Metallosilicate catalyst solvent

Abstract

A method for producing an alkylene glycol monoalkyl ether includes contacting an olefin, an alcohol, a metallosilicate catalyst, and a solvent blend, wherein the solvent blend comprises 30% to 90% by weight of an oxygenated solvent, based on the total weight of the solvent blend, and 10% to 70% by weight of a non-oxygenated solvent, based on the total weight of the solvent blend; and producing the alkylene glycol monoalkyl ether.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates generally to metallosilicate catalysts, and more specifically to solvent blends used in conjunction with metallosilicate catalysts. [Background technology]

[0002] Introduction The production of secondary alcohol ethoxylate surfactants can be carried out by catalytic ethoxylation of (poly)alkylene glycol monoalkyl ethers ("monoalkyl ethers"). Monoalkyl ethers are formed from olefins and (poly)alkylene glycols via an etherification reaction using a metallosilicate catalyst. (Poly)alkylene glycol dialkyl ethers ("dialkyl ethers") are also produced by the etherification reaction. The selectivity of a catalyst or reaction indicates the relative proportions of reaction products produced. Typically, high selectivity for the desired reaction product is advantageous for maximizing reaction yield. Metallosilicate catalysts provide greater than 80% selectivity to monoalkyl ethers, which is advantageous because dialkyl ethers are detrimental to the properties of secondary alcohol ethoxylate surfactants.

[0003] Another important metric for etherification reactions is olefin conversion. Olefin conversion measures the amount of olefin converted in the reaction. Similar to selectivity, maximizing olefin conversion is advantageous for maximizing reaction yield. Because monoalkyl ethers are intermediates for the formation of undesired dialkyl ethers, it is difficult to simultaneously achieve high monoalkyl ether selectivity and high olefin conversion. In other words, a higher olefin conversion results in a higher content of dialkyl ethers produced and less monoalkyl ether remaining (i.e., lower selectivity). Without the use of a solvent, olefin conversions of 20% to 40% and monoalkyl ether selectivities of 70% to 75% can be achieved. Relatively low conversions and low selectivities can lead to excessive dialkyl ether formation, hindering the large-scale implementation of etherification reactions. Ideally, etherification reactions used to produce monoalkyl ethers should have an olefin conversion of greater than 40% and a monoalkyl ether selectivity of greater than 75% to be considered successful.

[0004] Attempts have been made to utilize solvents to improve selectivity and olefin conversion. For example, U.S. Patent No. 5,741,948 and U.S. Patent No. 6,417,408 both disclose that the reaction of olefins with (poly)alkylene glycols can be carried out in the presence or absence of solvents such as "nitromethane, nitroethane, nitrobenzene, dioxane, ethylene glycol dimethyl ether, sulfolane, benzene, toluene, xylene, hexane, cyclohexane, decane, paraffin, and the like." U.S. Patent No. 5,741,948 and U.S. Patent No. 6,417,408 do not indicate a preference for the type of solvent, nor do they disclose the mixing of different solvents. Similarly, U.S. Patent Application Publication No. 20220274903(A1) discloses the use of oxygen-containing solvents in the production of monoalkyl ethers, but reveals through Comparative Examples 5 and 8 that hexane as a solvent does not offer advantages in terms of monoalkyl ether selectivity or olefin conversion. WO2023278187 also discloses the use of cresols and other oxygen-containing solvents in connection with the production of monoalkyl ethers.

[0005] Despite the obvious advantages of using some types of solvents, adding more material to the reaction adds greater cost. For example, oxygen-containing solvents such as those described in the prior art above are relatively expensive, which can make commercial production of mono-alkyl ethers prohibitively expensive.

[0006] In view of the above, it would be surprising to find a process for producing alkylene glycol monoalkyl ethers with an olefin conversion of greater than 40% and a monoalkyl ether selectivity of greater than 75%, which is also economically viable. Summary of the Invention

[0007] The inventors of the present application have discovered a process for producing alkylene glycol monoalkyl ethers with an olefin conversion of greater than 40% and a monoalkyl ether selectivity of greater than 75%, which is also economically viable.

