched Cio to C 30 monoolefin represented by Structure 1-1, a branched Cio to C 30 monoolefin represented by Structure J-l, a branched Cio to C 30 monoolefin represented by Structure K-l, a branched Cio to C 30 monoolefin represented by Structure L-l, or combinations thereof.
  • a C 20+ sulfides composition can consist of or consist essentially of branched C 20 to C 60 sulfides represented by structure R 10 -S-R u , wherein both R 10 and R 11 can each independently be a functional group derived from an olefin, and wherein the olefin comprises a branched Cio to C 30 monoolefin, alternatively a branched Cn to C 30 monoolefin, alternatively a branched C 12 to C 30 monoolefin, alternatively a branched Ci 4 to C 30 monoolefin, alternatively a branched Ci 6 to C 28 monoolefin, or alternatively a branched Cis to C 26 monoolefin.
  • the olefin comprises a branched Cio to C 30 monoolefin, alternatively a branched Cn to C 30 monoolefin, alternatively a branched C 12 to C 30 monoolefin, alternatively a
  • the olefin can comprise a branched Cio to C 30 monoolefin represented by Structure 1-1, a branched Cio to C 30 monoolefin represented by Structure J-l, a branched Cio to C 30 monoolefin represented by Structure K-l, a branched Cio to C 30 monoolefin represented by Structure L-l, or combinations thereof.
  • a C 20+ sulfides composition can comprise at least about 5 wt.%, alternatively at least about 10 wt.%, alternatively at least about 15 wt.%, or alternatively at least about 20 wt.% branched C20 to Obo sulfides represented by structure R 10 -S-R u , wherein both R 10 and R 11 can each independently be a functional group derived from an olefin, and wherein the olefin comprises a branched C10 to C30 monoolefm, alternatively a branched Cn to C30 monoolefm, alternatively a branched C12 to C30 monoolefm, alternatively a branched C14 to C30 monoolefm, alternatively a branched Ci 6 to C28 monoolefm, or alternatively a branched Cis to C26 monoolefm.
  • the olefin can comprise a branched C10 to C30 monoolefm represented by Structure 1-1, a branched C10 to C30 monoolefm represented by Structure J-l, a branched C10 to C30 monoolefm represented by Structure K-l, a branched C10 to C30 monoolefm represented by Structure L-l, or combinations thereof.
  • a C20 + sulfides composition comprises at least about 1, 5, 10, 15, 20,
  • R 10 and R 11 can each independently be a functional group derived from an olefin, and wherein the olefin comprises a branched Cio to C30 monoolefm, alternatively a branched Cn to C30 monoolefm, alternatively a branched C12 to C30 monoolefm, alternatively a branched C14 to C30 monoolefm, alternatively a branched Ci 6 to C28 monoolefm, or alternatively a branched Cis to C26 monoolefm.
  • the olefin can comprise a branched Cio to C30 monoolefm represented by Structure 1-1, a branched Cio to C30 monoolefm represented by Structure J-l, a branched Cio to C30 monoolefm represented by Structure K-l, a branched Cio to C30 monoolefm represented by Structure L-l, or combinations thereof.
  • a C 10+ mercaptans/C 2 o + sulfides composition can comprise one or more mercaptans and one or more sulfides of the type disclosed herein.
  • a composition comprising (i) mercaptans, wherein at least a portion of the mercaptans are branched Cio to C 30 mercaptans, and (ii) sulfides, wherein at least a portion of the sulfides are branched C 20 to C 60 sulfides, can also be referred to as a“branched C 10+ mercaptans/branched C 20+ sulfides composition.”
  • the C 10+ mercaptans/C 2 o+ sulfides composition can comprise any suitable amount of branched Cio to C 30 mercaptans, and any suitable amount of branched C 20 to C 60 sulfides.
  • a C10 + mercaptans/C2o + sulfides composition can comprise (A) at least about 1 wt.%, alternatively at least about 5 wt.%, alternatively at least about 10 wt.%, alternatively at least about 15 wt.%, alternatively at least about 20 wt.%, alternatively at least about 25 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% mercaptans, wherein at least a portion of the mercaptans can be branched Cio to C30 mercaptans characterized by the general formula R 14
  • the branched Cio to C 30 mercaptans characterized by the general formula R 14 -SH can be selected from the group consisting of a branched Cio to C 30 mercaptan represented by Structure A-l, a branched Cio to C 30 mercaptan represented by Structure B-l, a branched Cio to C 30 mercaptan represented by Structure C-l, a branched Cio to C 30 mercaptan represented by Structure D-l, a branched Cio to C 30 mercaptan represented by Structure E-l, a branched Cio to C 30 mercaptan represented by Structure F-l, a branched Cio to C 30 mercaptan represented by Structure G-l, a branched Cio to C 30 mercaptan represented by Structure H-l, and combinations thereof; and the olefin can comprise a branched Cio to C 30 monoolefm represented by Structure 1-1, a branched Cio
  • a C 10+ mercaptans/C 2 o + sulfides composition can comprise Cio to C 30 mercaptans characterized by the general formula R 14 -SH and/or C 20 to C 60 sulfides represented by structure R 10 -S-R u that are formed by reacting an olefin feedstock comprising olefins with EES as described in more detail herein, wherein the olefins present in the olefin feedstock provide the alkyl group represented by R 10 , R 11 , and R 14 .
  • R 10 and R 11 groups of the C 20 to C 60 sulfides and/or the R 14 group of the Cio to C 30 mercaptans are provided by or derived from the counterpart R 10 , R 11 , and R 14 groups present in the olefins in the olefin feedstock.
  • R 10 , R 11 , and R 14 can each independently be an alkyl group, wherein at least a portion of the alkyl groups can comprise a functional group derived from an olefin, wherein the olefin is present in a feedstock as disclosed herein (e.g., a first Cio to C 30 feedstock; a second Cio to C 30 feedstock).
  • a C 10+ mercaptans composition and/or a C 10+ mercaptans/C 2 o + sulfides composition comprising equal to or greater than about 25 wt.% C 10+ branched mercaptans as disclosed herein can advantageously have an odor less unpleasant and less offensive than an odor of an otherwise similar composition comprising equal to or greater than about 25 wt.% n-decyl mercaptan, as perceived by equal to or greater than about 51% of human subjects exposed to the odor of each composition.
  • a C 10+ mercaptans composition and/or a C 10+ mercaptans/C 2 o + sulfides composition comprising equal to or greater than about 25 wt.% C 10+ branched mercaptans as disclosed herein can advantageously have an odor less unpleasant than an odor of an otherwise similar composition comprising equal to or greater than about 25 wt.% n-dodecyl mercaptan and/or tert-dodecyl mercaptan, as perceived by equal to or greater than about 51% of human subjects exposed to the odor of each composition.
  • a process of the present disclosure comprises reacting branched Cio + mercaptans and a sulfur-containing material to produce a C 20+ crude product.
  • a process of the present disclosure comprises reacting a feedstock comprising one or more branched C 10+ mercaptans and a sulfur- containing material in the presence of a catalyst to produce a C 20+ crude product; wherein the C 20+ crude product comprises branched C 20+ polysulfides and branched C 20+ monosulfides.
  • a process of the present disclosure comprises reacting feedstock comprising one or more branched C 10+ mercaptans and a sulfur-containing material (e.g., elemental sulfur) in the presence of a catalyst to produce a branched C 20+ polysulfides crude product; wherein the branched C 10+ mercaptans comprise C 10 to C30 mercaptans, alternatively Cn to C30 mercaptans, alternatively C 12 to C30 mercaptans, alternatively C 14 to C 30 mercaptans, alternatively Ci 6 to C 28 mercaptans, or alternatively Cis to C 26 mercaptans; and wherein the branched C 20+ polysulfides crude product comprises branched C 20+ polysulfides and branched C 20+ monosulfides.
  • a sulfur-containing material e.g., elemental sulfur
  • the branched C 10+ mercaptans are derived from one or more branched C 10+ monoolefms wherein the branched C 10+ monoolefms are produced by reacting, in a reactor, a sulfur source (e.g., H 2 S) and a feedstock comprising the branched C 10+ monoolefms in the presence of an initiating agent, as previously described herein.
  • a sulfur source e.g., H 2 S
  • a feedstock comprising the branched C 10+ monoolefms in the presence of an initiating agent, as previously described herein.
  • the branched C 20+ polysulfides crude product can be further processed, for example via distillation, as previously described herein for the branched C 10+ mercaptans, to yield one or more products (also referred to as distilled, purified, refined, finished, or final products) selected from the group consisting of C 20+ polysulfide compositions (e.g., a composition comprising one or more branched C 20+ polysulfides); C 20+ monosulfide compositions (e.g., a composition comprising one or more branched C 20+ monosulfides); and compositions having both branched C 20+ polysulfides and branched C 20+ monosulfides, referred to as C 20+ metasulfide compositions.
  • C 20+ polysulfide compositions e.g., a composition comprising one or more branched C 20+ polysulfides
  • C 20+ monosulfide compositions e.g., a composition comprising one
  • a C 20+ polysulfides composition comprises one or more branched C 20+ polysulfides represented by the general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, and wherein R ⁇ S 1 and R 16 S 2 are each independently a functional group derived from a mercaptan, wherein the mercaptan comprises a branched C 10+ mercaptan as disclosed herein.
  • the branched C 20+ polysulfides may comprise C 20 to C60 polysulfides, alternatively C 21 to Obo polysulfides, alternatively C 22 to Obo polysulfides, alternatively C 24 to C60 polysulfides, alternatively C 28 to Obo polysulfides, alternatively C3 2 to C56 polysulfides, or alternatively C36 to C5 2 poly sulfides.
  • a C 20+ monosulfides composition comprises one or more branched C 20+ monosulfides represented by the general formula R 17 -S-R 18 , wherein R 17 and R 18 are each independently an alkyl group, wherein the alkyl group comprises a branched C 10+ alkyl group as disclosed herein.
  • the branched C 20+ monosulfides comprise C 20 to Obo monosulfides, alternatively C 21 to Obo monosulfides, alternatively C 22 to Obo monosulfides, alternatively C 24 to Obo monosulfides, alternatively C 28 to Obo monosulfides, alternatively C3 2 to C56 monosulfides, or alternatively C36 to C5 2 monosulfides.
  • a C 20+ metasulfides composition (e.g., a C 20+ polysulfides/C 2 o+ monosulfides composition) comprises (A) one or more branched C 20+ polysulfides represented by the general formula R l 5 S 1 [S] friendship-S 2 R 16 , wherein n is an integer from 1 to 10; and (B) one or more branched C 20+ monosulfides represented by the general formula R 17 -S-R 18 .
  • the C 20+ polysulfide compositions, the C 20+ monosulfides compositions, and the C 20+ metasulfides compositions can be salable or otherwise used for a variety of end uses such as mining ore collector compositions and chain transfer agents.
  • compositions disclosed herein can be prepared by a process comprising reacting branched C 10+ mercaptans and a sulfur-containing material to produce a branched C 20+ polysulfides crude product, wherein the branched C 10+ mercaptans may comprise a branched C 10+ mercaptan represented by Structure A-l, Structure B-l, Structure C-l, Structure D-l, Structure E-l, Structure F-l, Structure G-l, Structure H-l, or combinations thereof; wherein R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively a C 3 to C 21 alkyl group, alternatively a C 5 to C 21 alkyl group, alternatively a C 7 to C 19 alkyl group, or alternatively a C 9 to Cn alkyl group.
  • the R 9 group can be a linear Ci to C 21 alkyl group or a branched Ci to C 21 alkyl group.
  • the branched C 10+ mercaptans comprising the R 9 alkyl group are branched mercaptans, regardless of whether R 9 is linear or branched, owing to a branched sub-structure that is linked to the R 9 alkyl group, as it can be seen in Structure A-l, Structure B-l, Structure C-l, Structure D-l, Structure E-l, Structure F-l, Structure G-l, and Structure H-l, as previously disclosed herein.
  • R 9 can be selected from the group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a henicosyl group, and combinations thereof.
  • the branched Cio + mercaptans comprise one or more branched Cio mercaptans, as previously disclosed herein.
  • the branched Cio mercaptans may comprise 5 -methyl- l-mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto-heptane (represented by Structure B), 4-ethyl- l-mercapto-octane (represented by Structure C), 2-butyl- l-mercapto-hexane (represented by Structure D), 5 -methyl -2-mercapto-nonane (represented by Structure E), 3-propyl-2-mercapto- heptane (represented by Structure F), 4-ethyl-2-mercapto-octane (represented by Structure G), 5-methyl-5- mercapto-nonane (represented by Structure H), or combinations thereof.
  • Any feedstock comprising one or more branched Cio + mercaptans of the type described herein can be used, for example a reaction product of the process of reacting ]3 ⁇ 4S and one or more branched Cio + monoolefms (alternatively, one or more branched Cio monoolefms), in the presence of an initiating agent as previously described herein.
  • a feedstock of branched Cio + mercaptans may comprise any mercaptan composition previously described herein such as a “Cio + mercaptans composition”, a “Cn + mercaptans composition”, a“mercaptan composition” (also referred to as a“branched Cio mercaptan composition”), or combinations thereof.
  • the feedstock of branched Cio + mercaptans may comprise any mercaptan/sulfide composition previously described herein such as a “Cio + mercaptans/C2o + sulfides composition”, a“Cn + mercaptans/C22 + sulfides composition”, a“mercaptan/sulfide composition” (also referred to as a“branched Cio mercaptan/C2o sulfide composition”), or combinations thereof.
  • Such feedstocks can comprise other mercaptans in addition to the branched Cio + mercaptans of the type described herein, for example linear Cio + mercaptans as well as mercaptans having less than 10 carbon atoms.
