Oxygen-containing metal complexes and their use as preoxidizers

Abstract

The present invention provides an oxygen-containing metal complex having a transition metal element as a central atom and an oxygen-containing heterocyclic organic compound having a substituent as a ligand, wherein the ligand is a compound having a structure represented by formula (I). [Formula 1] JPEG2025535489000008.jpg27169

Description

[Technical Field]

[0001] The present invention relates to the technical field of chemical feedstock preparation, and in particular to oxygen-containing metal complexes and their use as pre-oxidants. [Background technology]

[0002] As the semiconductor industry's transition to tertiary industry accelerated in the 21st century, China's integrated circuit market has expanded year by year. Ultra-high-purity reagents (wet electronic chemicals) are important basic functional chemicals in the IC manufacturing process, primarily used for chip cleaning and etching. Their purity and cleanliness have a crucial impact on the yield and reliability of integrated circuits, and the narrower the linewidth of integrated circuits, the higher the quality requirements become. Currently, G3 to G4 grade wet electronic chemicals are used in 8-inch wafer production. However, with the change in processing methods for 12-inch wafers, the amount of wet electronic chemicals used has increased significantly, leading to higher requirements for wet electronic chemical grades, generally G4 to G5 grades.

[0003] Isopropanol is the most widely used organic solvent in wet electronic chemicals, primarily used for cleaning and drying. Isopropanol for integrated circuits has strict requirements regarding trace organic impurity content, metal cation impurity content, particle size and particle number, and anion impurity content. With the continuous breakthrough of advanced integrated circuit process nodes, the demand for high-grade G4 to G5 isopropanol is gradually increasing.

[0004] CN111675598A discloses a production system for preparing electronic-grade isopropanol by hydrogenating acetone, where the electronic-grade isopropanol product is obtained through an acetone hydrogenation unit, a variable pressure adsorption unit, a distillation unit, and an adsorption filtration unit. However, because this process employs a variable pressure adsorption separation process, the process is complicated and the measured trace organic impurities in the resulting isopropanol product are not effectively removed, failing to meet the requirements of high-end wafer manufacturing (line width ≦ 90 nm).

[0005] CN102898275A discloses a process for preparing high-purity isopropanol, which involves molecular sieve dehydration, resin dehydration, reverse osmosis, high-temperature distillation, ion exchange, and cyclic adsorption filtration. However, this process does not address the removal of trace organic impurities and cannot meet the cleanliness requirements of wet electronic chemicals used in high-end wafer manufacturing (line widths ≤ 90 nm). Summary of the Invention

[0006] Therefore, one objective of the present invention is to provide a process and system for producing electronic-grade isopropanol by hydrogenating acetone to overcome the problem of ineffective removal of reductive oxygen-containing organic impurities in the isopropanol obtained from the production process, which cannot meet the requirements for high-end wafer manufacturing (line width ≦ 90 nm). The organic impurity content of the isopropanol product obtained by this process is low, at 5 ppm or less, and the anion and cation, particle content, water content, etc. can all meet the requirements for high-end wafer manufacturing (line width ≦ 90 nm).

[0007] For this purpose, the present inventors have conducted extensive research. During the research, the present inventors have found that for some specific crude materials, including acetone crude materials for electronic-grade isopropanol production, including ketone crude materials and monocyclic aromatic crude materials, when the crude materials contain specific impurities, such as reducing impurities, a specific oxygen-containing metal complex can be used as a pre-oxidizing agent to pretreat the crude materials, which is particularly beneficial for reducing the content of organic impurities in the desired product and meeting various requirements, such as anion and cation content, particle content, and water content.

[0008] To achieve the above object, in one aspect, the present invention provides an oxygen-containing metal complex containing a transition metal element as a central atom and a substituted oxygen-containing heterocyclic organic compound as a ligand; wherein the ligand is a compound having a structure represented by formula (I): [ka] In formula (I), n is an integer of 0 to 5, and A is -CH(R5)-; R1 and R2 at each occurrence are each independently selected from C1-C8 alkyl, and R3, R4, and R5 at each occurrence are each independently selected from H, C1-C8 alkyl, phenylC1-C8 alkyl, and C1-C8 alkylphenyl.

[0009] In another aspect, the present invention provides a process for treating a crude feedstock using an oxygen-containing metal complex of the present invention, the process comprising using the oxygen-containing metal complex as a pre-oxidant in contact with the crude feedstock, thereby pre-oxidizing at least a portion of impurities contained in the crude feedstock, wherein the impurities comprise reducing impurities.

[0010] In another aspect, the present invention provides a process for preparing electronic grade isopropanol by hydrogenating acetone, the process comprising: (1) introducing acetone raw material into an acetone pre-oxidation treatment device and pre-oxidizing impurities to obtain pre-oxidized acetone; (1-2) sequentially introducing the pre-oxidized acetone raw material into an acetone dehydration device and an acetone purification device to dehydrate and purify acetone, thereby obtaining purified acetone; (2) introducing the purified acetone into an acetone hydrogenation reactor for hydrogenation reaction to obtain a crude isopropanol product; (3) Passing the crude isopropanol product through an isopropanol dehydration unit, an isopropanol purification unit, and an adsorption filtration unit in sequence to perform isopropanol dehydration, isopropanol purification, and at least one type of isopropanol adsorption filtration to obtain electronic grade isopropanol.

[0011] In another aspect, the present invention provides a system for preparing electronic grade isopropanol by hydrogenating acetone, the system comprising: an acetone purification unit, which is used to purify acetone raw material to obtain acetone feed; an acetone hydrogenation unit used to hydrogenate acetone feed to obtain a crude isopropanol product; an isopropanol purification unit used to purify the crude isopropanol product to obtain electronic grade isopropanol; Here, the acetone purification unit includes an acetone pre-oxidation treatment device, an acetone dehydration device, and an acetone purification device, which are connected in sequence; the acetone hydrogenation unit includes an acetone hydrogenation reactor; and the isopropanol purification unit includes an isopropanol dehydration device, an isopropanol purification device, and an adsorption filtration device, which are connected in sequence.

[0012] The present invention provides an oxygen-containing metal complex that can be used as a pre-oxidant for treating a crude selected from a ketone crude and a monocyclic aromatic hydrocarbon crude, particularly for use in a process for hydrogenating acetone to produce electronic-grade isopropanol. Compared with the prior art, the oxygen-containing metal complex provided by the present invention has at least the following beneficial effects when used to hydrogenate acetone to produce electronic-grade isopropanol: (1) The content of organic reducing impurities in the isopropanol product obtained by the present invention is as low as 5 ppm or less, and the anion and cation, particle content, water content, etc. can all meet the requirements for high-end wafer manufacturing (line width ≦ 90 nm); (2) The raw material used in this invention is acetone, which is inexpensive and readily available. Electronic grade isopropanol can be produced through an acetone purification unit, an acetone hydrogenation unit, and an isopropanol purification unit. The entire process is simple and has high added value. (3) The acetone purification unit used in the present invention has mild reaction conditions and good oxidation effect, with almost no loss of raw acetone, complete removal of reducing impurities, and little by-product generation; (4) In the present invention, by removing organic impurities that are difficult to separate from isopropanol in the acetone purification unit, it is possible to avoid the difficulty of separation from isopropanol and the increase in energy consumption in the subsequent stages. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is a system for hydrogenating acetone to produce electronic grade isopropanol, in accordance with a preferred embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0014] [Table 1]

[0015] The range endpoints and any values ​​disclosed herein are not intended to be limited to the exact ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the range endpoints, range endpoints, and individual point values ​​can be combined with each other to create one or more new numerical ranges, which should be considered specifically disclosed herein.

