Acetone and its purification method and application

Abstract

The present application relates to the field of chemical reagent purification, and discloses a kind of acetone and its purification method and application.The method comprises contacting acetone raw material with metal oxygen complex, and optionally sequentially dehydrating and refining effluent after contacting.The method can effectively remove reducing impurities and high-boiling impurities in acetone, has the advantages of high product purity, easy operation, etc., and can realize large-scale production of high-purity acetone.

Description

Technical Field

[0001] This invention relates to the field of chemical reagent purification technology, specifically to acetone, its purification method, and its application. Background Technology

[0002] Acetone is an extremely widely used solvent and cleaning agent. High-purity acetone is an indispensable basic reagent in microelectronics industrial production and food and pesticide residue analysis. Currently, the purity of acetone is one of the factors hindering its expansion into high-end applications. However, existing purification methods have relatively limited purification effects. Therefore, how to further improve the purity of acetone is a technical problem that needs to be solved.

[0003] CN104245655B discloses a method for purifying crude acetone streams: the crude acetone stream is treated with a solid acid catalyst, reacting acetone with low-boiling-point impurities to form high-boiling-point impurities, which, after separation, can be used to produce purified isopropanol. The disclosure indicates that this method can reduce acetaldehyde content by 47-88%, propionaldehyde content by 75-99%, and isobutyraldehyde content by 28-75%. However, this method is not suitable for high-end ultrapure reagents used in integrated circuits (purity requirements: single metal impurity ion content less than 0.1 ppb, moisture content less than 50 ppm, and particles larger than 0.2 μm less than 100 mL / particle). Therefore, the removal rate of acetone impurities using this method cannot meet the requirements for high-end applications. Furthermore, this method results in the loss of acetone raw materials and produces numerous byproducts while reacting with low-boiling-point impurities. Summary of the Invention

[0004] The purpose of this invention is to overcome the problem that acetone purification cannot produce high-end ultrapure acetone reagents for integrated circuits. This invention provides acetone, its purification method, and its application. This method can effectively remove reducing impurities from acetone and improve its purity. This method has the advantages of high product purity and convenient operation, and can realize the large-scale production of high-end ultrapure acetone.

[0005] To achieve the above objectives, the present invention provides a method for purifying acetone, which includes contacting acetone raw material with a metal oxygen-containing complex, and optionally dehydrating and purifying the effluent after contact.

[0006] A second aspect of the present invention provides acetone obtained by the above purification method.

[0007] The third aspect of this invention provides the use of acetone obtained by the above purification method in the production of isopropanol and / or its use in integrated circuits after deionization and departiculation.

[0008] This invention involves contacting acetone raw material with a metal oxygen-containing complex, and then optionally dehydrating and purifying the effluent after contact. This effectively removes reducing impurities and high-boiling-point impurities from the acetone raw material, resulting in a high-purity acetone product suitable for use as a high-end ultrapure reagent in integrated circuits. Furthermore, this operation is convenient and enables large-scale production of high-purity acetone. Detailed Implementation

[0009] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0010] The first aspect of the present invention provides a method for purifying acetone, the method comprising contacting acetone raw material with a metal oxygen-containing complex, and optionally dehydrating and purifying the effluent after contact in sequence.

[0011] According to the present invention, those skilled in the art will understand that when purifying acetone raw materials, it is only necessary for the acetone raw materials to come into sufficient contact with the metal oxygen-containing complex, and the two can come into contact in any way.

[0012] In this invention, after acetone raw material is contacted with metal oxygen-containing complex, the effluent after contact can be optionally dehydrated and purified in sequence, which can effectively remove reducing impurities and high-boiling point impurities in acetone raw material. The final acetone product has high purity. After deionization and departiculate removal, the obtained acetone product can be used as a high-end ultrapure reagent for integrated circuits. Moreover, the operation is convenient and can realize the large-scale production of high-purity acetone.

[0013] Existing processes use small-molecule organic oxidants to remove reducing impurities from acetone. This requires high temperatures and may introduce impurities from the small-molecule oxidants themselves, ultimately making it difficult to obtain high-purity acetone. According to the present invention, in some embodiments, the metal-oxygenated complex is an organic ligand compound with a metal element as the central atom. Using the aforementioned embodiments, reducing impurities and high-boiling-point impurities in acetone can be effectively removed, offering advantages such as high product purity and ease of operation, enabling large-scale production of high-purity acetone.