  • the feedstock can comprise one or more branched Cio to C30 mercaptans.
  • Any feedstock comprising branched Cio to C30 mercaptans of the type described herein can be used, for example a reaction product of the process of reacting H2S and one or more branched C10 + monoolefms in the presence of an initiating agent as described herein.
  • Such feedstocks can comprise other mercaptans in addition to the branched Cio to C30 mercaptans of the type described herein, for example C9- mercaptans, C31 + mercaptans, as well as linear Cio to C30 mercaptans.
  • the feedstock can comprise at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, alternatively at least about 85 wt.%, alternatively at least about 90 wt.%, or alternatively at least about 95 wt.% branched Cio to C30 mercaptans, based on the total weight of the feedstock.
  • the feedstock can comprise (a) less than about 15 wt.%, alternatively less than about 10 wt.%, alternatively less than about 5 wt.%, or alternatively less than about 1 wt.% C9- mercaptans; and (b) less than about 15 wt.%, alternatively less than about 10 wt.%, alternatively less than about 5 wt.%, or alternatively less than about 1 wt.% C31 + mercaptans; based on the total weight of the feedstock.
  • a feedstock comprising at least about 70 wt.% branched Cio to C 30 mercaptans, based on the total weight of the feedstock, can also be referred to as a“first Cio to C 30 mercaptans feedstock.”
  • the feedstock can comprise at least about 95 wt.%, alternatively at least about
  • a feedstock comprising at least about 95 wt.% branched Cio to C 30 mercaptans, based on the total weight of the feedstock can also be referred to as a“second Cio to C 30 mercaptans feedstock.”
  • the second Cio to C 30 mercaptans feedstock can be produced by purifying the first Cio to C 30 mercaptans feedstock, such as for example by distillation of the first Cio to C 30 mercaptans feedstock.
  • the branched Cio to C 30 mercaptans of any feedstock described herein e.g., a first
  • Cio to C 30 mercaptans feedstock or a second Cio to C 30 mercaptans feedstock can comprise, can consist essentially of, or can be, a branched C 10+ mercaptan represented by Structure A-l, Structure B-l, Structure C-l, Structure D-l, Structure E-l, Structure F-l, Structure G-l, Structure H-l, wherein R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively a C 3 to C 21 alkyl group, alternatively a C 5 to C 21 alkyl group, alternatively a C 7 to C 19 alkyl group, or alternatively a C 9 to C 17 alkyl group.
  • the Cio to C 30 mercaptans of any feedstock described herein can further comprise non-branched C 10+ mercaptans, such as for example a linear Cio to C 30 mercaptan represented by Structure M-l, Structure N-l, Structure O-l, Structure P-l, or combinations thereof, wherein R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively a C 3 to C 21 alkyl group, alternatively a C 5 to C 21 alkyl group, alternatively a C 7 to C 19 alkyl group, or alternatively a C 9 to C 17 alkyl group.
  • non-branched C 10+ mercaptans such as for example a linear Cio to C 30 mercaptan represented by Structure M-l, Structure N-l, Structure O-l, Structure P-l, or combinations thereof, wherein R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively
  • the non-branched Cio + mercaptans can further comprise non-branched Cio mercaptans, as previously disclosed herein.
  • the non-branched Cio mercaptans can comprise l-mercapto-decane (represented by Structure M), 4-mercapto-decane (represented by Structure N), 5-mercapto- decane (represented by Structure O), 2-mercapto-decane (represented by Structure P), or combinations thereof.
  • the Cio to C 30 mercaptans of any feedstock described herein can comprise linear Cio to C 30 mercaptans.
  • the Cio to C 30 mercaptans of any feedstock described herein can comprise less than or equal to about 26 mol%, alternatively less than or equal to about 24 mol%, alternatively less than or equal to about 22 mol%, alternatively less than or equal to about 20 mol%, or alternatively less than or equal to about 18 mol% linear Cio to C 30 mercaptans.
  • the Cio to C 30 mercaptans of any feedstock described herein can comprise from about 0.1 mol% to about 26 mol%, alternatively from about 0.5 mol% to about 24 mol%, alternatively from about 1 mol% to about 22 mol%, alternatively from about 1.5 mol% to about 20 mol%, or alternatively from about 2.5 mol% to about 18 mol% linear Cio to C 30 mercaptans.
  • the first Cio to C 30 mercaptans feedstock disclosed herein can further comprise C 9 - mercaptans, C 31+ mercaptans, or combinations thereof; alternatively, C 9 - mercaptans; or alternatively, C 31+ mercaptans.
  • the C 9 - mercaptans can comprise, can consist essentially of, or can be, C 7 mercaptans, C 8 mercaptans, C 9 mercaptans, or combinations thereof; alternatively, C 7 mercaptans; alternatively, C x mercaptans; or alternatively, C 9 mercaptans.
  • the C 9 - mercaptans can comprise, can consist essentially of, or can be, Cs mercaptans.
  • the C 31+ mercaptans can comprise, can consist essentially of, or can be, C 31 mercaptans, C 32 mercaptans, C 33 mercaptans, C 34 mercaptans, C 35 mercaptans, C 36 mercaptans, C 37 mercaptans, C 38 mercaptans, or combinations thereof; alternatively, C 31 mercaptans; alternatively, C 32 mercaptans; alternatively, C 33 mercaptans; alternatively, C 34 mercaptans; alternatively, C 35 mercaptans; alternatively, C 36 mercaptans; alternatively, C 37 mercaptans; or alternatively, C 38 mercaptans.
  • the C 31+ mercaptans can comprise, can consist essentially of, or can be, C 32 mercaptans, C 36 mercaptans, C 38 mercaptans, or combinations thereof; alternatively, C 32 mercaptans; alternatively, C 36 mercaptans; or alternatively, C 38 mercaptans.
  • the first Cio to C 30 mercaptans feedstock can further comprise from about 0.1 mol% to about 5 mol%, alternatively from about 0.25 mol% to about 4 mol%, or alternatively from about 0.5 mol% to about 3 mol% Cs mercaptans.
  • the Cs mercaptans can comprise at least about 95 mol%, alternatively at least about 96 mol%, alternatively at least about 97 mol%, alternatively at least about 98 mol%, or alternatively at least about 99 mol% l-octanethiol.
  • a feedstock comprising branched C 10+ mercaptans and a sulfur-containing material can be reacted in the presence of a catalyst to produce a branched C 20+ polysulfides crude product wherein the sulfur-containing material comprises any sulfur-containing material suitable to provide sulfur for the conversion of mercaptans to polysulfides.
  • the sulfur-containing material comprises elemental sulfur.
  • elemental sulfur suitable for use herein comprises one or more allotropes of elemental sulfur, e.g., cyclo-Ss or amorphous sulfur.
  • the sulfur-containing material may further comprise one or more polymorphs of elemental sulfur, e.g., a-sulfur (a-cyclo-Ss) or b-sulfur (b-cyc/o-Ss).
  • the sulfur-containing material does not comprise hydrogen sulfide (TfiS).
  • an equivalent molar ratio of sulfur-containing material to mercaptans is in a range of from about 0.01 : 1 to about 20: 1, alternatively from about 0.04 : 1 to about 10: 1, alternatively from about 0.07: 1 to about 1.2: 1, or alternatively, from about 0.4: 1 to about 0.8: 1.
  • a feedstock comprising branched Cio + mercaptans and a sulfur-containing material can be reacted in the presence of a catalyst to produce a branched C20 + polysulfides crude product wherein the catalyst comprises a surfactant and an alkaline material.
  • the surfactant may be any surfactant suitable for conversion of mercaptans to polysulfides as disclosed herein.
  • Non-limiting examples of surfactants suitable for use in the present disclosure include nonionic surfactants, ionic surfactants, amphoteric surfactants, or combinations thereof.
  • the surfactant may be a nonionic surfactant.
  • the surfactant comprises one or more functional groups including but not limited to alkoxylates, polyalkoxylates, ethoxylates, polyethoxylates, glucosides, sulfates, sulfonates, disulfonates, phosphate esters, sulfosuccinates, quaternary ammonium salts, betaines, or combinations thereof.
  • the surfactant may be a nonionic surfactant comprising one or more functional groups including polyalkoxylates, polyethoxylates, or glucosides; alternatively, polyalkoxylates; alternatively, polyethoxylates; or alternatively, glucosides.
  • the surfactant may be a nonionic surfactant comprising a polyethoxylated alcohol, a polyethoxylated mercaptan, or a combination thereof; alternatively, a polyethoxylated alcohol; or alternatively, a polyethoxylated mercaptan.
  • the polyethoxylated alcohol may be any polyethoxylated alcohol suitable for conversion of mercaptans to polysulfides.
  • the polyethoxylated alcohol is represented by the formula Cio-isEFi- 37 0[C 2 H 4 0] X H; wherein C 10-18 H 21-37 O is a functional group derived from a secondary alcohol comprising from about 10 to about 18 carbons atoms; and wherein x is an integer from 3 to 20, alternatively, from 4 to 10, or alternatively, from 6 to 8.
  • the polyethoxylated mercaptan may be any polyethoxylated mercaptan suitable for conversion of mercaptans to polysulfides.
  • the polyethoxylated mercaptan is represented by the formula C 8-16 H 17-33 S[C 2 H 4 0] X H; wherein C 8-16 H 17-33 S is a functional group derived from a tertiary mercaptan comprising from about 8 to about 16 carbons atoms; and wherein x is an integer from 3 to 20, alternatively, from 4 to 10, or alternatively, from 6 to 8.
  • the surfactant may be chosen from the group consisting of l-Oleoyl- rac-glycerol, Brij ® 58, Brij ® L23, Brij ® L4, Brij ® O10, CYMAL-2 ® , CYMAL-5 ® , CYMAL-6 ® , Decaethylene glycol monododecyl ether, Decyl b-D-glucopyranoside, Decyl b-D-maltopyranoside, Deoxy-BigCHAP, Digitonin, ECOSURFTM EH-9, ECOSURFTM SA-9, Genapol ® X-100, Igepal ® CA-630, Igepal ® CA-720, Kolliphor ® P 188, Kolliphor ® P 407, Kolliphor ® EL, MEGA-8, MEGA-9, MEGA-10, Methoxypolyethylene glycol, N,N-Dimethyldodec
  • the surfactant may comprise TERGITOL ® 15-S-7 or AQUA- CLEEN ® .
  • the alkaline material may comprise any alkaline material suitable for conversion of mercaptans to polysulfides as disclosed herein.
  • the alkaline material may be a metal hydroxide.
  • the metal hydroxide may be a Group 1 metal hydroxide, a Group 2 metal hydroxide, or a combination thereof.
  • the metal hydroxide may be LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, or combinations thereof.
  • the metal hydroxide comprising a catalyst suitable for use in the present disclosure may be a solid or, alternatively, may be a component of an aqueous solution.
  • an amount of metal hydroxide comprising the aqueous solution may be about 5 wt.%; alternatively, about 10 wt.%; alternatively, about 20 wt.%; or alternatively, about 50 wt.% based on the total weight of the aqueous solution.
  • the surfactant and the alkaline material may be contacted and subsequently heated.
  • the surfactant and the alkaline material may be heated to a temperature in a range of from about 40 °C to about 120 °C, or alternatively, from about 60 °C to about 100 °C.
  • the temperature may be maintained for a time period in a range of from 5 min to about 12 h, or alternatively, from about 30 min to about 2 h.
  • a weight ratio of catalyst to mercaptans is in a range of from about 0.001 : 1 to about
  • a weight ratio of surfactant to alkaline material is in a range of from about 5 : 1 to about 500: 1, alternatively from about 10: 1 to about 200: 1, alternatively from about 25: 1 to about 40: 1, or alternatively from about 30: 1 to about 35: 1.
  • a feedstock comprising branched Cio + mercaptans and a sulfur-containing material can be reacted in the presence of a catalyst to produce a branched C20 + polysulfides crude product wherein a mercaptan scavenger (i.e., quenching agent) may be utilized to produce the branched C20 + polysulfides crude product.
  • a mercaptan scavenger i.e., quenching agent
  • the mercaptan scavenger may be any mercaptan scavenger suitable for conversion of mercaptans to polysulfides.
  • the mercaptan scavenger may be an epoxide, an oxetane, or a combination thereof.
  • the epoxide may be ethylene oxide or propylene oxide; alternatively, ethylene oxide; or alternatively, propylene oxide.
  • an equivalent molar ratio of mercaptan scavenger to mercaptans is in a range of from about 0.001 : 1 to about 1 : 1, alternatively from about 0.01 : 1 to about 0.5: 1, alternatively from about 0.05: 1 to about 0.1 : 1, or alternatively from about 0.06: 1 to about 0.08: 1.
  • a feedstock comprising branched Cio + mercaptans and a sulfur-containing material can be reacted in the presence of a catalyst to produce a branched C20 + polysulfides crude product wherein a decolorizing agent may be utilized to produce the branched C20 + polysulfides crude product.
  • the decolorizing agent may be any decolorizing agent suitable for use in the conversion of mercaptans to polysulfides.
  • the decolorizing agent comprises activated carbon, decolorizing carbon, mineral carbon, charcoal black, graphite (natural), purified charcoal, or a combination thereof.
  • the decolorizing agent may comprise Darco G-60, Darco ® , Norit A ® and combinations thereof, available commercially from Sigma- Aldrich, Inc.
  • a weight ratio of decolorizing agent to mercaptans is in a range of from about
  • a process e.g., a first Cio to C30 mercaptans feedstock or a second Cio to C30 mercaptans feedstock
  • a sulfur-containing material in the presence of a catalyst to produce a branched C20 + polysulfides crude product.
