Crude ethylene glycol hydrofining method and hydrofining agent

Abstract

The present invention relates to a crude ethylene glycol hydrofining agent and an ethylene glycol hydrofining method, the refining agent comprises a carrier, an active component and an auxiliary agent, the active component comprises ruthenium, and the auxiliary agent comprises at least one of an alkaline earth metal oxide and a transition metal oxide. When the refining agent is used for refining crude ethylene glycol, the refined ethylene glycol is high in ultraviolet transmittance, the reduction is not obvious in the storage process, and meanwhile, the refining agent is stable and long in service life.

Description

[0001] The present invention is a divisional application of patent application number 201910824527.9, filed on September 2, 2019, and entitled “Crude Ethylene Glycol Hydrogenation Refining Method and Hydrogenation Refining Agent”. Technical Field

[0002] The invention relates to a method for refining crude ethylene glycol, and in particular to the preparation of a Ru-based refining agent and the application of the Ru-based refining agent in refining ethylene glycol. Background Art

[0003] Ethylene glycol (EG) is an important basic organic raw material for petrochemical industry, from which more than 100 kinds of chemicals can be derived. Among them, polyester (including polyester fiber, polyester bottle, polyester film, etc.) is the main consumption area of ​​ethylene glycol in my country, accounting for about 90% of the total domestic consumption. Another 10% is used for antifreeze, adhesives, paint solvents, cold-resistant lubricants and surfactants. At present, the industrial production routes of ethylene glycol can be mainly divided into two types: petroleum method and synthesis gas method. The petroleum method mainly produces ethylene glycol by hydrating ethylene oxide generated by ethylene oxidation produced by naphtha cracking. Although this production process is relatively mature and stable, it still has many disadvantages. For example, in the production process, in addition to ethylene oxide, ethylene oxidation will also produce aldehydes, ketones, acids, esters and other by-products containing carbon-oxygen double bonds. Ethylene oxide will also isomerize to form aldehyde by-products, and these species containing carbon-oxygen double bonds will affect the permeability of ethylene glycol, thereby affecting the quality of the final ethylene glycol product. The synthesis gas method mainly uses CO in the synthesis gas to oxidatively couple to produce oxalate, and then the oxalate is hydrogenated to obtain ethylene glycol. In the process of oxalate hydrogenation, due to incomplete hydrogenation, some byproducts containing carbon-oxygen double bonds that affect the UV transmittance will be generated, which will also affect the quality of the final ethylene glycol product in the subsequent process. Therefore, it is very important to remove these impurities containing carbon-oxygen double bonds to improve the UV transmittance of ethylene glycol and improve the quality of ethylene glycol products.

[0004] Liu Juntao et al. (CN 102649688) used a supported copper catalyst to hydrogenate crude ethylene glycol, which could increase the UV transmittance of ethylene glycol at 220 nm from less than 30% to more than 75%, thus meeting the national standard for premium products.

[0005] Qiao Jinliang et al. (CN 104945227) used carbon-loaded Raney nickel alloy as a hydrogenation refining agent for ethylene glycol at 100 °C, 0.5 MPa, and a space velocity of 6 h -1 Under the condition of , the ultraviolet transmittance at 220nm can be increased from the original 26% to more than 80%.

[0006] How to use new refining agents to significantly improve the UV transmittance of ethylene glycol and enable it to be used for a long time while preventing a significant drop in UV value during storage is an urgent problem to be solved in industrial production practice. Summary of the invention

[0007] One of the technical problems to be solved by the present invention is the problem of low ultraviolet transmittance of ethylene glycol products in previous refining technologies. A crude ethylene glycol hydrogenation refining agent is provided. The refining agent is used in the refining of crude ethylene glycol to make the ultraviolet transmittance of the refined ethylene glycol high and not significantly reduced during storage. At the same time, the refining agent is stable and has a long service life.

[0008] The second technical problem to be solved by the present invention is a method for preparing a refined preparation corresponding to one of the above technical problems.

