Catalyst supports, catalysts for ethylene glycol preparation, and related preparation methods and applications

Abstract

This invention proposes a modified catalyst support, belonging to the field of catalyst technology. The modified catalyst support is prepared by modifying an unmodified support with a support additive; the support additive contains at least one rare earth metal element; preferably, the molar ratio of the unmodified support to the support additive and complexing agent is 1:(0.012~0.300):(0.012~0.300). The preparation method of this modified catalyst support includes: mixing the support additive, complexing agent, and water to obtain material 1; mixing the unmodified support with material 1, drying, and calcining to obtain the modified catalyst support. The catalyst prepared using this catalyst support can solve the technical problems of high precious metal content and low hydrothermal stability in existing biomass-to-ethylene glycol processes.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, specifically to a catalyst support, a catalyst for ethylene glycol preparation, and related preparation methods and applications. Background Technology

[0002] Ethylene glycol is an important bulk chemical with a wide range of applications. It can be used to produce polyethylene terephthalate, polyethylene naphthalate, automotive antifreeze, unsaturated polyester resins, nonionic surfactants, plasticizers, and more.

[0003] Currently, the main technological route for industrial ethylene glycol production is the ethylene oxide hydration method, while the coal-to-ethylene glycol method has also seen rapid development in recent years. It is reported that the ethylene oxide method currently accounts for approximately 56% of ethylene glycol production capacity, and the coal-to-ethylene glycol method accounts for approximately 35%. Both routes rely on fossil resources, but fossil resources are finite and non-renewable. With the depletion of fossil resources and the increasing prominence of environmental problems, there is an urgent need to develop a sustainable route for ethylene glycol production to supplement existing methods, increase ethylene glycol output, and reduce dependence on fossil resources to some extent. Biomass is the only renewable organic carbon source that can provide chemicals for humans. Using biomass to produce ethylene glycol has advantages such as abundant raw material resources, flexible process routes, energy conservation and emission reduction, and green and low-carbon characteristics. Therefore, developing a highly efficient catalytic system for converting biomass feedstock into ethylene glycol is of great significance.

[0004] According to current research, there are multiple routes for producing ethylene glycol from biomass feedstocks. Among them, the route of producing ethylene glycol from cellulose / hemicellulose, starch, sugars, etc. by direct catalytic hydrogenation cracking has fewer steps, higher selectivity for the target product ethylene glycol, and is more efficient and energy-saving, which has attracted increasing attention. In particular, the conversion of non-edible cellulose is the focus of current research.

[0005] In 2008, researchers at the Dalian Institute of Chemical Physics first reported that nickel-promoted tungsten carbide catalysts could be used to directly catalyze the conversion of cellulose into ethylene glycol (Angew. Chem. Int. Ed. 2008, 47, 8510-8513).

[0006] CN101735014B discloses a method for preparing ethylene glycol from polyhydroxy compounds. The method uses polyhydroxy compounds as reactants and a multi-metal catalyst composed of metallic states, carbides, nitrides, and phosphides of group 8, 9, and 10 transition metals (iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, molybdenum, and tungsten) as catalytic active components. The process involves a one-step catalytic conversion at 120-300℃ and a hydrogen pressure of 1-13 MPa, achieving efficient, highly selective, and high-yield preparation of ethylene glycol from polyhydroxy compounds.

[0007] CN101768050B discloses a method for producing ethylene glycol and 1,2-propanediol. The method involves hydrolyzing cellulose under hot water conditions (200-250℃), and introducing WO3, supported WO3 and Ru / C catalysts to provide acidity and promote cellulose hydrolysis, while converting the hydrolysis intermediates into low-carbon substances, which are then hydrogenated to obtain ethylene glycol and 1,2-propanediol.

[0008] CN105771975A discloses a carbon nanotube-supported Ru-based catalyst and its preparation and application. The catalyst uses carbon nanotubes as a support, Ru as the active component, and the auxiliary agent is selected from one or more of W, Mo, Re, Ir or La metals or metal oxides. It is used for the hydrogenolysis of sugars or sugar alcohols to prepare low-carbon diols.

[0009] CN109485543B discloses a method for preparing ethylene glycol and 1,2-diethyl glycol from cellulose in one step. A method for producing propylene glycol and a catalyst thereof, wherein the catalyst is a heterogeneous catalyst composed of a metal oxide as a support and a hydrogenated metal supported on the support. The hydrogenated metal is Co, and the metal oxide is one or more selected from CeOx, MoOx, and LaOx, and the mass content of the hydrogenated metal is 0.1% to 30% based on the total mass of the catalyst.

[0010] CN113083299A discloses a Yolk Shell-structured bifunctional catalysts and their application in the catalytic hydrogenolysis of glucose to prepare ethylene glycol.

[0011] However, the above methods for preparing ethylene glycol from biomass still suffer from problems such as high precious metal content in the catalyst or low hydrothermal stability. Summary of the Invention

[0012] The purpose of this invention is to solve the technical problems of high precious metal content and low hydrothermal stability in existing biomass-to-ethylene glycol production processes.

[0013] To achieve the above objectives, the first aspect of the present invention provides a modified catalyst support, which is prepared by modifying an unmodified support with a support additive and a complexing agent; wherein the support additive contains at least one rare earth metal element.

[0014] As a specific embodiment of the present invention, the molar ratio of the unmodified carrier to the carrier additive and complexing agent is 1:(0.012~0.300):(0.012~0.300).

