CROSS REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims priority to U.S. Provisional Application No. 62/748,899, filed October 22, 2018 and EP 19152177.2 filed January 16, 2019, the disclosures of which are hereby incorporated by reference in their entirety.

FIELD

[0002] This disclosure relates to processes for forming glycols. In particular, this disclosure relates to processes for making glycols by oxidative coupling of an ether using a peroxide derived from a hydrocarbon. The processes of this disclosure are useful for, e.g., making ethylene glycol and upgraded products from hydrocarbons such as light paraffins.

BACKGROUND

[0003] Monoethylene glycol (MEG, also referred to as ethylene glycol) is an important chemical raw material and monomer material for the manufacture of polyesters (which can be used to further produce polyester fibers, PET bottles, films) or glyoxal. MEG can also be used as an antifreeze, plasticizer, hydraulic fluid or solvent. Current worldwide production capacity of MEG is about 25 million metric tons annually, with a projected annual growth rate in the 4% to 5% range. Currently MEG is produced by two major technologies: 1) ethylene oxidation to ethylene oxide (EO), followed by hydrolysis of EO to MEG; or 2) a syngas route via oxidative carbonylation of methanol. In the ethylene oxidation route, about 25% of ethylene is combusted. The syngas route employs nitrogen oxides as an active oxygen carrier, which can be difficult to handle. Therefore, alternative routes using readily available starting materials to make MEG are still needed. Furthermore, there is a need for more commercially relevant processes with improved recycling feed of by-products formed during the MEG production.

[0004] In addition, increasing availability of hydrocarbons (e.g., C2-C5 paraffins) in the North American region creates many opportunities for upgrading of the hydrocarbons. There is thus a need to have a process for upgrading these abundant hydrocarbons to higher value molecules. SUMMARY

[0005] This disclosure provides processes for forming glycols by oxidative coupling of an ether using a peroxide, while upgrading hydrocarbons to more valuable products.

[0006] In one embodiment, a process for forming a glycol includes introducing a first ether to a dihydrocarbyl peroxide to form a diether and a first alcohol. The process includes introducing the diether to water to form a glycol and a second alcohol.

[0007] In another embodiment, a process for forming a glycol includes introducing a first ether to a dihydrocarbyl peroxide to form a diether and a first alcohol. The process includes introducing the diether to water to form a glycol and a second alcohol. The Processes includes introducing a hydrocarbyl hydroperoxide to a third alcohol to form the dihydrocarbyl peroxide.

[0008] In another embodiment, a process for forming a glycol includes introducing a first ether to a dihydrocarbyl peroxide to form a diether and a first alcohol. The Processes includes introducing the diether to water to form a glycol and a second alcohol. The Processes includes oxidizing a first feed stream comprising a branched hydrocarbon to form a hydrocarbyl hydroperoxide and the first alcohol.

[0009] In another embodiment, a process for forming a glycol includes introducing a first ether to a dihydrocarbyl peroxide to form a diether and a first alcohol. The process includes introducing the diether to water to form a glycol and a second alcohol. The process includes introducing the second alcohol to a catalyst to form a second ether.

[0010] In one specific embodiment, this disclosure provides a process for making ethylene glycol, the process comprising (I) contacting dimethyl ether with a dihydrocarbyl peroxide to obtain dimethoxy ethane and a first alcohol; and (II) reacting the dimethoxy ethane with water to obtain ethylene glycol and methanol.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] FIG. 1 is a schematic diagram showing an exemplary process for producing glycols by oxidative coupling of an ether while upgrading branched hydrocarbons, according to one embodiment.

[0012] FIG. 2 is a schematic diagram showing an exemplary process for producing ethylene glycol by oxidative coupling of dimethyl ether while upgrading isobutane, according to one embodiment. DETAILED DESCRIPTION

[0013] In this disclosure, a process is described as comprising at least one“step.” It should be understood that each step is an action or operation that may be carried out once or multiple times in the process, in a continuous or discontinuous fashion. Unless specified to the contrary or the context clearly indicates otherwise, multiple steps in a process may be conducted sequentially in the order as they are listed, with or without overlapping with one or more other step, or in any other order, as the case may be. In addition, one or more or even all steps may be conducted simultaneously with regard to the same or different batch of material. For example, in a continuous process, while a first step in a process is being conducted with respect to a raw material just fed into the beginning of the process, a second step may be carried out simultaneously with respect to an intermediate material resulting from treating the raw materials fed into the process at an earlier time in the first step. Preferably, the steps are conducted in the order described.

[0014] Unless otherwise indicated, all numbers indicating quantities in this disclosure are to be understood as being modified by the term“about” in all instances. It should also be understood that the numerical values used in the specification and claims constitute specific embodiments. Efforts have been made to ensure the accuracy of the data in the examples. However, it should be understood that any measured data inherently contain a certain level of error due to the limitation of the technique and equipment used for making the measurement.

[0015] As used herein, the indefinite article“a” or“an” shall mean“at least one” unless specified to the contrary or the context clearly indicates otherwise. Thus, embodiments using“an ether” include embodiments where one, two or more ethers are used, unless specified to the contrary or the context clearly indicates that only one ether is used.

[0016] For the purposes of this disclosure, the nomenclature of elements is pursuant to the version of Periodic Table of Elements as described in CHEMICAL AND ENGINEERING NEWS, 63(5), pg. 27 (1985).

[0017] The following abbreviations may be used herein for the sake of brevity: i- C4 is iso-butane, TBHP is /c/7 -butyl hydroperoxide, TBA is icri-butanol or icri-BuOH, DTBP is di-/c/7-butyl peroxide, RT is room temperature (and is 23°C unless otherwise indicated), DME is dimethyl ether, MEG is monoethylene glycol (also referred to as ethylene glycol, i.e., ethane- l,2-diol), kPag is kilopascal gauge, psig is pound-force per square inch gauge, psia is pounds per square inch absolute, WHSV is weight hourly space velocity, GC is Gas Chromatography. Abbreviations for atoms are as given in the periodic table (Li = lithium, for example).

[0018] An“olefin,” alternatively referred to as“alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one carbon-carbon double bond.

[0019] For purposes of this disclosure and claims thereto, the term“substituted” means that a hydrogen atom in the compound or group in question has been replaced with a group or atom other than hydrogen. The replacing group or atom is called a substituent. Substituents can be, e.g., a substituted or unsubstituted hydrocarbyl group, a heteroatom, a heteroatom-containing group, and the like. For example, a“substituted hydrocarbyl” is a group derived from a hydrocarbyl group made of carbon and hydrogen by substituting at least one hydrogen in the hydrocarbyl group with a non hydrogen atom or group. A heteroatom can be nitrogen, sulfur, oxygen, halogen, etc.

[0020] The terms“hydrocarbyl,”“hydrocarbyl group,” or“hydrocarbyl radical” interchangeably mean a group consisting of carbon and hydrogen atoms. For purposes of this disclosure, "hydrocarbyl radical" is defined to be C1-C100 radicals, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.

[0021] The term“branched hydrocarbon” means a hydrocarbon comprising at least 4 carbon atoms and at least one carbon atom connecting to three carbon atoms.

[0022] The terms "alkyl,” "alkyl group,” and "alkyl radical" interchangeably mean a saturated monovalent hydrocarbyl group. A“cyclic alkyl” is an alkyl comprising at least one cyclic carbon chain. An“acyclic alkyl’ is an alkyl free of any cyclic carbon chain therein. A“linear alkyl” is an acyclic alkyl having a single unsubstituted straight carbon chain. A“branched alkyl” is an acyclic alkyl comprising at least two carbon chains and at least one carbon atom connecting to three carbon atoms. Examples of alkyl groups can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, .vec-butyl, ieri-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like including their substituted analogues.

[0023] The terms “alkylene” and “alkylene group” interchangeably means a saturated divalent hydrocarbyl group. A“linear alkylene group” means an alkylene group comprising a single straight carbon chain. A“branched alkylene group” means an alkylene group comprising at least two straight carbon chains therein at least one carbon atom connecting to three carbon atoms. Thus, -CH2CH2- is a linear alkylene, while -CH2CH(CH3)CH2- is a branched alkylene.

[0024] The term "alkenyl" means a straight-chain, branched-chain, or cyclic hydrocarbyl group having one or more carbon-carbon double bonds therein. These alkenyl radicals may be optionally substituted. Examples of suitable alkenyl radicals can include ethenyl, propenyl, allyl, l,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl, and the like, including their substituted analogues.

[0025] The term“alkoxy” or“alkoxy group” means a group having a structure R- O-, wherein R is an alkyl.

[0026] The term“Cn” compound or group, wherein n is a positive integer, means a compound or a group comprising carbon atoms therein at the number of n. Thus, a “Cm to Cn” alkyl means an alkyl group comprising carbon atoms therein at a number in a range from m to n. Thus, a C1-C3 alkyl means methyl, ethyl, n-propyl, or 1- methylethyl-. The term“Cn+” compound or group, wherein n is a positive integer, means a compound or a group comprising carbon atoms therein at the number of equal to or greater than n. The term“Cn-” compound or group, wherein n is a positive integer, means a compound or a group comprising carbon atoms therein at the number of equal to or lower than n.