[0009] The third technical problem to be solved by the present invention is to provide a new method for refining ethylene glycol.

[0010] The first aspect of the present invention provides a crude ethylene glycol hydrogenation refining agent, which comprises a carrier, an active component and an auxiliary agent, wherein the active component comprises ruthenium, and the auxiliary agent comprises at least one of an alkaline earth metal oxide and a transition metal oxide.

[0011] According to some embodiments of the present invention, the transition metal oxide is selected from at least one of oxides of Ni, Zn, Co and Mn, such as NiO, ZnO, Co3O4 and MnO2.

[0012] According to some embodiments of the present invention, the transition metal oxide is selected from at least one of Ni and Zn oxides, such as NiO or ZnO.

[0013] According to some embodiments of the present invention, the alkaline earth metal oxide is selected from at least one of oxides of Mg and Ca, such as MgO.

[0014] According to some embodiments of the present invention, the carrier is selected from one or more of alumina, silica and molecular sieve.

[0015] According to some embodiments of the present invention, the carrier is selected from one or more of θ-alumina, η-alumina, and γ-alumina.

[0016] According to some embodiments of the present invention, the carrier is γ-alumina.

[0017] According to some embodiments of the present invention, the γ-alumina precursor includes one or more of amorphous aluminum hydroxide, pseudo-boehmite and boehmite, preferably includes pseudo-boehmite or boehmite.

[0018] According to some embodiments of the present invention, the refined preparation comprises, by weight, 0.1-10 parts of active ingredients, 0.5-15 parts of auxiliary agents and 75-99.4 parts of carriers.

[0019] According to some embodiments of the present invention, the refined preparation includes, by weight, 0.5-4 parts of active ingredients, 1-9 parts of auxiliary agents and 87-98.5 parts of carriers.

[0020] According to some embodiments of the present invention, the refined preparation comprises, by weight, 1-3 parts of active ingredient, 4-6 parts of auxiliary agent and 91-95 parts of carrier.

[0021] According to some embodiments of the present invention, the specific surface area of ​​the carrier is 240-320m 2 / g, for example, 240m 2 / g, 250m 2 / g, 255m 2 / g, 259m 2 / g, 260m 2 / g, 270m 2 / g, 280m 2 / g, 290m 2 / g, 296m 2 / g、300m 2 / g, 310m 2 / g and 320m 2 / g and any value therebetween, preferably 250 to 300 m 2 / g.

[0022] According to some embodiments of the present invention, the pore volume of the carrier is 0.30-0.80 mL / g, for example, it can be 0.30 mL / g, 0.40 mL / g, 0.45 mL / g, 0.50 mL / g, 0.55 mL / g, 0.60 mL / g, 0.65 mL / g, 0.70 mL / g and 0.80 mL / g and any value therebetween, preferably 0.40-0.60 mL / g.

[0023] The second aspect of the present invention provides a method for preparing the above-mentioned refined preparation, comprising the following steps:

[0024] (I) providing a solution I comprising a soluble salt of an active ingredient and a soluble salt of an adjuvant;

[0025] (II) mixing the carrier with the solution I, drying and roasting to obtain a refined preparation precursor;

[0026] (III) treating the precursor of the refined product with a reducing agent to obtain the refined product.

[0027] According to some embodiments of the present invention, the soluble salt in step (I) is selected from at least one of halide, nitrate and sulfate.

[0028] According to some embodiments of the present invention, the calcination temperature in step (II) is 300-600° C., and the calcination time is 2-6 hours.

[0029] According to some embodiments of the present invention, the reducing agent in step (III) is hydrogen, the reduction treatment pressure is 0.1-1 MPa, and the reducing agent gas hourly space velocity is 200-1000 h -1 , the reduction temperature is 120-200℃, and the reduction time is 2-10h.

[0030] According to some preferred embodiments of the present invention, the preparation method of the refined preparation is as follows:

[0031] 1) At room temperature, ruthenium chloride and metal salt of the auxiliary agent are dissolved in deionized water to obtain an impregnation solution; an alumina carrier is added to the impregnation solution and stirred for 20 minutes.