  • a process of producing a C20 + poly sulfides crude product may be referred to as a process of producing a C20 + poly sulfides crude product.
  • the entirety of the processes i.e., each process step), disclosed herein may be conducted under an atmosphere comprising an inert gas.
  • the inert gas may comprise any inert gas suitable for use in the present disclosure, nonlimiting examples of which include nitrogen, argon, and a combination thereof.
  • a process of producing a C20 + polysulfides crude product comprising contacting a feedstock comprising branched C10 + mercaptans (e.g., a first Cio to C30 mercaptans feedstock or a second Cio to C30 mercaptans feedstock) and a catalyst to form a mixture.
  • the feedstock comprises one or more branched Cio to C30 mercaptans as disclosed herein.
  • the process further comprises heating the mixture to a temperature in a range of from about 40 °C to about 200 °C; alternatively, from about 60 °C to about 85 °C; or alternatively, from about 70 °C to about 80 °C.
  • the mixture may then be contacted with a sulfur-containing material (e.g., elemental sulfur) wherein evolution of a reaction by-product occurs.
  • a sulfur-containing material e.g., elemental sulfur
  • the reaction by-product may be gas-phase hydrogen sulfide.
  • the mixture may then be agitated for a time period in a range of from 30 min to about 24 h; alternatively, from about 1 h to about 12 h; alternatively, from about 2 h to about 6 h; or alternatively, from about 3 h to about 4 h.
  • the process of producing a C20 + poly sulfides crude product comprises raising the temperature of the mixture .
  • the mixture may be heated to a temperature in a range of from about 40 °C to about 250 °C; alternatively, from about 60 °C to about 200 °C; alternatively, from about 90 °C to about 150 °C; or alternatively, from about 90 °C to about 100 °C.
  • the mixture may then be agitated for a time period in a range of from 30 min to about 24 h; alternatively, from about 1 h to about 12 h; alternatively, from about 2 h to about 4 h; or alternatively, from about 3 h to about 4 h.
  • the mixture may then be sparged with an inert gas (e.g., nitrogen), for a time period in a range of from 5 min to about 24 h; alternatively, from about 10 min to about 12 h; alternatively, from about 30 min to about 4 h; or alternatively, from about 1 h to about 4 h.
  • an inert gas e.g., nitrogen
  • the process of producing a C20 + polysulfides crude product comprises lowering the temperature of the mixture.
  • the temperature of the mixture may be adjusted to a temperature in a range of from about 50 °C to about 100 °C; alternatively, from about 65 °C to about 85 °C; or alternatively, from about 70 °C to about 75 °C.
  • the process further comprises addition of a mercaptan scavenger (e.g., propylene oxide), to the mixture.
  • a mercaptan scavenger e.g., propylene oxide
  • the mercaptan scavenger e.g., propylene oxide
  • the mixture may then be agitated for a time period in a range of from 10 min to about 24 h; alternatively, from about 30 min to about 12 h; alternatively, from about 1 h to about 4 h; or alternatively, from about 2 h to about 3 h.
  • the mixture may then be sparged with an inert gas (e.g., nitrogen), for a time period in a range of from 5 min to about 24 h; alternatively, from about 10 min to about 12 h; alternatively, from about 30 min to about 4 h; or alternatively, from about 1 h to about 4 h.
  • an inert gas e.g., nitrogen
  • the process of producing a C20 + polysulfides crude product comprises collecting a C20 + polysulfides crude product.
  • the C20 + polysulfides crude product may be collected by any suitable liquid/solid separation technique known to the ordinary skilled artisan.
  • suitable liquid/solid separation technique known to the ordinary skilled artisan.
  • Non-limiting examples of techniques for collecting the C20 + polysulfides crude product include filtration (e.g., gravity, in-line, membrane, pressure, vacuum), centrifugation, gravimetric settling, hydrocyclone methods, sedimentation, or combinations thereof.
  • the mixture subsequent to sparging the mixture with the inert gas, may be cooled to a temperature in a range of from about 15 °C to about 50 °C, or alternatively, from about 20° C to about 35° C to form a cooled mixture.
  • the cooled mixture may be filtered to collect the C20 + polysulfides crude product.
  • activated carbon of the type disclosed herein is added to the cooled mixture and the temperature of the cooled mixture is raised to a temperature in a range of from about 40 °C to about 80 °C; or alternatively, from about 50 °C to about 70 °C.
  • the mixture is then agitated for a time period in a range of from 10 min to about 12 h; alternatively, from about 1 h to about 4 h; or alternatively, from about 2 h to about 3 h.
  • the process further comprises cooling the mixture to a temperature in a range of from about 15 °C to about 50 °C, or alternatively, from about 20° C to about 35° C and collecting (e.g., filtering), the C20 + polysulfides crude product.
  • a process of producing a C20 + polysulfides crude product comprising contacting a feedstock comprising branched C10 + mercaptans (e.g., a first Cio to C30 mercaptans feedstock or a second Cio to C30 mercaptans feedstock), a catalyst and a sulfur-containing material to form a mixture.
  • a feedstock comprising branched C10 + mercaptans (e.g., a first Cio to C30 mercaptans feedstock or a second Cio to C30 mercaptans feedstock), a catalyst and a sulfur-containing material to form a mixture.
  • the sulfur-containing material comprises elemental sulfur and the feedstock comprises one or more branched Cio to C30 mercaptans as disclosed herein.
  • the process further comprises heating the mixture to a temperature in a range of from about 40 °C to about 200 °C; alternatively, from about 60 °C to about 85 °C; or alternatively, from about 70 °C to about 80 °C wherein evolution of a reaction by-product occurs.
  • the reaction by-product may be gas-phase hydrogen sulfide.
  • the mixture may then be agitated for a time period in a range of from 30 min to about 24 h; alternatively, from about 1 h to about 12 h; alternatively, from about 2 h to about 6 h; or alternatively, from about 3 h to about 4 h.
  • the process of producing a C20 + poly sulfides crude product comprises raising the temperature of the mixture .
  • the mixture may be heated to a temperature in a range of from about 40 °C to about 250 °C; alternatively, from about 60 °C to about 200 °C; alternatively, from about 90 °C to about 150 °C; or alternatively, from about 90 °C to about 100 °C.
  • the mixture may then be agitated for a time period in a range of from 30 min to about 24 h; alternatively, from about 1 h to about 12 h; alternatively, from about 2 h to about 4 h; or alternatively, from about 3 h to about 4 h.
  • the mixture may then be sparged with an inert gas (e.g., nitrogen), for a time period in a range of from 5 min to about 24 h; alternatively, from about 10 min to about 12 h; alternatively, from about 30 min to about 4 h; or alternatively, from about 1 h to about 4 h.
  • an inert gas e.g., nitrogen
  • the process of producing a C20 + polysulfides crude product comprises lowering the temperature of the mixture.
  • the temperature of the mixture may be adjusted to a temperature in a range of from about 50 °C to about 100 °C; alternatively, from about 65 °C to about 85 °C; or alternatively, from about 70 °C to about 75 °C.
  • the process further comprises addition of a mercaptan scavenger (e.g., propylene oxide), to the mixture.
  • a mercaptan scavenger e.g., propylene oxide
  • the mercaptan scavenger e.g., propylene oxide
  • the mixture may then be agitated for a time period in a range of from 10 min to about 24 h; alternatively, from about 30 min to about 12 h; alternatively, from about 1 h to about 4 h; or alternatively, from about 2 h to about 3 h.
  • the mixture may then be sparged with an inert gas (e.g., nitrogen), for a time period in a range of from 5 min to about 24 h; alternatively, from about 10 min to about 12 h; alternatively, from about 30 min to about 4 h; or alternatively, from about 1 h to about 4 h.
  • an inert gas e.g., nitrogen
  • the process of producing a C20 + polysulfides crude product comprises collecting a C20 + polysulfides crude product.
  • the C20 + polysulfides crude product may be collected by any suitable bquid/solid separation technique known to the ordinary skilled artisan.
  • Non-limiting examples of techniques for collecting the C20 + polysulfides crude product include filtration (e.g., gravity, in-line, membrane, pressure, vacuum), centrifugation, gravimetric settling, hydrocyclone methods, sedimentation, or combinations thereof.
  • the mixture subsequent to sparging the mixture with the inert gas, may be cooled to a temperature in a range of from about 15 °C to about 50 °C, or alternatively, from about 20° C to about 35° C to form a cooled mixture.
  • the cooled mixture may be fdtered to collect the C20 + polysulfides crude product.
  • activated carbon of the type disclosed herein is added to the cooled mixture and the temperature of the cooled mixture is raised to a temperature in a range of from about 40 °C to about 80 °C; or alternatively, from about 50 °C to about 70 °C.
  • the mixture is then agitated for a time period in a range of from 10 min to about 12 h; alternatively, from about 1 h to about 4 h; or alternatively, from about 2 h to about 3 h.
  • the process further comprises cooling the mixture to a temperature in a range of from about 15 °C to about 50 °C, or alternatively, from about 20° C to about 35° C and collecting (e.g., filtering), the C20 + polysulfides crude product.
  • a process of producing a C20 + polysulfides crude product comprises reacting, in a reactor, a sulfur source (e.g., H2S) and a feedstock comprising one or more branched C10 + monoolefms in the presence of an initiating agent, to produce a branched Cio + mercaptans crude composition, i.e., the process previously described herein for the branched C10 + monoolefms.
  • the process further comprises recovering an intermediate reaction product from the branched C10 + mercaptans crude composition.
  • the intermediate reaction product recovered from the branched C10 + mercaptans crude composition may be a branched C10 + mercaptans composition, a branched C10 + mercaptans/branched C20 + sulfides composition, or a combination thereof as previously described herein for the reaction of the branched C10 + monoolefms.
  • the intermediate reaction product comprises one or more branched Cioto C30 mercaptans as previously described herein.
  • the intermediate reaction product may be recovered from the branched C10 + mercaptans crude composition, for example by flashing, distillation, fractionation, stripping, absorption, etc. as previously described herein.
  • the process of producing a C20 + polysulfides crude product comprises contacting the intermediate reaction product and a catalyst to form a mixture.
  • the process further comprises heating the mixture to a temperature in a range of from about 40 °C to about 200 °C; alternatively, from about 60 °C to about 85 °C; or alternatively, from about 70 °C to about 80 °C.
  • the mixture may then be contacted with a sulfur-containing material (e.g., elemental sulfur) wherein evolution of a reaction by-product occurs.
  • the reaction by-product may be gas-phase hydrogen sulfide.
  • the mixture may then be agitated for a time period in a range of from 30 min to about 24 h; alternatively, from about 1 h to about 12 h; alternatively, from about 2 h to about 6 h; or alternatively, from about 3 h to about 4 h.
  • the mixture may be heated to a temperature in a range of from about 40 °C to about 250 °C; alternatively, from about 60 °C to about 200 °C; alternatively, from about 90 °C to about 150 °C; or alternatively, from about 90 °C to about 100 °C.
  • the mixture may then may be agitated for a time period in a range of from 30 min to about 24 h; alternatively, from about 1 h to about 12 h; alternatively, from about 2 h to about 4 h; or alternatively, from about 3 h to about 4 h.
  • the mixture may then be sparged with an inert gas (e.g., nitrogen), for a time period in a range of from 5 min to about 24 h; alternatively, from about 10 min to about 12 h; alternatively, from about 30 min to about 4 h; or alternatively, from about 1 h to about 4 h.
  • an inert gas e.g., nitrogen
  • the mixture may be cooled to a temperature in a range of from about 50 °C to about 100 °C; alternatively, from about 65 °C to about 85 °C; or alternatively, from about 70 °C to about 75 °C.
  • the process further comprises addition of a mercaptan scavenger (e.g., propylene oxide), to the mixture.
  • a mercaptan scavenger e.g., propylene oxide
  • the mercaptan scavenger e.g., propylene oxide
  • the mixture may then be agitated for a time period in a range of from 10 min to about 24 h; alternatively, from about 30 min to about 12 h; alternatively, from about 1 h to about 4 h; or alternatively, from about 2 h to about 3 h.
  • the mixture may be sparged with the inert gas (e.g., nitrogen), for a time period in a range of from 5 min to about 24 h; alternatively, from about 10 min to about 12 h; alternatively, from about 30 min to about 4 h; or alternatively, from about 1 h to about 4 h.
  • the inert gas e.g., nitrogen
  • the process of producing a C20 + polysulfides crude product comprises collecting a C20 + polysulfides crude product.
  • the C20 + polysulfides crude product may be collected by any suitable liquid/solid separation technique known to the ordinary skilled artisan.
  • suitable liquid/solid separation technique known to the ordinary skilled artisan.
  • Non-limiting examples of techniques for collecting the C20 + polysulfides crude product include filtration (e.g., gravity, in-line, membrane, pressure, vacuum), centrifugation, gravimetric settling, hydrocyclone methods, sedimentation, or combinations thereof.
  • the mixture subsequent to sparging the mixture with the inert gas, may be cooled to a temperature in a range of from about 15 °C to about 50 °C, or alternatively, from about 20° C to about 35° C to form a cooled mixture.
  • the cooled mixture may be filtered to collect the C20 + polysulfides crude product.
  • activated carbon of the type disclosed herein is added to the cooled mixture and the temperature of the cooled mixture is raised to a temperature in a range of from about 40 °C to about 80 °C; or alternatively, from about 50 °C to about 70 °C.
  • the mixture is then agitated for a time period in a range of from 10 min to about 12 h; alternatively, from about 1 h to about 4 h; or alternatively, from about 2 h to about 3 h.