[0008] The present invention is the result of the discovery that by utilizing a solvent blend containing both an oxygen-containing solvent and a non-oxygen-containing solvent in an etherification reaction, it is possible to achieve an olefin conversion of greater than 40% and a mono-alkyl ether selectivity of greater than 75% while remaining economically viable. While oxygen-containing solvents are typically expensive and non-oxygen-containing solvents cannot achieve both the desired olefin conversion or selectivity by themselves, it has been discovered that a solvent blend containing 30 wt% to 90 wt% of an oxygen-containing solvent, based on the total weight of the solvent blend, and 10 wt% to 70 wt% of a non-oxygen-containing solvent, based on the total weight of the solvent blend, can achieve all desired objectives. Furthermore, such a combination surprisingly exhibits minimal or no decrease in olefin conversion and selectivity despite the addition of the non-oxygen-containing solvent.

[0009] According to a first aspect of the present disclosure, a method for producing an alkylene glycol monoalkyl ether includes contacting an olefin, an alcohol, a metallosilicate catalyst, and a solvent blend, wherein the solvent blend comprises 30 wt % to 90 wt % of an oxygen-containing solvent, based on the total weight of the solvent blend, and 10 wt % to 70 wt % of a non-oxygen-containing solvent, based on the total weight of the solvent blend; and producing an alkylene glycol monoalkyl ether.

[0010] According to a second aspect of the present disclosure, the metallosilicate catalyst is an aluminosilicate compound having a crystal lattice with one or more metal elements substituting for silicon atoms in the crystal lattice.

[0011] According to a third aspect of the present disclosure, the olefin is C 12 ~C14 Contains alpha-olefins.

[0012] According to a fourth aspect of the present disclosure, the alcohol is monoethylene glycol, diethylene glycol, glycerol, or a combination thereof.

[0013] According to a fifth feature of the present disclosure, the molar ratio of alcohol to olefin is 0.5 to 1.5.

[0014] According to a sixth aspect of the present disclosure, the solvent blend is 10% to 80% by weight of the total combined weight of the olefin, alcohol, and solvent.

[0015] According to a seventh aspect of the present disclosure, the solvent blend comprises 40 wt % to 60 wt % of a non-hydrogenated solvent, based on the total weight of the solvent blend.

[0016] According to an eighth aspect of the present disclosure, the oxygen-containing solvent is selected from the group consisting of cresol, o-cresol, m-cresol, p-cresol, phenol, guaiacol, methyl benzoate, dimethyl phthalate, diglyme, triglyme, diethyl phthalate, dibutyl phthalate, ethyl benzoate, trimethyl 1,2,4-benzenetricarboxylate, glyme, dimethoxybenzene, and combinations thereof.

[0017] According to a ninth feature of the present disclosure, the non-oxygen-containing solvent is xylene, m-xylene, p-xylene, o-xylene, benzene, toluene, hexane, heptane, octane, nonane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, cyclohexane, cycloheptane, cyclooctane, linear C6-C 16 Alkanes, cyclic C6-C 16 alkanes, and combinations thereof.

[0018] According to a tenth feature of the present disclosure, the non-oxygenated solvent is xylene and the oxygenated solvent is cresol. DETAILED DESCRIPTION OF THE INVENTION

[0019] As used herein, the term "and / or," when used in a list of two or more items, means that any one of the listed items can be used by itself, or any combination of two or more of the listed items can be used. For example, if a composition is described as containing components A, B, and / or C, the composition can contain A alone, B alone, C alone, A and B in combination, A and C in combination, B and C in combination, or A, B, and C in combination.

[0020] Unless otherwise stated, all ranges are inclusive of the endpoints.

[0021] Test methods refer to the most current test method as of the priority date of this document unless a date is indicated with the test method number as a two-digit number with a hyphen. References to test methods include references to both the testing society and the test method number. Test method organizations are referred to by one of the following abbreviations: ASTM refers to ASTM International (formerly the American Society for Testing and Materials), EN refers to European Norm, DIN refers to Deutsches Institut fuer Normung, and ISO refers to the International Organization for Standards.

[0022] IUPAC codes describing crystalline structures as drawn by the Structure Commission of the International Zeolite Association refer to their current designations as of the priority date of this document, unless otherwise specified.