[0032] 2) The mixture obtained in step 1) is dried in an oven for 24 hours, and then calcined for 4 hours to obtain an Al2O3-supported Ru-based refining agent precursor.

[0033] 3) The refined product precursor obtained in step 2) is placed in a fixed bed reactor and reduced with hydrogen at a pressure of 0.1-1 MPa and a gas hourly space velocity of 200-1000 h -1 The reduction temperature is 120-200°C and the reduction time is 2-10h to obtain alumina-supported ruthenium-based refining agent Ru-M / Al2O3.

[0034] According to some preferred embodiments of the present invention, the metal salt of the auxiliary agent used in step 1) can be at least one of a halide, a nitrate and a sulfate; the drying temperature used in step 2) is 100-150°C

[0035] The method of the present invention adopts an impregnation method to load Ru and an auxiliary agent onto an alumina carrier, and then uses hydrogen reduction to obtain an alumina-loaded metal Ru-based hydrogenation refining agent. The Ru and the auxiliary agent in the refining agent work together to better remove impurities containing carbon-oxygen double bonds in crude ethylene glycol.

[0036] The third aspect of the present invention provides a method for hydrogenating and refining crude ethylene glycol, comprising introducing ethylene glycol and hydrogen to react in the presence of the above-mentioned refining agent.

[0037] According to some embodiments of the present invention, the reaction temperature is 60-140°C, preferably 80-120°C, and more preferably 100-120°C.

[0038] According to some embodiments of the present invention, the reaction pressure is 0.2-3 MPa, preferably 0.5-2.5 MPa, and more preferably 1.5-2.5 MPa.

[0039] According to some embodiments of the present invention, the mass space velocity of ethylene glycol is 1-20h -1 , preferably 3-8h -1 , more preferably 3-5h -1 . ,

[0040] According to some embodiments of the present invention, the feed volume ratio of the reducing agent to ethylene glycol (standard state) is 200-1400, preferably 300-1200, and more preferably 600-1200.

[0041] The Ru-based hydrogenation refining agent supported by alumina of the present invention is used in the hydrogenation refining of crude ethylene glycol. At a reaction temperature of 100°C and a crude ethylene glycol space velocity of 5h -1 Under the conditions of hydrogen pressure of 1.5MPa and feed volume ratio of hydrogen to crude ethylene glycol (standard state) of 600, the ultraviolet transmittance of ethylene glycol after hydrotreating is greater than 90%, 95% and 99% at 220nm, 275nm and 350nm, respectively, and the hydrotreating activity can be maintained within 400 days. Moreover, the decrease in ultraviolet transmittance of the refined ethylene glycol after storage for 10 days is less than 5%.

[0042] The term "standard state" used in the present invention refers to the standard state of a gas at a temperature of 25°C and a pressure of 101.325 KPa.

[0043] A fourth aspect of the present invention provides the use of the above-mentioned refining agent or the above-mentioned method in the refining of crude ethylene glycol. DETAILED DESCRIPTION

[0044] The present invention is further described below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and cannot be construed as limiting the scope of protection of the present invention.

[0045] [Example 1]

[0046] 27.9g carrier Al2O3-1 (γ-Al2O3, the precursor is boehmite, the specific surface area is 256m 2 / g, pore volume of 0.55mL / g) was dispersed in 100mL of deionized water, and then 50mL of an aqueous solution containing 1.21g of ruthenium chloride and 5.84g of nickel nitrate hexahydrate was added. After stirring for 20min, the obtained mixture was baked at 120°C for 24h and calcined at 500°C for 4h to obtain a catalyst precursor. 10g of the precursor was loaded in a fixed bed reactor, and the hydrogen pressure was maintained at 0.5MPa, the flow rate was 100mL / h (standard state), the reduction temperature was 150°C, and the reduction time was 5h. The obtained hydrogenation refining agent was RA-1, in which the weight fraction of Ru was 2.0, the auxiliary agent M was NiO, the weight fraction was 5.0, and the weight fraction of the carrier Al2O3-1 was 93.0.