  • the process further comprises cooling the mixture to a temperature in a range of from about 15 °C to about 50 °C, or alternatively, from about 20° C to about 35° C and collecting (e.g., filtering), the C20 + polysulfides crude product.
  • a feedstock comprising branched C10 + mercaptans e.g., a first C10 to C30 mercaptans feedstock or a second C10 to C30 mercaptans feedstock
  • a sulfur-containing material can be reacted to produce a C20 + crude product wherein a mercaptan conversion is achieved.
  • the mercaptan conversion achieved is equal to or greater than about 70%, alternatively equal to or greater than about 75%, alternatively equal to or greater than about 80%, alternatively equal to or greater than about 85%, or alternatively equal to or greater than about 90%.
  • a mercaptan conversion refers to the mol% of mercaptans that have reacted during the reaction between the sulfur-containing material (e.g., elemental sulfur) and the feedstock in a reactor, with respect to the amount of mercaptans introduced into the reactor during the same time period.
  • the sulfur-containing material e.g., elemental sulfur
  • any suitable feedstock comprising branched C10 + mercaptans as described herein can be reacted with a sulfur-containing material in the presence of a catalyst to produce a branched C20 + polysulfides crude product.
  • the branched C 20+ polysulfides crude product can be further refined (e.g., distilled or otherwise separated into one or more fractions such as lights, intermediate, and heavies) to yield various compositions described herein.
  • the type and/or amounts of the constituent components that form the branched C 20+ poly sulfides crude product can vary depending upon the feedstock (e.g., the amount and types of mercaptans therein), the reaction conditions, the catalysts employed, etc., and the ordinary skilled artisan can tailor the post reactor processing of the branched C 20+ polysulfides crude product to account for the specific compounds present in a given branched C 20+ polysulfides crude product to yield various desired products and compositions of the types described herein.
  • a reactor effluent may be collected (e.g., filtered) to yield a branched C 20+ polysulfides crude product, as previously described herein.
  • branched C 20+ polysulfides crude product or“branched C 20+ polysulfides crude product” refers to an unrefined effluent stream collected from the reaction process (e.g., filtered), and in particular to an effluent stream that has not undergone any additional post-reactor processing such as flashing, distillation, or other separation techniques or processes to remove any components from the effluent stream other than the initial removal of by-products and/or solid reaction components (e.g., via filtering).
  • additional post-reactor processing such as flashing, distillation, or other separation techniques or processes to remove any components from the effluent stream other than the initial removal of by-products and/or solid reaction components (e.g., via filtering).
  • the branched C 20+ polysulfides crude product comprises branched C 20 to Obo polysulfides and branched C 20 to Obo monosulfides formed by the reaction of one or more branched C 10 to C 30 mercaptans and the a sulfur-containing material and the structures of these branched C 20 to Obo polysulfides and branched C 20 to C 60 monosulfides are described in more detail herein.
  • the branched C 20+ polysulfides crude composition can comprise a number of other compounds such as unreacted mercaptans (e.g., unreacted branched C 10 to C 30 mercaptans, unreacted CV mercaptans), non-branched C 20 to Obo polysulfides, non-branched C 20 to Obo monosulfides, non-C 2 o to Obo polysulfides, non-C 2 o to Obo monosulfides, and other impurities (e.g., inert compounds).
  • unreacted mercaptans e.g., unreacted branched C 10 to C 30 mercaptans, unreacted CV mercaptans
  • non-branched C 20 to Obo polysulfides e.g., unreacted branched C 10 to C 30 mercaptans, unreacted CV mercaptans
  • non-branched C 20 to Obo polysulfides e.g., un
  • the constituent components contained within the branched C 20+ polysulfides crude product can vary depending upon the composition of the feedstock (e.g., an unpurified first C 10 to C 30 mercaptans feedstock as compared to a purified second C 10 to C 30 mercaptans feedstock as described herein) as well as reaction conditions, catalyst, etc.
  • a branched C 20+ polysulfides crude product can comprise light, intermediate, and heavy fractions as described herein.
  • the branched C 20+ polysulfides crude product can contain a variety of non-C 2 o to
  • C60 polysulfides and non-C 2 o to Obo monosulfides components such as C 14 to C 19 polysulfides represented by the general formula R 19 S-[S] n -SR 20 , wherein n is an integer from 1 to 10, wherein R 19 and R 20 are each independently a functional group derived from a C 7+ mercaptan, and wherein R 19 and R 20 are not both derived from a branched C 10+ mercaptan; Cei to C 78 polysulfides represented by the general formula R 19 S-[S] n - SR 20 , wherein n is an integer from 1 to 10, wherein R 19 and R 20 are each independently a functional group derived from a C 31 to C 38 mercaptan, and wherein R 19 and R 20 are not both derived from a branched C 10+ mercaptan; C 14 to C 19 monosulfides represented by the general formula R 21 -S-R 22
  • the branched C 20+ polysulfides crude product can contain a variety of non-branched
  • C 20 to C60 polysulfides and non-branched C 20 to Obo monosulfides such as C 20 to Obo polysulfides represented by the general formula R 19 S-[S] n -SR 20 wherein n is an integer from 1 to 10, and wherein R 19 and R 20 are each independently a non-branched C 10 to C 30 alkyl group; and C 20 to G,o monosulfides represented by the general formula R 21 -S-R 22 wherein R 21 and R 22 are each independently a non-branched C 10 to C 30 alkyl group.
  • the non-branched C 20 to Obo polysulfides can comprise C 20 to Obo polysulfides represented by the general formula R 19 S-[S] n -SR 20 wherein n is an integer from 1 to 10, wherein SR 19 and SR 20 are each independently a functional group derived from a linear C 10 to C 30 mercaptan represented by Structure M-l, Structure N-l, Structure O-l, or Structure P-l, as previously disclosed herein, and wherein R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively a C 3 to C 21 alkyl group, alternatively a C 5 to C 21 alkyl group, alternatively a C 7 to C 19 alkyl group, or alternatively a C 9 to C 17 alkyl group, as previously disclosed herein; and the non-branched C 20 to Obo monosulfides can comprise C 20 to Obo monosulfides represented by the general formula R 21 -S
  • the branched C 20+ polysulfides crude product can contain a variety of non mercaptan impurities selected from the group consisting of Cs to C 78 olefins, Cs to C 14 alkanes, cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene, hexamethylbenzene, C 4 to C 12 alcohols, 2-ethyl- l-hexanol, and 2-ethylhexyl-2-ethylhexanoate, and combinations thereof.
  • non mercaptan impurities selected from the group consisting of Cs to C 78 olefins, Cs to C 14 alkanes, cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene, ethyl
  • a process of reacting a feedstock comprising branched C 10+ mercaptans and a sulfur-containing material to produce a C 20+ crude product can further comprise recovering a process product from the branched C 20+ polysulfides crude product, wherein the process product can comprise branched C 20+ polysulfides and/or branched C 20+ monosulfides, wherein the branched C 20+ polysulfides comprise branched C 20 to C 60 polysulfides represented by the general formula R 15 S 1 -[S] n -S 2 R 16 wherein n is an integer from 1 to 10, wherein the branched C 20+ monosulfides comprise branched C 20 to Obo monosulfides represented by the general formula R 17 -S-R 18 , wherein R 15 , R 16 , R 17 , and R 18 are each independently an alkyl group, and wherein the alkyl group comprises a branched Cio to C 30 al
  • the process product can comprise a branched C 20+ polysulfides composition (heavy fraction; primary reaction product), a branched C 20+ monosulfides composition (intermediate fraction; side reaction product), a branched C 20+ polysulfides/branched C 20+ monosulfides composition (intermediate and heavy fractions; primary and side reaction products), or combinations thereof.
  • a branched C 20+ polysulfides crude product comprising branched C 20+ polysulfides and branched C 20+ monosulfides as disclosed herein can be separated into two or more fractions (e.g., light fraction, intermediate fraction, heavy fraction, etc.) by any process or unit operation known in the art.
  • a branched C 20+ polysulfides crude product can be processed (e.g., distilled) to remove a fraction of light compounds.
  • a branched C 20+ polysulfides crude product can be processed to recover both a light fraction and an intermediate fraction (e.g., a rough cut), followed by further processing to obtain one or more fine cuts.
  • a branched C 20+ polysulfides crude product can be processed to recover a heavy fraction (e.g., a C 20+ polysulfides fraction).
  • a branched C 20+ polysulfides crude product can be processed to separate out any combination of a light fraction, an intermediate fraction (e.g., comprising C 20+ monosulfides, including branched C 20+ monosulfides), and a heavy fraction (e.g., comprising C 20+ polysulfides, including branched C 20+ polysulfides).
  • a light, intermediate or heavy fraction e.g., a rough cut
  • one or more desired fine cuts e.g., a C 20 to Obo polysulfides fraction
  • a branched C 20+ polysulfides crude product can be separated to produce a high-purity C 20+ polysulfides stream and/or a high-purity C 20+ monosulfides (e.g., to obtain a desired fine cut or fraction such as a C 20 to C 60 polysulfides fraction).
  • these separated streams can be blended in any combination of ratios to produce a mixture with specific concentrations of one of more components (e.g., desired blend ratios of branched C 20+ polysulfides and/or branched C 20+ monosulfides, for example to aid in a particular end use).
  • the unit operations/processes used for these separations are known to one of skill and the art and include, but are not limited to, distillation, fractionation, flashing, stripping, and absorption, and others.
  • the unit operation conditions such as for example, temperature, pressure, flow rates, and others at which these unit operations produce one or more of the desired fractions can be determined by one of ordinary skill in the art.
  • a light fraction is removed from the C20 + polysulfides mercaptans crude composition, for example by flashing, distillation, fractionation, stripping, absorption, etc.
  • the light fraction removed from the branched C20 + polysulfides crude product can comprise at least about 90 wt.%, alternatively at least about 92 wt.%, alternatively at least about 95 wt.%, alternatively at least about 96 wt.%, alternatively at least about 97 wt.%, alternatively at least about 98 wt.%, or alternatively at least about 99 wt.% C19- metasulfides based on the total weight of the light fraction, wherein the C19- metasulfides comprise C19- polysulfides, C19- monosulfides, or a combination thereof.
  • the light fraction removed from the branched C20 + polysulfides crude product can comprise at least about 90 wt.%, alternatively at least about 92 wt.%, alternatively at least about 95 wt.%, alternatively at least about 96 wt.%, alternatively at least about 97 wt.%, alternatively at least about 98 wt.%, or alternatively at least about 99 wt.% unreacted mercaptans based on the total weight of the light fraction, wherein the unreacted mercaptans comprise unreacted C 10 + mercaptans, unreacted C9- mercaptans, or a combination thereof.
  • the light fraction removed from the branched C20 + polysulfides crude product can comprise at least about 90 wt.%, alternatively at least about 92 wt.%, alternatively at least about 95 wt.%, alternatively at least about 96 wt.%, alternatively at least about 97 wt.%, alternatively at least about 98 wt.%, or alternatively at least about 99 wt.% C9- compounds, based on the total weight of the light fraction.
  • Non-limiting examples of C9- compounds include C9- monoolefms, C9- alkanes, cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene, C9- alcohols, 2-ethyl- l-hexanol, and the like, or combinations thereof.
  • the light fraction removed from the branched C20 + polysulfides crude product can comprise less than about 10 wt.%, alternatively less than about 5 wt.%, alternatively less than about 4 wt.%, alternatively at less than about 3 wt.%, alternatively less than about 2 wt.%, or alternatively less than about 1 wt.% C20 + compounds, based on the total weight of the light fraction.
  • C20 + compounds include C20 + polysulfides, C20+ monosulfides, C20+ monoolefms and C20+ alkanes.
  • a combined intermediate and heavy fraction i.e., C20 + polysulfides and C20 + monosulfides
  • the combined intermediate and heavy fraction can be used“as is” or can be further processed, for example separated or split into separate intermediate and heavy fractions (and said separate intermediate and heavy fractions can be subsequently recombined in various blends and associated blend ratios), as described in more detail herein.
  • the combined intermediate and heavy fraction formed by removal of the light fraction from the branched C20 + polysulfides crude product can comprise less than about 15 wt.%, alternatively less than about 10 wt.%, alternatively less than about 9 wt.%, alternatively less than about 8 wt.%, alternatively less than about 7 wt.%, alternatively less than about 6 wt.%, alternatively less than about 5 wt.%, alternatively less than about 4 wt.%, alternatively less than about 3 wt.%, alternatively less than about 2 wt.%, or alternatively less than about 1 wt.% C9- products, based on the total weight of the combined intermediate and heavy fraction.
  • a combined intermediate and heavy fraction (i.e., C20 + polysulfides and C20 + monosulfides) recovered from the branched C20 + polysulfides crude product can comprise (A) at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% polysulfides, based on the total weight of the combined intermediate and heavy fraction; wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the polysulfides can be branched C20 to Obo polysulf
  • the branched C20 + polysulfides crude product can be flashed to remove a light fraction as described herein to produce a combined intermediate and heavy fraction (i.e., C20 + polysulfides and C20 + monosulfides), comprising: (A) at least about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt.% branched C20 + polysulfides selected from the group consisting of a branched C20 to Obo polysulfide represented by structure R 15 S 1 -[S] n- S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 can each independently be a branched C10 to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates
  • the branched C20 + polysulfides crude product can be flashed to remove a lights fraction as described herein to produce a combined intermediate and heavy fraction (i.e., C20 + polysulfides and C20 + monosulfides), comprising: (A) from at least about 50 wt.% to at least about 90 wt.%, alternatively from at least about 55 wt.% to at least about 85 wt.%, or alternatively from at least about 60 wt.% to at least about 80 wt.% polysulfides, wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the polysulfides can be branched C20 to Obo polysulfides selected from the group consisting of a branched C20 to Obo polys
  • the branched C 20+ polysulfides crude product can be flashed to remove a light fraction and subsequently further separated to produce an intermediate fraction and a heavy fraction.