[0027] The term“hydroperoxide” means a compound having a formula R-O-OH, wherein R is a substituted or unsubstituted hydrocarbyl group.

[0028] The term“peroxide” means a compound having a formula R-O-O-R’, wherein R and R’ are independently each a substituted or unsubstituted hydrocarbyl group.

[0029] Likewise, reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and ieri-butyl).

[0030] In the description herein, the catalyst may be described as a catalyst precursor, a pre-catalyst compound, or a catalyst compound, and these terms are used interchangeably.

[0031] The term“conversion” refers to the degree to which a given reactant in a particular reaction (e.g., dehydration, coupling, etc.) is converted to products. Thus 100% conversion of an ether refers to complete consumption of the ether, and 0% conversion of the ether refers to no measurable reaction of the ether. [0032] The term“selectivity” refers to the degree to which a particular reaction forms a specific product, rather than another product. For example, for the dehydration of iso-pentanol, 50% selectivity for iso-pentylene means that 50% of the products formed are iso-amylene (also referred to as 2-methyl-2-butene), and 100% selectivity for iso-amylene means that 100% of the product formed is iso-amylene. The selectivity is based on the product formed, regardless of the conversion of the particular reaction. The selectivity for a given product produced from a given reactant can be defined as weight percent (wt%) of that product relative to the total weight of the products formed from the given reactant in the reaction.

[0033] The term“dehydration” refers to a chemical reaction that converts an alcohol into its corresponding alkene while producing water as a byproduct. For example, the dehydration of isobutanol produces isobutylene and water.

[0034] The term“reaction zone” refers to the part of a reactor or series of reactors where the substrates and chemical intermediates are brought into contact, with or without a catalyst, to ultimately form at least one product. The reaction zone for a reaction may be a single vessel including a single catalyst. In the case of a reaction requiring two different catalysts, the reaction zone can be a single vessel including a mixture of the two catalysts, a single vessel such as a tube reactor which contains the two catalysts in two separate layer

[0035] This disclosure provides processes for producing glycols by oxidative coupling of ethers using dihydrocarbyl peroxides produced by upgrading branched hydrocarbons. Processes include oxidizing a branched hydrocarbon (e.g., a C2-C5 paraffin), such as a branched hydrocarbon, to form an oxidized product mixture that can include one or more hydrocarbyl hydroperoxides and/or one or more alcohols. Processes include introducing the oxidized product mixture to a catalyst to form a dihydrocarbyl peroxide. Processes can include introducing the dihydrocarbyl peroxide to an ether to form a diether. Processes include converting the diether to form a glycol. The alcohol from the oxidized products and/or formed during the diether formation can be recovered, or converted to the corresponding ether for overall enhancement of diether production. Additionally or alternatively, the alcohol may be dehydrated to an iso-olefin, or used as a high-octane gasoline blend.

[0036] For example, in at least one embodiment, processes of this disclosure provide ethylene glycol (“MEG”) with high selectivity. Processes include oxidizing a branched hydrocarbon, such as isobutane, to form oxidized products that can include a hydrocarbyl hydroperoxide, such as / _<?/7 - butyl hydroxyperoxide (“TBHP”), and an alcohol such as feri-butanol (also referred to as feri-BuOH, also referred to as“TBA”). Processes include introducing the TBHP and TBA to a catalyst to form a dihydrocarbyl peroxide, such as di-ieri-butyl peroxide (“DTBP”). Processes can include introducing DTBP to an ether (e.g., dimethyl ether also referred to as“DME”) to form a diether, such as l,2-dimethoxyethane (also referred to as“glyme”) and an alcohol such as TBA. Processes include converting (e.g., hydrolyzing) glyme to form ethylene glycol and methanol, and subsequently converting the methanol formed during the hydrolysis process to form DME, which can be recycled to the step of introducing DTBP to DME, thus to further enhance the production of glyme with little to no material loss. The alcohol from the oxidized products and/or formed during the diether formation (e.g., TBA) can be recovered, or dehydrated to an iso-olefin, or used as a high-octane gasoline blend. The alcohol byproduct can be recycled to the peroxide formation stage or provided to an olefin formation stage. Such recycling/olefin formation system of the alcohol to the corresponding ether and/or olefin, respectively, provides manufacturers with competitive and economic advantages such as reducing energy consumption and waste disposal, sustaining use of resources, and increasing cost-efficiency by minimizing the production expenditure.

[0037] Furthermore, this disclosure relates to a process for upgrading branched hydrocarbons to higher value products. The process can be applicable to the upgrading of branched hydrocarbons (e.g., C4-C12). Such branched hydrocarbons can be found in Natural Gas Liquids (NGL), tight oils (light crude oil contained in petroleum-bearing formations of low permeability, often shale or tight sandstone, also referred to as light tight oils), as well as fractions from various refining and/or chemical streams.

Oxidation of Branched Hydrocarbons to Hydrocarbyl Hydroperoxides and Alcohols

[0038] FIG. 1 is a schematic diagram for producing glycols by upgrading branched hydrocarbons, according to one embodiment. As shown in FIG. 1, a branched hydrocarbon feedstock is supplied by line 10 to an oxidation reactor 4.

[0039] In at least one embodiment of this disclosure, a branched hydrocarbon feedstock is represented by Formula (F-I) (Scheme 1) including one or more C2 to C20 alkanes (such as Cl to C 15 alkane, such as Cl to C10 alkane, such as one or more of methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and isomers thereof). For example, a branched hydrocarbon represented by Formula (F-I) can be an iso-butane, iso-pentane, iso-hexane, iso-heptane, iso-octane, iso-nonane, iso-decane, or a mixture thereof. In at least one embodiment, R ¹ , R ² , and R ³ are independently methyl, such as the branched hydrocarbon is iso-butane (i-C4).

Scheme 1

+ Oxidizing agent

R ² R K ² OOH + ^R R ² O ^r H ³

(F-I) (F-II) (F-III) wherein:

R ¹ , R ² , and R ³ in Formulas (F-I), (F-II), and (F-III) are independently each a substituted or unsubstituted hydrocarbyl, preferably an alkyl, more preferably a linear or branched alkyl, still more preferably a linear alkyl. Such substituted or unsubstituted hydrocarbyl groups may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof; and

Adjacent R groups (R ¹ and R ² , and/or R ² and R ³ , and/or R ³ and R ¹ ) and/or substituents in Formulas (F-I), (F-II), and (F-III) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.

[0040] A feed comprising the branched hydrocarbon (e.g., i-C4, i-C5, i-C6, etc.) can be introduced to an oxidation reactor 4 via line 10, and an oxidizing agent is fed to oxidation reactor 4 via line 2. The efficiency of the oxidation reaction can be improved as the oxidizing agent can be broadly and widely distributed within the reactor. The oxidizing agent can be introduced into a batch, semi-batch, or continuous, for example, fixed bed or fluid bed, reactor in a number of different ways, such as via a single injection point, several injection points, or even via a sparger arrangement. The oxidizing agent can be dispersed into the reactor either through nozzles that are flush to the reactor vessel or through an internal distribution network. The number of nozzles flush to the reactor can be one, a few or many. Alternatively, the oxidizing agent can be introduced into a reactor through an internal distributor. The internal distributor may be a single injection point, a few injection points or many injection points. In the case of a few or many injection points, the distributor may contain arteries branching off of one or more common headers, and additional sub-arteries may branch off of each artery to form a network of arteries. The arteries may be designed to have a uniform diameter, either the same or different diameter as the common headers, or be tapered in various diameters and different lengths. Along each common header or artery there may be one or several or many nozzles to introduce the oxidizing agent. The size and length of these nozzles may be similar or different depending on the distribution of the oxidizing agent into the reactor. The internal distributor, arteries, and nozzles may be insulated if used in a fluid bed or fixed bed reactor. The decision to insulate or not can change the metallurgical requirements, which can range from carbon steel or to stainless steels or to titanium or other suitable types of alloys.