[0047] [Example 2]

[0048] The preparation method of the hydrogenation refining agent is the same as that of [Example 1], except that the auxiliary salt used is 5.51 g of zinc nitrate hexahydrate, and the obtained hydrogenation refining agent is RA-2, in which the weight fraction of Ru is 2.0, the auxiliary agent M is ZnO, the weight fraction is 5.0, and the weight fraction of the carrier Al2O3-1 is 93.0.

[0049] [Example 3]

[0050] The preparation method of the hydrogenation refining agent is the same as that of [Example 1], except that the auxiliary salt used is 9.62g of magnesium nitrate hexahydrate, and the obtained hydrogenation refining agent is RA-3, in which the weight fraction of Ru is 2.0, the auxiliary agent M is MgO, the weight fraction is 5.0, and the weight fraction of the carrier Al2O3-1 is 93.0.

[0051] [Example 4]

[0052] The preparation method of the hydrogenation refining agent is the same as that of [Example 1], except that the auxiliary salt used is 5.46 g of cobalt nitrate hexahydrate, and the obtained hydrogenation refining agent is RA-4, in which the weight fraction of Ru is 2.0, the auxiliary agent M is Co3O4, the weight fraction is 5.0, and the weight fraction of the carrier Al2O3-1 is 93.0.

[0053] [Example 5]

[0054] The preparation method of the hydrogenation refining agent is the same as that of [Example 1], except that the auxiliary salt used is 6.17g of 50wt% manganese nitrate solution, and the obtained hydrogenation refining agent is RA-5, in which the weight fraction of Ru is 2.0, the auxiliary agent M is MnO2, the weight fraction is 5.0, and the weight fraction of the carrier Al2O3-1 is 93.0.

[0055] [Example 6]

[0056] The preparation method of the hydrogenation refined agent is the same as that of Example 1, except that the carrier used is Al2O3-2 (γ-Al2O3, the precursor is boehmite, and the specific surface area is 296m 2 / g, pore volume is 0.45mL / g), the obtained hydrogenation refining agent is RA-6, in which the weight fraction of Ru is 2.0, the auxiliary agent M is NiO, the weight fraction is 5.0, and the weight fraction of the carrier Al2O3-2 is 93.0.

[0057] [Example 7]

[0058] The preparation method of the hydrogenation refining agent is the same as that of [Example 1], except that the mass of ruthenium chloride used is 0.30 g, the auxiliary salt is 8.60 g of nickel chloride hexahydrate, the mass of the carrier Al2O3-1 used is 27.2 g, and the obtained hydrogenation refining agent is RA-7, in which the weight fraction of Ru is 0.5, the auxiliary agent M is NiO, the weight fraction is 9.0, and the weight fraction of the carrier Al2O3-1 is 90.5.

[0059] [Example 8]

[0060] The preparation method of the hydrogenation refining agent is the same as that of [Example 1], except that the mass of ruthenium chloride used is 2.42 g, the auxiliary salt is 1.75 g of nickel nitrate hexahydrate, the mass of the carrier Al2O3-1 used is 28.4 g, and the obtained hydrogenation refining agent is RA-8, in which the weight fraction of Ru is 4.0, the auxiliary agent M is NiO, the weight fraction is 1.5, and the weight fraction of the carrier Al2O3-1 is 94.5.

[0061] [Comparative Example 1]

[0062] The preparation method of the hydrogenated refined agent is the same as that of [Example 1], except that no auxiliary salt is added. The mass of the carrier Al2O3-1 used is 29.4 g. The obtained hydrogenated refined agent is CRA-1, in which the weight fraction of Ru is 2.0 and the weight fraction of the carrier Al2O3-1 is 98.0.