[0016] The "crude material" of the present invention, such as a ketone crude material (such as an acetone crude material) and a monocyclic aromatic crude material, contains a target substance (for example, the target substance in an acetone crude material is acetone) and impurities. For further processing or application, the target substance needs to be subjected to an appropriate treatment, such as purification, to improve the purity of the target substance and / or to facilitate further processing or application of the target substance. In the present invention, the crude material may particularly refer to an acetone raw material used in hydrogenation to produce isopropanol (particularly electronic grade isopropanol).

[0017] In one aspect, the present invention provides an oxygen-containing metal complex containing a transition metal element as a central atom and a substituted oxygen-containing heterocyclic organic compound as a ligand; The ligand is a compound having a structure according to formula (I): [ka] In formula (I), n is an integer of 0 to 5, and A is -CH(R5)-; R1 and R2 at each occurrence are each independently selected from C1-C8 alkyl, and R3, R4, and R5 at each occurrence are each independently selected from H, C1-C8 alkyl, phenylC1-C8 alkyl, and C1-C8 alkylphenyl.

[0018] According to a preferred embodiment of the present invention, R1 and R2 at each occurrence are each independently selected from C1-C5 alkyl, preferably each independently selected from C1-C4 alkyl; R3, R4 and R5 are each independently selected from H, C1-C5 alkyl, phenyl C1-C5 alkyl, and C1-C5 alkyl-substituted phenyl, preferably each independently selected from H, C1-C4 alkyl, benzyl, and C1-C3 alkyl-substituted phenyl.

[0019] According to a preferred embodiment of the present invention, in formula (I), n is an integer of 0 to 3; R1 and R2 are each independently selected from H, C1-C3 alkyl, R3 and R4 are each independently selected from H, C1-C3 alkyl, benzyl, and methyl-substituted phenyl; and R5 is H or C1-C3 alkyl. Preferably, in formula (I), n is 0 or 1; and R1 and R2 are each independently selected from C1-C3 alkyl, R3 and R4 are each independently selected from H, C1-C3 alkyl, benzyl, and methyl-substituted phenyl, and R5 is H.

[0020] According to the present invention, the type of transition metal element in the oxygen-containing metal complex is not limited as long as the object of the present invention can be achieved. In some embodiments, the transition metal element is selected from one or more of chromium, molybdenum, tungsten, iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum, manganese, technetium, and rhenium, and preferably one or more of manganese, cobalt, and molybdenum.

[0021] According to the present invention, when n is 0, A is absent and in that case, formula (I) is a 5-membered ring structure; when n is 1, formula (I) is a 6-membered ring structure, R5 is selected from H, C1-C8 alkyl, phenylC1-C8 alkyl and C1-C8 alkylphenyl, or preferably selected from H, C1-C5 alkyl, benzyl, C1-C3 alkyl-substituted phenyl; when n is 2, A = -CH(R5)-CH(R5), formula (I) is a 7-membered ring structure, and each occurrence of R5 is independently selected from H, C1-C8 alkyl, phenylC1-C8 alkyl and C1-C8 alkylphenyl, or preferably selected from H, C1-C5 alkyl, benzyl, C1-C3 alkyl-substituted phenyl. Similarly, for example: When n is 0, R1 is methyl, R2 is methyl, R3 is H, and R4 is H, the ligand is 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol; When n is 0, R1 is ethyl, R2 is ethyl, R3 is H, and R4 is H, the ligand is 2,2-diethyl-1,3-dioxolane-4,5-dimethanol.

[0022] Similarly, compounds of formula (I) useful in the present invention also include 2,2-dimethyl-1,3-dioxolane-4,5-di-1-ethanol, 2,2-dimethyl-1,3-dioxolane-4,5-dibenzyl alcohol, and 2,2-dimethyl-1,3-dioxolane-4,5-di-p-methylbenzyl alcohol.

[0023] According to the present invention, the oxygen-containing metal complex can be prepared by any process, as long as the object of the present invention can be achieved. The complex can be prepared by appropriately selecting a ligand solution containing the ligand of the present invention and a metal salt solution containing the transition metal of the present invention and performing a complex formation reaction. The conditions required for the complex formation reaction are not particularly limited and can be selected appropriately. In some embodiments, the process for preparing the oxygen-containing metal complex includes adding a ligand solution and a metal salt solution in equimolar amounts of the ligand and transition metal under an anhydrous, oxygen-free, nitrogen atmosphere, and stirring at room temperature for 1 to 10 hours to perform the complex formation reaction; in some optional embodiments, the solvent is evaporated after the complex formation reaction.

[0024] According to the present invention, the ligand solution refers to a solution formed by dissolving a ligand in a solvent, generally an organic solvent. The metal salt solution refers to a solution formed by dissolving a metal salt in a solvent, generally water. Since the present invention is not particularly limited, the metal salt solution will not be described in detail in this specification.

[0025] According to the present invention, the ligand can be prepared as needed. For example, in formula (I), when n is 0, R1 is methyl, R2 is methyl, R3 is H, and R4 is H, the ligand is 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol. The ligand preparation process includes the following: 2,2-dimethoxypropane, dimethyl 2,3-dihydroxysuccinate, p-toluenesulfonic acid, and anhydrous dichloromethane are added sequentially under an anhydrous and oxygen-free nitrogen atmosphere, reacted at 20-100°C for 2-10 hours, and then the solvent is evaporated after natural cooling; anhydrous methanol and sodium borohydride are added under a nitrogen atmosphere, stirred at room temperature for 5-24 hours, diluted with water, the organic solvent is evaporated, the residual liquid is extracted and dried, the organic solvent is filtered and evaporated, and the residue is recrystallized to obtain the ligand.

[0026] The source of the ligand is not described in detail in this invention. The ligand in this invention can be prepared by the same preparation process as 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol, which involves changing the raw materials 2-dimethoxypropane and dimethyl 2,3-dihydroxysuccinate, selecting the raw materials to prepare the required ligand, reacting them under the action of p-toluenesulfonic acid, and then carrying out a reduction reaction.

[0027] The oxygen-containing metal complex of the present invention has certain oxidation properties and is particularly suitable as a preoxidant. Therefore, in another aspect, the present invention provides use of the oxygen-containing metal complex of the present invention as a preoxidant for preoxidizing a substance to be oxidized. Without being limited to known theory, according to the present invention, the substances to be particularly oxidized by the redox properties of the oxygen-containing metal complex of the present invention may be, for example, ketones and single-ring aromatic compounds.

[0028] Correspondingly, in another aspect, the present invention provides a process for treating a crude material selected from a ketone crude material and a monocyclic aromatic hydrocarbon crude material by using an oxygen-containing metal complex of the present invention, the process comprising contacting the crude material with an oxygen-containing metal complex of the present invention as a pre-oxidizing agent, thereby pre-oxidizing at least a portion of impurities contained in the crude material, wherein the impurities include reducing impurities.