[0023] As used herein, the term weight percent ("wt %") indicates that a component is a weight percent of the total weight of the indicated composition.

[0024] As used herein, "CAS Number" is a Chemical Service Registry Number assigned by the Chemical Abstracts Service.

[0025] method The method of the present invention relates to the use of a solvent blend in the metallosilicate-catalyzed reaction of an alcohol with an olefin. The method may include (a) contacting an olefin, an alcohol, a metallosilicate catalyst, and a solvent blend, and (b) producing an alkylene glycol monoalkyl ether.

[0026] olefin The olefins used in the present process can be linear, branched, acyclic, cyclic, or mixtures thereof. Olefins can be from 5 carbons to 30 carbons (i.e., C5 to C6). 30The olefin may have 5 or more carbons, or 6 or more carbons, or 7 or more carbons, or 8 or more carbons, or 9 or more carbons, or 10 or more carbons, or 11 or more carbons, or 12 or more carbons, or 13 or more carbons, or 14 or more carbons, or 15 or more carbons, or 16 or more carbons, or 17 or more carbons, or 18 or more carbons, or 19 or more carbons, or 20 or more carbons, or 21 or more carbons, or 22 or more carbons, or 23 or more carbons, or 24 or more carbons, or 25 or more carbons, or 26 or more carbons, or 27 or more carbons, or 28 or more carbons, or 29 or more carbons, while At the same time, it may have 30 or fewer carbons, or 29 or fewer carbons, or 28 or fewer carbons, or 27 or fewer carbons, or 26 or fewer carbons, or 25 or fewer carbons, or 24 or fewer carbons, or 23 or fewer carbons, or 22 or fewer carbons, or 21 or fewer carbons, or 20 or fewer carbons, or 19 or fewer carbons, or 18 or fewer carbons, or 17 or fewer carbons, or 16 or fewer carbons, or 15 or fewer carbons, or 14 or fewer carbons, or 13 or fewer carbons, or 12 or fewer carbons, or 11 or fewer carbons, or 10 or fewer carbons, or 9 or fewer carbons, or 8 or fewer carbons, or 7 or fewer carbons, or 6 or fewer carbons.

[0027] The olefin may be an alpha (α) olefin, an internally disubstituted olefin, or a cyclic structure (e.g., C3-C 12The α-olefin may include an alkene such as cycloalkene. The α-olefin contains an unsaturated bond at the α-position of the olefin. Suitable α-olefins may be selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icosene, 1-docosene, and combinations thereof. The internal disubstituted olefin contains an unsaturated bond that is not at the terminal position of the olefin. The internal olefin may be selected from the group consisting of 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4-octene, 2-nonene, 3-nonene, 4-nonene, 2-decene, 3-decene, 4-decene, 5-decene, and combinations thereof. Other exemplary olefins may include butadiene and styrene.

[0028] Examples of suitable commercially available olefins include NEODENE™ 6-XHP, NEODENE™ 8, NEODENE™ 10, NEODENE™ 12, NEODENE™ 14, NEODENE™ 16, NEODENE™ 1214, NEODENE™ 1416, NEODENE™ 16148 manufactured by Shell (The Hague, Netherlands).

[0029] alcohol The alcohols utilized in the present methods may contain a single hydroxyl group, two hydroxyl groups (i.e., glycols), or three hydroxyl groups. The alcohols may contain 1 or more carbons, or 2 or more carbons, or 3 or more carbons, or 4 or more carbons, or 5 or more carbons, or 6 or more carbons, or 7 or more carbons, or 8 or more carbons, or 9 or more carbons, while also containing 10 or fewer carbons, or 9 or fewer carbons, or 8 or fewer carbons, or 7 or fewer carbons, or 6 or fewer carbons, or 5 or fewer carbons, or 4 or fewer carbons, or 3 or fewer carbons, or 2 or fewer carbons. The alcohol may be selected from the group consisting of methanol, ethanol, monoethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanemethanediol, glycerol, and / or combinations thereof. According to various examples, the alcohol is a (poly)alkylene glycol, such as monoethylene glycol, diethylene glycol, propylene glycol, and triethylene glycol.