[0041] Oxidation of branched hydrocarbons represented by Formula (F-I) in accordance with this disclosure can be performed with any suitable oxidizing agent. For instance, suitable oxidizing agents can be air, oxygen gas (0 ₂ ), 9- azabicyclo[3.3.l]nonane N-oxyl (ABNO), acetone, acrylonitrile, ammonium cerium (IV) nitrate, ammonium peroxydisulfate, 2-azaadamantane N-oxyl, 9- azanoradamantane N-oxyl, l,4-benzoquinone, benzaldehyde, benzoyl peroxide, bleach, N-bromosaccharin, N-bromosuccinimide,

(methoxycarbonylsulfamoyl)triethylammonium hydroxide (Burgess reagent), (E)-but- 2-enenitrile, N-fluoro-2,4,6-trimethylpyridinium triflate, N-/ _<?/7 - butylbenzenesulfonamide chloride, /<?/7- butyl hydroperoxide, ieri-butyl hypochlorite, feri-butyl nitrite, cerium (IV) ammonium nitrate ((NH ₄ ) ₂ Ce(N0 ₃ ) ₆ ), carbon tetrabromide, cerium ammonium nitrate, choline peroxydisulfate, chloramine-T, chloranil, chloromethyl-4-fluoro-l,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate), 3-chloroperoxybenzoic acid, choline peroxydisulfate (ChPS), chromium compounds (e.g., chromium trioxide, dipyridine chromium (VI) oxide (Collins reagent), Pyridinium chlorochromate (PCC also referred to as Corey-Suggs reagent), cumene hydroperoxide (CMHP), copper compounds, crotononitrile, cumene hydroperoxide, l,3-dibromo-5,5-dimethylhydantoin (DBDMH), 2,3-dichloro-5,6- dicyanobenzoquinone (DDQ), diethyl azodicarboxylate (DEAD), l,l,l-triacetoxy-l,l- dihydro-l,2-benziodoxol-3(lH)-one (Dess-Martin periodinane), formic acid, hydrogen peroxide, iodine, manganese compounds, N-bromosuccinimide, oxone, oxygen, ozone, potassium peroxomonosulfate, sodium bromate, sodium chlorate, sodium chlorite, sodium hypochlorite, /<?/7- butyl hydroperoxide, ieri-butyl hypochlorite, ieri-butyl nitrite, tetrabutylammonium peroxydisulfate, l,l,l-trifluoroacetone, trifluoroacetic peracid, water. Examples of oxidation processes are described in U.S. Pub. No. 2016/0168048 and U.S. Pat. No. 9,637424, each incorporated herein by reference. In at least one embodiment, the oxidizing agent is air or O2 (gas).

[0042] An oxidation reaction can be performed at a temperature of from l00°C to 200°C, such as from 1 l0°C to l90°C, such as from l20°C to l80°C, such as from l30°C to l70°C, such as from l40°C to l60°C; a pressure of from 300 psig to 800 psig, such as from 400 psig to 700 psig, such as from 500 psig to 600 psig; and/or a residence time of from 1 hour to 48 hours, such as from 2 hours to 24 hours, such as from 4 hours to 20 hours, such as from 6 hours to 10 hours. In at least one embodiment, an oxidation reaction is performed at a weight hourly space velocity (WHSV) from 0.01 hr ¹ to 100 hr ¹ , such as from 0.02 hr ¹ to 50 hr ¹ , such as from 0.02 hr ¹ to 10 hr ¹ .

[0043] In a particularly advantageous embodiment of Scheme 1 above, R ¹ , R ² , and R ³ are all methyl. In this reaction, isobutane of Formula (F-I) is oxidized by, e.g., air, to form tert-butyl hydroperoxide of Formula (F-II) and tert-butyl alcohol of Formula (F-III).

[0044] The oxidation of a branched hydrocarbon represented by Formula (F-I) results in the formation of one or more oxidized product(s). In at least one embodiment, the oxidized products are a hydrocarbyl hydroperoxide, such as a hydrocarbyl hydroperoxide represented by Formula (F-II), and an alcohol, such as an alcohol represented by Formula (F-III). R ¹ , R ² , and R ³ are independently each a hydrocarbyl and substituted hydrocarbyl, and adjacent R groups (R ¹ and R ² , and/or R ² and R ³ , and/or R ³ and R ¹ ) and/or substituents in Formulas (F-I), (F-II), and (F-III) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings. Such substituted or unsubstituted hydrocarbyl groups may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons. For example, a hydrocarbyl group can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof. The oxidized products represented by Formulas (F- II) and (F-III) are introduced to reactor 12 via line 6. Unreacted branched hydrocarbons remaining in the oxidized products stream can be separated (e.g., using a separator (not shown)) from the oxidized products stream and further recycled to the oxidation reactor 4 via line 8. Processes for Making Dihvdrocarbyl Peroxides

[0045] The oxidation mixture including the hydrocarbyl hydroperoxide (F-II) and the alcohol (F-III), is sent via line 6 to a reactor 12 where a dihydrocarbyl peroxide represented by Formula (F-IV) is formed over an acid catalyst (e.g., Amberlyst™, acidic clay) (Scheme 2). An exemplary configuration for reactor 12 can be a reactive distillation reactor/column where water can be continuously removed as an overhead by-product via line 14.

Scheme 2

wherein:

R ¹ , R ² , and R ³ in Formulas (F-II) and (F-IV) are independently each a substituted or unsubstituted hydrocarbyl, preferably alkyl, more preferably linear alkyl or branched alkyl, still more preferably linear alkyl. Preferably R ¹ , R ² , and R ³ are the same. Such substituted or unsubstituted hydrocarbyl groups for R ¹ , R ² , and R ³ may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof; preferably methyl, ethyl, and n-propyl;

Adjacent R groups (R ¹ and R ² , and/or R ² and R ³ , and/or R ³ and R ¹ ) and/or substituents in Formulas (F-I), (F-II), and (F-IV) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;

R ¹ , R ² , and R ³ of Formulas (F-III) and (F-IV) are independently each a substituted or unsubstituted hydrocarbyl, preferably an alkyl, more preferably a linear or branched alkyl, still more preferably a linear alkyl. Preferably R ¹ , R ² , and R ³ are the same. Such substituted or unsubstituted hydrocarbyl groups for R ^1’ , R ^2’ , and R ^3’ may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof. Preferably R ¹ in Formula (F-II) and R ^1’ are the same, R ² in Formula (F-II) and R ^2’ are the same, and R ³ in Formula (F-II) and R ³ are the same. More preferably R ¹ , R ² , R ³ , R ¹ , R ² , and R ^3’ are all the same group; and Adjacent R groups (R ¹ and R ² , and/or R ² and R ³ , and/or R ³ and R ¹ ) of Formula (F- IV) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.

[0046] Suitable examples of the conversion of a hydrocarbyl hydroperoxide and an alcohol to a dihydrocarbyl peroxide using an acid catalyst, such as an inorganic heteropoly- and/or isopoly-acid catalyst, are described in U.S. Pat. No. 5,288,919 and U.S. Pat. No. 7,034,189, each incorporated herein by reference. Any suitable acid catalyst can be used for the conversion of the hydrocarbyl hydroperoxide (F-II) and the alcohol (F-III) to the dihydrocarbyl peroxide (F-IV). For example, an acid catalyst can be Amberlyst™ resin, Nafion™ resin, aluminosilicates, acidic clay, zeolites (natural or synthetic), silicoaluminophosphates (SAPO), heteropolyacids, acidic oxides such as tungsten oxide on zirconia, molybdenum oxide on zirconia, sulfated zirconia, liquid acids such as sulfuric acid, or acidic ionic liquids.

[0047] Conditions for the production of the dihydrocarbyl peroxide (F-IV) in reactor 12 can be a temperature from 50°C to 200°C, such as from 60°C to l50°C, such as from 80°C to l20°C; and/or a residence time of from 0.01 hour to 24 hours, such as from 0.1 hours to 20 hours, such as from 0.5 hours to 10 hours. In at least one embodiment, the catalytic conversion of the hydrocarbyl hydroperoxide (F-II) and the alcohol (F-III) to the dihydrocarbyl peroxide (F-IV) is performed at a weight hourly space velocity (WHSV) from 0.01 hr ¹ to 100 hr ¹ , such as from 0.02hr ^_1 to 50 hr ¹ , such as from 0.02 hr ¹ to 10 hr ¹ . The hydrocarbyl hydroperoxide (F-II) to alcohol (F-III) mole ratio can be in the range of from 0.5 to 2, such as from 0.8 to 1.5, such as from 0.9 to 1.1. In at least one embodiment, the pressure of the reaction is held at appropriate ranges to ensure that the reaction occurs substantially in a liquid phase, for example, from 0 psig to 300 psig, such as from 5 psig to 100 psig, such as from 15 psig to 50 psig. A reaction that occurs substantially in a liquid phase provides substantial mixing of the reactants and prevents fouling or clogging of a reactor and/or lines of the reactor.

[0048] The reaction can be performed with or without a solvent. Suitable solvents may include hydrocarbons having a carbon number (e.g., number of carbons in the molecule) of greater than 3, such as paraffins, naphthenes, or aromatics, or a mixture thereof. Conveniently, any unreacted branched hydrocarbons (F-I) from the oxidation can be used as solvent for the dihydrocarbyl peroxide synthesis. [0049] The dihydrocarbyl peroxide represented by Formula (F-IV) is then provided via line 16 to a reactor 18 to form the corresponding diethers (e.g., glyme), represented by Formula (F-VI).

[0050] In a particularly advantageous embodiment of Scheme 2 above, R ¹ , R ² , R ³ , R ^1’ , R ^2’ , and R ^3’ are all methyl. In this reaction, feri-butyl hydroperoxide of Formula

(F-II) reacts with feri-butyl alcohol of Formula (F-III) in the presence of a catalyst such as an acid to produce di-feri-butyl peroxide and water.

