Method for producing (poly)alkylene glycol monoalkyl ethers

Abstract

The embodiments relate to a method for producing (poly)alkylene glycol monoalkyl ethers. The method includes providing a mixture of a crystalline metal silicate molecular sieve catalyst and a metal oxide, and reacting an olefin and a (poly)alkylene glycol in the presence of the mixture in a liquid-phase process to produce the (poly)alkylene glycol monoalkyl ether. The reaction of the olefin and the (poly)alkylene glycol in the presence of the mixture is carried out at a temperature of 80°C to 200°C.

Description

Technical Field

[0001] The embodiments disclosed herein relate to the production of (poly)alkylene glycol monoalkyl ethers. Background Technology

[0002] Crystalline metal silicate molecular sieve catalysts, particularly β-zeolites, have been used to produce (poly)alkylene glycol monoalkyl ethers from olefins and (poly)alkylene glycols. At typical reaction temperatures of 100°C to 200°C, crystalline metal silicate molecular sieve catalysts exhibit approximately 10% to 50% olefin conversion percentage and approximately 60% to 95% monoether selectivity and approximately 5% to 40% diether selectivity, respectively. With increasing olefin conversion, the monoether and diether selectivity typically decrease and increase, respectively. Monoethers are the desired product, used in downstream ethoxylation processes to produce the desired alcohol ethoxylated surfactant product. Conversely, the presence of diethers can affect the properties of the surfactant product and is therefore undesirable. Since monoethers are the desired product, it is desirable to maintain increased monoether selectivity at high olefin conversion rates.

[0003] The global market for alcohol ethoxylated surfactants is currently dominated by primary alcohol ethoxylated surfactants (PAEs). While offering excellent properties (e.g., wetting, foaming, treating, etc.), secondary alcohol ethoxylated surfactants (SAEs) have only a small market share due to their higher price compared to PAEs. One reason for their higher cost is that SAEs require several cost-intensive reactions using starting materials (e.g., (poly)alkylene glycol monoalkyl ether intermediates), which have limited availability and therefore associated high costs.

[0004] Given the limited availability and high cost of starting materials for (poly)alkylene glycol monoalkyl ethers used in SAE production, there is a need in the art for cost-effective alternatives to the production of (poly)alkylene glycol monoalkyl ethers. Therefore, the development of catalytic methods with high selectivity, good olefin conversion (>10%), and catalyst stability in the production of (poly)alkylene glycol monoalkyl ethers is both desirable and necessary in the art. Summary of the Invention

[0005] This disclosure provides a cost-effective method for producing (poly)alkylene glycol monoalkyl ethers for the production of secondary alcohol ethoxylates (SAE). The method of this disclosure helps address the aforementioned problems of the prior art by providing a way to produce (poly)alkylene glycol monoalkyl ethers with high selectivity and high yield. Specifically, this disclosure provides a mixture of a crystalline metal silicate molecular sieve catalyst and a metal oxide, which together provide high selectivity and high olefin conversion for (poly)alkylene glycol monoalkyl ethers. Furthermore, as discussed herein, the improved stability of the crystalline metal silicate molecular sieve catalyst due to the presence of the metal oxide helps maintain the selectivity and activity of the crystalline metal silicate molecular sieve catalyst.

[0006] This disclosure provides a method for producing (poly)alkylene glycol monoalkyl ethers, the method comprising providing a mixture of a crystalline metal silicate molecular sieve catalyst and a metal oxide, wherein the metal is selected from the group consisting of: Group 3 metals, lanthanides and combinations thereof; and reacting an olefin and a (poly)alkylene glycol in a liquid-phase process in the presence of the mixture of the crystalline metal silicate molecular sieve catalyst and the metal oxide to produce (poly)alkylene glycol monoalkyl ethers.

[0007] For various embodiments, the crystalline metal silicate molecular sieve catalyst is a crystalline metal silicate molecular sieve catalyst with a pore size of 0.5 nm to 1.2 nm. In another embodiment, the crystalline metal silicate molecular sieve catalyst is an aluminosilicate zeolite catalyst. Preferably, the crystalline metal silicate molecular sieve catalyst has a BEA-type zeolite structure. In another embodiment, the crystalline metal silicate molecular sieve catalyst contains protons (H... + This provides Brønsted acid sites on the crystalline metal silicate molecular sieve catalyst. For various embodiments, the crystalline metal silicate molecular sieve catalyst may also contain at least one metal element selected from the group consisting of Fe, Ga, and B. For various embodiments, the crystalline metal silicate molecular sieve catalyst has a silicon-to-metal atomic ratio of 5 to 150.

[0008] For various implementation schemes, the metal of the oxide is selected from the group consisting of elements yttrium, lanthanum, neodymium, gadolinium, holmium, ytterbium, and combinations thereof. In specific examples, the metal of the oxide is selected from the group consisting of Y₂O₃, La₂O₃, Nd₂O₃, Gd₂O₃, Ho₂O₃, Yb₂O₃, and combinations thereof.