[0029] According to the present invention, there is no limitation on the pre-oxidation method as long as the object of the present invention can be achieved. In some preferred embodiments, in step (1), the pre-oxidation is carried out by contacting the crude material with a pre-oxidizing agent. By adopting the above-mentioned embodiments, reducing impurities in the crude material can be effectively removed.

[0030] According to the present invention, there are no limitations on the pre-oxidation conditions as long as the objectives of the present invention can be achieved. In some embodiments, the pre-oxidation conditions in step (1) include the following: the amount of pre-oxidant added is 0.01 to 0.1% by weight of the crude material, for example, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.08%, or 0.1%. By employing the above embodiment, reducing impurities in the crude material can be removed.

[0031] According to the present invention, crude materials selected from ketone crude materials and monocyclic aromatic hydrocarbon crude materials can be treated using the oxygen-containing metal complexes described in the present invention. Without being limited to known theory, it is believed that ketones containing C1-C8 alkanes, C6-C8 aromatic rings, C2-C8 ester groups, halogens, or monocyclic aromatic hydrocarbons containing C1-C8 alkanes are particularly suitable for treatment by the process of the present invention. The halogens can be selected from F, Cl, Br, and I, and are preferably selected from F and Cl.

[0032] In various cases, particularly for different crude feedstocks, the process of the present invention can be applied to a variety of different reducing impurities, such as alcohols, aldehydes, ketones, esters, ethers, and olefins. Generally, when the crude feedstock treated by the process of the present invention is a ketone crude or a monocyclic aromatic crude, the reducing impurities that can be pre-oxidized by the process of the present invention are selected from saturated or unsaturated C1-C4 primary or secondary alcohols, such as methanol, ethanol, isopropanol, propenol, and propargyl alcohol; C1-C4 aldehydes, such as formaldehyde, acetaldehyde, and propionaldehyde; C1-C4 alkyl formates, such as methyl formate and ethyl formate; C2-C4 olefins or alkynes, such as ethylene and propylene; and aniline optionally substituted with C1-C4 alkyl and phenol optionally substituted with C1-C4 alkyl, such as aniline, phenol, and alkyl-substituted compounds thereof.

[0033] According to the present invention, in some embodiments, the pre-oxidation conditions include room temperature and atmospheric pressure. By adopting the above-mentioned embodiment, the pre-oxidation has mild reaction conditions and good oxidation effect, and can completely remove reducing impurities with little loss of raw materials, and produce few by-products.

[0034] In the present invention, room temperature refers to a temperature of 10 to 30°C.

[0035] According to the present invention, in order to increase the activity of the oxygen-containing metal complex, in some embodiments, the pre-oxidant is subjected to an oxidation treatment using an oxidizing agent before being used to carry out the pre-oxidation.

[0036] According to the present invention, in some preferred embodiments, the oxidizing agent is selected from one or more of oxygen, hydrogen peroxide, cumene peroxide, peracetic acid, perchlorate, permanganate, and dichromate.

[0037] According to the present invention, after the complexation reaction for preparing an oxygen-containing metal complex is completed, the pre-oxidant can be oxidized by directly adding an oxidizing agent to carry out the oxidation reaction. For example, in some embodiments, a ligand solution and a metal salt solution are added in equimolar amounts of the ligand and the transition metal in an anhydrous and oxygen-free nitrogen atmosphere, and the mixture is stirred at room temperature for 1 to 10 hours to carry out the complexation reaction. Then, an appropriate amount of an oxidizing agent is added thereto and the mixture is stirred for 1 to 10 hours to carry out the oxidation treatment. The solvent is then evaporated to obtain the oxidized pre-oxidant.

[0038] According to the present invention, in another embodiment, the pre-oxidant can be oxidized by subjecting an oxygen-containing metal complex to an oxidation reaction with an oxidizing agent under oxidizing conditions in the presence of a solvent, followed by evaporation of the solvent to obtain the pre-oxidant.

[0039] According to the present invention, those skilled in the art can select appropriate oxidation treatment conditions depending on the type of oxidizing agent, and the present invention is not particularly limited thereto.

[0040] As shown in FIG. 1 , in another aspect, the present invention provides a process for preparing electronic grade isopropanol by hydrogenating acetone, the process comprising: (1) introducing an acetone raw material into an acetone pre-oxidation treatment unit R1, and pre-oxidizing impurities using the pre-oxidizing agent of the present invention to obtain pre-oxidized acetone; (1-2) introducing the pre-oxidized acetone into an acetone dehydration device and an acetone purification device in sequence to dehydrate and purify the acetone, thereby obtaining purified acetone; (2) introducing the purified acetone liquid into an acetone hydrogenation reactor R2 for hydrogenation reaction to obtain a crude isopropanol product; (3) Passing the crude isopropanol product through an isopropanol dehydration unit, an isopropanol purification unit, and an adsorption filtration unit in sequence to perform isopropanol dehydration, isopropanol purification, and at least one isopropanol adsorption filtration to obtain electronic grade isopropanol.

[0041] According to the present invention, purified acetone can be obtained by pre-oxidizing an inexpensive and readily available acetone feedstock, dehydrating the acetone, and purifying the acetone. The purified acetone can then be hydrogenated to produce a crude isopropanol product. The crude isopropanol product can then be simply dehydrated, purified, and subjected to at least one adsorption filtration to produce an isopropanol product with an organic reducing impurity content of 5 ppm or less, and with anions, cations, particle content, water content, etc. that meet the requirements for high-end wafer manufacturing (line width ≦90 nm). The present invention removes organic impurities that are difficult to separate from isopropanol from the acetone feedstock, thereby avoiding the drawbacks of difficult separation from isopropanol and the resulting high energy consumption in the downstream process.

[0042] According to the present invention, there is no limitation on the pre-oxidation method as long as the object of the present invention can be achieved. In some preferred embodiments, pre-oxidation is carried out by contacting the acetone raw material with a pre-oxidant in step (1). By adopting the above-mentioned embodiments, impurities in acetone can be effectively removed.

[0043] According to the present invention, there are no limitations on the pre-oxidation conditions as long as the object of the present invention can be achieved. In some embodiments, the pre-oxidation conditions in step (1) include adding a pre-oxidizing agent in an amount of 0.01 to 0.1% by weight of the acetone feedstock, for example, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.08%, or 0.1%. By employing the above embodiment, reducing impurities in the acetone feedstock can be removed.

[0044] According to some embodiments of the present invention, the pre-oxidation conditions include room temperature and atmospheric pressure, which allows for mild reaction conditions for pre-oxidation, good oxidation effect, almost no loss of raw material acetone, complete removal of reducing impurities, and few by-products.

[0045] In the present invention, room temperature refers to a temperature of 10 to 30°C.

[0046] The present inventors have unexpectedly found that in addition to the compounds of formula (I) of the present invention, ligands that can be used as pre-oxidants, particularly when used in the hydrogenation of acetone to isopropanol, can also be compounds having the structure of formula (I-1): [ka] In formula (I), n is an integer from 0 to 5 (e.g., 0, 1, 2, 3, 4, or 5), A is -CH(R5)-; and R1, R2, R3, R4, and R5 at each occurrence are each independently selected from H, C1-C5 alkyl, benzyl, and C1-C3 alkyl-substituted phenyl. For purposes of the present invention, it is understood that compounds of formula (I) and (I-1) have the same primary structure but different definitions of groups R1-R5.