Processes for Making Diethers and Alcohols: Oxidative Coupling Reactions of Ethers in the Presence of Dihydrocarbyl Peroxides

[0051] Processes of this disclosure can include introducing an ether represented by

Formula (F-V) to a dihydrocarbyl peroxide represented by Formula (F-IV) to form a diether represented by Formula (F-VI) and recycling at least a portion of the oxidized product mixture (e.g., a tertiary alcohol (F-III)) to the reactor 12 for further dihydrocarbyl peroxide (F-IV) production (Scheme 3). In at least one embodiment in Formula (F-V), R ⁴ and R ⁵ are independently substituted or unsubstituted Cl to C20 hydrocarbyl, such as Cl to C15 hydrocarbyl, substituted Cl to C15 hydrocarbyl, such as Cl to C10 hydrocarbyl or substituted Cl to C10 hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof). The dihydrocarbyl peroxide (F-IV) is configured to provide coupling of the ether (F-V), thus providing formation of the corresponding diether (F-VI). In one or more embodiments, a mixed ether feed is used (e.g., two or more compounds of Formula (F- V)) which can provide a mixed diether product (e.g., two or more compounds of Formula (F-VI).

Scheme 3

(F-VI) (F-III) (F-III)

wherein: R ¹ , R ² , and R ³ in Formulas (F-IV), and (F-III) are independently each a substituted or unsubstituted hydrocarbyl, preferably an alkyl, more preferably a linear or branched alkyl, still more preferably a linear alkyl. Preferably R ¹ , R ² , and R ³ are the same. Such substituted or unsubstituted hydrocarbyl groups for R ¹ , R ² , and R ³ may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof; preferably methyl, ethyl, and n-propyl;

Adjacent R groups (R ¹ and R ² , and/or R ² and R ³ , and/or R ³ and R ¹ ) and/or substituents in Formulas (F-IV) and (F-III) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;

R ¹ , R ² , and R ³ in Formulas (F-III) and (F-IV) are independently each a substituted or unsubstituted hydrocarbyl, preferably an alkyl, more preferably a linear or branched alkyl, still more preferably a linear alkyl. Preferably R ¹ , R ² , and R ³ are the same. Such substituted or unsubstituted hydrocarbyl groups for R ¹ , R ² , and R ³ may have 1 to 20 carbons, such as 1 to 15 carbons, such as 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof. Preferably R ¹ in Formula (F-IV) and R ^1’ are the same, R ² in Formula (F-IV) and R ^2’ are the same, and R ³ in Formula (F-IV) and R ³ are the same. More preferably R ¹ , R ² , R ³ , R ¹ , R ² , and R ^3’ are all the same group; and

Adjacent R groups (R ^r and R ^2’ , and/or R ^2’ and R ^3’ , and/or R ^3’ and R ^1’ ) and/or substituents in Formulas (F-III) and (F-IV) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;

R ⁴ and R ⁵ in Formulas (F-V) are independently substituted or unsubstituted Cl to C20 hydrocarbyl, such as Cl to C15 hydrocarbyl, such as Cl to C15 substituted hydrocarbyl, such as Cl to C10 hydrocarbyl, such as Cl to C10 substituted hydrocarbyl. In at least one embodiment, each of R ⁴ and R ⁵ is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomer(s) thereof. Preferably, R ⁴ and R ⁵ are methyl, ethyl, or n-propyl. Preferably, R ⁴ and R ⁵ are identical. In one embodiment, R ⁴ and R ⁵ are methyl. In such embodiments, R ⁶ and R ⁷ in Formula (F-VI) are methylene. In one embodiment, R ⁴ and R ⁵ are ethyl. In such embodiments, R ⁶ and R ⁷ in Formula (F-VI) can be 1l ³ ,2l ³ -ethane and/or ^ ² -ethane.

In one embodiment, R ⁴ and R ⁵ in Formula (F-V) are not the same. In such embodiments, the diether of Formula (F-VI) formed is a mixed diether product. For example, for Formula (F-V), R ⁴ may be methyl and R ⁵ may be ethyl to provide a diether product that is a mixture of 1, 2-diethoxy ethane, 1 -ethoxy-3 -methoxypropane, 1- ethoxy-2-methoxypropane, l,4-dimethoxybutane, l,3-dimethoxybutane, 2,3- dimethoxybutane.

R ⁸ and R ⁹ in Formula (F-VI) are independently each a substituted or unsubstituted hydrocarbyl, preferably an alkyl, more preferably a linear or branched alkyl, still more preferably a linear alkyl, and R ⁶ and R ⁷ in Formula (F-VI) are independently each a divalent substituted or unsubstituted group comprising 1 to 20 carbon atoms. Two or more adjacent groups and/or substituents in Formula (F-VI) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, aromatic or non-aromatic ring, unsubstituted heterocyclic ring or substituted heterocyclic ring, wherein the ring has 5, 6, 7, or 8 ring carbon atoms and wherein substitutions on the ring can join to form additional rings.

[0052] Processes for making diether(s) (F-VI) and alcohol(s) (F-III) via a coupling reaction of an ether (F-V) in the presence of dihydrocarbyl peroxide(s) (F-IV) can be performed at a temperature of from l00°C to 200°C, such as from H0°C to l90°C, such as from l20°C to l80°C, such as from l30°C to l70°C (e.g., l50°C); a pressure of from 100 psig to 1,500 psig, such as from 500 psig to 1,200 psig, such as any suitable pressure to ensure that the feed remains in a liquid phase; and/or a residence time of from 1 hour to 48 hours, such as from 2 hours to 24 hours, such as from 4 hours to 16 hours. In at least one embodiment, the coupling reaction of the dihydrocarbyl peroxide (F-IV) and the ether (F-V) is performed at a weight hourly space velocity (WHSV) from 0.01 hr ¹ to 100 hr ¹ , such as from 0.02 hr ¹ to 50 hr ¹ , such as from 0.02 hr ¹ to 10 hr ¹ . The dihydrocarbyl peroxide (F-IV) to alcohol (F-III) mole ratio can be in the range of from 0.1 to 5, such as from 0.5 to 2.5, such as from 0.8 to 1.5, such as from 0.9 to 1.1. A conversion of dihydrocarbyl peroxide(s) (F-V) to a tertiary alcohol (F-III) can be achieved in the reactor 18.

[0053] Accordingly, a dihydrocarbyl peroxide represented by Formula (F-IV) can be introduced to a reactor (e.g., a coupling reactor) 18 via line 16. An ether represented by Formula (F-V) can be introduced to the reactor 18 via line 24 as a co-feed or separately from the dihydrocarbyl peroxide (F-IV) stream, either continuously or in batch mode or in semi -batch mode. Furthermore, the ether represented by Formula (F- V) can be introduced into a batch, semi-batch, or continuous, for example, fixed bed or fluid bed, reactor 18 in a number of different ways, such as via a single injection point, several injection points, or even via a sparger arrangement. The ether represented by Formula (F-V) can be dispersed into the reactor 18 either through nozzles that are flush to the reactor vessel or through an internal distribution network. The number of nozzles flush to the reactor 18 can be one, a few or many. Alternatively, the ether represented by Formula (F-V) can be introduced into a reactor 18, for example, through an internal distributor. The internal distributor may be a single injection point, a few injection points or many injection points. In the case of a few or many injection points, the distributor may contain arteries branching off of one or more common headers, and additional sub- arteries may branch off of each artery to form a network of arteries. The arteries may be designed to have a uniform diameter, either the same or different diameter as the common headers, or be tapered in various diameters and different lengths. Along each common header or artery there may be one or several or many nozzles to introduce the ether represented by Formula (F-V). The size and length of such nozzles may be similar or different depending on the distribution of the ether represented by Formula (F-V) into the reactor. The internal distributor, arteries, and nozzles may be insulated. The resulting reaction products (e.g., diether (F-VI) and alcohol (F-III)), by-products (e.g., ketone(s); C8+ aromatics), and unreacted ether (F-

V) are sent to one or more separation unit(s) (not shown) via line 20 for separation/fractionation, and recycling processes (further discussed in the following section). In at least one embodiment, the selectivity for the formation of the diether (F-

VI) is from 60 wt% to 100 wt%, such as from 70 wt% to 95 wt%, such as from 75 wt% to 90 wt%.

[0054] A high level of oxygenates can be produced via condensation side -reactions under traditional methods. However, under coupling reaction conditions in processes of this disclosure, less oxygenate by-products are formed, thus improving the selectivity to the formation of the diethers (F-VI). Hence, the present process provides a sustainable approach for the construction of carbon-carbon bonds, leading to access to diether precursors suitable for the formation of glycols, without using expensive metal- based catalyst(s), nor using additional solvent (because the reactants can be used as solvents/diluents), or any further costly reactants for the process. [0055] In at least one embodiment, a mixture of reaction products (e.g., diether (F- VI) recovered from line 30 and alcohol (F-III) recovered from line 28), by-products (e.g., ketone(s) recovered from line 26), and unreacted ether (F-V) from the coupling reactor 18 are sent to one or more separation unit(s) (not shown), such as one or more suitable column(s), one or more distillation system, and/or one or more suitable fractionator(s) via line 20 for separation/fractionation and further recycling processes. Thus, unreacted ether (F-V) can be recycled to the coupling reactor 18 via lines 22, while the remaining products are fractionated in order to separate the by-products, the alcohol (F-III), and the diether (F-VI).