[0009] In various embodiments, the olefin is an α-olefin having 6 to 30 carbon atoms. In some embodiments, the α-olefin has 10 to 20 carbon atoms. In various embodiments, the (poly)alkylene glycol has 2 to 8 carbon atoms. In a specific embodiment, the (poly)alkylene glycol is monoethylene glycol.

[0010] The methods disclosed herein can be carried out in batch reactors, continuous reactors, or semi-continuous reactors. The methods disclosed herein are also carried out in the liquid phase, wherein the crystalline metal silicate molecular sieve catalyst is in a fixed bed, a fluidized bed, or a suspension. The reaction of olefins and (poly)alkylene glycols in the presence of the mixture is carried out at a temperature of 80°C to 200°C. The reaction of olefins and (poly)alkylene glycols in the presence of the mixture is carried out at a temperature of 100°C to 150°C. Detailed Implementation

[0011] This disclosure provides a cost-effective method for producing (poly)alkylene glycol monoalkyl ethers for the production of secondary alcohol ethoxylates (SAE). The method of this disclosure helps address the aforementioned problems of the prior art by providing a liquid-phase approach for the production of (poly)alkylene glycol monoalkyl ethers with high selectivity and high yield. Specifically, this disclosure provides a mixture of a crystalline metal silicate molecular sieve catalyst and a metal oxide, which together provide a high reaction rate between olefins and (poly)alkylene glycols, as well as high selectivity for (poly)alkylene glycol monoalkyl ethers and high olefin conversion. Furthermore, as discussed herein, the improved stability of the crystalline metal silicate molecular sieve catalyst due to the presence of the metal oxide helps maintain the selectivity and activity of the crystalline metal silicate molecular sieve catalyst.

[0012] As provided herein, this disclosure has found that adding at least one oxide selected from Group 3 metals (e.g., yttrium oxide (Y₂O₃) or lanthanides (atomic numbers 57-71) to crystalline metal silicate molecular sieve catalysts (e.g., molecular sieve catalysts, such as zeolite β) can significantly improve the stability and lifetime of the catalyst during single ether production over extended periods (e.g., several hours at reaction temperatures of 100°C to 150°C). As discussed herein, mixtures of crystalline metal silicate molecular sieve catalysts and metal oxides enhance catalyst lifetime by reducing the generation of oxygen-containing compound byproducts that may be detrimental to subsequent downstream reactions, particularly aldehydes, ketones, esters, ethers, carboxylic acids, and other alcohols.

[0013] The chemical elements mentioned in this article (e.g., Group 3 metals and lanthanides (atomic numbers 57-71)) are from the IUPAC periodic table as of December 1, 2018.

[0014] This disclosure provides a method for producing (poly)alkylene glycol monoalkyl ethers, the method comprising providing a mixture of a crystalline metal silicate molecular sieve catalyst and a metal oxide, wherein the metal is selected from the group consisting of: Group 3 metals, lanthanides and combinations thereof; and reacting an olefin and a (poly)alkylene glycol in a liquid-phase process in the presence of the mixture of the crystalline metal silicate molecular sieve catalyst and the metal oxide to produce (poly)alkylene glycol monoalkyl ethers.

[0015] The crystalline metal silicate molecular sieve catalyst disclosed herein is composed of co-occurring SiO4 and AlO4. - Microporous crystalline silicate material composed of tetrahedra. Adjacent SiO4 and AlO4 - Tetrahedrons are bridged by oxygen atoms and arranged regularly into a three-dimensional system of cages and pores, with highly uniform pore sizes, which gives them their "molecular sieving" ability. Therefore, the crystalline metal silicate molecular sieve catalyst disclosed herein is preferably a crystalline metal silicate molecular sieve catalyst with a pore size of 0.5 nm to 1.2 nm. More preferably, the crystalline metal silicate molecular sieve catalyst is a crystalline metal silicate molecular sieve catalyst with a pore size of 0.5 nm to 0.8 nm.

[0016] Examples of such molecular sieves for crystalline metal silicate molecular sieve catalysts include framework zeolites and zeolite-type molecular sieves, whose structures are classified by the International Zeolite Association Structure Committee according to the rules of the IUPAC Zeolite Nomenclature Committee. Preferably, the crystalline metal silicate molecular sieve catalysts of this disclosure are aluminosilicate zeolite catalysts. As provided in Atlas of Zeolite Framework Types, 5th Edition, Elsevier, London, England (2001), the structures of such aluminosilicate zeolite catalysts are assigned three-letter codes, which are incorporated herein by reference. Non-limiting examples of aluminosilicate zeolite catalysts used in this disclosure include catalysts with medium pore sizes comprising AFO, AEL, EUO, HEU, FER, MEL, MFI, MTW, MTT, TON and their substituted forms; and catalysts with large pore sizes comprising EMT, BEA, LTL, FAU, MER, MOR and their substituted forms. Non-limiting examples of preferred molecular sieve structures for the aluminosilicate zeolite catalysts of this disclosure include MFI, MEL, BEA (e.g., BEA-type zeolite), FAU (e.g., Y-type zeolite), MOR, MTW, and LTL. Preferably, the crystalline metal silicate molecular sieve catalyst has a BEA-type zeolite structure.