[0015] As a specific embodiment of the present invention, the molar ratio of the unmodified carrier to the carrier additive and complexing agent is 1:(0.012~0.020):(0.012~0.020).

[0016] As a specific embodiment of the present invention, the above-mentioned unmodified carrier is selected from at least one of alumina, silicon oxide, titanium oxide, and zirconium oxide.

[0017] As a specific embodiment of the present invention, the above-mentioned unmodified carrier is aluminum oxide or titanium oxide.

[0018] As a specific embodiment of the present invention, the above-mentioned unmodified carrier is aluminum oxide.

[0019] As a specific embodiment of the present invention, the complexing agent is an organic complexing agent.

[0020] As a specific embodiment of the present invention, the complexing agent is any one of ethylenediaminetetraacetic acid, diethyltriaminepentaacetic acid, and ethylenediaminedi-o-phenylacetic acid.

[0021] As a specific embodiment of the present invention, the complexing agent is ethylenediaminetetraacetic acid.

[0022] As a specific embodiment of the present invention, the above-mentioned rare earth metal elements are selected from any one of scandium, yttrium, and lanthanides.

[0023] As a specific embodiment of the present invention, the above-mentioned rare earth metal element is a lanthanide metal.

[0024] In a specific embodiment of the present invention, the lanthanide metal is La or Pr.

[0025] A second aspect of the present invention provides a method for preparing the above-mentioned modified catalyst support, the method comprising the following steps:

[0026] 1) Mix the carrier additive, complexing agent and water to obtain material 1;

[0027] 2) Mix the unmodified support with material 1, dry and calcine to obtain the modified catalyst support.

[0028] In a specific embodiment of the present invention, the drying temperature is 110°C.

[0029] As a specific embodiment of the present invention, the calcination temperature is 500-600℃.

[0030] A third aspect of the present invention provides a catalyst for the preparation of ethylene glycol, the catalyst comprising: a noble metal component, a tungsten-containing active component, and a catalyst promoter, wherein the catalyst further comprises: the modified catalyst support described above or the modified catalyst support obtained by the above preparation method.

[0031] As a specific embodiment of the present invention, the molar ratio of alumina to noble metal component, tungsten-containing active component and catalyst promoter in the above modified catalyst support is 1:(0.010~0.025):(0.110~0.205):(0.100~0.180).

[0032] As a specific embodiment of the present invention, the molar ratio of the modified catalyst support to the noble metal component, the tungsten-containing active component, and the catalyst promoter is 1:(0.010~0.015):(0.110~0.135):(0.100~0.120).

[0033] As a specific embodiment of the present invention, the molar ratio of the modified catalyst support to the noble metal component, the tungsten-containing active component, and the catalyst promoter is 1:0.015:0.135:0.120.

[0034] As a specific embodiment of the present invention, the above-mentioned precious metal component contains at least one group VIII metal element.

[0035] In a specific embodiment of the present invention, the metal element of group VIII is Pt or Pd.

[0036] As a specific embodiment of the present invention, the above-mentioned tungsten-containing active component is an inorganic compound of tungsten.

[0037] As a specific embodiment of the present invention, the inorganic compound of tungsten mentioned above is tungstic acid or metatungstate.

[0038] As a specific embodiment of the present invention, the above-mentioned metatungstate is ammonium metatungstate.

[0039] As a specific embodiment of the present invention, the above-mentioned catalyst promoter contains at least one group VA element.

[0040] In a specific embodiment of the present invention, the above-mentioned VA group element is P.

[0041] As a specific embodiment of the present invention, P is selected from any one of bis(diphenylphosphine)methane, 1,2-bis(diphenylphosphine)ethane, and tris(2-methylphenyl)phosphine.

[0042] As a specific embodiment of the present invention, the above-mentioned catalyst for ethylene glycol preparation has WO3 content. 3-x Specific components, where x = 0.10 to 0.15;

[0043] As a specific embodiment of the present invention, the above-mentioned noble metal component satisfies CXPS / CICP = 0.6 to 0.9; wherein, CXPS is the molar content of noble metal elements in the catalyst characterized by X-ray photoelectron spectroscopy, and CICP is the molar content of noble metal elements in the catalyst characterized by plasmonic coupling.

[0044] As a specific embodiment of the present invention, the tungsten-containing active component satisfies CXPS / CICP = 1.3 to 2.1; wherein CXPS is the molar content of tungsten in the catalyst characterized by X-ray photoelectron spectroscopy, and CICP is the molar content of tungsten in the catalyst characterized by plasma coupling.

[0045] A fourth aspect of the present invention provides a method for preparing a catalyst for ethylene glycol preparation, characterized in that the preparation method includes the following steps:

[0046] 1) Mix the tungsten-containing active component, the noble metal component, the catalyst additive, and the solvent to obtain material 2; preferably, the solvent is acetone;

[0047] 2) Mix material 2 with the modified catalyst support of any one of claims 1-4 or the modified catalyst support prepared by the preparation method of claim 5, dry and calcine, and then reduce to obtain a catalyst for ethylene glycol preparation.

[0048] As a specific embodiment of the present invention, drying is performed in an oven at 100-130°C, preferably in an oven at 110°C.

[0049] As a specific embodiment of the present invention, the product is calcined at a temperature of 550-700°C.

[0050] As a specific embodiment of the present invention, reduction is carried out at a temperature of 400–500°C.

[0051] The fifth aspect of the present invention provides a catalyst for the preparation of ethylene glycol prepared by the above-described preparation method.