  • Each of the intermediate fraction and the heavy fraction recovered from the branched C 20+ polysulfides crude product can then be optionally further processed (e.g., polished) and mixed in any appropriate ratio to produce blended compositions, as previously described herein for crude compositions derived from branched C 10+ monoolefms.
  • the heavy fraction recovered from the branched C 20+ polysulfides crude product can comprise at least about 25 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.%, alternatively at least about 75 wt.%, or alternatively at least about 85 wt.% C 20+ polysulfides, based on the total weight of the heavy fraction, wherein the C 20+ polysulfides are branched C 20 to C 60 polysulfides as disclosed herein.
  • an intermediate fraction recovered from the branched C 20+ polysulfides crude product can comprise at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt.%, C 20+ monosulfides, based on the total weight of the intermediate fraction, wherein the C 20+ monosulfides are branched C 20 to C 60 monosulfides as disclosed herein.
  • the branched C 20+ polysulfides crude product can be separated into light, intermediate, and heavy fractions by distillation, for example in a single distillation column having a light fraction recovered as an overhead stream, an intermediate fraction (e.g., comprising C 20+ monosulfides) recovered as a side stream, and a heavy fraction (e.g., comprising C 20+ polysulfides) recovered as a bottom stream.
  • a light fraction recovered as an overhead stream
  • an intermediate fraction e.g., comprising C 20+ monosulfides
  • a heavy fraction e.g., comprising C 20+ polysulfides
  • the separation can be in sequential steps such as removal of the lights fraction in a first distillation column, followed by separation of the intermediate fraction (e.g., comprising C 20+ monosulfides) as an overhead stream in a second distillation column and the heavy fraction (e.g., comprising C 20+ polysulfides) as a bottom stream of the second distillation column.
  • These“rough-cut” light, intermediate, and heavy streams can be used“as is” or they can be further processed (e.g., further refined or polished, for example by additional distillation or other separation techniques to produce“fine-cuts”) and/or blended to obtain a variety of products that are salable or otherwise available for a variety of end uses such as mining ore collector compositions or chain transfer agents.
  • C 20+ polysulfides compositions for example, a variety of C 20+ polysulfides compositions, C 20+ monosulfides compositions, and C 20+ metasulfides compositions (i.e., mixed C 20+ polysulfides/C 2 o + monosulfides compositions) of the type disclosed herein can be produced as disclosed herein.
  • C 20+ polysulfides compositions for example, a variety of C 20+ polysulfides compositions, C 20+ monosulfides compositions, and C 20+ metasulfides compositions (i.e., mixed C 20+ polysulfides/C 2 o + monosulfides compositions) of the type disclosed herein can be produced as disclosed herein.
  • the mercaptan feedstock e.g., mercaptan feedstock reacted with a sulfur- containing material to produce the branched C 20+ polysulfides crude product
  • the intermediate fraction comprises C 20 to C 38 monosulfides
  • the heavy fraction comprises C 20 to C 38 polysulfides.
  • the mercaptan feedstock (e.g., mercaptan feedstock reacted with a sulfur- containing to produce the branched C 20+ polysulfides crude product) comprises C 20 to C 30 mercaptans
  • the intermediate fraction comprises C 40 to Go monosulfides
  • the heavy fraction comprises C 40 to Obo polysulfides.
  • the intermediate and heavy fractions recovered by distillation can comprise mercaptans and sulfides as follows.
  • the intermediate fraction can comprise Cio to C 19 monosulfides
  • the heavy fraction can comprise C 20 to C 30 monosulfides and C 20 to G,o polysulfides.
  • intermediate fraction can comprise Cio to C 30 monosulfides and C 20 to C 30 polysulfides
  • the heavy fraction can comprise C 31 to Go polysulfides.
  • a first intermediate fraction can comprise Cio to C 19 monosulfides
  • a second intermediate fraction can comprise C 20 to C 30 monosulfides and C 20 to C 30 polysulfides
  • the heavy fraction can comprise Gi to Go polysulfides.
  • Intermediate and heavy fractions comprising both monosulfides and polysulfides could be used as recovered (e.g., mixed monosulfides / polysulfides compositions) or can be further processed to separate and recover further monosulfides compositions and polysulfides compositions.
  • an intermediate fraction can comprise at least about 25, 30, 40, 50, 75, or 85 wt.% branched C 20+ monosulfides.
  • the branched C 20+ monosulfides can be selected from the group consisting of a branched C 20 to G,o monosulfide represented by general formula R 17 -S-R 18 , wherein R 17 and R 18 can each independently be a branched Cio to C 30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an attachment point with a sulfur atom of the branched C 20 to Obo monosulfide, and wherein R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively a C 3 to C 21 alkyl group, alternatively a C 5
  • the heavy fraction can comprise at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50,
  • the branched C20 + polysulfides can be selected from the group consisting of a branched C20 to Obo polysulfide represented by general formula R 15 S 1 -[S] n- S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 can each independently be a branched Cio to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group
  • a C 20+ polysulfides composition can comprise C 20+ polysulfides, wherein at least a portion of the C 20+ polysulfides comprise branched C 20+ polysulfides.
  • branched C 20+ polysulfides refer to polysulfides that are represented by the general formula R ' ⁇ S 1 —
  • the branched C 20+ polysulfides of the present disclosure comprise branched C 20 to Ceo polysulfides wherein the branched C 20 to Ceo polysulfides can comprise a branched C 20 to Ceo polysulfide represented by general formula R 15 S 1 -[S] n- S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 can each independently be a branched Cio to C 30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively a C 3 to C 21 alkyl group, alternatively
  • a polysulfide e.g., a branched C 20 to Obo polysulfide
  • the total number of carbon atoms as opposed to the number of carbons of only one of the alkyl groups present in the polysulfide.
  • a FFiCio-S x- CioFFi polysulfide will be referred to as a C 20 polysulfide (rather than a Cio polysulfide);
  • a FEsC ⁇ -S x- C ⁇ EG polysulfide will be referred to as a C 26 poly sulfide (rather than a C 12 polysulfide or a C 14 poly sulfide);
  • a H 45 C 22- S X- C 22 H 45 polysulfide will be referred to as a C 44 polysulfide (rather than a C 22 polysulfide); etc.
  • the polysulfides of the present disclosure comprise two alkyl groups linked by a group of sulfur atoms comprising from two to twelve, or alternatively three to six sulfur atoms. Further, for purposes of the disclosure herein, the specific number of sulfur atoms comprising the polysulfide is not distinguished.
  • the C 20 trisulfide, the C 20 tetrasulfide, and the C 20 pentasulfide are referred to as a C 20 polysulfide.
  • a polysulfide of the present disclosure may be termed a “Mixed Intermediate Polysulfide” (MIPS) and described with an average number of sulfur atoms within the polysulfide and a weight percentage of sulfur within the polysulfide.
  • MIPS Mated Intermediate Polysulfide
  • a C 20 polysulfide having an average molecular formula FFiCio-lSSSJ-CioFFi represents a polysulfide comprising an average of three sulfur atoms (i.e.,“ ⁇ ” brackets indicate an average number of sulfur atoms) and further comprising 25 wt.% sulfur based on the formula weight of the average molecular formula and may be termed a MIPS 325.
  • a C 20 polysulfide having an average molecular formula FbiCio- ⁇ SSSSS ⁇ -CioFl 2i represents a polysulfide comprising an average of five sulfur atoms and further comprising 37 wt.% sulfur based on the formula weight of the average molecular formula and may be termed a MIPS 537.
  • compositions comprising polysulfides, wherein at least a portion of the polysulfides are branched C 20+ polysulfides (e.g., branched C 20 to Obo polysulfides as disclosed herein) can also be referred to as a“branched C 20+ polysulfides composition.”
  • the branched C 20+ polysulfides composition can comprise any suitable amount of branched C 20 to G,o polysulfides.
  • the C 20+ polysulfides can further comprise non-branched C 20+ polysulfides, such as linear C 20 to Obo polysulfides represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R ⁇ S 1 and R 16 S 2 can each independently be a functional group derived from a mercaptan, wherein the mercaptan may be a C 10 to C 30 mercaptan represented by Structure M-l, Structure N-l, Structure O-l, or Structure P-l, as previously disclosed herein, and wherein R 9 is a Ci to C 21 alkyl group, alternatively a C 2 to C 21 alkyl group, alternatively a C 3 to C 21 alkyl group, alternatively a C 5 to C 21 alkyl group, alternatively a C 7 to C 19 alkyl group, or alternatively a C 9 to C 17 alkyl group.
  • the C 20+ polysulfides can further comprise non-branched
  • the non-branched C 10 polysulfides can be represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R ⁇ S 1 and R 16 S 2 can each independently be a functional group derived from a mercaptan, wherein the mercaptan may be a Cio mercaptan represented by Structure M, Structure N, Structure O, or Structure P, as previously disclosed herein.
  • a C 20+ polysulfides composition can comprise at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% C 20+ polysulfides, based on the total weight of the C 20+ polysulfides composition; wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least 85 wt.% of the C20 + polysulfides can be C20 to Obo polysulfides represented by the general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from
  • the branched C20 to Obo polysulfides can be selected from the group consisting of a branched C20 to Obo polysulfide represented by the general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 can each independently be a branched C10 to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5 to C21 alkyl group, alternatively a C7 to C19 alkyl
  • a C20 + polysulfides composition can comprise at least about 1 wt.%, alternatively at least about 5 wt.%, alternatively at least about 10 wt.%, alternatively at least about 20 wt.%, alternatively at least about 30 wt.%, alternatively at least about 40 wt.%, alternatively at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% polysulfides, wherein at least a portion of the polysulfides can be branched C20 to Obo polysulfides represented by the general R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 are each
  • the branched C20 to Obo polysulfides can be selected from the group consisting of a branched C20 to Obo polysulfide represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 can each independently be a branched C10 to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R' ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5 to C21 alkyl group, alternatively a C7 to C19 alky
  • a C20 + polysulfides composition can comprise at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 80 wt.%, alternatively at least about 90 wt.%, alternatively at least about 95 wt.%, or alternatively at least about 99 wt.% polysulfides; wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least 85 wt.% of the polysulfides can be branched C20 to Obo polysulfides represented by the general formula R 15 S 1 -[S] n- S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 are each a branched alkyl
  • the branched C20 to Obo polysulfides can be selected from the group consisting of a branched C20 to Obo polysulfide represented by general formula R 15 S 1 -[S] n- S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 can each independently be a branched Cio to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R' ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5 to C21 alkyl group, alternatively a C7 to C19 alkyl group
  • a C20 + polysulfides composition can comprise at least about 50, 55, 60,
  • polysulfides wherein at least about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of the polysulfides can be branched C20 to C60 polysulfides represented by the general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 are each a branched alkyl group, and wherein R 15 and R 16 can each independently have from 10 to 30 carbon atoms, alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.
  • the branched C20 to Obo polysulfides can be selected from the group consisting of a branched C20 to Obo polysulfide represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 can each independently be a branched Cio to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5 to C21 alkyl group, alternatively a C7 to C19 alkyl group
  • a C20 + poly sulfides composition can comprise from at least about 50 wt.% to at least about 90 wt.%, alternatively from at least about 55 wt.% to at least about 85 wt.%, or alternatively from at least about 60 wt.% to at least about 80 wt.% polysulfides, wherein at least about 50 wt.%, alternatively at least about 60 wt.%, alternatively at least about 70 wt.%, alternatively at least about 75 wt.%, alternatively at least about 80 wt.%, or alternatively at least about 85 wt.% of the polysulfides can be branched C20 to C60 polysulfides represented by the general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 are each a branched alkyl group, and wherein R 15 and R 16 can
  • the branched C20 to C60 polysulfides can be selected from the group consisting of a branched C20 to Obo polysulfide represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 can each independently be a branched Cio to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5 to C21 alkyl group, alternatively a C7 to C 19 alkyl group
  • a C20 + polysulfides composition can consist of, or consist essentially of, branched C20 to Obo polysulfides represented by the general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 are each a branched alkyl group, and wherein R 15 and R 16 can each independently have from 10 to 30 carbon atoms, alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.
  • the branched C20 to Obo polysulfides can be selected from the group consisting of a branched C20 to C MI polysulfide represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 can each independently be a branched Cio to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5 to C21 alkyl group, alternatively a C7 to C19 alkyl group
  • a C20 + polysulfides composition can comprise at least about 1, 5, 10,
  • R 15 S 1 -[S] n -S 2 R 16 wherein n is an integer from 1 to 10, wherein R 15 and R 16 are each a branched alkyl group, and wherein R 15 and R 16 can each independently have from 10 to 30 carbon atoms, alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.
  • the branched C20 to C60 polysulfides can be selected from the group consisting of a branched C20 to C60 polysulfide represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 can each independently be a branched Cio to C30 alkyl group represented by Structure K30- A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5 to C21 alkyl group, alternatively a C7 to C19 alkyl group
  • a C20 + polysulfides composition can comprise polysulfides, wherein at least about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of the polysulfides are branched C20 to Cgo polysulfides represented by the general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 are each a branched alkyl group, and wherein R 15 and R 16 can each independently have from 10 to 30 carbon atoms, alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.