[0030] The molar ratio of alcohol to olefin in the process may be 20:0.5 or less, or 20:1 or less, or 15:1 or less, or 10:1 or less, or 9:1 or less, or 8:1 or less, or 7:1 or less, or 6:1 or less, or 5:1 or less, or 4:1 or less, or 3:1 or less, or 2:1 or less, or 0.2:1 or less, while being 0.1:1 or greater, or 1:1 or greater, or 1:2 or greater, or 1:3 or greater, or 1:4 or greater, or 1:5 or greater, or 1:6 or greater, or 1:7 or greater, or 1:8 or greater, or 1:9 or greater, or 1:10 or greater, or 1:15 or greater, or 1:20 or greater, or 0.5:20 or greater. In specific examples, the molar ratio of alcohol to olefin may be 2.0 to 15 or 2.0 to 8. The molar ratio is calculated by dividing the number of moles of alcohol present by the number of moles of olefin present.

[0031] Solvent Blend The solvent blend is contacted with the olefin, alcohol, and metallosilicate catalyst to promote the chemical reaction. The solvent blend includes an oxygen-containing solvent and a non-oxygen-containing solvent. As used herein, the term "oxygenated solvent" refers to a compound that contains carbon, hydrogen, and oxygen atoms and solubilizes one or more of the alcohol and the olefin. As used herein, the term "non-oxygenated solvent" refers to a compound that does not contain oxygen atoms and solubilizes one or more of the alcohol and the olefin.

[0032] The solvent blend may be from 0.1% to 85% by weight of the combined weight of the olefin, alcohol, and solvent blend, The solvent blend may be 0.1% or more, or 0.5% or more, or 1% or more, or 5% or more, or 10% or more, or 15% or more, or 20% or more, or 25% or more, or 30% or more, or 35% or more, or 40% or more, or 45% or more, or 50% or more, or 55% or more, or 60% or more, or 65% or more, or 70% or more by weight of the combined weight of the olefin, alcohol, and solvent blend, may be 75% by weight or more, or 80% by weight or more, and at the same time 85% by weight or less, or 80% by weight or less, or 75% by weight or less, or 70% by weight or less, 65% by weight or less, or 60% by weight or less, 55% by weight or less, or 50% by weight or less, 45% by weight or less, or 40% by weight or less, 35% by weight or less, or 30% by weight or less, 25% by weight or less, or 20% by weight or less, 15% by weight or less, or 10% by weight or less, 5% by weight or less, or 1% by weight or less, or 0.5% by weight or less.

[0033] The solvent blend comprises 30% to 90% by weight of oxygen-containing solvent, based on the total weight of the solvent blend, and 10% to 70% by weight of non-oxygen-containing solvent, based on the total weight of the solvent blend. For example, the solvent blend may comprise 30% or more, or 35% or more, or 40% or more, or 45% or more, or 50% or more, or 55% or more, or 60% or more, or 65% or more, or 70% or more, or 75% or more, or 80% or more, or 85% or more by weight of oxygen-containing solvent, based on the total weight of the solvent blend, while at the same time comprising 90% or less, 85% or less, or 80% or less, or 75% or less, or 70% or less, or 65% or less, or 60% or less, or 55% or less, or 50% or less, or 45% or less, or 40% or less, or 35% or less by weight of oxygen-containing solvent. The solvent blend may comprise 10% by weight or more, or 15% by weight or more, or 20% by weight or more, or 25% by weight or more, or 30% by weight or more, or 35% by weight or more, or 40% by weight or more, or 45% by weight or more, or 50% by weight or more, or 55% by weight or more, or 60% by weight or more, or 65% by weight or more, while comprising 70% by weight or less, or 65% by weight or less, or 60% by weight or less, or 55% by weight or less, or 50% by weight or less, or 45% by weight or less, or 40% by weight or less, or 35% by weight or less, or 30% by weight or less, or 25% by weight or less, or 20% by weight or less, or 15% by weight or less of non-oxygen-containing solvents, based on the total weight of the solvent blend.

[0034] The oxygen-containing solvent is selected from the group consisting of cresol, o-cresol, m-cresol, p-cresol, phenol, guaiacol, methyl benzoate, dimethyl phthalate, diglyme, triglyme, diethyl phthalate, dibutyl phthalate, ethyl benzoate, trimethyl 1,2,4-benzenetricarboxylate, glyme, dimethoxybenzene, and combinations thereof. As used herein, the term "cresol" refers to a blend of o-cresol, p-cresol, and m-cresol isomers.