[0017] The crystalline metal silicate molecular sieve catalyst disclosed herein can also be converted into cations containing substances outside its lattice. Such cations can contain H+. + NH4 +Li + Na + 、Rb + C + Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ ,Sc 3+ Y 3+ La 3+ R4N + R4P + (R is H or an alkyl group) and combinations thereof. Preferably, the crystalline metal silicate molecular sieve catalyst of this disclosure contains H. + (Protons) provide Brønsted acid sites on crystalline metal silicate molecular sieve catalysts. The number of Brønsted acid sites is related to AlO4. - The content is proportional and therefore related to the silicon-metal (e.g., aluminum) atomic ratio of the structure. The overall Brønsted acidity of the zeolite of this disclosure is a combination of its site strength and density, and therefore its silicon-metal atomic ratio. For various embodiments, the crystalline metal silicate molecular sieve catalyst of this disclosure preferably has a silicon-metal atomic ratio of 5 to 1500. More preferably, the crystalline metal silicate molecular sieve catalyst has a silicon-metal atomic ratio of 5 to 300. Most preferably, the crystalline metal silicate molecular sieve catalyst has a silicon-metal atomic ratio of 5 to 150.

[0018] For various embodiments, the crystalline metal silicate molecular sieve catalyst may further comprise at least one other metal introduced into the crystal lattice in place of Al atoms. Specific examples of such metal elements include B, Ga, In, Ge, Sn, P, As, Sb, Sc, Y, La, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn. Preferably, the crystalline metal silicate molecular sieve catalyst of this disclosure may contain at least one metal element selected from the group consisting of Fe, Ga, and B. Any of the above metals may be used alone or in combination of two or more metals.

[0019] For various implementation schemes, the crystalline metal silicate molecular sieve catalysts provided herein can be used alone (e.g., pure) or as a mixture of two or more crystalline metal silicate molecular sieve catalysts.

[0020] The crystalline metal silicate molecular sieve catalysts described herein can be synthesized as is known in the art. Typically, crystalline metal silicate molecular sieve catalysts can be synthesized via a hydrothermal synthesis method. The hydrothermal synthesis method for producing crystalline metal silicate molecular sieve catalysts involves heating a composition of a silica source, a metal source, and a quaternary ammonium salt (such as tetrapropylammonium salt) at a temperature of 100°C to 175°C until crystals are formed. The crystals are then filtered, washed with water, and dried. The dried crystals are then calcined at a temperature of 350°C to 600°C. As an example, the silica source can be selected from sodium silicate, silica sol, silica gel, alkoxysilanes, and other sources. The metal source can be selected from various inorganic or organometallic compounds known in the art.

[0021] Examples of metal compounds are metal salts, such as metal sulfates [e.g., Al2(SO4)3], metal nitrates [e.g., Fe(NO3)3], alkali metal salts of metal oxides [e.g., NaAlO2], etc.; metal halides, such as metal chlorides [e.g., TiCl4], metal bromides [e.g., MgBr2], etc.; and metal alkoxides [e.g., Ti(OC2H5)4].

[0022] The crystalline metal silicate molecular sieve catalyst disclosed herein is also commercially available from sources such as ZEOLYST INTERNATIONAL from Conshohocken, PA. TM CP814E, CP814C, CP811C-300, CBV 712, CBV720, CBV 760, CBV 2314, CBV 10A.

[0023] The crystalline metal silicate molecular sieve catalysts obtained above can be converted into cations containing substances outside their lattice, as needed. For example, those containing H... + Crystalline metal silicate molecular sieve catalysts can be prepared as follows: The crystalline metal silicate molecular sieve catalyst is stirred in an aqueous solution of HCl, NH4Cl, NH3, etc., to convert the cations contained in the metal silicate into H+. + or NH4 + The resulting solid product was then filtered, washed with water, dried, and calcined at 350°C to 600°C. It contained H+. + Crystalline metal silicate molecular sieve catalysts targeting cations other than the target cation can be prepared by using an aqueous solution or a volatile precursor of the target cation and subjecting the crystalline metal silicate molecular sieve catalyst to the ion exchange process described above. Examples of such teachings include ion exchange with alkali metals and alkaline earth metals in solution, such as Na, Ca, and Mg, and gas-phase ion exchange using volatile molecular precursors, such as Ga, Mo, and Re.

[0024] The crystalline metal silicate molecular sieve catalysts disclosed herein can be in various forms, including powders, particles, and / or predetermined molded shapes.

[0025] The metal oxides used in this disclosure comprise oxides of Group 3 metals and lanthanides, containing elements with atomic numbers from 57 to 71. As mentioned above, the chemical elements provided herein are from the IUPAC periodic table as of December 1, 2018. Preferred oxides contain metals selected from the group consisting of elements yttrium, lanthanum, neodymium, gadolinium, holmium, ytterbium, and combinations thereof. Most preferred metal oxides are yttrium oxide, lanthanum oxide, neodymium oxide, gadolinium oxide, holmium oxide, ytterbium oxide, and mixtures thereof. Particularly preferred oxides of the metals identified above comprise metals selected from oxides of the group consisting of Y₂O₃, La₂O₃, Nd₂O₃, Gd₂O₃, Ho₂O₃, Yb₂O₃, and combinations thereof. Preferably, the metal oxide used in this disclosure is Y₂O₃.