  • the branched C20 to Obo polysulfides can be selected from the group consisting of a branched C20 to Obo polysulfide represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 can each independently be a branched C10 to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alkyl group, alternatively a C5 to C21 alkyl group, alternatively a C7 to C19 alkyl group
  • a C 20+ monosulfides composition can comprise monosulfides, wherein at least a portion of the monosulfides comprise C 20+ monosulfides, and wherein at least a portion of the C 20+ monosulfides comprise branched C 20 to Obo monosulfides.
  • monosulfide as used herein refers to a thioether that is characterized by the general formula R 17 -S-R 18 , wherein R 17 and R 18 are alkyl groups.
  • the term monosulfide is used herein in place of the term sulfide, which is a common name for a thioether, to distinguish a sulfide comprising a single sulfur atom (i.e., monosulfide), from a sulfide comprising more than one sulfur atom (i.e., polysulfide).
  • the C 20+ monosulfides composition of the present disclosure is comparable to a C 20+ sulfides composition previously disclosed herein that is produced by reacting, in a reactor, a sulfur source (e.g., TbS) and a feedstock comprising one or more branched C 10+ monoolefms in the presence of an initiating agent.
  • the components of the C 20+ monosulfides composition of the present disclosure are identical to the components of the C 20+ sulfides composition previously disclosed herein, (e.g., the sulfides, the C 20+ sulfides and the branched C 20 to Obo sulfides, respectively).
  • the C 20+ monosulfides composition is thoroughly described as the C 20+ sulfides composition that is produced by reacting, in a reactor, a sulfur source (e.g., TbS) and a feedstock comprising one or more branched C 10+ monoolefms in the presence of an initiating agent as previously disclosed herein.
  • a sulfur source e.g., TbS
  • a feedstock comprising one or more branched C 10+ monoolefms in the presence of an initiating agent as previously disclosed herein.
  • an initiating agent as previously disclosed herein.
  • a C 20+ polysulfides/C 2 o + monosulfide composition i.e., a C 20+ metasulfides composition
  • a composition comprising (i) polysulfides, wherein at least a portion of the polysulfides are branched C 20 to Obo polysulfides, and (ii) monosulfides, wherein at least a portion of the monosulfides are branched C 20 to Obo monosulfides, can also be referred to as a “branched C 20+ polysulfides/branched C 20+ monosulfides composition.”
  • the C 20+ polysulfides /C 20+ monosulfides composition can comprise any suitable amount of branched Cio to C 30 polysulfides and any suitable amount of branched C 20 to Obo monosulfides.
  • a C20 + poly sulfide S/C20 + monosulfides composition can comprise (A) at least about
  • R 15 and R 16 can each independently be a branched C10 to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and R 17 and R 18 can each independently be a branched C10 to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an attachment point with a sulfur atom of the branched C20 to C60 monosulfide, wherein R 9 is a Ci to C21 alkyl group, alternatively a C2 to C21 alkyl group, alternatively a C3 to C21 alky
  • a C 20+ polysulfides/C 2 o+ monosulfides composition can comprise C 20 to C60 polysulfides represented by the general formula R 15 S 1 -[S] n -S 2 R 16 , and/or C 20 to C 60 monosulfides represented by the general formula R 17 -S-R 18 that are formed by reacting a mercaptan feedstock comprising mercaptans with a sulfur-containing material (e.g., elemental sulfur), as described in more detail herein, wherein the mercaptans present in the mercaptan feedstock provide the alkyl group represented by R 15 , R 16 , R 17 , and R 18 .
  • a sulfur-containing material e.g., elemental sulfur
  • the R 15 and R 16 groups of the C 20 to C 60 polysulfides and/or the R 17 and R 18 groups of the C 20 to C 60 monosulfides are provided by or derived from the counterpart R 15 , R 16 , R 17 , and R 18 groups present in the mercaptans in the mercaptan feedstock.
  • R 15 , R 16 , R 17 , and R 18 can each independently be an alkyl group, wherein at least a portion of the alkyl groups can comprise a functional group derived from a mercaptan, wherein the mercaptan is present in a feedstock as disclosed herein (e.g., a first Cio to C 30 mercaptans feedstock; a second C 10 to C 30 mercaptans feedstock).
  • a process of reacting branched mercaptans to produce polysulfides as disclosed herein can advantageously be more facile than an otherwise similar process comprising tertiary mercaptans.
  • tert- butyl polysulfide and / -dodecyl polysulfide are produced from the tertiary mercaptans tert- butyl mercaptan and / -dodecyl mercaptan, respectively, by a process similar to the one disclosed herein.
  • Steric bulk proximal to the sulfur atom of the tertiary mercaptans decreases the reaction rate of the tertiary mercaptans.
  • the majority of the branched mercaptans disclosed herein are primary branched mercaptans that have minimal steric bulk proximal to the sulfur atom.
  • the branched mercaptans therefore display much greater reactivity in the reaction with a sulfur-containing material (e.g., elemental sulfur), when compared to tertiary mercaptans.
  • a sulfur-containing material e.g., elemental sulfur
  • Hydrogen sulfide (H2S) and a feedstock comprising branched C10 monoolefms were reacted in the presence of various initiating agents: UV radiation, an acid catalyst, and a hydrodesulfurization (HDS) catalyst.
  • various initiating agents UV radiation, an acid catalyst, and a hydrodesulfurization (HDS) catalyst.
  • feedstocks e.g., olefin feedstocks
  • olefin feedstocks obtained from 1 -hexene production processes were used as feedstocks for reacting with 3 ⁇ 4S to produce mercaptans.
  • Gas chromatography (GC) - mass spectrometry (MS) (GC-MS) and nuclear magnetic resonance (NMR) spectroscopy were used for analyzing the composition of olefin feedstocks obtained from 1 -hexene production processes.
  • compositions comprising Cio monoolefms i.e., the feedstocks obtained from a l-hexene production process, were analyzed by gas chromatography -mass spectrometry (GC-MS) using a 15 m x 0.25 mm x 0.5 pm DB-5 column and/or a 40 m x 0.1 mm x 0.1 pm DB-l column to determine component identities, and standard gas chromatography (GC) using a 60 m x 0.32 mm x 1 pm DB-l column to determine the quantity of the components present in the compositions. As described previously, these compositions are measured in area %, which is substantially similar and analogous to wt.%.
  • Table 1 provides representative information about the composition of such an olefin feedstock obtained from l-hexene production processes to react with 3 ⁇ 4S to produce mercaptans - Samples #1-4 in Example 1.
  • Table 1 provides representative information about the composition of such an olefin feedstock obtained from l-hexene production processes to react with 3 ⁇ 4S to produce mercaptans - Samples #1-4 in Example 1.
  • the olefin feedstock was produced from the trimerization of ethylene in a l-hexene production process.
  • the total product content of this particular olefin feedstock sample (excluding the compounds that are not products of the l-hexene process) is 94.44 area %, and 84.16 area % of the feedstock is C io olefin isomers.
  • the C io olefins represent over 89 area % of the total olefin content when the sample is normalized to remove the compounds that are not products of the l-hexene process.
  • Cyclohexane, ethylbenzene, and 2- ethylhexanol can be present in the olefin feedstock as residual components of the l-hexene oligomerization process.
  • the structures of C 10 isomers that can be present in the olefin feedstock are shown in Table 2. Table 2
  • the first column provides the name of the isomer, the GC area % of that component in the feedstock from Table 1, and the normalized amount of the isomer typically found in the Cio fraction of the feedstock.
  • Table 2 also displays the structure of the mercaptans that are produced from the Cio olefin isomers.
  • the second column shows the structure of the major Cio olefin isomers in the feedstock;
  • the third column displays the structure of the major mercaptan isomers produced by a UV-initiated reaction with H2 S;
  • the fourth column displays the structure of the major mercaptan isomers produced by acid catalysis, such as Filtrol ® 24 or Filtrol ® 24X.
  • a sample of the olefin feedstock was fractionated (e.g., distilled) and only the Cio fraction was isolated in high purity (e.g., a purified feedstock).
  • This product was submitted for H 1 and C 13 NMR.
  • the NMR analysis (in mol %) was consistent the GC-MS results.
  • the NMR confirmed that about 11 mol % of the total purified feedstock was vinylidene (2 butyl- 1 -hexene isomer) and about 11 mol % of the total purified feedstock was internal olefins (linear decene isomers).
  • the nomenclature for the various Cio isomer products is shown in
  • Reaction of 3 ⁇ 4S with the olefin feedstock e.g., a feedstock comprising branched Cio monoolefins
  • UV-initiation e.g., using UV radiation
  • primary mercaptans since the terminal olefin and vinylidene isomers yield predominately the anti-Markovnikov product.
  • the minor components were secondary mercaptans from the terminal olefin and a tertiary mercaptan from the vinylidene isomer.
  • UV-initiation of a terminal olefin produced primary mercaptans in 92-96 area% range and secondary mercaptans in 4-8 area% range.
  • the linear internal olefin isomers present in the feedstock primarily produced secondary mercaptan isomers.
  • the distribution of mercaptans i.e., the distribution within the Cio fraction
  • Secondary mercaptans were present at 10-20 area%
  • tertiary mercaptans were present at about 0-3 area%.
  • the major mercaptan isomers comprised secondary mercaptans with some tertiary mercaptans.
  • the relative ratio of mercaptans was estimated at 85-90 area% secondary mercaptans and 10-15 area% tertiary mercaptans.
  • composition of the resultant crude product will ultimately depend on a number of factors including composition of the feedstock; the ratio of 3 ⁇ 4S to olefin that is used to produce the thiols; the catalytic method and reaction conditions used to react the 3 ⁇ 4S and olefin (UV-initiated, acid catalysis, or HDS catalysis) to produce the crude product; etc.
  • the final product (e.g., any cuts separated from the crude to form, for example, a commercial product) will also depend on the purification step to remove lights and whether a final product containing both mercaptan and sulfide fractions is desired or just one of the fractions, e.g., a mercaptan fraction or a sulfide fraction, is desired.
  • H 3 ⁇ 4 S to Olefin Molar Ratio The 3 ⁇ 4S to olefin molar ratio can be an important parameter in determining the amount of mercaptan and sulfide produced during the reaction step. This can be true regardless of the catalytic method employed. Without wishing to be limited by theory and in general, the higher the 3 ⁇ 4S to olefin molar ratio, the greater the amount of mercaptans that will be produced compared to the amount of sulfides produced.
  • Cio olefin fraction e.g., a second feedstock as disclosed herein
  • a sulfide fraction can be produced by further reaction of a mercaptan isomer with an olefin.
  • the total number of carbon atoms of the two portions of the sulfide can also have different values for R+R’+R”, although the most dominant combination will be where both sides each have a total sum of 8 carbon atoms since the Cio fraction predominates in the first feedstock and in the second feedstock.
  • H3 ⁇ 4S Removal In laboratory experimentation, 3 ⁇ 4S was removed using a rotovapor apparatus under conditions of reduced pressure. Under these conditions, 3 ⁇ 4S was removed without removing significant quantities of light compounds.
  • Analytical Methods The weight percentage of thiol sulfur (wt.% SH) was determined analytically by titration using iodine in water as the titrant and methylene chloride/isopropanol as the solvent system. Such titration can also be done by using a silver nitrate titration method. Total sulfur was measured by X-ray using a model SLFA-20 Horiba sulfur-in-oil analyzer.
  • Olefin conversion was monitored using Raman spectroscopy with a Kaiser Optical System RXN2 4-channel spectrometer. The peak centered at 1640 cm 1 was the vinyl olefin, while the peak centered at about 1670 cm 1 was the internal olefin.
  • UV-initiation reactions were performed using either a 1.5 L or a 5-liter UV reactor equipped with a 100 watt lamp and ballast.
  • the two reactors are substantially the same configuration, and the only difference in operation is the amount of reactants added to the reactor.
  • the reaction mixture was stirred at 500-1,000 RPM.
  • the reaction temperature was controlled with a bath set at 25 °C, but the heat of reaction did reach about 40 °C.
  • the lamp operated at 1.1 -1.5 amps and 28-103 volts over the course of the reaction, operating at lower amps and higher voltage as it warmed up.
  • the reaction pressure was 220-280 psig (1,516 kPag-l,930 kPag) during the actual reaction time.
  • the reaction was completed in about 30 minutes based on the results of Raman spectroscopy but was allowed to continue for 60 minutes to ensure completion.
  • Table 4 shows the results of four reactions by UV-initiation, wherein the reactions produced Samples #1, #2, #3, and #4.
  • TEP triethyl phosphite
  • TBP tributyl phosphite
  • Samples #1-4 were prepared using samples of an olefin feedstock composition comparable to that shown in Table 1.
  • Samples #la, #2a, #3a, and #4a were prepared by distilling the crude reaction product, Samples #1, #2, #3, and #4, respectively.
  • the distillation process proceeded as follows: The first 7 fractions removed from the crude reaction product were considered to be the light fractions. This distillation step was considered to be complete when the kettle temperature increased from 100 °C to 121 °C and the head temperature increased from room temperature to 98.9 °C. Cuts 8-13 were considered to be the intermediate fractions and included the Cio mercaptans.
  • Cuts 14 and 15 were collected at kettle and head temperatures of from 122 °C to 154 °C and 103.4 °C to 107.2 °C, respectively. These cuts and whatever remained in the kettle were considered the heavies.
  • the head temperature was allowed to increase from room temperature to 107.2 °C before the distillation was stopped. For a typical distillation, only the light fractions were distilled (e.g., removed) and the reaction product was what remained (e.g., including Cio mercaptans and C20 sulfides) in the kettle after the lights were removed.
  • the relative amount of Cio mercaptan isomers, intermediate mercaptans (e.g., non-Cio mercaptans such as C12 to Ci 6 mercaptans) and sulfide heavies (e.g., C20 sulfides) depended on the ratio of EfiS to olefin during the reaction step.