[0035] Non-oxygen-containing solvents include xylene, m-xylene, p-xylene, o-xylene, benzene, toluene, hexane, heptane, octane, nonane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, cyclohexane, cycloheptane, cyclooctane, and linear C6-C 16 Alkanes, cyclic C6-C 16 The oxygen-containing solvent is selected from the group consisting of alkanes, m-xylene, p-xylene, and o-xylene, and combinations thereof. As used herein, the term "xylene" refers to a blend of the xylene isomers m-xylene, p-xylene, and o-xylene. In a specific example, the oxygen-containing solvent is cresol and the non-oxygen-containing solvent is xylene.

[0036] Metallosilicate Catalyst As used herein, the term "metallosilicate catalyst" refers to an aluminosilicate (commonly referred to as a zeolite) compound having a crystalline lattice with one or more metal elements replacing silicon atoms in the crystalline lattice. The crystalline lattice of the metallosilicate catalyst forms cavities and channels within which cations, water, and / or small molecules may reside. The alternative metal elements may include one or more metals selected from the group consisting of B, Al, Ga, In, Ge, Sn, P, As, Sb, Sc, Y, La, Ti, Zr, V, Cr, Mn, Pb, Pd, Pt, Au, Fe, Co, Ni, Cu, and Zn. The metallosilicate catalyst may be substantially free of Hf. According to various examples, the metallosilicate may have a silica-to-alumina molar ratio of 5:1 to 1,500:1 as measured using neutron activation analysis. The molar ratio of silica to alumina can be from 5:1 to 1,500:1, or from 10:1 to 500:1, or from 10:1 to 400:1, or from 10:1 to 300:1, or from 10:1 to 200:1. Such molar ratios of silica to alumina can be advantageous in providing a metallosilicate catalyst with suitable hydrophobic selectivity for adsorbing non-polar organic molecules.

[0037] The metallosilicate catalyst may have one or more exchangeable cations outside the crystal lattice. The exchangeable cations may be H+ , Li + , Na + , Rb + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ ,Sc. 3+ , Y 3+ , La 3+ , R4N + , R4P + (wherein R is H or alkyl).

[0038] Metallosilicate catalysts can have a variety of crystalline structures, including, for example, MFI (e.g., ZSM-5), MEL (e.g., ZSM-11), BEA (e.g., β-type zeolite), FAU (e.g., Y-type zeolite), MOR (e.g., mordenite), MTW (e.g., ZSM-12), and LTL (e.g., Linde L), when described using IUPAC codes according to the nomenclature of the International Zeolite Association's Structure Commission.

[0039] The crystalline framework of metallosilicate catalysts is represented by a network of molecular-sized channels and cages composed of corner-sharing tetrahedron [TO4] (T = Si or Al) primary building blocks. Negative charge can be introduced onto the framework through isomorphous substitution of tetravalent silicon atoms with trivalent metal (e.g., aluminum) atoms. Overall charge neutrality is then achieved by the introduction of cationic species that compensate for the resulting negative lattice charge. When such charge compensation is provided by protons, Brønsted acid sites are formed, making the resulting H-form of the zeolite a strong solid Brønsted acid.

[0040] The metallosilicate catalyst can be used in the present process in various forms, for example, the metallosilicate catalyst can be a powder (e.g., particles having a longest linear dimension of less than 100 micrometers), granular (e.g., particles having a longest linear dimension of 100 micrometers or more), or a shaped article (e.g., pellets or extrudates) of powder and / or granular metallosilicate catalyst.

[0041] The metallosilicate catalyst is 100m 2 / g or more, or 200m 2 / g or more, or 300m 2 / g or more, or 400m 2 / g or more, or 500m 2 / g or more, 600m 2 / g or more, or 700m 2 / g or more, or 800m 2 / g or more, or 900m 2 / g or more, while at the same time, 1000m 2 / g or less, or 900m 2 / g or less, or 800m 2 / g or less, or 700m 2 / g or less, or 600m 2 / g or less, or 500m 2 / g or less, or 400m 2 / g or less, or 300m 2 / g or less, or 200m 2 The surface area may be measured in accordance with ASTM D4365-19.