[0026] The metal oxides used in this disclosure can be prepared using a variety of techniques known in the art. The metal oxides used in this disclosure, as provided herein, are also commercially available from sources such as Sigma-Aldrich.

[0027] When used as a mixture with the crystalline metal silicate molecular sieve catalysts of this disclosure, such oxides of the metals provided herein offer benefits in catalytic conversion methods, particularly the conversion of olefins and (poly)alkylene glycols to produce (poly)alkylene glycol monoalkyl ethers. Furthermore, the mixture of the crystalline metal silicate molecular sieve catalyst and the metal oxide helps to surprisingly reduce the formation of harmful byproducts during the reaction, which may include oxygenated byproducts. Examples of such oxygenated byproducts include, but are not limited to, alkanols, aldehydes, ketones, esters, ethers, and carboxylic acids.

[0028] The use of the metal oxide and crystalline metal silicate molecular sieve catalysts disclosed herein is also effective in extending the service life of crystalline metal silicate molecular sieve catalysts.

[0029] The mixture disclosed herein comprises 5 wt.% to 95 wt.% of a crystalline metal silicate molecular sieve catalyst and 95 wt.% to 5 wt.% of a metal oxide, wherein the wt.% is based on the total weight of the mixture. Preferably, the mixture comprises 25 wt.% to 90 wt.% of a crystalline metal silicate molecular sieve catalyst and 75 wt.% to 10 wt.% of a metal oxide, wherein the wt.% is based on the total weight of the mixture. More preferably, the mixture comprises 50 wt.% to 87.5 wt.% of a crystalline metal silicate molecular sieve catalyst and 50 wt.% to 12.5 wt.% of a metal oxide, wherein the wt.% is based on the total weight of the mixture. For various embodiments, the mixture comprises only a crystalline metal silicate molecular sieve catalyst and a metal oxide, wherein the total wt.% of these two components is 100 wt%. This mixture can be produced by mixing the crystalline metal silicate molecular sieve catalyst and the metal oxide at room temperature (23°C) and atmospheric pressure (101,325 Pa).

[0030] The (poly)alkylene glycols disclosed herein comprise homopolymers of ethylene oxide, propylene oxide, or butane oxide; or copolymers of ethylene oxide, propylene oxide, and / or butane oxide. For various embodiments, the (poly)alkylene glycols of this disclosure have 2 to 8 carbon atoms. Specific examples of the (poly)alkylene glycols of this disclosure include, but are not limited to, ethane-1,2-diol; propane-1,2-diol; propane-1,3-diol; butane-1,2-diol; butane-1,3-diol; butane-1,4-diol; butane-2,3-diol; 2,2'-oxydi(ethylene-1-ol); and 2,2'-[ethane-1,2-diylbis(oxy)]di(ethylene-1-ol). Other (poly)alkylene glycols are also possible (e.g., hexane-1,6-diol). Preferably, the (poly)alkylene glycol is a monoethylene glycol. The (poly)alkylene glycols disclosed herein can be used alone (e.g., pure) or as a mixture of two or more (poly)alkylene glycols.

[0031] The olefins disclosed herein comprise olefins having 6 to 30 carbon atoms. Preferably, the olefins disclosed herein are α-olefins having an acyclic structure, which may be straight-chain (unbranched) or branched. Preferably, the olefins disclosed herein have a single carbon-carbon double bond (e.g., a monoene). Preferably, the olefins disclosed herein are α-olefins having 10 to 20 carbon atoms. More preferably, the olefins disclosed herein are α-olefins having 12 to 14 carbon atoms. Specific examples of the olefins disclosed herein include: ethylene, propylene, but-1-ene, but-2-ene, 2-methylprop-1-ene, but-1,3-diene, hex-1-ene, hex-2-ene, hex-3-ene, oct-1-ene, dec-1-ene, dodec-1-ene, tridec-1-ene, tetradec-1-ene, octadec-1-ene, and eicos-1-ene. Preferably, the olefin may be dodec-1-ene. The olefins disclosed herein can be used alone (e.g., pure) or as a mixture of two or more olefins.

[0032] In this disclosure, the reaction between olefins and (poly)alkylene glycols is carried out in a liquid-phase process. The reaction is carried out in the liquid phase with or without a solvent. Examples of such solvents (when present) include, but are not limited to, nitromethane, nitrobenzene, dioxane, ethylene glycol dimethyl ether, sulfolane, benzene, toluene, xylene, hexane, cyclohexane, decane, paraffin, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl benzoate, dimethyl phthalate, guaiacol, cresol, and combinations thereof.

[0033] Suitable molar ratios of olefins to (poly)alkylene glycols in methods for producing (poly)alkylene glycol monoalkyl ethers may include 0.01 to 20, 0.1 to 10, 0.5 to 5, and 0.9 to 4.