  • Sample #1 was prepared at a 1: 1 ratio of EfiS per olefin to maximize the amount of sulfide content.
  • Conventional wisdom would suggest that the Cio mercaptan fraction would have too strong of an odor to be acceptable for certain applications, and that the sulfide fraction might have a better odor.
  • the odor of this crude reaction product was good.
  • Figure 2 displays a GC trace of reactor crude Sample # 1 (after removal of residual FfiS).
  • the intermediate cut (peaks at 6.5-14 minutes) included mercaptans produced from the C12 to Ci 6 olefins present in the olefin feedstock stream and accounted for 5.7 area % of this particular sample.
  • the heavies cut (peaks at >14 minute retention time) included the sulfides, primarily C10H21-S-C10H21 isomers plus higher sulfides from combinations with other olefins in the mixed feed. It is believed that any Cis mercaptans that may have been produced eluted with the sulfide peaks.
  • the amount of Cis that could be present was estimated at about 0.2 area %.
  • the sulfide fraction accounted for about 37.2 area% of the product composition.
  • the amount of the intermediate fraction was primarily dependent on the amount of C 14 olefin isomers that were present in the olefin feed stream. Analysis of several samples showed that this intermediate fraction ranged from 4-10 area %.
  • Figure 4 displays a GC trace of reactor crude Sample #3, after removal of residual FfiS.
  • FIG. 5 displays a GC trace of kettle product Sample #3a, after removal of lights.
  • Figures 4 and 5 compare GC results of product produced at a 10: 1 FfiS to olefin molar ratio. The observed trends are similar to the trends seen in Figures 2 and 3, and the primary difference is in the ratio of Cio mercaptan isomers to the sulfide fraction. This difference is the result of increasing the ratio of FfiS to olefin feedstock used in the reaction.
  • the type and relative amounts of the isomers in the Cio mercaptan fraction are essentially unchanged, and the compositions of the sulfide heavies fractions are similar.
  • the mam difference between Sample 3 and Sample 1 a is the relative amounts of Cio mercaptan isomers, intermediate mercaptans, and sulfides.
  • the resulting reaction product contained a greater amount of Cio mercaptan isomers (84.1 area % vs. 56.8 area %) and much less sulfide (10.1 area % vs. 37.2 area%).
  • the removal of lights was done using a simple lab distillation unit, wherein the distillation column was 12” long and 1” in diameter and was packed with a stainless steel sponge.
  • the composition of the UV-produced product can be described in broad terms as follows: a feedstock was reacted with EES; removal of EES after the reaction yielded a crude reaction product. Subsequent removal of the lights fraction to yields a kettle product, which can be used“as is” (e.g., a composition comprising both mercaptans and sulfides) or can be further separated into one or more products or cuts corresponding to a desired compound or combination of compounds (e.g., a Cio mercaptan fraction, an intermediate mercaptan fraction, and/or a heavy /sulfide fraction).
  • the product consists of three general fractions as produced from the kettle product after removal of the unwanted lights fraction.
  • the Cio mercaptan fraction comprised from 50-100 wt.% of the kettle product.
  • the mercaptan functionality of the Cio mercaptan fraction was 80-90% primary mercaptan, 5-18% secondary mercaptan and 0-3% tertiary mercaptan. This was the fraction that eluted in the 3.8-6.5 minute range under the GC conditions used.
  • the intermediate fraction which eluted in the 6.5-14 minute region, was predominately mercaptan isomers in the C 12 to Cis range with a distribution of functionality that can be similar to that for the Cio isomer fraction.
  • the intermediate fraction comprised from 0 to 12 area% of the kettle product.
  • the heavy fraction (> 14 minute retention time) consisted essentially of sulfides, primarily of formula C 10H21-S-C 10H21 isomers, as well as sulfides from C 12, C 14, Ci 6 or Cis olefins and mercaptans or the asymmetric sulfides produced from the various combinations.
  • These sulfide components comprised from 0-70 area% of the kettle product, depending on the reaction conditions used.
  • Acid Catalysis produced a different distribution of isomer products than those produced by
  • the product produced via the acid catalyzed addition of EES to the feedstock comprising branched Cio monoolefins was prepared in a continuous flow reactor over Filtrol ® 24 acid catalyst.
  • the reactor contained 43.22 g of catalyst and the WHSV (weight hourly space velocity) was maintained at 1.0 grams of olefin per gram of catalyst per hour.
  • the EES to olefin molar ratio ranged from 10: 1 to 1: 1.
  • the reaction temperature was between 120 °C to 220 °C, and the reactor pressure was 450-460 psig (3,100 kPag-3,200 kPag).
  • Acid catalysis produced the Markovnikov product.
  • the vinyl components of the feedstock comprising branched Cio monoolefms produced secondary mercaptans.
  • the internal olefin components produced secondary mercaptans, while the vinylidene components produced tertiary mercaptans.
  • the composition of the Cio mercaptan fraction isomers was different when compared to the composition of the product obtained by UV-initiation.
  • the 5 -methyl- l-nonene isomer produced 5-methyl-2- mercapto-nonane by acid catalysis; and 5-methyl- l-mercapto-nonane was the major product produced by UV- initiation, with a minor amount of the 2-mercapto isomer as a by-product.
  • the 2-butyl- 1 -hexene isomer produced 5 -methyl-5 -mercapto-nonane by acid catalysis; while UV-initiation produced 2- butyl- l-mercapto- hexane.
  • Comparative GC traces of the product produced by acid catalysis and that produced by UV-initiation are shown in Figure 6 and Figure 7.
  • Figure 6 shows a comparison of crude product (e.g., only FFS removed) by UV-initiation and acid catalysis routes
  • Figure 7 compares the Cio mercaptan fraction produced by the UV-initiation and acid catalysis routes.
  • the product obtained by acid catalysis consisted of three general fractions as produced as a kettle product after removal of the unwanted lights fraction.
  • the Cio mercaptan fraction comprised from 50-100 area % of the crude kettle composition.
  • the mercaptan functionality of the Cio fraction was 85-95 area % secondary mercaptan and the remainder tertiary mercaptan. These isomers eluted in the 3.1-6.5 minute range under the utilized GC conditions.
  • the intermediate fraction consisted of those mercaptan peaks in the 6.5-14 minute range. However, the functionality of the mercaptans was secondary and tertiary C12 to Cis mercaptans.
  • the intermediate fraction comprised 5-15 area % of the total kettle composition.
  • the sulfide fraction comprised 0-70 area % of the composition of the kettle product, depending on the specific reaction conditions.
  • the fraction consisted of sulfides primarily of formula C10H21-S-C10H21. However, the isomer identity was different than that for the product produced by UV-initiation.
  • the acid produced sulfide product was based on secondary and tertiary mercaptans rather than predominately primary mercaptans as in the UV-initiated produced product.
  • HDS Catalysis produced mercaptans that were primarily similar in distribution to those produced by acid catalysis, which is the Markovnikov distribution. However, there was a tendency to also produce some of the anti -Markovnikov distribution depending on the specific conditions utilized in the reaction step. Thus the product produced by the HDS catalyst appeared to be a blend of product produced primarily via acid catalysis with some of the components of the UV-initiated reaction.
  • the HDS reaction conditions were as follows: WHSV was varied from 0.75 to 2 grams of olefin per gram of catalyst per hour; the molar ratio of 3 ⁇ 4S per olefin was varied from 2: 1 to 10: 1; the average reaction temperature was 180 °C to 220 °C.
  • the catalyst used was cobalt molybdenum on alumina, examples being to Haldor Topsoe TK-554, TK-570, or similar. Olefin conversion, as determined by Raman spectroscopy, was in the 88-97 mol% range.
  • the HDS test runs were performed using the feedstock comprising branched Cio monoolefins comparable to the composition as outlined in Table 1 are shown in Table 6 and Table 7.
  • FIG. 8 A typical GC trace of reactor crude produced from the HDS catalyzed reaction of 3 ⁇ 4S and branched C10 monoolefins is shown in Figure 8. Comparison of the Cio fraction (3.5 to 6 minute retention time) of the HDS reaction product, as shown in Figure 8, with the same reaction product for both the acid catalyzed and UV-initiated processes as shown in Figure 6 or Figure 7, shows that the HDS product was a blend of the acid catalyzed and UV-initiated products.
  • Cio mercaptans can minimize the loss of Cio mercaptans by controlling operating parameters including the number of distillation columns used, the number of theoretical trays in the column(s), the rate of reflux and take-off, and whether the distillation is done in continuous or batch mode. These parameters can readily be determined with research, allowing one of reasonable skill in the art to scale up and optimize the distillation process. It is within the scope of this disclosure that operating a continuous mode distillation system using two columns can provide satisfactory separation. For example, operating a the first column at an overhead temperature of 80 °C to 85 °C at 9 torr and a second column at about 95 °C-97 °C would provide a satisfactory separation.
  • the distillation column used in the lab was 1” x 12” packed with stainless steel sponge. As stated earlier, it is believed that the separation was not as good as desired, and significant Cio mercaptan was removed overhead, even with the initial cut.
  • a distillation run at 9 torr and a reflux to take-off ratio of 18:3 required the removal of 12.5 area % of the crude overhead to reach a level of ⁇ 0.1 area % lights in the kettle product. According to the GC analysis of the crude, only 8.1 area % of the crude product was lights that needed to be removed overhead.
  • the kettle temperature was in the 100 °C-l 15 °C range at 9 torr. In another distillation batch, 8.8 area % of the crude was taken overhead, while the lights composed only 4.0 area % of the crude. In several other batches, nearly 20 area % of the crude was lost overhead.
  • the nearest boiling point impurities are the ethylbenzene, 2- ethylhexanol and n-octylmercaptan.
  • the amount of these impurities that are present will determine how many theoretical trays are be needed, as well as the best pressure and temperature profile to optimize yield and keep the level of the n-octylmercaptan to as low a value as feasible.
  • a feedstock comprising branched Cio monoolefins produced in a l-hexene process can be purified (e.g., distilled), for improved olefin reactivity and resulting mercaptan purity.
  • the lights up to l-octene can be removed and the Cio olefin isomers taken overhead to high purity (>98%).
  • This high purity Cio monoolefin cut would then be free of the C12 to Cis olefins.
  • the high purity C10 olefin can then be reacted with EES to produce the mercaptan products.
  • the reaction conditions would be identical for the high purity Cio olefin stream (e.g., second feedstock) as already indicated for the feedstock comprising branched Cio monoolefins produced in a 1 -hexene process used as received (e.g., first feedstock).
  • the major difference will be in the composition of the crude stream and product stream.
  • the crude product would consist of any residual EES and unreacted Cio olefin, the Cio mercaptan isomers and the C10H21-S-C10H21 fraction.
  • the product will contain the Cio mercaptan isomers and the C2o-sulfide, but will not contain any of the intermediate mercaptans and asymmetric sulfide components, which come from reaction of Cio mercaptan with the other non-Cio olefins.
  • the mercaptan functionality for the various routes will be the same as already indicated.
  • UV-initiation reactions of NEODENE 1112 IO higher olefins were performed in a 1.5 L UV reactor equipped with a 100 watt lamp and ballast.
  • 650 g of EES was charged after sealing the reactor.
  • the reaction mixture was stirred at 500-1,000 RPM.
  • the reaction temperature was controlled with a bath set at 25 °C, but the heat of reaction did reach about 40 °C.
  • the lamp operated at 1.0-1.7 amps and 25-112 volts over the course of the reaction, operating at lower amps and higher voltages as it warmed up.
  • the reaction pressure varied from 315-350 psig (2, 172 kPag-2,4l3 kPag) during the actual reaction time.
  • the reaction was typically completed in approximately 30 minutes as monitored by RAMAN spectroscopy analysis but was allowed to continue for 90 min to ensure completion.
  • the EES was vented and the reaction mixture was purged three times with nitrogen to remove excess EES to the extent possible. Additional EES removal was conducted using a rotary evaporator.
  • the conversion was measured as 98% by gas chromatography (GC) with the constituent components determined to be 41 wt.% Cn mercaptan, 41 wt.% C 12 mercaptan, ⁇ 4 wt.% sulfides and 14 wt.% unreacted olefin.
  • GC gas chromatography
  • UV-initiation reactions of NEODENE 1314 IO higher olefins were performed in a 1.5 L UV reactor equipped with a 100 watt lamp and ballast.
  • the UV prepared sample was prepared in the 1.5L UV reactor equipped with a 100 watt lamp and ballast.
  • 650 g of EES was charged after sealing the reactor.
  • the reaction mixture was stirred at 500-1,000 RPM.
  • the reaction temperature was controlled with a bath set at 25 °C, but the heat of reaction did reach about 40 °C.
  • the lamp operated at 1.0-1.5 amps and 25-110 volts over the course of the reaction, operating at lower amps and higher voltages as it warmed up.
  • the reaction pressure varied from 305-340 psig (2,103 kPag-2,344 kPag) during the actual reaction time.
  • the reaction was typically completed in approximately 30 minutes as monitored by RAMAN spectroscopy analysis but was allowed to continue for 70 min to ensure completion.
  • the 3 ⁇ 4S was vented and the reaction mixture purged three times with nitrogen to remove excess ThS to the extent possible. Additional ThS removal was conducted using a rotary evaporator.
  • the conversion was measured as 79% by GC with the constituent components determined to be 38 wt.% C13 mercaptan, 39.4 wt.% C14 mercaptan, ⁇ 2 wt.% sulfides and 21 wt.% unreacted olefin.