[0052] The sixth aspect of the present invention provides a catalyst for preparing ethylene glycol as described above, or the application of the catalyst for preparing ethylene glycol as described above in the preparation of ethylene glycol from biomass feedstock.

[0053] As a specific embodiment of the present invention, the above-mentioned biomass is selected from at least one of cellulose, starch, hemicellulose, fructan, xylan, disaccharide, and glucose.

[0054] In a specific embodiment of the present invention, the above-mentioned biomass is glucose.

[0055] Compared with the prior art, the present invention has at least the following advantages:

[0056] (1) In the process of preparing ethylene glycol from biomass raw materials, the present invention introduces rare earth metals to modify the alumina support by complexation, which reduces the surface acidity and reduces the occurrence of isomerization side reactions. Therefore, the catalyst made by using the catalyst support of the present invention has high ethylene glycol selectivity and fewer side reactions.

[0057] (2) The present invention uses phosphorus-containing catalysts such as bis(diphenylphosphine)methane, 1,2-bis(diphenylphosphine)ethane, and tris(2-methylphenyl)phosphine, which can promote dispersion and promote WO3. 3-x The formation of W and noble metals can be controlled by adjusting the surface content of the catalyst, mainly through coordination. The W content is much higher than the noble metal content, making it easier to form aggregated WO3 on the surface. 3-x The precious metals are encapsulated inside, which reduces the loss of precious metals during the reaction and improves the hydrothermal stability of the catalyst.

[0058] (3) The present invention divides the roasting process of the mixture into two stages. The first stage is roasting at a higher temperature, and then the temperature is slightly reduced for reduction. Through the reduction step, a product with WO3 is obtained. 3-x The final catalyst with this structure allows for the full utilization of precious metals, resulting in a catalyst with higher selectivity and further enabling higher ethylene glycol yields. Attached Figure Description

[0059] Figure 1 The XRD diffraction pattern is shown for the catalyst used in the preparation of ethylene glycol in Example 4 and Comparative Example 1 of this invention. Detailed Implementation

[0060] The present invention will be further described below with reference to specific embodiments, but this does not constitute any limitation on the invention. The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values; these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0061] Unless otherwise specified, all operations in the examples and comparative examples are performed at room temperature.

[0062] In this invention, the reaction products are quantitatively determined by high-performance liquid chromatography (Waters Alliance e2695), and signal detection is performed by a refractive index detector (RID). The chromatographic column used is an SC1011 column, with water as the mobile phase, a flow rate of 0.7 mL / min, and a column temperature of 80 °C.

[0063] In this invention, the X-ray diffraction (XRD) is measured using a Bruker AXS D8 Avance X-ray diffractometer with a scanning range of 10° to 80°.

[0064] X-ray photoelectron spectroscopy (XPS) was performed using the NexS spectrometer from Thermo Fisher Scientific. TM Measured by X-ray photoelectron spectroscopy.

[0065] Plasma coupling (ICP, also known as inductively coupled plasma) was measured using the THERMO IRIS IntrepidXSP inductively coupled plasma atomic emission spectrometer.

[0066] Calculate the carbohydrate conversion rate, ethylene glycol selectivity, and yield using the following formulas:

[0067]

[0068]

[0069] Ethylene glycol yield = carbohydrate conversion rate × ethylene glycol selectivity.

[0070] Example 1: A method for preparing a modified catalyst support

[0071] The preparation method includes:

[0072] Mix 0.392g praseodymium nitrate, 0.351g ethylenediaminetetraacetic acid with 20ml of water, and stir at 40 degrees Celsius for 2 hours to obtain material 1;

[0073] Alumina (support) was mixed with material 1, evaporated to dryness, and then dried overnight in an oven at 110 degrees Celsius. The mixture was then calcined at 500 degrees Celsius for 2 hours to obtain modified catalyst support-1.

[0074] Example 2: A method for preparing a modified catalyst support

[0075] The preparation method includes:

[0076] Mix 0.981g praseodymium nitrate, 0.876g ethylenediaminetetraacetic acid with 20ml water, and stir at 40 degrees Celsius for 2 hours to obtain material 1;

[0077] Alumina (support) was mixed with material 1, evaporated to dryness, and then dried overnight in an oven at 110 degrees Celsius. The mixture was then calcined at 500 degrees Celsius for 2 hours to obtain modified catalyst support-2.

[0078] Example 3: A method for preparing a modified catalyst support

[0079] The preparation method includes:

[0080] Mix 0.654g praseodymium nitrate, 0.584g ethylenediaminetetraacetic acid with 20ml of water, and stir at 40 degrees Celsius for 2 hours to obtain material 1;

[0081] Alumina (support) was mixed with material 1, evaporated to dryness, and then dried overnight in an oven at 110 degrees Celsius. The mixture was then calcined at 500 degrees Celsius for 2 hours to obtain modified catalyst support-3.

[0082] Example 4: A method for preparing a catalyst for ethylene glycol preparation

[0083] The specific steps of this preparation method include:

[0084] 5.383g of tungsten isopropoxide, 0.393g of platinum acetylacetonate, and 4.228g of tris(2-methylphenyl)phosphine were mixed with 100ml of acetone and refluxed at 40 degrees Celsius for 3 hours to obtain material 2.

[0085] Material 2 was mixed with the modified catalyst support in Example 1, stirred at 50 degrees for 2 hours, dried at room temperature, and then dried overnight in an oven at 110 degrees. The mixture was first calcined at 550 degrees for 4 hours and then reduced at 400 degrees for 4 hours to obtain the catalyst for ethylene glycol preparation.