[0063] [Comparative Example 2]

[0064] The preparation method of the hydrogenated refining agent is the same as that of [Example 1], except that no auxiliary salt is added. The carrier used is Al2O3-2, with a mass of 29.4 g. The obtained hydrogenated refining agent is CRA-2, in which the weight fraction of Ru is 2.0 and the weight fraction of the carrier Al2O3-2 is 98.0.

[0065] [Comparative Example 3]

[0066] The preparation method of the hydrogenation refining agent is the same as that of [Example 1], except that no auxiliary salt is added, the mass of the carrier Al2O3-1 used is 27.9 g, the mass of the ruthenium chloride used is 4.30 g, and the obtained hydrogenation refining agent is CRA-3, in which the weight fraction of Ru is 7.0, and the weight fraction of the carrier Al2O3-1 is 93.0.

[0067] [Comparative Example 4]

[0068] The preparation method of the hydrogenation refining agent is the same as that of [Example 1], except that no active component is added, the mass of the carrier Al2O3-1 used is 27.9 g, the mass of the auxiliary agent nickel nitrate hexahydrate used is 8.15 g, and the obtained hydrogenation refining agent is CRA-4, in which the weight fraction of NiO is 7.0, and the weight fraction of the carrier Al2O3-1 is 93.0.

[0069] [Comparative Example 5]

[0070] The preparation method of the hydrogenated refined agent is the same as that of [Example 1], except that no active component is added, the mass of the carrier Al2O3-1 used is 27.9 g, the mass of the auxiliary agent zinc nitrate hexahydrate used is 7.70 g, and the obtained hydrogenated refined agent is CRA-4, in which the weight fraction of ZnO is 7.0, and the weight fraction of the carrier Al2O3-1 is 93.0.

[0071] [Comparative Example 6]

[0072] The preparation method of the hydrogenated refined agent is the same as that of [Example 1], except that no active component is added, the mass of the carrier Al2O3-1 used is 27.9 g, the mass of the auxiliary agent magnesium nitrate hexahydrate used is 13.4 g, and the obtained hydrogenated refined agent is CRA-6, in which the weight fraction of MgO is 7.0, and the weight fraction of the carrier Al2O3-1 is 93.0.

[0073] [Comparative Example 7]

[0074] The preparation method of the hydrogenated refined agent is the same as that of [Example 1], except that no active component is added, the mass of the carrier Al2O3-1 used is 27.9 g, the mass of the auxiliary agent cobalt nitrate hexahydrate used is 8.18 g, and the obtained hydrogenated refined agent is CRA-7, in which the weight fraction of Co3O4 is 7.0, and the weight fraction of the carrier Al2O3-1 is 93.0.

[0075] [Comparative Example 8]

[0076] The preparation method of the hydrogenated refined agent is the same as that of [Example 1], except that no active component is added, the mass of the carrier Al2O3-1 used is 27.9 g, the mass of the auxiliary agent 50% manganese nitrate solution used is 8.64 g, and the obtained hydrogenated refined agent is CRA-8, in which the weight fraction of MnO2 is 7.0, and the weight fraction of the carrier Al2O3-1 is 93.0.

[0077] [Example 9]

[0078] 10.0 g of the hydrogenation refining agent RA-1 prepared in Example 1 was charged into a fixed bed reactor, the temperature was controlled at 100 ° C, hydrogen was added, the hydrogen pressure was controlled at 1.5 MPa, the flow rate was 460 mL / min, and crude ethylene glycol (mass percentage 99.8%, UV transmittance at 220 nm, 275 nm, 350 nm were 45.1%, 66.3%, 90.5%, respectively) was uniformly passed through the hydrogenation refining agent bed at a speed of 50.0 g / h, and the mass space velocity was 5.0 h -1 The volume ratio of hydrogen to ethylene glycol (standard state) is 600. The collected refined ethylene glycol has UV transmittances of 92.1%, 98.0% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined ethylene glycol was stored under N2 protection for 10 days. After testing, the UV transmittances at 220nm, 275nm and 350nm were 91.5%, 97.5% and 99.9%, respectively.