[0034] The temperature used to react olefins and (poly)alkylene glycols in the liquid phase in the presence of the mixture can be from 80°C to 200°C, preferably from 100°C to 150°C.

[0035] The pressure used to react the olefin and (poly)alkylene glycol in the liquid phase in the presence of the mixture can be a pressure reduced from atmospheric pressure (101,325 Pa), atmospheric pressure, or a pressure higher than atmospheric pressure. Preferably, the pressure used to react the olefin and (poly)alkylene glycol in the liquid phase in the presence of the mixture is atmospheric pressure.

[0036] The reactions disclosed herein can be carried out as a liquid-phase process in a batch, semi-batch, or continuous manner. When using a continuous method, the reaction can be carried out in a fluidized bed reactor, a fixed bed reactor, and / or a stirred tank reactor.

[0037] For liquid-phase methods, a mixture, olefin, and (poly)alkylene glycol as provided herein are fed into a reactor of a given method, where they are mixed at desired temperatures and pressures to allow the olefin and (poly)alkylene glycol to react in the presence of a mixture of crystalline metal silicate molecular sieve catalyst and metal oxide to produce (poly)alkylene glycol monoalkyl ethers.

[0038] When olefins react with (poly)alkylene glycols, the amount of the mixture present in the liquid phase process can be from 1 wt.% to 30 wt%, based on the total weight of the reaction mixture. Preferably, when olefins react with (poly)alkylene glycols, the amount of the mixture present in the liquid phase process is from 5 wt% to 15 wt%, based on the total weight of the reaction mixture.

[0039] The reaction time for the liquid-phase method of this disclosure can be from 0.1 hours to 10 hours. Preferably, the reaction time for the liquid-phase method of this disclosure is from 0.5 hours to 5 hours, more preferably from 1 hour to 3 hours. As understood, the reaction time varies based on many factors, including reaction temperature, reaction pressure, the amount of catalyst present in the reaction, and the amount and type of olefins and (poly)alkylene glycols used in the reaction.

[0040] After the reaction, the catalyst can be separated from the reaction product by centrifugation and / or filtration. After catalyst separation, the (poly)alkylene glycol monoalkyl ether can be separated from other components of the reaction product (e.g., (poly)alkylene glycols and olefins) by extraction or distillation.

[0041] Example

[0042] Material

[0043] Unless otherwise stated, each of the following materials is commercially available from Sigma-Aldrich: Ethylene glycol (MEG, 62.07 g / mol, ≥99%); Lanthanum(III) oxide (La₂O₃, 99.999%); Holmium(III) oxide (Ho₂O₃, ≥99.9%); Gadolinium(III) oxide (Gd₂O₃, 99.9%); Neodymium(III) oxide (Nd₂O₃, 99.99%); Ytterbium(III) oxide (Yb₂O₃, 99.9%); Yttrium(III) nitrate hexahydrate (Y(NO₃)₃·6H₂O, 99.8%); Dodecyl-1-ene (1-C₁₂, 168.32 g / mol, linear, ≥99.0%). The molecular weight of dodecyl-MEG is 230.39 g / mol.

[0044] Ammonium (NH4) with a SiO2 / Al2O3 molar ratio of 25 +β-zeolite CP814E in its original form was purchased from Zeolyst International. Prior to use, CP814E β-zeolite was calcined in a muffle furnace (Lindberg Blue M) at 550°C for at least 12 hours with a constant air flow (~40-60 L / min). Yttrium(III) oxide (Y₂O₃) was prepared by thermally decomposing yttrium(III) nitrate hexahydrate at 600°C for at least 5 hours (h) in an air flow (100 mL / min). The air flow referred to herein is atmospheric air.

[0045] Gas chromatography (GC) of the following examples was performed on an Agilent 7890B gas chromatograph equipped with an FID detector. The GC sample was prepared by mixing 100 μL of the example with 10 mL of GC solution, which was prepared by adding 1 mL of hexadecane to 1 L of ethyl acetate. The total amount of 1-dodecene derivatives, including monoalkyl ethers, dialkyl ethers, and 2-dodecanol; and the total amount of dodecene, including 1-dodecene and all other C-molecules not 1-dodecene. 12 Isomers. Table 1 provides the relevant gas chromatograph parameters.

[0046] Table 1 :

[0047] column: Agilent HP88, 100m×0.25mm×0.20μm detector FID Column oven: 50℃-7min-6℃ / min-260℃-1min Injector: 250℃ Detector: 300℃ Carrier gas: Helium 2.0 mL / min constant flow mode Flow split ratio: 10 composition: Nitrogen gas 25 mL / min Air: 400mL / min hydrogen: 40mL / min Inlet liner: Restek PN 23305.5 Sky Precision Liner with glass wool Injection volume: 1μL GC vial rinse solvent: Ethyl acetate

[0048] calculate

[0049] In the following examples (EX) and comparative examples (CE), the yields (mol%) of products and byproducts and catalyst performance parameters were calculated based on GC results as follows.