[0056] In a particularly advantageous embodiment of Scheme 3 above, R ¹ , R ² , R ³ , R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are all methyl. In this reaction, dimethyl ether of Formula (F- V) dimerizes to form glyme of Formula (F-VI) wherein R ⁸ and R ⁹ are methyl, and R ⁵ and R ⁶ are methylene via oxidative coupling by reacting with di-feri-butyl peroxide of Formula (F-II), resulting in two moles of / _<?/7 -butyl alcohol of Formula (F-III).

[0057] The alcohol (F-III) from a primary fractionator (not shown) can be recycled, when needed, either fully or partially for further formation of dihydrocarbyl peroxides (F-IV). Accordingly, an excess of alcohol (F-III) can be converted to a corresponding ether (not shown) by reacting with an alcohol (such as methanol or ethanol). The alcohol (F-III) can be converted to olefins as chemical products via dehydration (e.g., iso-butylene), or etherified with an alcohol such as methanol or ethanol making ether as gasoline blend (e.g., methyl ieri-butyl ether (also referred to as“MTBE”) or ethyl feri-butyl ether (also referred to as“ETBE”) from isobutane). The reaction to convert alcohol (F-III) to an ether can be carried out in a fixed-bed reactor or a catalytic distillation reactor where an acid catalyst can be employed. Examples of suitable acid catalysts may include, but are not limited to, resins such as Dowex™, Amberlyst™, Nafion™, sulfuric acid, sulfonic acid, phosphoric acid (neat or solid-supported on silica, alumina, or clay), acidic clay, aluminosilicate, zeolite, silicoaluminophosphate, acidic oxides such as tungsten oxide on zirconia, molybdenum oxide on zirconia, sulfated zirconia, acidic ionic liquids; Lewis acids such as aluminum chloride or boron trifluoride. The reaction to convert alcohol (F-III) to an ether can be carried out at a temperature of l00°C to 400°C, such as from l50°C to 350°C, and/or a pressure of 700 kPag to 3450 kPag (100 psig to 500 psig), such as 1,000 kPag to 2760 kPag (150 psig to 400 psig). The alcohol (F-III) recovered from a primary fractionator (not shown) can also be used as a chemical product, fuel blend, or dehydrated to an olefin, such as iso- olefin. Dehydration can be carried out in a dehydration unit (not shown), such as a vapor phase unit, at a temperature of from l50°C to 450°C, such as from 200°C to 350°C, and/or a pressure of from 700 kPag to 3450 kPag (100 psig to 500 psig), such as 1,000 kPag to 2,070 kPag (150 psig to 300 psig) in fixed-bed or slurry reactors. An acidic catalyst can be used, such as those described above for the etherification reaction. Water is separated from the product stream. The iso-olefin formed after the alcohol (F- III) dehydration can be used as a chemical intermediate for the production of polymers, rubber, or hydrocarbon resins. Optionally, the iso-olefin formed after the alcohol (F- III) dehydration can be converted to higher molecular weight products such as gasoline, kero-jet, or diesel via alkylation (not shown). Alkylation can be carried out using an acid catalyst such as sulfuric acid, hydrofluoric acid, or zeolites in the faujasite (FAU), mordenite (MOR), MFI, or MWW families.

[0058] Such recycling system of the alcohol to the corresponding olefin provides manufacturers with competitive and economic advantages such as reducing energy consumption and waste disposal, sustaining use of resources, and increasing cost- efficiency by minimizing the production expenditure. Additionally, natural gas liquids, liquid petroleum gas, and refinery light gas such as light virgin naphtha (LVN) or light catalytic naphtha (LCN), can also be upgraded using processes of this disclosure. Processes for Making Glycols: Hydrolysis Reaction of Diether

[0059] Processes of this disclosure include converting the diether (F-VI) to a glycol represented by Formula (F-VII), and one or more alcohol(s) represented by Formula (F-VIII) and Formula (F-IX) when R ⁴ and R ⁵ are different).

[0060] The diether (F-VI) is sent via line 30 to a hydrolysis reactor 32 where glycol represented by Formula (F-VII) is formed in the presence of water, over an acid catalyst (e.g., acidic clay) (Scheme 4). The water is introduced to the hydrolysis reactor 32 via line 34.

Scheme 4

(F-VI) (F-VII) (F-VIII) (F-IX) wherein:

R ⁴ and R ⁵ in Formulas (F-VIII) and (F-IX) are independently substituted or unsubstituted Cl to C20 hydrocarbyl, such as Cl to C15 hydrocarbyl, such as Cl to C15 substituted hydrocarbyl, such as Cl to C10 hydrocarbyl, such as Cl to C10 substituted hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof). In one embodiment, R ⁴ and R ⁵ are methyl.

R ⁶ and R ⁷ in Formula (F-VII) have the same meaning as R ⁶ and R ⁷ , respectively, for Formula (F-VI) described above.

[0061] For example, the diether (F-VI) and water can be mixed and fed through a reaction zone (e.g., hydrolysis reactor 32), loaded with a solid catalyst, such as an acid catalyst, and reacting the same. The reaction zone 32 can be one or more reactors connected in series and/or in parallel. In at least one embodiment, glycol(s) (F-VII) and one or more alcohol(s) (represented by Formulas (F-VIII) and (F-IX)) are formed. The resulting product mixtures obtained after the hydrolysis reaction can be separated via a separation unit (such as a distillation unit, column, not shown) upon exiting the reaction zone 32.

[0062] R ⁴ in Formula (F-VIII) is substituted or unsubstituted Cl to C20 hydrocarbyl, such as Cl to Cl 5 hydrocarbyl, such as Cl to C 15 hydrocarbyl, such as Cl to C10 hydrocarbyl, such as Cl to C10 substituted hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof). In one embodiment, R ⁴ is methyl.

[0063] R ⁵ in Formula (F-IX) is substituted or unsubstituted Cl to C20 hydrocarbyl, such as Cl to C15 hydrocarbyl, such as Cl to C15 substituted hydrocarbyl, such as Cl to C10 hydrocarbyl, such as Cl to C10 substituted hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof). In one embodiment, R ⁵ is methyl.

[0064] Representative solid acid catalysts for the hydrolysis process may include, but are not limited to, acidic clays, amorphous aluminosilicates, acidic alumina (e.g., gamma-alumina, chloride- alumina, and/or fluoride alumina), zeolites, silicoaluminophosphates, acidic mixed metal oxides (e.g., tungsten oxide/zirconium oxide, or molybdenum oxide/zirconium oxide), acidic resins (Amberlyst™ resin, Nafion™ resin, Dowex™ resin), supported phosphoric acid, etc. The acid can also be a Lewis acid such as BF ₃ , BCL, A1CL, either neat or supported on a solid support. The solid acid catalyst(s) can be one or both of an acidic molecular sieve catalyst and an acidic resin catalyst, as described in W.O. 2017/054317.

[0065] Conditions for the production of the glycol (F-VII) in the reaction zone 32 can be a temperature from 50°C to 450°C, such as from 75°C to 350°C, such as from l00°C to 250°C; a pressure of from 0 psig (such as ambient pressure) to 2,000 psig, such as from 50 psig to 1,500 psig, such as from 100 psig to 1,000 psig; and/or a residence time of from 0.1 hour to 48 hours, such as from 0.5 hours to 24 hours, such as from 1 hours to 10 hours, such as from 2 hours to 8 hours. In at least one embodiment, the hydrolysis of the diether (F-VI) is performed at a weight hourly space velocity (WHSV) from 0.01 hr ¹ to 100 hr ¹ , such as from 0.02 hr ¹ to 50 hr ¹ , such as from 0.02 hr ¹ to 10 hr ¹ .

[0066] In a particularly advantageous embodiment of Scheme 4 above, R ⁸ , R ⁹ , R ⁴ , and R ⁵ are all methyl. In this reaction, dimethoxy ethane of Formula (F-VI) hydrolyzes to form ethylene glycol of Formula (F-VII) and two moles of methanol of Formulas (F-

VIII) and (F-IX).

[0067] One or more alcohol(s) represented by Formula (F-VIII) and/or Formula (F-

IX) can be sent to a dehydration reactor 40 where a conversion to ether (F-V) can be carried out using a catalyst, such as a solid catalyst, such as a solid acid catalyst (Scheme 5). The ether (F-V) can be recycled to the oxidative coupling reactor 18 via line 44. Water can be separated from the product stream 44 via line 42, and optionally recycled back to the hydrolysis reactor 32 (not shown). Recyclization of ether (F-V) to the coupling reactor 18 via lines 22 and 44 provides a time- and cost-effective process for the production of the diether (F-VI), thus reducing any reactants loss while improving the chemical equilibrium of the coupling reaction towards an increase of the yield of diether (F-VI).