[0086] Figure 1 The XRD diffraction pattern of the catalyst for ethylene glycol preparation is shown. The XRD diffraction pattern has 2θ characteristic peaks at 23.28±0.15, 23.97±0.15, 33.15±0.15, 33.66±0.20, 41.15±0.20, 47.70±0.20, 54.05±0.20, and 59.55±0.20, which belong to WO3. 3-x Characteristic peaks.

[0087] The Pt component was found to satisfy CXPS / CICP = 0.6; the W component was found to satisfy CXPS / CICP = 1.3.

[0088] Example 5: A method for preparing a catalyst for ethylene glycol preparation

[0089] The specific steps of this preparation method include:

[0090] 5.383g of tungsten isopropoxide, 0.393g of platinum acetylacetonate, and 4.228g of tris(2-methylphenyl)phosphine were mixed with 100ml of acetone and refluxed at 40 degrees Celsius for 3 hours to obtain material 2.

[0091] Material 2 was mixed with the modified catalyst support in Example 2, stirred at 50 degrees for 2 hours, dried at room temperature, and then dried overnight in an oven at 110 degrees. The mixture was first calcined at 550 degrees for 4 hours and then reduced at 400 degrees for 4 hours to obtain the catalyst for ethylene glycol preparation.

[0092] The Pt component was found to satisfy CXPS / CICP = 0.62; the W component was found to satisfy CXPS / CICP = 1.42.

[0093] Example 6: A method for preparing a catalyst for ethylene glycol preparation

[0094] The specific steps of this preparation method include:

[0095] 5.383g of tungsten isopropoxide, 0.393g of platinum acetylacetonate, and 4.228g of tris(2-methylphenyl)phosphine were mixed with 100ml of acetone and refluxed at 40 degrees Celsius for 3 hours to obtain material 2.

[0096] Material 2 was mixed with the modified catalyst support in Example 3, stirred at 50 degrees for 2 hours, dried at room temperature, and then dried overnight in an oven at 110 degrees. The mixture was then calcined at 550 degrees for 4 hours and reduced at 400 degrees for 4 hours to obtain the catalyst for ethylene glycol preparation.

[0097] The Pt component was found to satisfy CXPS / CICP = 0.65; the W component was found to satisfy CXPS / CICP = 1.55.

[0098] Example 7: A method for preparing a catalyst for ethylene glycol preparation

[0099] The specific steps of this preparation method include:

[0100] 5.383g of tungsten isopropoxide, 0.305g of palladium acetylacetone, and 4.228g of tris(2-methylphenyl)phosphine were mixed with 100ml of acetone and refluxed at 40 degrees Celsius for 3 hours to obtain material 2.

[0101] Material 2 was mixed with the modified catalyst support in Example 3, stirred at 50 degrees for 2 hours, dried at room temperature, and then dried overnight in an oven at 110 degrees. The mixture was then calcined at 550 degrees for 4 hours and reduced at 400 degrees for 4 hours to obtain the catalyst for ethylene glycol preparation.

[0102] The Pt component was found to satisfy CXPS / CICP = 0.7; the W component was found to satisfy CXPS / CICP = 1.75.

[0103] Example 8: A method for preparing a catalyst for ethylene glycol preparation

[0104] The specific steps of this preparation method include:

[0105] 5.383g of tungsten isopropoxide, 0.983g of platinum acetylacetonate, and 4.805g of tris(2-methylphenyl)phosphine were mixed with 100ml of acetone and refluxed at 40 degrees Celsius for 3 hours to obtain material 2.

[0106] Material 2 was mixed with the modified catalyst support in Example 3, stirred at 50 degrees for 2 hours, dried at room temperature, and then dried overnight in an oven at 110 degrees. The mixture was then calcined at 550 degrees for 4 hours and reduced at 400 degrees for 4 hours to obtain the catalyst for ethylene glycol preparation.

[0107] The Pt component was found to satisfy CXPS / CICP = 0.9; the W component was found to satisfy CXPS / CICP = 1.8.

[0108] Example 9: A method for preparing a catalyst for ethylene glycol preparation

[0109] The specific steps of this preparation method include:

[0110] 9.689g of tungsten isopropoxide, 0.393g of platinum acetylacetonate, and 7.304g of tris(2-methylphenyl)phosphine were mixed with 100ml of acetone and refluxed at 40 degrees Celsius for 3 hours to obtain material 2.

[0111] Material 2 was mixed with the modified catalyst support in Example 3, stirred at 50 degrees for 2 hours, dried at room temperature, and then dried overnight in an oven at 110 degrees. The mixture was then calcined at 550 degrees for 4 hours and reduced at 400 degrees for 4 hours to obtain the catalyst for ethylene glycol preparation.

[0112] The Pt component was found to satisfy CXPS / CICP = 0.73; the W component was found to satisfy CXPS / CICP = 2.1.

[0113] Example 10: A method for preparing a catalyst for ethylene glycol preparation

[0114] The specific steps of this preparation method include:

[0115] 5.383g of tungsten isopropoxide, 0.590g of platinum acetylacetonate, and 4.421g of tris(2-methylphenyl)phosphine were mixed with 100ml of acetone and refluxed at 40 degrees Celsius for 3 hours to obtain material 2.

[0116] Material 2 was mixed with the modified catalyst support in Example 3, stirred at 50 degrees for 2 hours, dried at room temperature, and then dried overnight in an oven at 110 degrees. The mixture was then calcined at 550 degrees for 4 hours and reduced at 400 degrees for 4 hours to obtain the catalyst for ethylene glycol preparation.