[0047] By adopting the above-described preferred embodiment, it is possible to remove organic impurities that are difficult to separate from isopropanol in the acetone raw material, and to avoid the drawback of the difficulty in separating from isopropanol and the resulting large energy consumption in the downstream stage.

[0048] According to the present invention, the type of reducing impurities is not limited as long as the objectives of the present invention can be achieved. In some embodiments, the reducing impurities include at least one of alcohols, aldehydes, ketones, esters, ethers, and olefins. The pre-oxidation of the present invention can efficiently remove reducing impurities such as alcohols, aldehydes, ketones, esters, ethers, and olefins, ultimately producing isopropanol that meets the requirements of high-end wafer manufacturing (line width ≦ 90 nm) in terms of anions and cations, particle content, water content, etc. Generally, the reducing impurities that can be treated in the process of the present invention are selected from saturated or unsaturated C1-C4 primary or secondary alcohols such as methanol, ethanol, isopropanol, propenol, propargyl alcohol, etc.; C1-C4 aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, etc.; C1-C4 alkyl formates such as methyl formate, ethyl formate, etc.; C2-C4 olefins or alkynes such as ethylene, propylene, etc.; and C1-C4 alkyl-substituted phenols such as C1-C4 alkyl-substituted aniline, phenol, and alkyl-substituted compounds thereof.

[0049] According to the present invention, the source of the acetone raw material is not limited as long as the objectives of the present invention can be achieved. In some embodiments, the acetone raw material includes one or more of industrial grade acetone, analytical grade acetone, and electronic grade acetone.

[0050] According to the present invention, according to the standards in this field, the purity of industrial grade acetone is 95-99.5%, the purity of analytical grade acetone is 99.5-99.9%, and the purity of electronic grade acetone is above 99.9%.

[0051] In the present invention, unless otherwise specified, purity and content refer to purity and content by weight.

[0052] According to some embodiments of the present invention, the dehydration materials used in the dehydration of acetone in step (1-2) and the dehydration of isopropanol in step (3) each include one or more of molecular sieves, silica gel, membranes, resins, and salts capable of forming crystalline hydrates. By employing the above-described embodiments, the water content of the final isopropanol product can meet the requirements for ultra-high purity isopropanol used in the integrated circuit industry.

[0053] According to the present invention, the dehydration material can be selected as needed, and the types of dehydration material will not be detailed herein.

[0054] According to some embodiments of the present invention, in step (1-2), acetone is purified in a plate distillation column or a packed distillation column.

[0055] According to the present invention, there are no limitations on the acetone purification conditions as long as the objectives of the present invention can be achieved. In some embodiments, the acetone purification conditions include an operating reflux ratio of 0.5 to 10; an operating pressure of -0.5 to 10 bar; and an overhead operating temperature of 30 to 70°C.

[0056] According to some preferred embodiments of the present invention, the acetone purification conditions include an operating reflux ratio of 0.5 to 5; an operating pressure of 0.5 to 1 bar; and an overhead operating temperature of 35 to 65° C. By employing the above embodiments, high-boiling impurities in acetone can be removed.

[0057] According to the present invention, there is no limitation on the manner and conditions of the hydrogenation reaction as long as the object of the present invention can be achieved. In some embodiments, the hydrogenation catalyst used in the hydrogenation reaction includes one or more of a Cu-based catalyst, a Ni-based catalyst, and a Mn-based catalyst.

[0058] According to the present invention, "Cu-based" refers to a hydrogenation catalyst in which Cu is supported on a carrier as an active component; "Mn-based" refers to a hydrogenation catalyst in which Mn is supported on a carrier as an active component; the type of carrier can be selected as needed, and examples include, but are not limited to, SiO2 carriers, molecular sieve carriers, and Al2O3 carriers.

[0059] According to the present invention, there are no limitations on the hydrogenation reaction conditions as long as the objectives of the present invention can be achieved. In some embodiments, the hydrogenation reaction conditions include a reaction inlet temperature of 70 to 140°C (e.g., 70°C, 80°C, 90°C, 110°C, 120°C, 130°C, or 140°C); a reaction pressure of 2 to 8 MPaG (e.g., 2 MPaG, 4 MPaG, 5 MPaG, 7 MPaG, or 8 MPaG); and a hydrogen to acetone molar ratio of 4 to 40:1 (e.g., 4:1, 8:1, 12:1, 16:1, 20:1, 21:1, 23:1, 30:1, 32:1, 35:1, or 40:1). In some embodiments, the hydrogenation reaction conditions include a reaction time of 0.6 to 3 h. -1 Acetone space velocity (e.g., 0.6 h -1 , 1h -1 , 1.6h -1 , 2h -1 , 2.5h -1 or 3h -1 ).

[0060] According to the present invention, in order to more effectively remove light and heavy impurity components from isopropanol, in some embodiments, a de-light separation is performed using a plate distillation column or a packed distillation column to separate the light impurity components, and the de-light separation conditions include the following: an operating reflux ratio of 2 to 20 (e.g., 2, 4, 5, 8, 10, 12, 15, or 20), preferably 5 to 15.

[0061] According to the present invention, in some embodiments, the conditions for de-lightening include an operating pressure of −0.5 to 10 bar (e.g., −0.5 bar, 0.25 bar, 1 bar, 1.5 bar, 2.0 bar, 5.0 bar, 8.0 bar, or 10 bar), preferably 0.25 to 1.0 bar.

[0062] According to the present invention, in some embodiments, the conditions for de-lightening separation include: a bottom operating temperature of 40 to 95°C (e.g., 40°C, 50°C, 60°C, 75°C, 85°C, or 95°C), preferably 50 to 85°C.

[0063] According to some embodiments of the present invention, to separate heavy impurity components, deheavying separation is carried out using a plate distillation column or a packed distillation column, and the deheavying separation conditions include the following: an operating reflux ratio of 1 to 10 (e.g., 1, 2, 4, 6, 8, or 10), preferably 2 to 8.

[0064] According to the present invention, in some embodiments, the conditions for deheavy separation include: an operating pressure of −0.5 to 10 bar (e.g., −0.5 bar, 0.5 bar, 1.0 bar, 2.0 bar, 4.0 bar, 6.0 bar, or 10 bar), preferably 0.5 to 1 bar.

[0065] According to the present invention, in some embodiments, the conditions for deheavy separation include: a column overhead operating temperature of 50 to 90°C (e.g., 50°C, 60°C, 65°C, 75°C, 85°C, or 90°C), preferably 65 to 85°C.

[0066] According to the present invention, "at least one isopropanol adsorption filtration" means that the adsorption filtration operation can be repeated one or more times as necessary.

[0067] According to the present invention, in some embodiments, the adsorbent material used in isopropanol adsorptive filtration to remove anions and cations in isopropanol comprises one or more of anion exchange resin and cation exchange resin.

[0068] According to the present invention, those skilled in the art can use anion exchange resin or cation exchange resin alone as the adsorption material as needed, or can select a mixed resin of anion exchange resin and cation exchange resin as the adsorption material as needed, which will not be described in detail in this specification.

[0069] According to the present invention, in some embodiments, the filter material used in isopropanol adsorptive filtration to remove particles in isopropanol includes one or more of a polymer membrane, a ceramic membrane, and a metal membrane.