[0014] According to the present invention, in some preferred embodiments, the metal oxygen-containing complex uses a cyclic ether organic compound as a ligand. Using the aforementioned embodiments, impurities present in small amounts in acetone can be effectively removed. The inventors hypothesize that the metal oxygen-containing complex using a cyclic ether organic compound as a ligand can react well with reducing impurities in acetone.

[0015] According to the present invention, the type of metal element is not limited as long as the purpose of the present invention can be achieved. In some embodiments, the metal element includes at least one of Group VIB metal elements, Group VIIB metal elements and Group VIII metal elements.

[0016] According to a preferred embodiment of the present invention, the group VIB metal element includes one or more of Cr, Mo and W, preferably Mo.

[0017] According to a preferred embodiment of the present invention, the Group VIIB metal element includes one or more of Mn, Tc and Re, with Mn being preferred.

[0018] According to a preferred embodiment of the present invention, the Group VIII metallic element includes one or more of Fe, Co, Ni, Ru, Rh, Pd and Pt, with Co being preferred.

[0019] According to the present invention, by adopting the aforementioned embodiments, the activation effect of the metal oxygen-containing complex itself can be increased, thereby further increasing the removal of reducing impurities and high-boiling-point impurities in acetone.

[0020] According to some preferred embodiments of the present invention, the metal oxygen-containing complex has the structure shown in formula (I).

[0021]

[0022] In formula (I), R1 and R2 are each independently selected from H, C1-C10 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), substituted or unsubstituted benzyl, substituted or unsubstituted aromatic; M is a metal element; X includes elements or groups that provide nonmetallic anions; n is an integer from 0 to 6 (e.g., 0, 1, 2, 3, 4, 5, or 6).

[0023] According to the present invention, it is understood that the plurality of R1s and the plurality of R2s may be the same or different.

[0024] According to the present invention, when n is 0, the cyclic ether organic compound has a five-membered ring structure; when n is 1, the cyclic ether organic compound has a six-membered ring structure, and so on.

[0025] According to the present invention, in some preferred embodiments, in formula (I), R1 and R2 are each independently selected from H, C1-C3 alkyl, benzyl, C1-C2 alkyl-substituted phenyl, and C1-C2 alkyl-substituted naphthyl; in some preferred embodiments, n is an integer from 0 to 3. Using the aforementioned embodiments, acetone with higher purity can be obtained. The inventors speculate that when acetone raw material comes into contact with metal oxygen-containing complexes, a homogeneous system is more easily formed, which can better remove reducing impurities.

[0026] According to the present invention, it is understood that the element or group providing the nonmetallic anion refers to a metal salt that X can form with a metallic element. There is no limitation on the type of element or group providing the nonmetallic anion, as long as the objectives of the present invention are achieved. In some embodiments, the element or group providing the nonmetallic anion includes at least one of chloride, iodine, and acetate.

[0027] According to the present invention, the preparation method of the metal oxygen-containing complex is not limited as long as the purpose of the present invention can be achieved. In some embodiments, the preparation method of the metal oxygen-containing complex includes: performing a coordination reaction between a ligand solution providing the ligand and a metal salt solution providing the central atom, followed by an oxidation reaction under the action of an oxidant.

[0028] According to the present invention, a ligand solution refers to a mixture of a ligand and a solvent. The type of solvent is not limited, and those skilled in the art can select a solvent to prepare the ligand solution based on the type of ligand. The present invention does not impose any limitations on this and will not elaborate further.

[0029] According to the present invention, it is understood that the types of ligands and metal salts can be selected according to the structure of the metal oxygen-containing complex shown in formula (I). For example, when M is Mn, R1 is methyl, R2 is H, n is 0, and X is Cl in formula (I), the ligand is 2,2-dimethyl-1,3-dioxolane-4,5-diethanol and the metal salt is manganese chloride; or when M is Co, R1 is methyl, R2 is H, n is 1, and X is OAc in formula (I), the ligand is 2,2-dimethyl-1,3-dioxolane-4,6-diethanol and the metal salt is cobalt acetate.

[0030] According to the present invention, a metal salt solution refers to a mixture of a metal salt and a solvent. The type of solvent is not limited, and those skilled in the art can select the solvent according to the type of salt to prepare the metal salt solution. The present invention does not limit this, nor will it elaborate further.

[0031] According to the present invention, there are no limitations on the conditions for coordination reaction and oxidation reaction. Any coordination reaction conditions and oxidation reaction conditions that can be conceived as ligands with the desired metal oxygen-containing complex structure are applicable to the present invention. In some embodiments, the conditions for coordination reaction include: room temperature reaction for 1-10 hours; in some embodiments, the conditions for oxidation reaction include: reaction time of 1-10 hours.