Scheme 5

(F-VIII) (F-IX) (F-V)

[0068] Examples of suitable solid acid catalysts for the conversion of the alcohol(s) represented by Formula (F-VIII) and/or Formula (F-IX) to ether (F-V) may be, but are not limited to, acidic clays, amorphous aluminosilicates, acidic alumina (e.g., gamma- alumina, chloride- alumina, and/or fluoride alumina), zeolites, silicoaluminophosphates, acidic mixed metal oxides (e.g., tungsten oxide/zirconium oxide, or molybdenum oxide/zirconium oxide), acidic resins (Amberlyst™ resin, Nafion™ resin, Dowex™ resin), or supported phosphoric acid. The acid can also be a Lewis acid such as BF ₃ , BCL, A1CL, either neat or supported on a solid support.

[0069] Conditions for the production of the ether (F-V) in the dehydration reactor 40 can be a temperature from 50°C to 450°C, such as from 75 °C to 350°C, such as from l00°C to 250°C; a pressure of from 0 psig (such as ambient pressure) to 2,000 psig, such as from 50 psig to 1,500 psig, such as from 100 psig to 1,000 psig; and/or a residence time of from 0.1 hour to 48 hours, such as from 0.5 hours to 24 hours, such as from 1 hours to 10 hours, such as from 2 hours to 8 hours. In at least one embodiment, the production of the ether (F-V) is performed at a weight hourly space velocity (WHSV) from 0.01 hr ¹ to 100 hr ¹ , such as from 0.02 hr ¹ to 50 hr ¹ , such as from 0.02 hr ¹ to 10 hr ¹ .

[0070] R ⁴ and R ⁵ in Formulas (F-V) and (F-VI) are independently substituted or unsubstituted Cl to C20 hydrocarbyl, such as Cl to C15 hydrocarbyl, such as Cl to C15 substituted hydrocarbyl, such as Cl to C10 hydrocarbyl, such as Cl to C10 substituted hydrocarbyl. In at least one embodiment, each of R ⁴ and R ⁵ is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof. In one embodiment, R ⁴ and R ⁵ are methyl.

[0071] In a particularly advantageous embodiment of Scheme 5 above, R ⁴ and R ⁵ are both methyl. In this reaction, methanol of Formulas (F-VIII) and (F-IX) dehydrates to form dimethyl ether of Formula (F-V).

Processes for Making Monoethylene Glycol (MEG)

[0072] In at least one embodiment, the glycol represented by Formula (F-VII) is monoethylene glycol. FIG. 2 is a schematic diagram for producing ethylene glycol by upgrading isobutylene, according to one embodiment. As shown in FIG. 2, a branched hydrocarbon feedstock is an iso-butane (i-C4) feedstock supplied by line 110 to an oxidation reactor 104 where / _{<? /} - b u Ly 1 h y dro pero x i de (TBHP) and feri-butyl alcohol (TBA) are formed.

[0073] A feed comprising iso-butane feedstock can be introduced to an oxidation reactor 104 via line 110, and an oxidizing agent is fed to the oxidation reactor 104 via line 102. The efficiency of the oxidation reaction can be improved as the oxidizing agent can be broadly and widely distributed within the reactor. The oxidizing agent can be introduced into a batch, semi-batch, or continuous, for example, fixed bed or fluid bed, reactor in a number of different ways, such as via a single injection point, several injection points, or even via a sparger arrangement. The oxidizing agent can be dispersed into the reactor either through nozzles that are flush to the reactor vessel or through an internal distribution network. The number of nozzles flush to the reactor can be one, a few or many. Alternatively, the oxidizing agent can be introduced into a reactor through an internal distributor. The internal distributor may be a single injection point, a few injection points or many injection points. In the case of a few or many injection points, the distributor may contain arteries branching off of one or more common headers, and additional sub-arteries may branch off of each artery to form a network of arteries. The arteries may be designed to have a uniform diameter, either the same or different diameter as the common headers, or be tapered in various diameters and different lengths. Along each common header or artery there may be one or several or many nozzles to introduce the oxidizing agent. The size and length of these nozzles may be similar or different depending on the distribution of the oxidizing agent into the reactor. The internal distributor, arteries, and nozzles may be insulated if used in a fluid bed or fixed bed reactor. The decision to insulate or not can change the metallurgical requirements, which can range from carbon steel or to stainless steels or to titanium or other suitable types of alloys.

[0074] In accordance with the present process, oxidation of iso-butane can be performed with any suitable oxidizing agent. For instance, suitable oxidizing agents can be air, oxygen gas (0 ₂ ), 9-azabicyclo[3.3.l]nonane N-oxyl (ABNO), acetone, acrylonitrile, ammonium cerium (IV) nitrate, ammonium peroxydisulfate, 2- azaadamantane N-oxyl, 9-azanoradamantane N-oxyl, l,4-benzoquinone, benzaldehyde, benzoyl peroxide, bleach, N-bromosaccharin, N-bromosuccinimide, (methoxycarbonylsulfamoyl)triethylammonium hydroxide (Burgess reagent), (E)-but- 2-enenitrile, N-fluoro-2,4,6-trimethylpyridinium triflate, N-/ _<?/7 - butylbenzenesulfonamide chloride, /<?/7- butyl hydroperoxide, ieri-butyl hypochlorite, feri-butyl nitrite, cerium (IV) ammonium nitrate ((NH ₄ ) ₂ Ce(N0 ₃ ) ₆ ), carbon tetrabromide, cerium ammonium nitrate, choline peroxydisulfate, chloramine-T, chloranil, chloromethyl-4-fluoro-l,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate), 3-chloroperoxybenzoic acid, choline peroxydisulfate (ChPS), chromium compounds (e.g., chromium trioxide, dipyridine chromium (VI) oxide (Collins reagent), Pyridinium chlorochromate (PCC also referred to as Corey-Suggs reagent), cumene hydroperoxide (CMHP), copper compounds, crotononitrile, cumene hydroperoxide, l,3-dibromo-5,5-dimethylhydantoin (DBDMH), 2,3-dichloro-5,6- dicyanobenzoquinone (DDQ), diethyl azodicarboxylate (DEAD), l,l,l-triacetoxy-l,l- dihydro-l,2-benziodoxol-3(lH)-one (Dess-Martin periodinane), formic acid, hydrogen peroxide, iodine, manganese compounds, N-bromosuccinimide, oxone, oxygen, ozone, potassium peroxomonosulfate, sodium bromate, sodium chlorate, sodium chlorite, sodium hypochlorite, /<?/7- butyl hydroperoxide, ieri-butyl hypochlorite, ieri-butyl nitrite, tetrabutylammonium peroxy disulfate, l,l,l-trifluoroacetone, trifluoroacetic peracid, water. Examples of oxidation processes are described in U.S. Pub. No. 2016/0168048 and U.S. Pat. No. 9,637,424, the entire contents of which are incorporated herein by reference. In at least one embodiment, the oxidizing agent is air, or 0 ₂ (gas).

[0075] The oxidation reaction can be performed in reactor 104 at a temperature from l00°C to 200°C, such as from H0°C to l90°C, such as from l20°C to l80°C, such as from l30°C to l70°C, such as from l40°C to l60°C; a pressure of from 300 psig to 800 psig, such as from 400 psig to 700 psig, such as from 500 psig to 600 psig; and/or a residence time of from 1 hour to 48 hours, such as from 2 hours to 24 hours, such as from 4 hours to 20 hours, such as from 6 hours to 10 hours. In at least one embodiment, the oxidation reaction is performed at a weight hourly space velocity (WHSV) from 0.01 hr ¹ to 100 hr ¹ , such as from 0.02 hr ¹ to 50 hr ¹ , such as from 0.02 hr ¹ to 10 hr ¹ .

[0076] The oxidation of iso-butane results in the formation of TBHP and TB A. The oxidized products TBHP and TBA are then introduced to reactor 112 via line 106. Unreacted iso-butane remaining in the oxidized products stream can be separated (e.g., using a separator (not shown)) from the oxidized products stream of TBHP and TBA, and further recycled to the oxidation reactor 104 via line 108.

[0077] The oxidation mixture including TBHP and TBA is sent via line 106 to the reactor 112 where di-ieri-butyl peroxide (DTBP) is formed over an acid catalyst (e.g., Amberlyst™, acidic clay). An exemplary configuration for reactor 112 can be a reactive distillation reactor/column where water can be continuously removed as an overhead by-product via line 114.

[0078] Any suitable acid catalyst can be used for the conversion of TBHP and TBA to DTBP. For example, an acid catalyst can be Amberlyst™ resin, Nafion™ resin, aluminosilicates, acidic clay, zeolites (natural or synthetic), silicoaluminophosphates (SAPO), heteropoly acids, acidic oxides such as tungsten oxide on zirconia, molybdenum oxide on zirconia, sulfated zirconia, liquid acids such as sulfuric acid, or acidic ionic liquids.