[0070] By adopting the above-described embodiment, it is possible to avoid the influence on the purity of isopropanol caused by the elution of metal ions and particles that may be present in the materials of the components of the preliminary process section.

[0071] In another aspect, the present invention provides a system for preparing electronic grade isopropanol by hydrogenating acetone, the system comprising: an acetone purification unit, which is used to purify acetone raw material to obtain acetone feed; an acetone hydrogenation unit used to hydrogenate acetone feed to obtain a crude isopropanol product; an isopropanol purification unit used to purify the crude isopropanol product to obtain electronic grade isopropanol; Here, the acetone purification unit includes an acetone pre-oxidation treatment device, an acetone dehydration device, and an acetone purification device, which are connected in sequence; the acetone hydrogenation unit includes an acetone hydrogenation reactor; and the isopropanol purification unit includes an isopropanol dehydration device, an isopropanol purification device, and an adsorption filtration device, which are connected in sequence.

[0072] In the present invention, the acetone pre-oxidation treatment unit can be selected as a tubular reactor or a kettle reactor as needed. The specific structures of the tubular reactor, the kettle reactor and the acetone hydrogenation reactor are those commonly used in the art.

[0073] According to the present invention, organic impurities that are difficult to separate from isopropanol are removed in the acetone purification unit, thereby avoiding the drawbacks of difficulty in separating them from isopropanol and large energy consumption in the subsequent stage.

[0074] According to the present invention, in some embodiments, the acetone dehydration unit comprises an acetone dehydration tower.

[0075] According to the present invention, in some embodiments, the acetone purification unit comprises an acetone purification column.

[0076] According to the present invention, in some embodiments, the isopropanol dehydration unit comprises an isopropanol dehydration tower.

[0077] According to some embodiments of the present invention, the isopropanol purification apparatus includes an isopropanol delightening column for removing light impurity components having a boiling point lower than that of isopropanol, and an isopropanol deheavying column for removing heavy impurity components having a boiling point higher than that of isopropanol, which are connected in series.

[0078] According to some embodiments of the present invention, the isopropanol delightening column is a plate distillation column or a packed distillation column, and the isopropanol deheavying column is a plate distillation column or a packed distillation column.

[0079] In the present invention, the structures of the acetone dehydration column, plate distillation column and packed distillation column are those commonly used in the art and will not be described in detail in this specification.

[0080] According to the present invention, in some embodiments, the adsorptive filtration device comprises an adsorptive filtration device.

[0081] In the system according to the present invention, a raw material pump, inlets and outlets for raw materials and products, etc. may be provided as required.

[0082] A preferred embodiment of the process and system of the present invention is described below in conjunction with FIG.

[0083] As shown in Figure 1, The acetone raw material (1) is pressurized by a raw material pump and introduced into an acetone pre-oxidation treatment unit R1 filled with an oxidized pre-oxidant to perform pre-oxidation, thereby obtaining pre-oxidized acetone (2); the pre-oxidized acetone (2) is dehydrated in an acetone dehydration column C1 filled with a dehydration material to obtain dehydrated acetone (3); the dehydrated acetone (3) is introduced into an acetone purification column T1 to obtain a purified acetone feed (4), and heavy components (5) are discharged; the purified acetone feed (4) is introduced into an acetone hydrogenation reactor R2 filled with a hydrogenation catalyst to perform a hydrogenation reaction, thereby obtaining a crude isopropanol product (6); the crude isopropanol product (6) is dehydrated in an isopropanol dehydration column C2 filled with a dehydration material to obtain dehydrated isopropanol (7); the dehydrated isopropanol (7) is introduced into an isopropanol de-light column T2 to perform light separation, where light impurity components (8) are removed, thereby obtaining a de-light isopropanol product. The light isopropanol product (9) is then introduced into an isopropanol deheaving column T3 for deheavying separation to remove heavy impurity components (11) and obtain a primary isopropanol product (10); the primary isopropanol product (10) is then introduced into an adsorption filtration device C3 to remove anions, cations and particles to obtain electronic grade isopropanol (12). [Example]

[0084] The present invention will be described in detail below with reference to examples. In the following examples and comparative examples: Moisture content was measured with a Karl Fischer Moisture Meter; Single metal cation concentrations were measured by ICP-MS; Anion concentrations were measured by ion chromatography; The particle number (≥50 nm) was measured by an online particle size analyzer; Unless otherwise specified, various materials are commercially available.

[0085] Ligand Preparation Example 1: 4.2 g of diethyl tartrate, 3.2 g of 2,2-dimethylolpropane, 0.42 g of p-toluenesulfonic acid, and 100 g of anhydrous toluene were added to a completely dry 250 mL three-neck flask equipped with a reflux condenser. After purging with nitrogen, the mixture was heated at reflux for 12 hours and allowed to cool to room temperature. Saturated aqueous sodium bicarbonate was slowly added until the organic phase was nearly neutral, and the solvent was evaporated under reduced pressure. Under a nitrogen atmosphere, 120 g of anhydrous methanol was added, followed by 7.15 g of sodium borohydride in one portion, and the mixture was stirred at room temperature for 12 hours. After dilution with water, the organic solvent was evaporated, and the remaining liquid was extracted three times with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate, filtered, and evaporated. The residue was recrystallized to give 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol.

[0086] Ligand Preparation Example 2: 4.2 g of diethyl tartrate, 3.2 g of 2,2-dimethoxypropane, 0.42 g of p-toluenesulfonic acid, and 100 g of anhydrous toluene were added to a completely dry 250 mL three-neck flask equipped with a reflux condenser. After purging with nitrogen, the mixture was heated at reflux for 12 hours and then allowed to cool to room temperature. Saturated aqueous sodium bicarbonate solution was slowly added until the organic phase was nearly neutral, and the solvent was evaporated under reduced pressure. The residue was transferred to a completely dry 250 mL three-neck flask and 120 g of anhydrous tetrahydrofuran solution containing 7.3 g of methylmagnesium iodide was added. After purging with nitrogen, the mixture was stirred at room temperature for 24 hours. After completion of the reaction, the system was cooled to -10 °C in an ice-salt bath, and saturated aqueous ammonium chloride solution was slowly added until the organic phase was nearly neutral. The insoluble matter was filtered through diatomaceous earth, and the filtrate was evaporated under reduced pressure to remove the solvent. The residue was purified by column chromatography to give 2,2-dimethyl-1,3-dioxolane-4,5-di(1-ethanol).