  • UV-initiation reactions of NEODENE 14/16 higher olefins were performed in a 1.5 L UV reactor equipped with a 100 watt lamp and ballast.
  • 650 g of ThS was charged after sealing the reactor.
  • the reaction mixture was stirred at 500-1,000 RPM.
  • the reaction temperature was controlled with a bath set at 25 °C, but the heat of reaction did reach about 40 °C.
  • the lamp operated at 1.0-1.6 amps and 25-120 volts over the course of the reaction, operating at lower amps and higher voltages as it warmed up.
  • the reaction pressure varied from 310-340 psig (2, 137 kPag-2,344 kPag) during the actual reaction time.
  • the reaction was typically completed in approximately 30 minutes as monitored by RAMAN analysis but was allowed to continue for 55 min to ensure completion.
  • the ThS was vented and the reaction mixture purged three times with nitrogen to remove excess ThS to the extent possible. Additional ThS removal was conducted using a rotary evaporator.
  • the conversion was measured as 93% by GC with the constituent components determined to be 57.4 wt.% C14 mercaptan, 30.1 wt.% Ci 6 mercaptan, -6 wt.% sulfides and 7 wt.% unreacted olefin.
  • Mercaptan sulfur was determined using titration as well and determined to be 12 wt.% vs. a GC calculation of 11.6 wt.%. Total sulfur was determined by X-ray to be 12.9 wt.% versus a GC calculation of -12.5 wt.%.
  • a 2 L Resin flask was equipped with an overhead stirrer, a heating mantle controlled by an internal thermocouple, a condenser, and a N2 sparge.
  • a quantity of 125.25 grams of branched Cio mercaptans was added to the reaction flask followed by 0.08 grams of Tergitol ® 15-S-10 and 0.06 grams of aqueous sodium hydroxide solution, 50 % (w/w).
  • the mixture of components was placed under an atmosphere of N2 and heated to approximately 100 °C with continuous stirring that was maintained throughout the entire experimental procedure. To the heated mixture was added 17 grams of sulfur in several portions over approximately 30 minutes.
  • a first aspect which is a composition comprising polysulfides, wherein at least about 50 wt.% of the polysulfides are branched C20 to C60 polysulfides represented by general formula R 15 S 1 -[S] n -S 2 R 16 wherein R 15 and R 16 are each independently a branched C 10 to C30 alkyl group and wherein n is an integer from 1 to 10.
  • a second aspect which is the composition of the first aspect further comprising monosulfides represented by general formula R 17 -S-R 18 , wherein R 17 and R 18 are each independently a branched C10 to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an attachment point with a sulfur atom of the monosulfide; and R 9 is a Ci to C21 alkyl group.
  • a third aspect which is the composition of the first or second aspect wherein the branched C10 to C30 alkyl group is represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and R 9 is a Ci to C21 alkyl group.
  • a fourth aspect which is the composition of any of the first three aspects wherein the branched
  • Cio to C30 alkyl group is represented by Structure K-A, Structure K-B, Structure K-C, Structure K-D, Structure K-E, Structure K-F, Structure K-G, or Structure K-H, wherein * designates an S 1 atom of an R l 5 S 1 group or an S 2 atom of an R 16 S 2 group.
  • a fifth aspect which is a process of producing a polysulfides crude product comprising one or more branched C20 to C60 poly sulfides comprising: (A) reacting a feedstock comprising one or more branched Cio to C30 mercaptans and sulfur in the presence of a catalyst and (B) collecting the polysulfides crude product.
  • a sixth aspect which is the process of the fifth aspect wherein the one or more branched Cio to
  • C30 mercaptans are represented by Structure A-l, Structure B-l, Structure C-l, Structure D-l, Structure E-l, Structure F-l, Structure G-l, Structure H-l, or combinations thereof, wherein R 9 is a Ci to C21 alkyl group.
  • a seventh aspect which is the process of the fifth or sixth aspect wherein the one or more branched C20 to C60 polysulfides are polysulfides represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10; R 15 and R 16 are each independently a branched Cio to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group; and R 9 is a Ci to C21 alkyl group.
  • R 15 and R 16 are each independently a branched Cio to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F,
  • An eighth aspect which is the process of any of the fifth through seventh aspects wherein (A) reacting further comprises: (a) contacting the one or more branched Cio to C30 mercaptans and the catalyst to form a mixture wherein a weight ratio of catalyst to mercaptans is in a range of from about 0.005: 1 to about 0.013: 1; (b) heating the mixture to a temperature in a range of from about 60° C to about 85° C; (c) heating the mixture to a temperature in a range of from about 90° C to about 150° C; and (d) cooling the mixture to a temperature in a range of from about 65° C to about 85° C.
  • a ninth aspect which is the process of any of the fifth through eighth aspects wherein (B) collecting the crude product comprises: (e) cooling the mixture to a temperature in a range of from about 20° C to about 35° C; and (f) filtering the polysulfides crude product.
  • a tenth aspect which is the process of any of the fifth through ninth aspects wherein during step
  • An eleventh aspect which is the process of any of the fifth through tenth aspects wherein during step (c): (i) the mixture is agitated for a time period of from about 2 hours to about 4 hours; and (ii) the mixture is sparged with an inert gas for a time period of from about 0.5 hour to about 4 hours.
  • a twelfth aspect which is the process of any of the fifth through eleventh aspects wherein during step (d): (i) an epoxide is added to the mixture over atime period of from about 10 min to about 2 hours wherein an equivalent molar ratio of epoxide to mercaptans is in a range of from about 0.05: 1 to about 0.1 : 1; (ii) the mixture is agitated for a time period of from about 1 hour to about 4 hours; and (iii) the mixture is sparged with an inert gas for a time period of from about 0.5 hour to about 4 hours.
  • a thirteenth aspect which is the process of any of the fifth through twelfth aspects wherein the epoxide comprises ethylene oxide, propylene oxide, or a combination thereof.
  • a fourteenth aspect which is the process of any of the fifth through thirteenth aspects wherein the catalyst comprises: (i) a surfactant and (ii) a Group 1 or Group 2 metal hydroxide, wherein a weight ratio of (i) to (ii) is in a range of from about 25 : 1 to about 40: 1.
  • a fifteenth aspect which is the process of any of the fifth through fourteenth aspects wherein prior to contacting the catalyst with the one or more branched Cio to C30 mercaptans, (i) and (ii) are combined and heated to a temperature in a range of from about 60 °C to about 100 °C and the temperature is maintained for a time period of from about 30 min to about 2 hours.
  • a sixteenth aspect which is the process of the fourteenth or fifteenth aspects wherein the surfactant comprises a nonionic surfactant.
  • a seventeenth aspect which is the process of any of the fourteenth through sixteenth aspects wherein the surfactant comprises a polyethoxylated alcohol, a polyethoxylated mercaptan, or a combination thereof.
  • An eighteenth aspect which is the process of any of the fourteenth through seventeenth aspects wherein the Group 1 or Group 2 metal hydroxide is a solid or is dissolved in an aqueous solution.
  • a nineteenth aspect which is the process of any of the fourteenth through eighteenth aspects wherein the Group 1 or Group 2 metal hydroxide is sodium hydroxide.
  • a twentieth aspect which is the process of any of the fifth through nineteenth aspects wherein
  • (A) reacting further comprises: (a) contacting the one or more branched Cio to C30 mercaptans and the catalyst to form a mixture wherein a weight ratio of catalyst to mercaptans is in a range of from about 0.005: 1 to about 0.013: 1; (b) contacting the mixture with elemental sulfur wherein an equivalent molar ratio of sulfur to mercaptans is in a range of from about 0.07: 1 to about 1.2: 1; (c) heating the mixture to a temperature in a range of from about 60° C to about 85° C and maintaining the temperature while the mixture is agitated for a time period of from about 2 hours to about 6 hours; (d) heating the mixture to a temperature in a range of from about 90° C to about 150° C and maintaining the temperature while the mixture is agitated for a time period of from about 2 hours to about 4 hours and subsequently sparged with an inert gas for a time period of from about 0.5 hour to about 4 hours; and (e) cooling the mixture
  • a twenty-first aspect which is the process of any of the fifth through twentieth aspects wherein after cooling the mixture (d), the process further comprises: (e) adding a decolorizing agent to the mixture, wherein a weight ratio of decolorizing agent to mercaptans is in a range of from about 0.01 : 1 to about 0.02: 1; (f) heating the mixture to a temperature in a range of from about 40° C to about 60° C, and maintaining the temperature for a time period of from about 30 min to about 2 hours; (g) cooling the mixture to a temperature in a range of from about 20° C to about 35° C; and (h) collecting the polysulfides crude product.
  • a twenty-second aspect which is a process of producing one or more branched C20 to G,o polysulfides comprising: (a) reacting hydrogen sulfide (H2S) and a feedstock comprising one or more branched C10 to C30 olefins in the presence of an initiating agent to produce a branched C10 + mercaptans crude composition;(b) recovering an intermediate reaction product comprising one or more branched C10 to C30 mercaptans from the branched C10 + mercaptans crude composition; (c) reacting sulfur and the intermediate reaction product comprising one or more branched Cio to C30 mercaptans in the presence of a catalyst; and (d) collecting a C20 + polysulfides crude product comprising the one or more branched C20 to Obo polysulfides.
  • H2S hydrogen sulfide
  • a feedstock comprising one or more branched C10 to C30 olefins in the presence of
  • a twenty-third aspect which is the process of the twenty-second aspect wherein the one or more branched Cio to C30 olefins are represented by Structure 1-1, Structure J-l, Structure K-l, Structure L-l, or combinations thereof, wherein R 9 is a Ci to C21 alkyl group.
  • a twenty-fourth aspect which is the process of the twenty-second or the twenty-third aspect wherein the one or more branched Cio to C30 mercaptans are represented by Structure A-l, Structure B-l, Structure C-l, Structure D-l, Structure E-l, Structure F-l, Structure G-l, Structure H-l, or combinations thereof, wherein R 9 is a Ci to C21 alkyl group.
  • a twenty-fifth aspect which is the process of any of the twenty-second through twenty-fourth aspects wherein the one or more branched C20 to Go polysulfides are represented by general formula R ⁇ S 1 - [S] n -S 2 R 16 , wherein n is an integer from 1 to 10; and R 15 and R 16 are each independently a branched Cio to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R l 5 S 1 group or an S 2 atom of an R 16 S 2 group; and R 9 is a Ci to C21 alkyl group.
  • a twenty-sixth aspect which is the process of any of the twenty-second through twenty-fifth aspects wherein the one or more branched Cio to C30 olefins comprise 5-methyl- l-nonene (represented by Structure I), 3 -propyl- l-heptene (represented by Structure J), 4-ethyl- l-octene (represented by Structure K), 2- butyl-l -hexene (represented by Structure L), or combinations thereof:
  • a twenty-seventh aspect which is the process of any of the twenty-second through twenty-sixth aspects wherein the one or more branched Cio to C30 mercaptans comprise 5 -methyl- l-mercapto-nonane (represented by Structure A), 3 -propyl- l-mercapto-heptane (represented by Structure B), 4-ethyl- l-mercapto- octane (represented by Structure C), 2-butyl- l-mercapto-hexane (represented by Structure D), 5-methyl-2- mercapto-nonane (represented by Structure E), 3-propyl-2-mercapto-heptane (represented by Structure F), 4- ethyl-2-mercapto-octane (represented by Structure G), 5 -methyl-5 -mercapto-nonane (represented by Structure H), or combinations thereof:
  • a twenty-eighth aspect which is the process of any of the twenty-second through twenty-seventh aspects wherein the one or more branched C20 to C60 polysulfides are poly sulfides represented by general formula R 15 S 1 -[S] n- S 2 R 16 , wherein n is an integer from 1 to 10; and R 15 and R 16 are each independently a branched C10 alkyl group by Structure K-A, Structure K-B, Structure K-C, Structure K-D, Structure K-E, Structure K-F, Structure K-G, or Structure K-H, wherein * designates an S 1 atom of an R l 5 S 1 group or an S 2 atom of an R 16 S 2 group.
  • a twenty-ninth aspect which is a composition comprising: (A) at least about 25 wt.% branched
  • a thirtieth aspect which is a composition comprising: (A) from at least about 50 wt.% to at least about 90 wt.% polysulfides, wherein at least about 50 wt.% of the polysulfides are branched C20 to C60 polysulfides represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 are each independently a branched Cio to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group; and (B) from at least about 10 wt.% to at least about
  • a thirty-first aspect which is a composition comprising: (A) at least about 25 wt.% branched C20 to C60 polysulfides represented by general formula R 15 S 1 -[S] n -S 2 R 16 , wherein n is an integer from 1 to 10, wherein R 15 and R 16 are each independently a branched Cio to C30 alkyl group represented by Structure K30-A, Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein * designates an S 1 atom of an R ⁇ S 1 group or an S 2 atom of an R 16 S 2 group, and wherein R 9 is a Ci to C21 alkyl group; and (B) at least about 5 wt.% branched C20 to Obo monosulfides represented by general formula R 17 -S-R 18 , wherein R 17 and R 18 are each independently a branched Ci
  • R Ri + k ⁇ (R u - Ri), wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, . 50 percent,
  • any numerical range defined by two R numbers as defined in the above is also specifically disclosed.
  • Use of the term“optionally” with respect to any element of a claim means that the element is required, or alternatively, the element is not required, both alternatives being within the scope of the claim.
  • Use of broader terms such as comprises, includes, and having should be understood to provide support for narrower terms such as consisting of, consisting essentially of, and comprised substantially of.

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US6051739A (en) * 1999-01-26 2000-04-18 Phillips Petroleum Company Process for producing organic polysulfides
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