[0079] [Examples 10-24]

[0080] The hydrorefining agents RA-2 to RA-8 and CRA1 to CRA-8 prepared in [Examples 2-8] and [Comparative Examples 1-9] were subjected to hydrorefining experiments according to the hydrorefining conditions adopted in [Example 9]. The results obtained are shown in Table 1.

[0081] Table 1

[0082]

[0083]

[0084] [Example 25]

[0085] The conditions were the same as those in Example 9, except that the feed rate of crude ethylene glycol was 80.0 g / h and the intake amount of hydrogen was 740 mL / min. Refined ethylene glycol was obtained, and its UV transmittance at 220 nm, 275 nm and 350 nm was measured to be 90.3%, 97.1% and 99.9%, respectively. The obtained refined ethylene glycol was stored under N2 protection for 10 days, and its UV transmittance at 220 nm, 275 nm and 350 nm was measured to be 89.1%, 97.0% and 99.9%, respectively.

[0086] [Example 26]

[0087] The conditions were the same as those in Example 9, except that the feed rate of crude ethylene glycol was 30.0 g / h and the intake amount of hydrogen was 280 mL / min. Refined ethylene glycol was obtained, and its UV transmittance at 220 nm, 275 nm and 350 nm was 92.5%, 98.1% and 99.9% respectively. The obtained refined ethylene glycol was stored under N2 protection for 10 days, and its UV transmittance at 220 nm, 275 nm and 350 nm was 92.0%, 98.0% and 99.9% respectively.

[0088] [Example 27]

[0089] The conditions were the same as those in Example 9, except that the reaction temperature was 80°C, and refined ethylene glycol was obtained, and its UV transmittance at 220nm, 275nm and 350nm was measured to be 85.3%, 96.9% and 99.7%, respectively. The refined ethylene glycol was stored under N2 protection for 10 days, and its UV transmittance at 220nm, 275nm and 350nm was measured to be 84.2%, 96.2% and 99.6%, respectively.

[0090] [Example 28]

[0091] The conditions were the same as those in Example 9, except that the reaction temperature was 120°C, and refined ethylene glycol was obtained, and its UV transmittance at 220nm, 275nm and 350nm was measured to be 92.6%, 98.5% and 99.9%, respectively. The refined ethylene glycol was stored under N2 protection for 10 days, and its UV transmittance at 220nm, 275nm and 350nm was measured to be 91.6%, 98.2% and 99.9%, respectively.

[0092] [Example 29]

[0093] The conditions were the same as those in Example 9, except that the flow rate of hydrogen was 920 mL / min, and the feed volume ratio of hydrogen to crude ethylene glycol (standard state) was 1200, and refined ethylene glycol was obtained, and its UV transmittance at 220 nm, 275 nm and 350 nm was measured to be 92.8%, 98.6% and 99.9%, respectively. The refined ethylene glycol obtained was stored under N2 protection for 10 days, and its UV transmittance at 220 nm, 275 nm and 350 nm was measured to be 92.0%, 98.4% and 99.9%, respectively.

[0094] [Example 30]

[0095] The conditions were the same as those in Example 9, except that the flow rate of hydrogen was 230 mL / min, and the feed volume ratio of hydrogen to crude ethylene glycol (standard state) was 300. Refined ethylene glycol was obtained, and its UV transmittance at 220 nm, 275 nm and 350 nm was measured to be 91.1%, 97.0% and 99.9%, respectively. The refined ethylene glycol was stored under N2 protection for 10 days, and its UV transmittance at 220 nm, 275 nm and 350 nm was measured to be 89.8%, 96.8% and 99.9%, respectively.

[0096] [Example 31]

[0097] The conditions were the same as those in Example 9, except that the hydrogen pressure was 0.5 MPa, and refined ethylene glycol was obtained, and its UV transmittance at 220 nm, 275 nm and 350 nm was measured to be 88.1%, 97.1% and 99.8%, respectively. The refined ethylene glycol was stored under N2 protection for 10 days, and its UV transmittance at 220 nm, 275 nm and 350 nm was measured to be 87.5%, 96.9% and 99.8%, respectively.