[0079] Conditions for the production of DTBP in reactor 112 can be a temperature from 50°C to 200°C, such as from 60°C to l50°C, such as from 80°C to l20°C; and/or a residence time of from 0.01 hour to 24 hours, such as from 0.1 hours to 20 hours, such as from 0.5 hours to 10 hours, such as from 1 hours to 5 hours. In at least one embodiment, the catalytic conversion of TBHP and TBA to DTBP is performed at a weight hourly space velocity (WHSV) from 0.01 hr ¹ to 100 hr ¹ , such as from 0.02 hr ¹ to 50 hr ¹ , such as from 0.02 hr ¹ to 10 hr ¹ . The TBHP:TBA mole ratio can be in the range of from 0.5:1 to 2:1, such as from 0.8:1 to 1.5:1, such as from 0.9:1 to 1.1:1. In at least one embodiment, the pressure of the reaction is held at appropriate ranges to ensure that the reaction occurs substantially in a liquid phase, for example, from 0 psig to 300 psig, such as from 5 psig to 100 psig, such as from 15 psig to 50 psig.

[0080] The reaction can be performed with or without a solvent. Suitable solvents may include hydrocarbons having a carbon number greater than 3, such as paraffins, naphthenes, or aromatics, or a mixture thereof. Conveniently, any unreacted iso-butane from the oxidation can be used as solvent for the DTBP synthesis. The DTBP is then provided via line 116 to a reactor 118 to form the corresponding l,2-dimethoxy ethane (glyme).

[0081] Processes of this disclosure include reacting dimethyl ether (DME) with DTBP to form glyme and TBA. The resulting TBA can be recycled to the reactor 112 in order to produce more DTBP. DTBP is configured to initiate a coupling of DME, thus providing formation of the corresponding glyme via a coupling reaction.

[0082] Processes for making glyme and TBA via coupling reaction of DME with DTBP can be performed at DTBP:DME mole ratio of from 0.1 to 5, such as from about 0.5 to 2.5, such as from 0.8 to 1.5, such as from 0.9 to about 1.1; a temperature of from l00°C to 200°C, such as from H0°C to l90°C, such as from l20°C to l80°C, such as from l30°C to l70°C (e.g., l50°C); a pressure of from 100 psig to 1,500 psig, such as from 500 psig to 1,200 psig, such as any suitable pressure to ensure that the feed remains in a liquid phase; and/or a residence time of from 1 hour to 48 hours, such as from 2 hours to 24 hours, such as from 4 hours to 16 hours. In at least one embodiment, the coupling reaction of DME and DTBP is performed at a weight hourly space velocity (WHSV) from 0.01 hr ¹ to 100 hr ¹ , such as from 0.02 hr ¹ to 50 hr ¹ , such as from 0.02 hr ¹ to 10 hr ¹ . A conversion of DTBP to TBA is achieved in the reactor 118.

[0083] Accordingly, DTBP can be introduced to a reactor (e.g., a coupling reactor) 118 via line 116. DME can be introduced to the reactor 118 via line 124 as a co-feed or separately from the DTBP stream, either continuously or in batch mode or in semi batch mode. Furthermore, the DME can be introduced into a batch, semi-batch, or continuous, for example, fixed bed or fluid bed, reactor 118 in a number of different ways, such as via a single injection point, several injection points, or even via a sparger arrangement. The DME can be dispersed into the reactor 118 either through nozzles that are flush to the reactor vessel or through an internal distribution network. The number of nozzles flush to the reactor 118 can be one, a few or many. Alternatively, the DME can be introduced into a reactor 118, for example, through an internal distributor. The internal distributor may be a single injection point, a few injection points or many injection points. In the case of a few or many injection points, the distributor may contain arteries branching off of one or more common headers, and additional sub- arteries may branch off of each artery to form a network of arteries. The arteries may be designed to have a uniform diameter, either the same or different diameter as the common headers, or be tapered in various diameters and different lengths. Along each common header or artery there may be one or several or many nozzles to introduce the DME. The size and length of such nozzles may be similar or different depending on the distribution of the DME into the reactor. The internal distributor, arteries, and nozzles may be insulated. The resulting reaction products (e.g., glyme and methanol), by-products (e.g., acetone; C8+ aromatics), and unreacted DME are sent to one or more separation unit(s) (not shown) via line 120 for separation/fractionation, and recycling processes (further discussed in the following section). In at least one embodiment, the selectivity for the DME oxidative coupling using DTBP for the formation of glyme is from 60 wt% to 100 wt%, such as from 70 wt% to 95 wt%, such as from 75 wt% to 90 wt%, such as 80 wt%.

[0084] High level of oxygenates can be produced via condensation side -reactions under traditional methods. However, under coupling reaction conditions of processes of this disclosure, less oxygenate by-products can be formed, thus improving the selectivity to the formation of the glyme. Hence, the present process provides a sustainable approach for the construction of carbon-carbon bonds, leading to access to diether precursors suitable for the formation of glycols, without using expensive catalyst(s), nor using any additional solvent (the reactants can be used as solvents/diluents), or any further costly reactants for the processes.

[0085] In at least one embodiment, a mixture of reaction products (e.g., glyme recovered from line 130 and methanol recovered from line 138), by-products (e.g., acetone recovered from line 126), and unreacted DME from the coupling reactor 118 are sent to one or more separation unit(s) (not shown), such as one or more suitable column(s), one or more distillation system, and/or one or more suitable fractionator(s) via line 120 for separation/fractionation and further recyclization processes. Thus, unreacted DME can be recycled to the coupling reactor 118 via lines 122, while the remaining products are fractionated in order to separate the by-products, the methanol, and the glyme.

[0086] The TBA from a primary fractionator (not shown) can be recycled, when needed, either fully or partially for further formation of DTBP. Accordingly, an excess of TBA can be converted to a corresponding ether (not shown) by reacting with an alcohol (such as methanol or ethanol). The TBA can be converted to an iso-olefin as chemical products via dehydration (e.g., iso-butylene), or etherified with an alcohol (such as methanol or ethanol), making ether as gasoline blend (e.g., MTBE, ETBE) from iso-butane). The etherification reaction can be carried out in a fixed-bed reactor or a catalytic distillation reactor where an acid catalyst can be used. Examples of suitable acid catalysts may include, but are not limited to, resins such as Dowex™, Amberlyst™, Nafion™, sulfuric acid, sulfonic acid, phosphoric acid (neat or solid- supported on silica, alumina, or clay), acidic clay, aluminosilicate, zeolite, silicoaluminophosphate, acidic oxides such as tungsten oxide on zirconia, molybdenum oxide on zirconia, sulfated zirconia, acidic ionic liquids; Lewis acids such as aluminum chloride or boron trifluoride. The etherification reaction can be carried out at a temperature of l00°C to 400°C, such as from l50°C to 350°C, and/or a pressure of 700 kPag to 3450 kPag (100 psig to 500 psig), such as 1,000 kPag to 2760 kPag (150 psig to 400 psig). The TBA recovered from a primary fractionator (not shown) can also be used as a chemical product, fuel blend, or dehydrated to an olefin, such as iso-olefin. Dehydration of TBA can be carried out in a dehydration unit (not shown), such as a vapor phase unit, at a temperature of from l50°C to 450°C, such as from 200°C to 350°C, and/or a pressure of from 700 kPag to 3450 kPag (100 psig to 500 psig), such as 1,000 kPag to 2,070 kPag (150 psig to 300 psig) in fixed-bed or slurry reactors. An acidic catalyst can be used for the dehydration of TBA, such as those described above for the etherification reaction. Water is separated from the product stream. The iso olefin formed after the TBA dehydration can be used as a chemical intermediate for the production of polymers, rubber, or hydrocarbon resins. Optionally, the iso-olefin formed after the TBA dehydration can be converted to higher molecular weight products such as gasoline, kero-jet, or diesel via alkylation (not shown). Alkylation can be carried out using an acid catalyst such as sulfuric acid, hydrofluoric acid, or zeolites in the faujasite (FAU), mordenite (MOR), MFI, or MWW families. [0087] Such recycling system of the TBA to the corresponding iso-butylene provides manufacturers with competitive and economic advantages such as reducing energy consumption and waste disposal, sustaining use of resources, and increasing cost-efficiency by minimizing the production expenditure. Additionally, natural gas liquids, liquid petroleum gas, and refinery light gas such as light virgin naphtha (LVN) or light catalytic naphtha (LCN), can also be upgraded using the process of this disclosure.

[0088] Furthermore, processes of this disclosure include converting glyme to ethylene glycol and methanol. In at least one embodiment, the glyme is sent via line 130 to a hydrolysis reactor 132 where ethylene glycol is formed in the presence of water, over an acid catalyst (e.g., acidic clay). The water is sent to the hydrolysis reactor

132 via line 134.

[0089] For example, glyme and water can be mixed and fed to a reaction zone (e.g., hydrolysis reactor 132), loaded with a solid catalyst, such as an acid catalyst, and reacting the same. The reaction zone 132 can be one or more reactors connected in series and/or in parallel. In at least one embodiment, ethylene glycol and methanol are formed, and the resulting product mixtures obtained after the hydrolysis reaction can be separated via a separation unit (such as a distillation unit, column, not shown) upon exiting the reaction zone 132.