[0042] The metallosilicate catalyst can be synthesized by hydrothermal synthesis. For example, the metallosilicate catalyst can be synthesized by heating a composition containing a silica source (e.g., silica sol, silica gel, and alkoxysilane), a metal source (e.g., metal sulfate, metal oxide, metal halide, etc.), and a quaternary ammonium salt such as tetraethylammonium salt or tetrapropylammonium salt to a temperature of about 100°C to about 175°C until a crystalline solid is formed. The resulting crystalline solid is then filtered, washed with water, dried, and then calcined at a temperature of 350°C to 600°C.

[0043] Examples of suitable commercially available metallosilicate catalysts include CP814E, CP814C, CP811EL, CP811C-300, CBV 712, CBV 720, CBV 760, CBV 2314, CBV 10A manufactured by ZEOLYST INTERNATIONAL™ of Conshohocken, PA.

[0044] Formation of monoalkyl ethers Contacting an olefin, an alcohol, a metallosilicate catalyst, and a solvent blend produces alkylene glycol monoalkyl ethers. The chemical reaction between the olefin and the alcohol is catalyzed by the metallosilicate catalyst in a reactor to produce the monoalkyl ether. Various monoalkyl ethers can be produced for different applications by varying which olefin is utilized and / or by varying which alcohol is utilized. Monoalkyl ethers are utilized in many applications, such as solvents, surfactants, and chemical intermediates.

[0045] The reaction of the olefin with the alcohol can be carried out at temperatures between 50°C and 300°C or between 100°C and 200°C. In an embodiment, the reaction can be carried out at 150°C. In another embodiment, the reaction can be carried out at 135°C. In another embodiment, the reaction can be carried out at a temperature between 120°C and 150°C. The reaction of the olefin with the alcohol can be carried out in a batch reactor, a continuous reactor, or a fluidized bed reactor. In a chemical reaction operation, the Bronsted acid sites of the metallosilicate catalyst catalyze the etherification of the olefin to the alcohol through an addition-type reaction. The reaction of the olefin with the alcohol produces a mono-alkyl ether.

[0046] The addition reaction of olefins to glycols can form not only monoalkyl ethers but also dialkyl ethers. Metallosilicate catalysts can exhibit selectivity to produce alkylene monoalkyl ethers but not dialkyl ethers. The selectivity to monoalkyl ethers can be 70% or more, or 75% or more, or 80% or more, or 85% or more, or 90% or more, or 95% or more, or 99% or more, while simultaneously being 100% or less, or 95% or less, or 90% or less, or 85% or less, or 80% or less, or 75% or less. The selectivity of the dialkyl ether can be 0% or more, or 2% or more, or 4% or more, or 6% or more, or 8% or more, or 10% or more, or 12% or more, or 14% or more, or 16% or more, or 18% or more, while simultaneously being 20% ​​or less, or 18% or less, or 16% or less, or 14% or less, or 12% or less, or 10% or less, or 8% or less, or 6% or less, or 4% or less, or 2% or less.

[0047] The monoalkyl ether yield is calculated by multiplying the amount of olefin conversion by the monoalkyl ether selectivity. The alkylene glycol monoalkyl ether yield can be 10% or more, or 15% or more, or 20% or more, or 25% or more, or 30% or more, or 35% or more, while simultaneously being 40% or less, or 35% or less, or 30% or less, or 25% or less, or 20% or less, or 15% or less. The monoalkyl ether yield is a measure of catalyst activity and selectivity, and is a good measure of the production rate of the metallosilicate catalyst.

[0048] During the reaction of olefins with alcohols, the catalyst becomes contaminated, resulting in deactivation of the catalyst (ie, loss of >90% of the etherification activity) within a few hours. [Example]

[0049] material Below is a list of materials used to form the inventive examples (IE) and comparative examples (CE).

[0050] The catalyst is a metallosilicate catalyst defined by the BEA structure, having a silica to alumina molar ratio of 25:1 and a surface area of 680 m 2 / g, and is commercially available as CP814E manufactured by ZEOLYST INTERNATIONAL™ of Conshohocken, PA.