[0087] Example 1 Oxidation treatment of pre-oxidant: Equimolar amounts of 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol obtained in Ligand Preparation Example 1 and manganese chloride salt were taken, and in an anhydrous and oxygen-free nitrogen atmosphere, a 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol solution containing 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol and a manganese chloride solution containing manganese chloride were added, followed by stirring at room temperature for 6 hours; potassium permanganate was added thereto, and the reaction was continued for 3 hours, after which the solvent was evaporated to obtain an oxidized pre-oxidant; As shown in FIG. 1, the acetone raw material (1) (industrial acetone, purity 98%) is pressurized by a raw material pump and introduced into the acetone pre-oxidation treatment unit R1 filled with an oxidizing pre-oxidant at a rate of 0.6 mL / min to perform pre-oxidation, thereby obtaining pre-oxidized acetone (2). This pre-oxidized acetone (2) is dehydrated in the acetone dehydration column C1 filled with a dehydrating material (4A molecular sieve) to obtain dehydrated acetone (3). The dehydrated acetone is introduced into the acetone purification column T1 (plate distillation column) for purification, thereby obtaining purified acetone feed (4). Heavy components (5) are discharged. The purified acetone feed is introduced into the acetone hydrogenation reactor R2 filled with a hydrogenation catalyst (5 wt.% Cu / SiO2 catalyst) for hydrogenation, thereby obtaining crude isopropanol product (6). The propanol product (6) is dehydrated in an isopropanol dehydration column C2 packed with a dehydrating material (4A molecular sieve) to obtain dehydrated isopropanol (7); the dehydrated isopropanol (7) is introduced into an isopropanol lightening column T2 (packed column) for light separation and light impurity components (8) are removed to obtain a dehydrated light isopropanol product (9); the dehydrated light isopropanol product (9) is passed through an isopropanol heavy impurity removal column T3 (packed column) for heavy separation and heavy impurity components (11) are removed to obtain a primary isopropanol product (10); the primary isopropanol product (10) is then passed through an adsorption filtration device C3 to remove anions, cations, and particles to obtain electronic grade isopropanol (12); The pre-oxidation conditions include: normal temperature and pressure, the amount of pre-oxidant added is 0.03 wt% of the acetone raw material; Operating reflux ratio 0.5, operating pressure 1 bar, top operating temperature 56°C; The hydrogenation reaction conditions included: reaction inlet temperature 100°C, reaction pressure 4 MPa, hydrogen to acetone molar ratio 8:1, acetone space velocity 1.0 h -1 ; The conditions for de-light separation include: operating reflux ratio 5, operating pressure 0.75 bar, and controlling the column bottom operating temperature to 75°C; The conditions for deheavy separation include: operating reflux ratio 5, operating pressure 1 bar, and controlling the column top operating temperature to 82°C; The adsorptive filtration device C3 was filled with a mixed resin of cation exchange resin and anion exchange resin and a polymer filtration membrane.

[0088] The purity, water content, single metal cation concentration, anion concentration, and particle number (≥50 nm) of electronic grade isopropanol (12) are shown in Table 1.

[0089] Example 2 The procedure of Example 1 was followed with the following exceptions: Oxidation treatment of pre-oxidant: 2,5-dimethyl-1,3-dioxane-4,6-dimethanol was obtained in the same manner as in the Ligand Preparation Example. Equimolar amounts of 2,5-dimethyl-1,3-dioxane-4,6-dimethanol and cobalt acetate were weighed, and in an anhydrous, oxygen-free, nitrogen atmosphere, a 2,5-dimethyl-1,3-dioxane-4,6-dimethanol solution containing 2,5-dimethyl-1,3-dioxane-4,6-dimethanol and a cobalt acetate solution containing cobalt acetate were added, and the mixture was stirred at room temperature for 6 hours. Potassium permanganate was added to the mixture, and the mixture was allowed to react for 3 hours. After that, the solvent was evaporated to obtain the oxidized pre-oxidant. Dehydration material (4A molecular sieve and anhydrous potassium carbonate composite bed layer, volume ratio 50%-50%); Acetone purification column T1 (packed distillation column); Hydrogenation catalyst (Ni / SiO2 catalyst); Here, the acetone purification conditions include: operating reflux ratio 2, operating pressure 1.5 bar, and controlling the column top operating temperature to 64°C; The hydrogenation reaction conditions included: reaction inlet temperature 90°C, reaction pressure 4 MPa, hydrogen / acetone molar ratio 8:1, acetone space velocity 1.0 h -1 ; The conditions for de-light separation include: operating reflux ratio 5, operating pressure 0.5 bar, and controlling the column bottom operating temperature to 65°C; The conditions for deheavy separation include: operating reflux ratio 5, operating pressure 1.5 bar, and controlling the column top operating temperature to 90°C; The purity, water content, single metal cation concentration, anion concentration, and particle number (≥50 nm) of electronic grade isopropanol (12) are shown in Table 1.

[0090] Example 3 The procedure of Example 1 was followed with the following exceptions: Oxidation treatment of pre-oxidant: 2,2-diethyl-1,3-dioxolane-4,5-dimethanol was obtained using the same method as in the Ligand Preparation Example. Equimolar amounts of 2,2-diethyl-1,3-dioxolane-4,5-dimethanol and manganese chloride were weighed, and in an anhydrous, oxygen-free, nitrogen atmosphere, a 2,2-diethyl-1,3-dioxolane-4,5-dimethanol solution containing 2,2-diethyl-1,3-dioxolane-4,5-dimethanol and a manganese chloride solution containing manganese chloride were added, followed by stirring at room temperature for 6 hours; potassium permanganate was added and the reaction was continued for 3 hours, after which the solvent was evaporated to obtain the oxidized pre-oxidant.

[0091] The hydrogenation reaction conditions include: reaction inlet temperature 70°C, reaction pressure 2 MPaG, hydrogen to acetone molar ratio 4:1, acetone space velocity 0.8 h -1 ; The conditions for de-light separation include: operating reflux ratio 15, operating pressure 1 bar, and column bottom operating temperature 85°C.

[0092] The conditions for deheavy separation include: operating reflux ratio 7, operating pressure 1 bar, and controlling the overhead operating temperature to 85°C.

[0093] The adsorptive filtration device C3 was filled with a mixed resin and a ceramic filtration membrane.

[0094] The purity, water content, single metal cation concentration, anion concentration, and particle number (≥50 nm) of electronic grade isopropanol (12) are shown in Table 1.

[0095] Example 4 The procedure of Example 2 was followed with the following exceptions: Here, the acetone purification conditions include: operating reflux ratio 2, operating pressure 0.5 bar, and controlling the column top operating temperature to 47°C; The conditions for de-light separation include: operating reflux ratio 5, operating pressure 1.5 bar, and controlling the column bottom operating temperature to 90°C; The conditions for deheavy separation include: operating reflux ratio 5, operating pressure 0.5 bar, and controlling the column top operating temperature to 65°C.

[0096] The purity, water content, single metal cation concentration, anion concentration, and particle number (≥50 nm) of electronic grade isopropanol (12) are shown in Table 1.

[0097] Example 5 The procedure of Example 2 was followed with the following exceptions: Oxidation treatment of pre-oxidant: Equimolar amounts of 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol obtained in Ligand Preparation Example 1 and molybdenum chloride were taken, and in an anhydrous, oxygen-free, nitrogen atmosphere, a 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol solution containing 2,2,2-dimethyl-1,3-dioxolane-4,5-dimethanol and a molybdenum chloride solution containing molybdenum chloride were added to the 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol solution, and the mixture was stirred at room temperature for 6 hours; potassium permanganate was added to the mixture, and the mixture was reacted for 3 hours, after which the solvent was evaporated to obtain an oxidized pre-oxidant.

[0098] The purity, water content, single metal cation concentration, anion concentration, and particle number (≥50 nm) of electronic grade isopropanol (12) are shown in Table 1.