[0117] The Pt component was found to satisfy CXPS / CICP = 0.81; the W component was found to satisfy CXPS / CICP = 1.65.

[0118] Example 11: A method for preparing a catalyst for ethylene glycol preparation

[0119] The specific steps of this preparation method include:

[0120] 6.460g of tungsten isopropoxide, 0.590g of platinum acetylacetonate, and 5.189g of tris(2-methylphenyl)phosphine were mixed with 100ml of acetone and refluxed at 40 degrees Celsius for 3 hours to obtain material 2.

[0121] Material 2 was mixed with the modified catalyst support in Example 3, stirred at 50 degrees for 2 hours, dried at room temperature, and then dried overnight in an oven at 110 degrees. The mixture was then calcined at 550 degrees for 4 hours and reduced at 400 degrees for 4 hours to obtain the catalyst for ethylene glycol preparation.

[0122] The measured values ​​for the Pt component were CXPS / CICP = 0.77; the values ​​for the W component were CXPS / CICP = 1.96.

[0123] Comparative Example 1: A method for preparing a catalyst for ethylene glycol preparation

[0124] This comparative example is the same as Example 4 except that the catalyst was not reduced.

[0125] The preparation method of this catalyst includes:

[0126] 5.383g of tungsten isopropoxide, 0.393g of platinum acetylacetonate, and 4.228g of tris(2-methylphenyl)phosphine were mixed with 100ml of acetone and refluxed at 40 degrees Celsius for 3 hours to obtain material 2.

[0127] Material 2 was mixed with the modified catalyst support in Example 1, stirred at 50 degrees for 2 hours, dried at room temperature, and then dried overnight in an oven at 110 degrees. The mixture was then calcined at 550 degrees for 4 hours to obtain the catalyst for ethylene glycol preparation.

[0128] Figure 1 The XRD diffraction pattern of the catalyst for ethylene glycol preparation obtained is shown. The XRD diffraction pattern has 2θ characteristic peaks at 23.00±0.15, 23.45±0.15, 24.11±0.15, 28.70±0.15, 33.93±0.20, 41.56±0.20, 50.10±0.15, and 55.45±0.15, which are characteristic peaks of WO3.

[0129] The Pt component was found to satisfy CXPS / CICP = 0.5; the W component was found to satisfy CXPS / CICP = 2.3.

[0130] Therefore, it can be seen that the restoration step is crucial for generating the WO. 3-x The structure plays an important role; after high-temperature calcination, a slight reduction calcination at a lower temperature can yield WO3. 3-x Catalysts with a specific structure.

[0131] Comparative Example 2: A method for preparing a catalyst for ethylene glycol preparation

[0132] The addition method of rare earth additives in this comparative example is different, lacking complexing agent modification, but otherwise it is the same as Example 1 and Example 4.

[0133] The preparation method of this catalyst includes:

[0134] Mix 0.981g of praseodymium nitrate with 20ml of water and stir at 40 degrees Celsius for 2 hours to obtain material 1;

[0135] Alumina (support) was mixed with material 1, evaporated to dryness, and then dried overnight in an oven at 110 degrees Celsius. The mixture was then calcined at 500 degrees Celsius for 2 hours to obtain modified catalyst support-4.

[0136] 5.383g of tungsten isopropoxide, 0.393g of platinum acetylacetonate, and 4.228g of tris(2-methylphenyl)phosphine were mixed with 100ml of acetone and refluxed at 40 degrees Celsius for 3 hours to obtain material 2.

[0137] Material 2 was mixed with the modified catalyst support in Comparative Example 2, stirred at 50 degrees for 2 hours, dried at room temperature, and then dried overnight in an oven at 110 degrees. The mixture was then calcined at 550 degrees for 4 hours and reduced at 400 degrees for 4 hours to obtain the catalyst for ethylene glycol preparation.

[0138] The Pt component was found to satisfy CXPS / CICP = 0.95; the W component was found to satisfy CXPS / CICP = 1.2.

[0139] Comparative Example 3: A method for preparing a catalyst for ethylene glycol preparation

[0140] This comparative example did not add P, and was otherwise the same as Example 4.

[0141] The specific steps of this preparation method include:

[0142] 5.383g of tungsten isopropoxide, 0.393g of platinum acetylacetonate, and 100ml of acetone were mixed and refluxed at 40 degrees Celsius for 3 hours to obtain material 2.

[0143] Material 2 was mixed with the modified catalyst support in Example 1, stirred at 50 degrees for 2 hours, dried at room temperature, and then dried overnight in an oven at 110 degrees. The mixture was first calcined at 550 degrees for 4 hours and then reduced at 400 degrees for 4 hours to obtain the catalyst for ethylene glycol preparation.

[0144] The Pt component was found to satisfy CXPS / CICP = 0.55; the W component was found to satisfy CXPS / CICP = 2.2.

[0145] Comparative Example 4: A method for preparing a catalyst for ethylene glycol preparation

[0146] The carrier used in this comparative example was not modified with tracing agent or carrier additive praseodymium nitrate, and was otherwise the same as in Example 4.

[0147] 5.383g of tungsten isopropoxide, 0.393g of platinum acetylacetonate, and 4.228g of tris(2-methylphenyl)phosphine were mixed with 100ml of acetone and refluxed at 40 degrees Celsius for 3 hours to obtain material 2.