[0051] The olefin is commercial 1-dodecene available as NEODENE™ 12 manufactured by the SHELL™ group of The Hague (Netherlands).

[0052] Monoethylene glycol is a polyester grade having a CAS number of 107-2,1-1 and is supplied by The Dow Chemical Company of Midland, Michigan.

[0053] Cresol is a mixture of O-cresol, P-cresol, and M-cresol isomers in phenol at 8 wt% or less and is available from SIGMA ALDRICH™ (St. Louis, Missouri).

[0054] M-cresol is 3-methylphenol having a CAS number of 108-39-4 and is commercially available.

[0055] Xylene is a mixture of o-xylene, m-xylene, and p-xylene with ethylbenzene as a co-solvent and is available from SIGMA ALDRICHTM (St. Louis, Missouri).

[0056] o-xylene is 1,2-dimethylbenzene and is commercially available from SIGMA ALDRICH™ (St. Louis, Missouri).

[0057] Decane is a non-oxygen-containing solvent and is commercially available from SIGMA ALDRICH™ (St. Louis, Missouri).

[0058] Methyl benzoate is a non-oxygen-containing solvent with a CAS number of 93-58-3 and is commercially available from SIGMA ALDRICH™ (St. Louis, Missouri).

[0059] Diglyme is bis(2-methoxyethyl) ether having a CAS number of 111-96-6 and is commercially available from SIGMA ALDRICH™ (St. Louis, Missouri).

[0060] Guaiacol is a 2-methoxyphenol having a CAS number of 90-05-1 and is commercially available from SIGMA ALDRICH™ (St. Louis, Missouri).

[0061] Toluene is a non-oxygen-containing solvent and is commercially available from SIGMA ALDRICH™ (St. Louis, Missouri).

[0062] Benzene is a non-oxygen-containing solvent and is commercially available from SIGMA ALDRICH™ (St. Louis, Missouri).

[0063] Test Method Gas Chromatography Samples A gas chromatography sample was prepared by mixing 100 μL of this example with 10 mL of gas chromatography solution prepared by adding 1 mL of hexadecane to 1 L of ethyl acetate. The sample was analyzed using an Agilent 7890B gas chromatography instrument. The total amount of 1-dodecene-derived species, including mono- and di-alkyl ethers, and 2-dodecanol, 1-dodecene and all non-1-dodecene species, other C 12 The total amount of dodecene, including isomers, is determined. Table 1 provides the relevant gas chromatography instrument parameters.

[0064] [Table 1]

[0065] Olefin Conversion Calculate the olefin conversion by dividing the total amount of dodecene-derived species by the sum of the total amount of dodecene-derived species and the amount of dodecene. Multiply the quotient by 100.

[0066] Monoalkyl ether selectivity Calculate the mono-alkyl ether selectivity by dividing the total amount of mono-alkyl ethers by the total amount of dodecene-derived species. Multiply the quotient by 100.

[0067] Monoether Yield The monoalkyl ether yield is calculated by multiplying the olefin conversion value by the monoalkyl ether selectivity value.

[0068] Sample preparation and results The etherification reactions were carried out in either a vial reactor or a Parr reactor. The reactants used were 1-dodecene, ethylene glycol, the indicated solvent, and catalyst. IE6 and IE7 were the only examples carried out in a Parr reactor. The vial reactor was a 40 mL vial into which the reactants were added along with a tumbling disk agitator. For the vial reactor, the reactor contained 0.75 g of beta zeolite and 15 grams of the reaction mixture (i.e., ethylene glycol, 1-dodecene, and solvent). The vial reactor was then placed in an apparatus that heated the vial reactor to the desired temperature and stirred in a tumbling manner with a stir bar. The Parr reactor was carried out using a scale 10 times larger than that used in the vial reactor. The Parr reactor contained 7.5 g of beta zeolite and 150 grams of the reaction mixture (i.e., ethylene glycol, 1-dodecene, and solvent). The Parr reactor was stirred using an overhead agitator. When run in a Parr reactor, the reaction was heated to 135° C. in 1 hour and held at 135° C. for 3 hours. When run in a vial reactor, the vial reactor was placed in a heater preheated to 135° C. and the reaction was held for 3 hours.