[0098] [Example 32]

[0099] The conditions were the same as those in Example 9, except that the hydrogen pressure was 2.5 MPa, and refined ethylene glycol was obtained, and its UV transmittance at 220 nm, 275 nm and 350 nm was measured to be 93.0%, 98.6% and 99.9%, respectively. The refined ethylene glycol was stored under N2 protection for 10 days, and its UV transmittance at 220 nm, 275 nm and 350 nm was measured to be 92.6%, 98.3% and 99.9%, respectively.

[0100] [Example 33]

[0101] The life test of the hydrofining agent RA-1 was carried out according to the conditions used in [Example 9], and the results are shown in Table 2.

[0102] Table 2

[0103]

[0104] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to 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 words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A crude ethylene glycol hydrogenation refining agent, comprising 91-95 parts of a carrier, 1-3 parts of an active component and 4-6 parts of an auxiliary agent, wherein the active component comprises ruthenium, the auxiliary agent comprises at least one of an alkaline earth metal oxide and a transition metal oxide, the transition metal oxide is selected from at least one of the oxides of Ni, Zn, Co and Mn, the alkaline earth metal oxide is selected from at least one of the oxides of Mg and Ca, and the carrier is selected from γ-alumina.

2. The refined preparation according to claim 1, characterized in that The transition metal oxide is selected from at least one of oxides of Ni and Zn.

3. The refined preparation according to claim 1 or 2, characterized in that The γ-alumina precursor includes one or more of amorphous aluminum hydroxide, pseudo-boehmite and boehmite, and preferably includes pseudo-boehmite or boehmite.

4. The refined preparation according to any one of claims 1 to 3, characterized in that The specific surface area of ​​the carrier is 240-320m 2 / g, preferably 250-300m 2 / g.

5. The refined preparation according to any one of claims 1 to 4, characterized in that The pore volume of the carrier is 0.30-0.80 mL / g, preferably 0.40-0.60 mL / g.

6. A method for preparing a refined preparation as claimed in any one of claims 1 to 5, comprising the following steps: (I) providing a solution I comprising a soluble salt of an active ingredient and a soluble salt of an adjuvant; (II) mixing the carrier with the solution I, drying and roasting to obtain a refined preparation precursor; (III) treating the precursor of the refined product with a reducing agent to obtain the refined product.

7. The preparation method according to claim 6, characterized in that: The soluble salt in step (I) is selected from at least one of halogen salts, nitrates and sulfates; and / or, The calcination temperature in step (II) is 300-600° C. and the calcination time is 2-6 hours; and / or, In step (III), the reducing agent is hydrogen, the reduction treatment pressure is 0.1-1 MPa, and the reducing agent gas hourly space velocity is 200-1000 h -1 , the reduction temperature is 120-200℃, and the reduction time is 2-10h.

8. A method for hydrogenating and refining crude ethylene glycol, comprising introducing crude ethylene glycol and hydrogen to react in the presence of the refining agent according to any one of claims 1 to 5 or the refining agent prepared by the method according to claim 6 or 7.

9. The method according to claim 8, characterized in that The reaction temperature is 60-140°C, preferably 80-120°C, more preferably 100-120°C; and / or, the reaction pressure is 0.2-3 MPa, preferably 0.5-2.5 MPa, more preferably 1.5-2.5 MPa; And / or, the mass space velocity of the crude ethylene glycol is 1-20h -1 , preferably 3-8h -1 , more preferably 3-5h -1 ; And / or, the feed volume ratio of the reducing agent to the crude ethylene glycol is 200-1400, preferably 300-1200, more preferably 600-1200.

10. Use of the refined preparation according to any one of claims 1 to 5, or the refined preparation obtained according to the method of claim 6 or 7, or the method according to claim 8 or 9 in the refining of crude ethylene glycol.

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