[0099] Example 6 The procedure of Example 1 was followed with the following exceptions: Pretreatment of oxidant: Equimolar amounts of 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol obtained in Ligand Preparation Example 1 and cupric chloride were taken, and in an anhydrous, oxygen-free, nitrogen atmosphere, a 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol solution containing 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol and a cupric chloride solution containing cupric chloride were added, followed by stirring at room temperature for 6 hours. Potassium permanganate was added to this and the reaction was allowed to proceed for 3 hours, after which the solvent was evaporated to obtain the oxidized preoxidant.

[0100] The purity, water content, single metal cation concentration, anion concentration, and particle number (≥50 nm) of electronic grade isopropanol (12) are shown in Table 1.

[0101] Example 7 The procedure of Example 1 was followed with the following exceptions: The oxidized pre-oxidant was replaced with the oxidizing metal salt KMnO4.

[0102] The purity, water content, single metal cation concentration, anion concentration, and particle number (≥50 nm) of electronic grade isopropanol (12) are shown in Table 1.

[0103] Example 8 The procedure of Example 1 was followed with the following exceptions: The oxidized pre-oxidant was replaced with 10 wt% Co oxide / SiO2 supported catalyst.

[0104] The purity, water content, single metal cation concentration, anion concentration, and particle number (≥50 nm) of electronic grade isopropanol (12) are shown in Table 1.

[0105] Example 9 The procedure of Example 1 was followed with the following exceptions: Oxidation treatment of pre-oxidant: Equimolar amounts of 2,2-dimethyl-1,3-dioxolane-4,5-di(1-ethanol) obtained in Ligand Preparation Example 2 and manganese chloride salt were taken, and in an anhydrous, oxygen-free, nitrogen atmosphere, a 2,2-dimethyl-1,3-dioxolane-4,5-di(1-ethanol) solution containing 2,2-dimethyl-1,3-dioxolane-4,5-di(1-ethanol) and a manganese chloride solution containing manganese chloride were added, and the mixture was stirred at room temperature for 6 hours. Potassium permanganate was added to the mixture, and the mixture was reacted for 3 hours. The solvent was then evaporated to obtain the oxidized pre-oxidant.

[0106] The results are shown in Table 1.

[0107] Example 10 The procedure of Example 1 was followed with the following exceptions: Oxidation treatment of pre-oxidant: 2,2-dimethyl-1,3-dioxolane-4,5-dibenzyl alcohol was obtained in the same manner as in the Ligand Preparation Example. Equimolar amounts of 2,2-dimethyl-1,3-dioxolane-4,5-dibenzyl alcohol and manganese chloride salt were weighed. Under an anhydrous, oxygen-free, nitrogen atmosphere, a 2,2-dimethyl-1,3-dioxolane-4,5-dibenzyl alcohol solution containing 2,2-dimethyl-1,3-dioxolane-4,5-dibenzyl alcohol and a manganese chloride solution containing manganese chloride were added and stirred at room temperature for 6 hours. Potassium permanganate was added to the mixture and the reaction was continued for 3 hours. The solvent was then evaporated to obtain the oxidized pre-oxidant.

[0108] The results are shown in Table 1.

[0109] Example 11 The procedure of Example 1 was followed with the following exceptions: Oxidation treatment of pre-oxidant: 2,2-dimethyl-1,3-dioxolane-4,5-di-p-methylbenzyl alcohol was obtained in the same manner as in the ligand preparation example. Equimolar amounts of 2,2-dimethyl-1,3-dioxolane-4,5-di-p-methylbenzyl alcohol and manganese chloride salt were weighed. Under an anhydrous, oxygen-free, nitrogen atmosphere, a 2,2-dimethyl-1,3-dioxolane-4,5-di-p-methylbenzyl alcohol solution containing 2,2-dimethyl-1,3-dioxolane-4,5-di-p-methylbenzyl alcohol and a manganese chloride solution containing manganese chloride were added and stirred at room temperature for 6 hours. Potassium permanganate was added to the mixture and the reaction was continued for 3 hours. The solvent was then evaporated to obtain the oxidized pre-oxidant.

[0110] The results are shown in Table 1.

[0111] Comparative Example 1 The procedure of Example 1 was followed with the following exceptions: The acetone raw material (1) was not subjected to a preliminary oxidation treatment. In other words, the acetone raw material (1) was pressurized by a raw material pump and directly introduced into an acetone dehydrating column C1 filled with a dehydrating material to remove water, thereby obtaining dehydrated acetone (3). This dehydrated acetone (3) was treated according to the post-procedure of Example 1 until isopropanol was obtained.

[0112] The purity, water content, single metal cation concentration, anion concentration, and particle number (≧50 nm) of isopropanol are shown in Table 1.

[0113] Comparative Example 2 The procedure of Example 2 was followed with the following exceptions: The pre-oxidized acetone (2) was not passed through the acetone dehydrating column C1 packed with a dehydrating material (4A molecular sieve) to remove water, but was directly introduced into an acetone purifying column T1 (plate distillation column) for purification to obtain a purified acetone feed (4). The acetone feed (4) was treated according to the post-procedure of Example 1 until isopropanol was obtained.

[0114] The purity, water content, single metal cation concentration, anion concentration, and particle number (≧50 nm) of isopropanol are shown in Table 1.

[0115] [Table 2]

[0116] As can be seen from the results in Table 1, Examples 1 to 10 use a process in which acetone raw material is introduced into an acetone pre-oxidation treatment vessel to pre-oxidize impurities and obtain the pre-oxidized acetone of the present invention. By combining acetone dehydration, acetone purification, isopropanol dehydration, isopropanol purification, and at least one type of isopropanol adsorption filtration, the overall process of Examples 1 to 10 is simple and has high added value. The organic impurity content of the resulting isopropanol product is low, at 5 ppm or less, and the anion and cation, particle content, water content, etc. can meet the requirements for high-end wafer manufacturing (line width ≦ 90 nm).

[0117] Example 12: (Treatment with acetone containing 35 ppm phenol) Oxidation treatment of pre-oxidant: Equimolar amounts of 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol obtained in the Ligand Preparation Example and manganese chloride salt were taken, and in an anhydrous, oxygen-free, nitrogen atmosphere, a 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol solution containing 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol and a manganese chloride solution containing manganese chloride were added, and the mixture was stirred at room temperature for 6 hours; potassium permanganate was added thereto, and the mixture was reacted for 3 hours, after which the solvent was evaporated to obtain the oxidized pre-oxidant.

[0118] As shown in Figure 1, the acetone raw material (1) (industrial acetone, purity 98%) was pressurized using a raw material pump and then introduced into an acetone pre-oxidation treatment unit R1 filled with an oxidized pre-oxidant at a flow rate of 0.6 mL / min to perform pre-oxidation, thereby obtaining pre-oxidized acetone (2) with a phenol content reduced to less than 1 ppm.

[0119] Example 13: (Treatment of methyl ethyl ketone containing 45 ppm acetaldehyde) Oxidation treatment of pre-oxidant: Equimolar amounts of 2,2-dimethyl-1,3-dioxolane-4,5-dimethylmethanol and manganese chloride salt obtained in the Ligand Preparation Example were taken, and in an anhydrous, oxygen-free, nitrogen atmosphere, a 2,2-dimethyl-1,3-dioxolane-4,5-dimethylmethanol solution containing 2,2-dimethyl-1,3-dioxolane-4,5-dimethylmethanol and a manganese chloride solution containing manganese chloride were added, followed by stirring at room temperature for 6 hours; potassium permanganate was added thereto, and the reaction was continued for 3 hours, after which the solvent was evaporated to obtain the oxidized pre-oxidant.