[0069] Table 1 provides the compositions and performance of examples of the present invention and comparative examples. In Table 1, "NO" is a non-oxygen-containing solvent, and "OXY solvent" is an oxygen-containing solvent.

[0070] [Table 2]

[0071] Referring now to Table 1, it is clear from IE1-IE11 that the use of a solvent blend comprising 30 wt% to 90 wt% oxygen-containing solvent, based on the total weight of the solvent blend, and 10 wt% to 70 wt% non-oxygen-containing solvent, based on the total weight of the solvent blend, allows the etherification reaction to achieve 40% olefin conversion and greater than 75% mono-alkyl ether selectivity without being prohibitively expensive. CE1 indicates that the etherification reaction can be carried out without a solvent, but the olefin conversion target of 40% or greater is not met. CE2 and CE3 indicate that the use of a non-oxygen-containing solvent alone is unable to simultaneously meet the olefin conversion and mono-alkyl ether selectivity targets. CE4-CE6 indicate that an oxygen-containing solvent can achieve the target olefin conversion and mono-alkyl ether selectivity requirements, but as previously discussed, the use of an oxygen-containing solvent alone proves to be too cost-prohibitive for commercial implementation. IE1-IE8 demonstrate that the etherification reaction can achieve the olefin conversion and mono-alkyl ether selectivity targets despite including a 50:50 ratio of non-oxygen-containing solvent with the oxygen-containing solvent. IE4, IE9, and IE8 demonstrate that the solvent blend can incorporate non-oxygen-containing solvent in a weight percent range of 10 wt% to 70 wt%, based on the total weight of the solvent blend. IE10 and IE11 demonstrate that the reaction time, ethylene glycol to 1-dodecene ratio, and total solvent concentration can be varied while still achieving the olefin conversion and mono-alkyl ether selectivity targets.

Claims

1. 1. A method for producing an alkylene glycol monoalkyl ether, comprising: contacting an olefin, an alcohol, a metallosilicate catalyst, and a solvent blend, wherein the solvent blend comprises 30 wt% to 90 wt% of an oxygen-containing solvent, based on the total weight of the solvent blend, and 10 wt% to 70 wt% of a non-oxygen-containing solvent, based on the total weight of the solvent blend; producing said alkylene glycol monoalkyl ether.

2. 2. The method of claim 1, wherein the metallosilicate catalyst is an aluminosilicate compound having a crystalline lattice with one or more metal elements substituting for silicon atoms in the crystalline lattice.

3. The olefin is １２ ~C １４ The method of claim 1 or 2, comprising an alpha-olefin.

4. The method of any one of claims 1 to 3, wherein the alcohol is monoethylene glycol, diethylene glycol, glycerol, or a combination thereof.

5. 5. The process according to any one of claims 1 to 4, wherein the molar ratio of alcohol to olefin is from 0.5 to 1.

5.

6. 6. The method of any one of claims 1 to 5, wherein the solvent blend is 10% to 80% by weight of the total combined weight of the olefin, alcohol, and solvent blend.

7. 7. The method of any one of claims 1 to 6, wherein the solvent blend comprises 40% to 60% by weight of the non-oxygen-containing solvent, based on the total weight of the solvent blend.

8. 8. The method of any one of claims 1 to 7, wherein the oxygen-containing solvent is selected from the group consisting of cresol, o-cresol, m-cresol, p-cresol, phenol, guaiacol, methyl benzoate, dimethyl phthalate, diglyme, triglyme, diethyl phthalate, dibutyl phthalate, ethyl benzoate, trimethyl 1,2,4-benzenetricarboxylate, glyme, dimethoxybenzene, and combinations thereof.

9. The non-oxygen-containing solvent is xylene, m-xylene, p-xylene, o-xylene, benzene, toluene, hexane, heptane, octane, nonane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, cyclohexane, cycloheptane, cyclooctane, linear C ６ ~C １６ Alkanes, cyclic C ６ ~C １６ The method of any one of claims 1 to 8, wherein the organic solvent is selected from the group consisting of alkanes, and combinations thereof.

10. 8. The method of claim 1, wherein the non-oxygen-containing solvent is xylene and the oxygen-containing solvent is cresol.