[0090] Representative solid acid catalysts for the hydrolysis process may include, but are not limited to, acidic clays, amorphous aluminosilicates, acidic alumina (e.g., gamma-alumina, chloride- alumina, and/or fluoride alumina), zeolites, silicoaluminophosphates, acidic mixed metal oxides (e.g., tungsten oxide/zirconium oxide, or molybdenum oxide/zirconium oxide), acidic resins (Amberlyst™ resin, Nafion™ resin, Dowex™ resin), supported phosphoric acid, etc. The acid can also be a Lewis acid such as BF ₃ , BCL, A1CL, either neat or supported on a solid support. The solid acid catalyst(s) can be one or both of an acidic molecular sieve catalyst and an acidic resin catalyst, as described in W.O. 2017/054317.

[0091] Conditions for the production of ethylene glycol in the reaction zone 132 can be a temperature of from 50°C to 450°C, such as from 75°C to 350°C, such as from l00°C to 250°C; a pressure of from 0 psig (such as ambient pressure) to 2,000 psig, such as from 50 psig to 1,500 psig, such as from 100 psig to 1,000 psig; and/or a residence time of from 0.1 hour to 48 hours, such as from 0.5 hours to 24 hours, such as from 1 hours to 10 hours, such as from 2 hours to 8 hours. In at least one embodiment, the hydrolysis of glyme is performed at a weight hourly space velocity (WHSV) from 0.01 hr ¹ to 100 hr ¹ , such as from 0.02 hr ¹ to 50 hr ¹ , such as from 0.02 hr ¹ to 10 hr ¹ .

[0092] The methanol can be sent to a dehydration reactor 140 where a conversion to DME can be carried out using a catalyst, such as a solid catalyst, such as a solid acid catalyst. The DME can be recycled to the oxidative coupling reactor 118 via line 144. Water can be separated from the product stream 144 via line 142, and optionally recycled to the hydrolysis reactor 132 (not shown). Recyclization of DME to the coupling reactor 118 via lines 122 and 144 provides a time- and cost-effective process for the production of the glyme, thus reducing reactants loss (if any) while improving the chemical equilibrium of the coupling reaction towards an increased yield of glyme.

[0093] Examples of suitable solid acid catalysts for the conversion of methanol to DME may be, but are not limited to, acidic clays, amorphous aluminosilicates, acidic alumina (e.g., gamma-alumina, chloride-alumina, and/or fluoride alumina), zeolites, silicoaluminophosphates, acidic mixed metal oxides (e.g., tungsten oxide/zirconium oxide, or molybdenum oxide/zirconium oxide), acidic resins (Amberlyst™ resin, Nafion™ resin, Dowex™ resin), supported phosphoric acid, etc. The acid can also be a Lewis acid such as BF ₃ , BCE, AlCb, either neat or supported on a solid support.

[0094] Conditions for the production of DME in the dehydration reactor 140 can be a temperature from 50°C to 450°C, such as from 75°C to 350°C, such as from l00°C to 250°C; a pressure of from 0 psig (such as ambient pressure) to 2,000 psig, such as from 50 psig to 1,500 psig, such as from 100 psig to 1,000 psig; and/or a residence time of from 0.1 hour to 48 hours, such as from 0.5 hours to 24 hours, such as from 1 hours to 10 hours, such as from 2 hours to 8 hours. In at least one embodiment, the production of DME is performed at a weight hourly space velocity (WHSV) from 0.01 hr ¹ to 100 hr ¹ , such as from 0.02 hr ¹ to 50 hr ¹ , such as from 0.02 hr ¹ to 10 hr ¹ .

EXAMPLES

Example 1 (comparative): Formation of ethylene glycol by coupling methanol using di- -butyl peroxide in an autoclave reactor

[0095] In a 300 cm ³ autoclave the following reactant were loaded: 71 g of methanol and 48 g of DTBP (trade name Luperox® DI from Aldich Chemicals, 98%). The autoclave was sealed, connected to a gas manifold, and pressurized with 600 psig nitrogen. The reactor content was heated under stirring (500 rpm) at a rate of 2°C/min to l50°C and held for 4 hours. The heat was turned off and the autoclave allowed to cool down to room temperature. A sample was taken and analyzed by GC analysis, showing complete conversion of DTBP. The autoclave was opened and the reactor content collected at the end of the ran, recovering 90% of the materials loaded. The products were analyzed by GC-MS using a FID detector: Product analyses were performed using GC (Agilent 6890 Plus) with an FID detector and GC/MS (Agilent 6890N-GC/5975-MS). Both instmments use the HP-PONA column (50 m length x 0.2 mm diameter x 0.5 pm film thickness). The GC conditions were the following: Injector: 225°C; 0.5 pL injection volume, 100/1 split ratio. Detector: 250°C. Oven: 35°C (10 min), 2.5°C/min to l35°C, l0°C/min to 320°C (6.5 min). The ran was repeated using a 2 hours-hold time. The GC results are shown in Table 1 which illustrates the product selectivity for oxidative coupling of methanol with DTBP. The selectivity for a given product (e.g., ethylene glycol) produced from methanol in Table 1 is calculated as weight percentage of that product in the product mixture relative to the total weight of products formed from methanol. The TBA product is considered as formed solely from DTBP, not from methanol, hence not included in the basis for calculating selectivity for ethylene glycol in this table. Although ethylene glycol was formed as the major product at a 56.4 wt% and 52.4 wt% selectivity when the coupling reaction carried out for 4 hours and 2 hours, respectively, a significant amount of by-products were also obtained. Formation of such by-products is mainly due to additional condensation reactions between acetone (which is a by-product derived from DTBP) and ethylene glycol, and/or between methanol and ethylene glycol.

Table 1

Example 2: Formation of glyme (l,2-dimethoxyethane) by coupling DME /dimethyl ether) using di-ferf-butyl peroxide in an autoclave reactor

[0096] In a 300 cm ³ autoclave, the following reactants were loaded: 103 g of DME and 16 g of DTBP (trade name Luperox® DI from Aldich Chemicals, 98%). The autoclave was sealed, connected to a gas manifold, and pressure tested. The reactor content was heated under stirring (800 rpm) at a rate of 2°C/min to l35°C and held for 22 hours. The heat was turned off and the autoclave allowed to cool down to room temperature. Unreacted DME was slowly vented through a dry-ice trap. The autoclave was opened and 45 g of liquid products was recovered. The products were analyzed by GC-MS using a FID detector: Product analyses were performed using GC (Agilent 6890 Plus) with an FID detector and GC/MS (Agilent 6890N-GC/5975-MS). Both instruments use the HP-PONA column (50 m length x 0.2 mm diameter x 0.5 pm film thickness). The GC conditions were the following: Injector: 225°C; 0.5 pL injection volume, 100/1 split ratio. Detector: 250°C. Oven: 35°C (10 min), 2.5°C/min to l35°C, l0°C/min to 320°C (6.5 min). The run was repeated using a 21 hours-hold time, 12 hours-hold time, and 4 hours-hold time. The GC results are shown in Table 2, which illustrates the product selectivity for DME oxidative coupling using DTBP (103 g DME and 16 g of DME for all runs). The selectivity for a given product (e.g., glyme) produced from DME coupling in Table 2 is calculated as weight percentage of that product in the product mixture relative to the total weight of products formed from DME. The TBA product is considered as formed solely from DTBP, not from DME, hence not included in the basis for calculating selectivity for ethylene glycol in this table. Significant selectivity to the expected coupling products was observed, with a selectivity for glyme being close to 80 wt% in all runs. A low amount of by-products (resulted from consecutive coupling of glyme) was obtained. It was observed that the formation of such by-products can be mitigated by controlling the ratio of DTBP/DME, reaction temperature, and ran length. Alternatively, the resulting by-products can be hydrolyzed to give valuable co-products. For example, l,2,3-trimethoxypropane can be converted to glycerol (1,2, 3-propane triol) and l,T-oxybis(2-methoxy)ethane can provide more ethylene glycol, in both cases via hydrolysis. Since glyme can be readily hydrolyzed to ethylene glycol and methanol, and methanol conversion to DME is facile and clean, the overall selectivity to ethylene glycol from a process of this disclosure was higher than the selectivity obtained from the methanol oxidative coupling as shown in the comparative example (Example 1). Table 2

[0097] Overall, this disclosure provides processes for producing glycols by upgrading branched hydrocarbons (using an optional recycling system). The glycols may be obtained with high selectivity. Processes of this disclosure can provide manufacturers with competitive and economic advantages such as reducing energy consumption and waste disposal, sustaining use of resources, and increasing efficiency by minimizing the production expenditure.

[0098] The phrases, unless otherwise specified, "consists essentially of" and

"consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of this disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[0099] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

[00100] All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of this disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of this disclosure. Accordingly, it is not intended that this disclosure be limited thereby. Likewise, the term“comprising” is considered synonymous with the term “including”. Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,”“consisting of,”“selected from the group of consisting of,” or“is” preceding the recitation of the composition, element, or elements and vice versa.

[00101] While this disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of this disclosure.