[0148] Material 2 was mixed with the unmodified carrier and stirred at 50 degrees for 2 hours. After drying at room temperature, it was placed in an oven at 110 degrees overnight for drying. It was then calcined at 550 degrees for 4 hours and reduced at 400 degrees for 4 hours to obtain the catalyst for ethylene glycol preparation.

[0149] The Pt component was found to satisfy CXPS / CICP = 1.1; the W component was found to satisfy CXPS / CICP = 1.1.

[0150] Comparative Example 5: A method for preparing a catalyst for ethylene glycol preparation

[0151] The carrier used in this comparative example was not modified with praseodymium nitrate or chelating agents, and P was not present. Otherwise, it was the same as in Example 4.

[0152] 5.383g of tungsten isopropoxide, 0.393g of platinum acetylacetonate, and 100ml of acetone were mixed and refluxed at 40 degrees Celsius for 3 hours to obtain material 2.

[0153] Material 2 was mixed with the unmodified carrier and stirred at 50 degrees for 2 hours. After drying at room temperature, it was placed in an oven at 110 degrees overnight for drying. It was then calcined at 550 degrees for 4 hours and reduced at 400 degrees for 4 hours to obtain the catalyst for ethylene glycol preparation.

[0154] The Pt component was found to satisfy CXPS / CICP = 1.2; the W component was found to satisfy CXPS / CICP = 1.0.

[0155] Test Example 1: Catalytic Conversion of Glucose to Ethylene Glycol

[0156] The catalysts prepared in Examples 4-11 and Comparative Examples 1-5 were evaluated for their catalytic performance under the same conditions. The reaction for the catalytic conversion of glucose to ethylene glycol was carried out in a closed reactor.

[0157] The catalytic conversion process includes: weighing 0.5g of glucose and 0.2g of catalyst and adding them to a high-pressure reactor (100mL) containing 40mL of water. The reactor is then sealed, and hydrogen gas is introduced to purge the mixture three times. The pressure is then increased to 4MPa, and the temperature is raised to 200℃. The reaction is allowed to proceed for 30 minutes. After the reaction is complete, the temperature is lowered, and the solid and reaction liquid (reaction products) are separated by filtration.

[0158] The liquid products were analyzed by high-performance liquid chromatography (HPLC), and the conversion rate of glucose and the yield of ethylene glycol were calculated according to the formulas described above. The evaluation results are shown in Table 1.

[0159] Table 1

[0160] Example Glucose conversion rate % Ethylene glycol yield % Example 4 96.9 34.50 Example 5 96.8 34.56 Example 6 98.2 36.33 Example 7 98.3 36.27 Example 8 98.4 36.60 Example 9 98.3 36.47 Example 10 99.2 38.49 Example 11 99.5 39.30 Comparative Example 1 (Reduction without calcination) 91.2 4.10 Comparative Example 2 (without complexing agent modification) 92.1 18.05 Comparative Example 3 (without P) 90.8 14.71 Comparative Example 4 (without complexing agents and carrier additives) 89.9 13.31 Comparative Example 5 (without complexing agent, carrier additive, and P) 90.1 9.46

[0161] As shown in Table 1, when using the catalyst of this invention to catalyze the conversion of glucose to ethylene glycol, the glucose conversion rate can reach up to 99.5%, and the ethylene glycol yield can reach up to 39.30%. The ethylene glycol yield is more than twice that of the catalyst without complexing agent modification, and more than four times that of the catalyst without complexing agent and catalyst promoter modification, and without the addition of phosphorus. This demonstrates that the catalyst prepared by modifying the catalyst support with a support promoter such as lanthanum and a complexing agent such as ethylenediaminetetraacetic acid has higher selectivity. The catalyst prepared by combining this modified catalyst support with a phosphorus-containing protective ligand and other active components exhibits the highest selectivity and good hydrothermal stability.

[0162] In addition, the calcined catalyst is cooled down and then further calcined and reduced to give the catalyst WO3 content. 3-x The WO3-x structure enhances the catalytic activity of the catalyst, thereby increasing the conversion rate of glucose and the yield of ethylene glycol. Without reduction treatment, the catalyst cannot achieve the WO3-x structure, and the role of the noble metal cannot be fully utilized.

[0163] Test Example 2: Catalytic Conversion of Cellulose to Ethylene Glycol

[0164] The catalysts prepared in Example 4, Comparative Example 1, and Comparative Example 4 were evaluated for their catalytic reaction performance under the same conditions.

[0165] The catalytic conversion process includes: weighing 0.5g of cellulose and 0.2g of catalyst and adding them to a high-pressure reactor (100mL) containing 40mL of water. The reactor is then sealed, and hydrogen gas is introduced three times to purge the mixture. The pressure is then increased to 4MPa, and the temperature is raised to 200℃. The reaction is allowed to proceed for 30 minutes. After the reaction is complete, the temperature is lowered, and the solid and reaction liquid (reaction products) are separated by filtration.

[0166] The liquid products were analyzed by high-performance liquid chromatography (HPLC), and the conversion rate of cellulose and the yield of ethylene glycol were calculated according to the formulas described above. The evaluation results are shown in Table 2.

[0167] Table 2

[0168] Example Cellulose conversion rate % Ethylene glycol yield % Example 4 90.9 37.81 Comparative Example 2 68.6 8.58 Comparative Example 5 52.6 5.15

[0169] As shown in Table 2, the catalyst obtained in Example 4 achieved better results in catalytic fiber performance, with an ethylene glycol yield of 37.81%, which is more than four times that of the catalyst obtained without complexing agent modification.