[0050] Olefin conversion (%): The olefin conversion percentage is calculated by dividing the total amount of dodecene derivatives by the sum of the total amount of dodecene derivatives and the amount of dodecene. Multiply the quotient by 100.

[0051] ME selectivity (%) The selectivity percentage of monoalkyl ethers is calculated by dividing the total amount of monoalkyl ethers by the total amount of dodecene derivatives. The quotient is then multiplied by 100.

[0052] ME yield (%) Monoalkyl ether yield is calculated by multiplying the olefin conversion value by the monoalkyl ether selectivity value.

[0053] reaction

[0054] The etherification reactions for the examples and comparative examples are described below. The reactor block consisted of a heating block housing 48 40 mL straight-walled glass scintillation vials. A flat, circular rare-earth disk (VP 772FN-13-13-150, V&P Scientific, Inc.) was used. The reactor consisted of a horizontally mounted rotating magnetic cylinder that caused a magnetic stirring element to tumble up and down. The stirring speed was controlled by a frequency converter; for typical operation, the stirring was set to 70, corresponding to a rotational speed of 800 RPM for the magnetic cylinder. GC samples were prepared by adding the liquid sample to 10 mL of internal standard solution (1 mL of hexadecane dissolved in 1 L of ethyl acetate) and analyzed offline using an Agilent 7890B GC with the instrument parameters described above.

[0055] result

[0056] Table 2: Catalytic performance of a physical mixture of β-zeolite (0.25 g) and Y2O3 (0.25 g) with SiO2 / Al2O3 = 25 for etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0057]

[0058] Table 2 shows the effect of adding 0.25 g Y₂O₃ to β-zeolite with SiO₂ / Al₂O₃ = 25 on the catalytic performance of MEG etherification of dodeca-1-ene at 135 °C for 1 h, 1.5 h, 2 h, and 3 h. The physical mixture of Y₂O₃ and catalyst showed an olefin conversion of 7.6% after 3 hours of reaction, with a cumulative yield of 23.2% / g zeolite for monoethers, while the catalyst without added Y₂O₃ showed an olefin conversion of 2.5%, with a cumulative yield of 15% / g catalyst for monoethers.

[0059] Table 3: Catalytic performance of a physical mixture of β-zeolite (0.375 g) and Y2O3 (0.125 g) with SiO2 / Al2O3 = 25 for the etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0060]

[0061] Table 3 shows the effect of adding 0.125 g Y₂O₃ to 0.375 g SiO₂ / Al₂O₃ = 25 β-zeolite on the catalytic performance of MEG etherification of dodeca-1-ene at 135 °C for 0.5 h, 1 h, 1.5 h, 2 h, and 3 h. The physical mixture of Y₂O₃ and catalyst showed an olefin conversion of 9.9% after 3 hours of reaction, with a cumulative yield of 27.8% / g zeolite, while the catalyst without added Y₂O₃ showed an olefin conversion of 1.6%, with a cumulative yield of 15.7% / g catalyst.

[0062] Table 4: Catalytic performance of a physical mixture of β-zeolite (0.4375 g) and Y2O3 (0.0625 g) with SiO2 / Al2O3 = 25 for the etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0063]

[0064] Table 4 shows the effect of adding 0.0625 g Y₂O₃ to 0.4375 g of β-zeolite with SiO₂ / Al₂O₃ = 25 on the catalytic performance of MEG etherification of dodeca-1-ene at 135 °C for 0.5 h, 1 h, 1.5 h, 2 h, and 3 h. The physical mixture of Y₂O₃ and catalyst showed an olefin conversion of 10.6% after 3 hours of reaction, with a cumulative yield of 24.6% / g zeolite, while the catalyst without added Y₂O₃ showed an olefin conversion of 2.4%, with a cumulative yield of 17.6% / g catalyst.

[0065] Table 5: Catalytic performance of a physical mixture of β-zeolite (0.25 g) and La2O3 (0.25 g) with SiO2 / Al2O3 = 25 for etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0066]

[0067]

[0068] Table 5 shows the effect of adding 0.25 g La2O3 to 0.25 g SiO2 / Al2O3 = 25 β-zeolite on the catalytic performance of MEG etherification of dodeca-1-ene at 135 °C for 1 h, 1.5 h, 2 h, and 3 h. The physical mixture of La2O3 and catalyst showed an olefin conversion of 4% after 3 hours of reaction, with a cumulative yield of 17.5% / g zeolite, while the catalyst without added La2O3 showed an olefin conversion of 2.5%, with a cumulative yield of 15% / g catalyst.

[0069] Table 6: Catalytic performance of a physical mixture of β-zeolite (0.375 g) and La2O3 (0.125 g) with SiO2 / Al2O3 = 25 for the etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0070]

[0071] Table 6 shows the effect of adding 0.125 g La2O3 to 0.375 g SiO2 / Al2O3 = 25 β-zeolite on the catalytic performance of MEG etherification of dodeca-1-ene at 135 °C for 0.5 h, 1 h, 1.5 h, 2 h, and 3 h. The physical mixture of La2O3 and catalyst showed an olefin conversion of 6.4% after 3 hours of reaction, with a cumulative yield of 18.3% / g zeolite, while the catalyst without added La2O3 showed an olefin conversion of 1.6%, with a cumulative yield of 15.7% / g catalyst.