[0120] As shown in FIG. 1, a methyl ethyl ketone raw material (1) (industrial methyl ethyl ketone, purity 98%) was pressurized using a raw material pump and introduced at a flow rate of 0.6 mL / min into an acetone pre-oxidation treatment unit R1 filled with an oxidized pre-oxidant, where pre-oxidation was carried out, thereby obtaining pre-oxidized acetone (2) with an acetaldehyde content reduced to less than 1 ppm.

[0121] Example 14: (Treatment of toluene containing 20 ppm aniline) Oxidation treatment of pre-oxidant: Equimolar amounts of 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol obtained in the Ligand Preparation Example and manganese chloride salt were taken, and in an anhydrous, oxygen-free, nitrogen atmosphere, a 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol solution containing 2,2-dimethyl-1,3-dioxolane-4,5-dimethanol and a manganese chloride solution containing manganese chloride were added, and the mixture was stirred at room temperature for 6 hours; potassium permanganate was added thereto, and the mixture was reacted for 3 hours, after which the solvent was evaporated to obtain the oxidized pre-oxidant.

[0122] As shown in Figure 1, the toluene raw material (1) (industrial toluene, purity 98%) was pressurized with a raw material pump and introduced at a flow rate of 0.6 mL / min into an acetone pre-oxidation treatment unit R1 filled with an oxidized pre-oxidant, where pre-oxidation was carried out, yielding pre-oxidized acetone (2) with a phenol content reduced to 1 ppm.

[0123] Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the scope of the technical idea of ​​the present invention, the technical solutions of the present invention may undergo various simple modifications, including the combination of various technical features in any other suitable aspects, and these simple modifications and combinations should also be considered as the contents disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. An oxygen-containing metal complex containing a transition metal element as a central atom and a substituted oxygen-containing heterocyclic organic compound as a ligand; wherein the ligand is a compound having a structure represented by formula (I): 【Chemical 1】 In formula (I), n is an integer from 0 to 5, and A is —CH(R ５ )- and; R at each appearance １ and R ２ are each independently selected from C1-C8 alkyl, and each occurrence of R ３ , R ４ and R ５ are each independently selected from H, C1-C8 alkyl, phenyl C1-C8 alkyl, and C1-C8 alkylphenyl.

2. R at each appearance １ and R ２ are each independently selected from C1 to C5 alkyl, preferably each independently selected from C1 to C4 alkyl; ３ , R ４ and R ５ are each independently selected from H, C1-C5 alkyl, phenyl C1-C5 alkyl, and phenyl substituted with C1-C5 alkyl, preferably are each independently selected from H, C1-C4 alkyl, benzyl, and phenyl substituted with C1-C3 alkyl.

3. 3. The oxygen-containing metal complex according to claim 1, wherein the transition metal element is selected from one or more of chromium, molybdenum, tungsten, iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum, manganese, technetium, and rhenium.

4. In formula (I), n is an integer from 0 to 3; R １ and R ２ are each independently selected from H, C1-C3 alkyl, and R ３ and R ４ are each independently selected from H, C1-C3 alkyl, benzyl, and methyl-substituted phenyl; and R ５ is H or C1-C3 alkyl; Preferably, in formula (I), n is 0 or 1; and R １ and R ２ are each independently selected from C1-C3 alkyl; R ３ and R ４ are each independently selected from H, C1-C3 alkyl, benzyl, and methyl-substituted phenyl; R ５ The oxygen-containing metal complex according to any one of claims 1 to 3, wherein is H.

5. The oxygen-containing metal complex according to any one of claims 1 to 4, prepared by the following process: A process comprising adding a ligand solution and a metal salt solution according to equimolar amounts of the ligand and the transition metal under anhydrous, oxygen-free, nitrogen atmosphere, stirring the mixture at room temperature for 1-10 hours to carry out the complexation reaction, and optionally evaporating the solvent after the complexation reaction.

6. 1. A process for treating a crude selected from a ketone crude and a monocyclic aromatic hydrocarbon crude, comprising: The oxygen-containing metal complex according to any one of claims 1 to 5 is used as a pre-oxidizing agent to be contacted with a crude material, thereby pre-oxidizing at least a portion of impurities contained in the crude material, wherein the impurities are reducing impurities. The process includes:

7. 7. The process of claim 6, wherein the reducing impurities are selected from alcohols, aldehydes, ketones, esters, ethers and olefins; preferably, the reducing impurities are selected from saturated or unsaturated C1-C4 primary or secondary alcohols, C1-C4 aldehydes, C1-C4 alkyl formates, C2-C4 olefins, anilines optionally substituted with C1-C4 alkyl, and phenols optionally substituted with C1-C4 alkyl.

8. 8. The process of claim 6 or 7, wherein the amount of pre-oxidant added is 0.01 to 0.1% by weight of the crude feedstock.

9. oxidizing the pre-oxidant with an oxidizing agent prior to performing the pre-oxidation; The process according to any one of claims 6 to 8, wherein the oxidizing agent is preferably selected from oxygen, hydrogen peroxide, cumene peroxide, peracetic acid, perchlorates, permanganates, and dichromates.

10. 10. The process according to any one of claims 6 to 9, wherein the ketone is a ketone comprising a C1 to C8 alkyl, a C6 to C8 aryl, a C2 to C8 ester group or a halogen, and the monocyclic aromatic hydrocarbons are monocyclic aromatic hydrocarbons comprising a C1 to C8 alkyl, a C2 to C8 ester group or a halogen; preferably the crude feed is an acetone feed.

11. The crude material is an acetone feedstock, and in step (1), pre-oxidation of the acetone feedstock is carried out in a pre-oxidation reactor to obtain a pre-oxidized acetone feedstock; and the steps of: (2) introducing an acetone feed into an acetone hydrogenation reactor to carry out a hydrogenation reaction and obtain a crude isopropanol product; wherein the acetone feed is a pre-oxidized acetone feed obtained from step (1), or the pre-oxidized acetone feed optionally undergoes intermediate treatment (1-2) to obtain a purified acetone feed; The process of claim 10, further comprising:

12. 11. The process according to claim 10, wherein the intermediate treatment (1-2) is carried out between step (1) and step (2), and the intermediate treatment (1-2) comprises sequentially introducing the pre-oxidized acetone feedstock into an acetone dehydration unit and an acetone purification unit to perform acetone dehydration and acetone purification, thereby obtaining purified acetone.

13. 12. The process of claim 10 or 11, further comprising the step of post-treating the crude isopropanol product (3): passing the crude isopropanol product through an isopropanol dehydration unit, an isopropanol purification unit, and an adsorption filtration unit in sequence to perform isopropanol dehydration, isopropanol purification, and at least one type of isopropanol adsorption filtration to obtain electronic grade isopropanol.

14. In step (1), the pre-oxidation conditions are as follows: The amount of the pre-oxidizer added is 0.01 to 0.1% by weight of the acetone feedstock; and At room temperature and pressure; The process according to any one of claims 10 to 13, comprising:

15. 15. The process of any one of claims 10 to 14, wherein in step (1), the acetone source comprises one or more of technical grade acetone, analytical grade acetone, and electronic grade acetone.

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