[0170] Test Example 3: Catalytic conversion of glucose to ethylene glycol, with the catalyst reused 3 times.

[0171] The catalysts prepared in Example 4, Comparative Examples 2 and 5 were evaluated for their catalytic reaction performance under the same conditions.

[0172] The catalytic conversion process included: weighing 0.5 g of glucose and 0.2 g of catalyst and adding them to a 100 mL high-pressure reactor containing 40 mL of water. The reactor was sealed, and hydrogen gas was introduced three times to purge the mixture. The pressure was then increased to 4 MPa, and the temperature was raised to 200 °C. The reaction was allowed to proceed for 30 minutes. After the reaction, the temperature was lowered, and the solid and reaction product were separated by filtration. The liquid product was analyzed by high-performance liquid chromatography (HPLC), and the conversion rate of glucose and the yield of ethylene glycol were calculated according to the formulas described above. The evaluation results are shown in Table 3.

[0173] The catalyst was recovered and the catalytic conversion process was repeated three times.

[0174] Table 3

[0175]

[0176] As shown in Table 3, the catalyst of Example 4, which has been used 3 times, can still achieve a glucose conversion rate of 96.8%, which is only 0.1% lower than the conversion rate of 96.9% in the first use, and the catalytic activity is almost not lost; the yield of ethylene glycol is also almost not reduced.

[0177] However, in Comparative Example 2, which was not modified with a complexing agent, the catalyst conversion rate in the third reaction was 76.6%, which was 13.5% lower than the 90.1% in the first reaction.

[0178] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A catalyst for ethylene glycol production, the catalyst comprising: Noble metal components, tungsten-containing active components, catalyst promoters, and modified catalyst supports; The catalyst promoter is selected from any one of bis(diphenylphosphine)methane, 1,2-bis(diphenylphosphine)ethane, and tris(2-methylphenylphosphine); The method for preparing the modified catalyst support includes: mixing a support additive, a complexing agent, and water to obtain material 1; mixing an unmodified support with material 1, drying and calcining to obtain the modified catalyst support; the support additive contains at least one rare earth metal element; the complexing agent is any one of ethylenediaminetetraacetic acid, diethyltriaminepentaacetic acid, and ethylenediaminedi-o-phenylacetic acid; The catalyst for the preparation of ethylene glycol has the specific components of WO 3-x wherein x = 0.10-0.

15.

2. The catalyst for ethylene glycol production according to claim 1, wherein The molar ratio of alumina to noble metal components, tungsten-containing active components, and catalyst promoters in the modified catalyst support is 1:(0.010~0.025):(0.110~0.205):(0.100~0.180).

3. The catalyst for ethylene glycol preparation according to claim 1, characterized in that, The molar ratio of the modified catalyst support to the noble metal component, the tungsten-containing active component, and the catalyst promoter is 1:(0.010~0.015):(0.110~0.135):(0.100~0.120).

4. The catalyst for ethylene glycol preparation according to claim 1, characterized in that, The molar ratio of the modified catalyst support to the noble metal component, the tungsten-containing active component, and the catalyst promoter is 1:0.015:0.135:0.

120.

5. The catalyst for ethylene glycol preparation according to any one of claims 1-4, characterized in that, The noble metal component contains at least one group VIII metal element; And / or, the tungsten-containing active component is an inorganic compound of tungsten.

6. The catalyst for ethylene glycol preparation according to claim 5, characterized in that, Group VIII metallic elements are Pt or Pd; And / or, the inorganic compound of tungsten is tungstic acid or metatungstate.

7. The catalyst for ethylene glycol preparation according to claim 6, characterized in that, The metatungstate is ammonium metatungstate.

8. The catalyst for ethylene glycol preparation according to any one of claims 1-4, characterized in that, The noble metal component satisfies CXPS / CICP=0.6~0.9; where CXPS is the molar content of noble metal elements in the catalyst characterized by X-ray photoelectron spectroscopy, and CICP is the molar content of noble metal elements in the catalyst characterized by plasmonic coupling. And / or, the tungsten-containing active component satisfies CXPS / CICP=1.3~2.1; where CXPS is the molar content of tungsten in the catalyst characterized by X-ray photoelectron spectroscopy, and CICP is the molar content of tungsten in the catalyst characterized by plasmonic coupling.

9. The catalyst for ethylene glycol preparation according to any one of claims 1-4, characterized in that, The molar ratio of the unmodified carrier to the carrier additive and complexing agent is 1:(0.012~0.300):(0.012~0.300).

10. The catalyst for ethylene glycol preparation according to any one of claims 1-4, characterized in that, The molar ratio of the unmodified carrier to the carrier additive and complexing agent is 1:(0.012~0.020):(0.012~0.020).

11. The catalyst for ethylene glycol preparation according to any one of claims 1-4, characterized in that, The unmodified carrier is selected from at least one of alumina, silicon dioxide, titanium dioxide, and zirconium oxide.

12. The catalyst for ethylene glycol preparation according to any one of claims 1-4, characterized in that, The unmodified carrier is aluminum oxide or titanium oxide.

13. The catalyst for ethylene glycol preparation according to any one of claims 1-4, characterized in that, The unmodified carrier is aluminum oxide.

14. The catalyst for ethylene glycol preparation according to any one of claims 1-4, characterized in that, The complexing agent is ethylenediaminetetraacetic acid.

15. The catalyst for ethylene glycol preparation according to any one of claims 1-4, characterized in that, The rare earth metal element is selected from any one of scandium, yttrium, and lanthanides.