[0072] Table 7: Catalytic performance of a physical mixture of β-zeolite (0.25 g) and Ho2O3 (0.25 g) with SiO2 / Al2O3 = 25 for etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0073]

[0074] Table 7 shows the effect of adding 0.25 g Ho2O3 to 0.25 g SiO2 / Al2O3 = 25 β-zeolite on the catalytic performance of MEG etherification of dodeca-1-ene at 135 °C for 1 h, 1.5 h, 2 h, and 3 h. The physical mixture of Ho2O3 and catalyst showed an olefin conversion of 6.6% after 3 hours of reaction, with a cumulative yield of 30.8% / g zeolite, while the catalyst without added Ho2O3 showed an olefin conversion of 2.5%, with a cumulative yield of 15% / g catalyst.

[0075] Table 8: Catalytic performance of a physical mixture of β-zeolite (0.375 g) and Ho2O3 (0.125 g) with SiO2 / Al2O3 = 25 for the etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0076]

[0077]

[0078] Table 8 shows the effect of adding 0.125 g Ho2O3 to 0.375 g SiO2 / Al2O3 = 25 β-zeolite on the catalytic performance of MEG etherification of dodeca-1-ene at 135 °C for 0.5 h, 1 h, 1.5 h, 2 h, and 3 h. The physical mixture of Ho2O3 and catalyst showed an olefin conversion of 5% after 3 hours of reaction, with a cumulative yield of 23.5% / g zeolite, while the catalyst without added Ho2O3 showed an olefin conversion of 1.6%, with a cumulative yield of 15.7% / g catalyst.

[0079] Table 9: Catalytic performance of a physical mixture of β-zeolite (0.25 g) and Gd2O3 (0.25 g) with SiO2 / Al2O3 = 25 for etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0080]

[0081] Table 9 shows the effect of adding 0.25 g Gd₂O₃ to 0.25 g SiO₂ / Al₂O₃ = 25 β-zeolite on the catalytic performance of MEG etherification of dodeca-1-ene at 135 °C for 1 h, 1.5 h, 2 h, and 3 h. The physical mixture of Gd₂O₃ and catalyst showed an olefin conversion of 6.4% after 3 hours of reaction, with a cumulative yield of 27.4% / g zeolite, while the catalyst without added Gd₂O₃ showed an olefin conversion of 2.5%, with a cumulative yield of 15% / g catalyst.

[0082] Table 10: Catalytic performance of a physical mixture of β-zeolite (0.375 g) and Gd2O3 (0.125 g) with SiO2 / Al2O3 = 25 for etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0083]

[0084] Table 10 shows the effect of adding 0.125 g Gd2O3 to 0.375 g SiO2 / Al2O3 = 25 β-zeolite on the catalytic performance of MEG etherification of dodeca-1-ene at 135 °C for 0.5 h, 1 h, 1.5 h, 2 h, and 3 h. The physical mixture of Gd2O3 and catalyst showed an olefin conversion of 4.2% after 3 hours of reaction, with a cumulative yield of 17.1% / g zeolite, while the catalyst without added Gd2O3 showed an olefin conversion of 1.6%, with a cumulative yield of 15.7% / g catalyst.

[0085] Table 11: Catalytic performance of a physical mixture of β-zeolite (0.25 g) and Nd2O3 (0.25 g) with SiO2 / Al2O3 = 25 for etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0086]

[0087]

[0088] Table 11 shows the effect of adding 0.25 g Nd2O3 to 0.25 g SiO2 / Al2O3 = 25 β-zeolite on the catalytic performance of MEG etherification of dodeca-1-ene at 135 °C for 1 h, 1.5 h, 2 h, and 3 h. The physical mixture of Nd2O3 and catalyst showed an olefin conversion of 5.6% after 3 hours of reaction, with a cumulative yield of 18.7% / g zeolite, while the catalyst without added Nd2O3 showed an olefin conversion of 2.5%, with a cumulative yield of 15% / g catalyst.

[0089] Table 12: Catalytic performance of a physical mixture of β-zeolite (0.375 g) and Nd2O3 (0.125 g) with SiO2 / Al2O3 = 25 for etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0090]

[0091] Table 12 shows the effect of adding 0.125 g Nd2O3 to 0.375 g SiO2 / Al2O3 = 25 β-zeolite on the catalytic performance of MEG etherification of dodeca-1-ene at 135 °C for 0.5 h, 1 h, 1.5 h, 2 h, and 3 h. The physical mixture of Nd2O3 and catalyst showed an olefin conversion of 8.4% after 3 hours of reaction, with a cumulative yield of 24.9% / g zeolite, while the catalyst without added Nd2O3 showed an olefin conversion of 1.6%, with a cumulative yield of 15.7% / g catalyst.