16. The catalyst for ethylene glycol preparation according to any one of claims 1-4, characterized in that, The rare earth metal element is a lanthanide metal.

17. The catalyst for ethylene glycol preparation according to claim 16, characterized in that, The lanthanide metal is La or Pr.

18. The catalyst for ethylene glycol preparation according to claim 16, characterized in that, The lanthanide metal is Pr.

19. The catalyst for preparing ethylene glycol according to any one of claims 1-4, characterized in that, In the preparation method of the modified catalyst support, the drying temperature is 110°C; and / or the calcination temperature is 500-600°C.

20. A method for preparing a catalyst for ethylene glycol preparation, characterized in that, The preparation method includes the following steps: 1) Mix the tungsten-containing active component, the noble metal component, the catalyst additive, and the solvent to obtain material 2; 2) Mix material 2 with the modified catalyst support, dry and calcine, and then reduce to obtain the catalyst for preparing ethylene glycol; The catalyst promoter is selected from any one of bis(diphenylphosphine)methane, 1,2-bis(diphenylphosphine)ethane, and tris(2-methylphenylphosphine); The method for preparing the modified catalyst support includes: mixing a support additive, a complexing agent, and water to obtain material 1; mixing an unmodified support with material 1, drying and calcining to obtain the modified catalyst support; the support additive contains at least one rare earth metal element; the complexing agent is any one of ethylenediaminetetraacetic acid, diethyltriaminepentaacetic acid, and ethylenediaminedi-o-phenylacetic acid.

21. The preparation method according to claim 20, characterized in that, The solvent is acetone; And / or, in step 2), dry in an oven at 100-130°C; And / or, in step 2), calcination is carried out at a temperature of 550-700℃; And / or, in step 2), reduction is carried out at a temperature of 400~500℃.

22. The preparation method according to claim 20 or 21, characterized in that, The molar ratio of alumina to noble metal components, tungsten-containing active components, and catalyst promoters in the modified catalyst support is 1:(0.010~0.025):(0.110~0.205):(0.100~0.180).

23. The preparation method according to claim 20 or 21, characterized in that, The molar ratio of the modified catalyst support to the noble metal component, the tungsten-containing active component, and the catalyst promoter is 1:(0.010~0.015):(0.110~0.135):(0.100~0.120).

24. The preparation method according to claim 20 or 21, characterized in that, The molar ratio of the modified catalyst support to the noble metal component, the tungsten-containing active component, and the catalyst promoter is 1:0.015:0.135:0.

120.

25. The preparation method according to claim 20 or 21, characterized in that, The noble metal component contains at least one group VIII metal element; And / or, the tungsten-containing active component is an inorganic compound of tungsten.

26. The preparation method according to claim 25, characterized in that, Group VIII metallic elements are Pt or Pd; And / or, the inorganic compound of tungsten is tungstic acid or metatungstate.

27. The preparation method according to claim 26, characterized in that, The metatungstate is ammonium metatungstate.

28. The preparation method according to claim 20 or 21, characterized in that, The noble metal component satisfies CXPS / CICP=0.6~0.9; where CXPS is the molar content of noble metal elements in the catalyst characterized by X-ray photoelectron spectroscopy, and CICP is the molar content of noble metal elements in the catalyst characterized by plasmonic coupling. And / or, the tungsten-containing active component satisfies CXPS / CICP=1.3~2.1; where CXPS is the molar content of tungsten in the catalyst characterized by X-ray photoelectron spectroscopy, and CICP is the molar content of tungsten in the catalyst characterized by plasmonic coupling.

29. The preparation method according to claim 20 or 21, characterized in that, The molar ratio of the unmodified carrier to the carrier additive and complexing agent is 1:(0.012~0.300):(0.012~0.300).

30. The preparation method according to claim 20 or 21, characterized in that, The molar ratio of the unmodified carrier to the carrier additive and complexing agent is 1:(0.012~0.020):(0.012~0.020).

31. The preparation method according to claim 20 or 21, characterized in that, The unmodified carrier is selected from at least one of alumina, silicon dioxide, titanium dioxide, and zirconium oxide.

32. The preparation method according to claim 20 or 21, characterized in that, The unmodified carrier is aluminum oxide or titanium oxide.

33. The preparation method according to claim 20 or 21, characterized in that, The unmodified carrier is aluminum oxide.

34. The preparation method according to claim 20 or 21, characterized in that, The complexing agent is ethylenediaminetetraacetic acid.

35. The preparation method according to claim 20 or 21, characterized in that, The rare earth metal element is selected from any one of scandium, yttrium, and lanthanides.

36. The preparation method according to claim 20 or 21, characterized in that, The rare earth metal element is a lanthanide metal.

37. The preparation method according to claim 36, characterized in that, The lanthanide metal is La or Pr.

38. The preparation method according to claim 36, characterized in that, The lanthanide metal is Pr.

39. The preparation method according to claim 20 or 21, characterized in that, In the preparation method of the modified catalyst support, the drying temperature is 110°C; and / or the calcination temperature is 500-600°C.

40. A catalyst for preparing ethylene glycol prepared according to any one of claims 20-39.

41. The use of a catalyst for preparing ethylene glycol according to any one of claims 1-19 or the catalyst for preparing ethylene glycol according to claim 40 in the preparation of ethylene glycol from biomass feedstock.

42. The application according to claim 41, characterized in that, The biomass is selected from at least one of cellulose, starch, hemicellulose, fructan, xylan, disaccharide, and glucose.

43. The application according to claim 42, characterized in that, The biomass is glucose.

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