[0092] Table 13: Catalytic performance of a physical mixture of β-zeolite (0.25 g) and Yb2O3 (0.25 g) with SiO2 / Al2O3 = 25 for etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0093]

[0094] Table 13 shows the effect of adding 0.25 g Yb2O3 to 0.25 g SiO2 / Al2O3 = 25 β-zeolite on the catalytic performance of MEG etherification of dodeca-1-ene at 135 °C for 1 h, 1.5 h, 2 h, and 3 h. The physical mixture of Yb2O3 and catalyst showed an olefin conversion of 5.1% after 3 hours of reaction, with a cumulative yield of 27.5% / g zeolite, while the catalyst without added Yb2O3 showed an olefin conversion of 2.5%, with a cumulative yield of 15% / g catalyst.

[0095] Table 14: Catalytic performance of a physical mixture of β-zeolite (0.375 g) and Yb2O3 (0.125 g) with SiO2 / Al2O3 = 25 for etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0096]

[0097]

[0098] Table 14 shows the effect of adding 0.125 g Yb2O3 to 0.375 g SiO2 / Al2O3 = 25 β-zeolite on the catalytic performance of MEG etherification of dodeca-1-ene at 135 °C for 0.5 h, 1 h, 1.5 h, 2 h, and 3 h. The physical mixture of Yb2O3 and catalyst showed an olefin conversion of 4.5% after 3 hours of reaction, with a cumulative yield of 21.3% / g zeolite, while the catalyst without added Yb2O3 showed an olefin conversion of 1.6%, with a cumulative yield of 15.7% / g catalyst.

[0099] Table 15: Catalytic performance of Y₂O₃ (0.5 g) tested for etherification reaction. Reaction conditions: 6.2 g dodeca-1-ene, 6.7 g MEG, 135 °C.

[0100]

[0101] Table 15 summarizes the catalytic performance of 0.5 g Y₂O₃ for the MEG etherification of dodec-1-ene at 135 °C for 0.5 h, 1 h, 1.5 h, 2 h, and 3 h. Y₂O₃ showed residual activity in the conversion of dodec-1-ene. After 3 hours, the olefin conversion was 0.2%.

Claims

1. A method for producing alkylene glycol monoalkyl ethers or polyalkylene glycol monoalkyl ethers, the method comprising: A mixture of a crystalline metal silicate molecular sieve catalyst and a metal oxide is provided, wherein the crystalline metal silicate molecular sieve catalyst is an aluminosilicate zeolite catalyst having a BEA-type zeolite structure, and wherein the metal oxide is selected from the group consisting of elements yttrium, lanthanum, neodymium, gadolinium, holmium, ytterbium, and combinations thereof, and wherein the mixture comprises 5% to 95% by weight of the crystalline metal silicate molecular sieve catalyst and 95% to 5% by weight of the metal oxide, wherein the weight percentage is based on the total weight of the mixture; as well as In the presence of the mixture of the crystalline metal silicate molecular sieve catalyst and the metal oxide, an olefin and an alkylene glycol or a polyalkylene glycol are reacted in a liquid-phase process to produce the alkylene glycol monoalkyl ether or the polyalkylene glycol monoalkyl ether.

2. The method according to claim 1, wherein the crystalline metal silicate molecular sieve catalyst is a crystalline metal silicate molecular sieve catalyst with a pore size of 0.5 nm to 1.2 nm.

3. The method according to any one of claims 1 to 2, wherein the crystalline metal silicate molecular sieve catalyst comprises protons (H... + ) to provide Brønsted acid sites.

4. The method according to any one of claims 1 to 2, wherein the crystalline metal silicate molecular sieve catalyst has a silicon-to-metal atomic ratio of 5 to 150.

5. The method according to any one of claims 1 to 2, wherein the metal oxide is selected from the group consisting of Y2O3, La2O3, Nd2O3, Gd2O3, Ho2O3, Yb2O3 and combinations thereof.

6. The method according to any one of claims 1 to 2, wherein the mixture comprises 25% to 90% by weight of the crystalline metal silicate molecular sieve catalyst and 75% to 10% by weight of the metal oxide, wherein the weight percentages are based on the total weight of the mixture.

7. The method according to any one of claims 1 to 2, wherein the mixture comprises 50% to 87.5% by weight of the crystalline metal silicate molecular sieve catalyst and 50% to 12.5% ​​by weight of the metal oxide, wherein the weight percentages are based on the total weight of the mixture.

8. The method according to claim 1, wherein the olefin is an α-olefin having 6 to 30 carbon atoms.

9. The method according to claim 8, wherein the α-olefin has 10 to 20 carbon atoms.

10. The method according to any one of claims 1 to 2, wherein the alkylene glycol or polyalkylene glycol has 2 to 8 carbon atoms.

11. The method of claim 10, wherein the alkylene glycol is monoethylene glycol.

12. The method according to any one of claims 1 to 2, wherein the reaction of the olefin and the alkylene glycol or polyalkylene glycol in the presence of the mixture is carried out at a temperature of 80°C to 200°C.

13. The method of claim 12, wherein the reaction of the olefin and the alkylene glycol or polyalkylene glycol in the presence of the mixture is carried out at a temperature of 100°C to 150°C.

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