[0032] In this invention, room temperature refers to 10-30°C.

[0033] According to some optional embodiments of the present invention, after the oxidation reaction is completed, the metal oxygen-containing complex is obtained by desolvation, extraction and drying.

[0034] According to the present invention, in some preferred embodiments, the coordination reaction and / or oxidation reaction are carried out in an inert atmosphere. By employing the aforementioned embodiments, the formation of the metal oxygen-containing complex in formula (I) can be effectively guaranteed.

[0035] According to some preferred embodiments of the present invention, the molar ratio of the metal salt to the ligand is 1:(1-1.2).

[0036] According to the present invention, the type of oxidant is not limited as long as the objective of the invention can be achieved. In some embodiments, the oxidant includes one or more of air, oxygen, hydrogen peroxide, cumene peroxide, peracetic acid, perchlorate, permanganate, and dichromate. Using the foregoing embodiments, the activity of the metal oxygen-containing complex can be increased, enabling the metal oxygen-containing complex to more effectively remove reducing impurities from ketones.

[0037] In this invention, as long as the metal oxygen-containing complex in formula (I) can be obtained, those skilled in the art can select a suitable method for preparing the metal oxygen-containing complex according to the embodiments of this invention. The preparation method of the metal oxygen-containing complex will not be described in detail in this invention.

[0038] According to a preferred embodiment of the present invention, the source of the acetone raw material is not limited as long as the purpose 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.

[0039] According to a preferred embodiment of the present invention, the purity of industrial-grade acetone is 99-99.5%; the purity of analytical-grade acetone is 99.5-99.9%; and the purity of electronic-grade acetone is 99.9-99.97%.

[0040] In this invention, purity and content refer to percentages obtained by gas chromatography using the area normalization method.

[0041] According to a preferred embodiment of the present invention, the contact method between the acetone raw material and the metal oxygen-containing complex is not limited as long as the purpose of the present invention can be achieved.

[0042] According to some embodiments of the present invention, the acetone feedstock is contacted with the metal oxygen-containing complex in a fully mixed flow manner.

[0043] According to the present invention, in some other embodiments, the acetone raw material is contacted with the metal oxygen-containing complex via a plug flow.

[0044] According to the present invention, those skilled in the art will understand that "full mixing" refers to the mixing of acetone raw material and metal oxygen-containing complex in a reactor. At the same time, in order to increase the contact area and purification efficiency, stirring, ultrasonication or shearing can be added during mixing as needed.

[0045] According to the present invention, those skilled in the art will understand that "push flow" refers to the introduction of acetone feedstock into a reaction tube filled with a metal oxygen-containing complex bed and its contact with the metal oxygen-containing complex bed. At the same time, in order to increase the contact area, the residence time of acetone feedstock in the metal oxygen-containing complex bed can be increased as needed. In order to ensure that the acetone feedstock can smoothly enter the metal oxygen-containing complex bed, the acetone feedstock can be pumped into the reactor. Preferably, the flow rate of the acetone feedstock is 0.1-1 mL / min.

[0046] According to the present invention, the contact conditions are not limited as long as the purpose of the present invention can be achieved. In some embodiments, the contact conditions include the addition of a metal oxygen-containing complex of more than 0.01% by weight of acetone raw material, preferably more than or equal to 0.02%, and more preferably 0.03-0.08%.

[0047] According to the present invention, in some embodiments, the contact conditions include: room temperature and normal pressure.

[0048] In this invention, room temperature refers to a temperature of 10-30℃.

[0049] According to the present invention, there are no restrictions on the dehydrating agent used during dehydration, as long as the purpose of the present invention can be achieved. In some embodiments, the dehydrating agent includes one or more of molecular sieves, silica gel, membranes, resins, and salts that can form crystalline hydrates.

[0050] According to the present invention, it is understood that during dehydration, it is sufficient for the dehydrating agent to come into contact with the material to be dehydrated. The present invention does not limit this, and will not elaborate further here.

[0051] According to the present invention, the purification conditions are not limited as long as the purpose of the present invention can be achieved. In some embodiments, the apparatus used for purification includes a plate distillation column or a packed distillation column, preferably a plate column.

[0052] According to the present invention, in some embodiments, the refining conditions include an operating reflux ratio of 0.1-10 (e.g., 0.1, 0.3, 0.5, 0.8, 1, 3, 6, 7, 9 or 10), preferably 0.5-5.

[0053] According to the present invention, in some embodiments, the refining conditions include an operating pressure of -0.5 to 10 bar (e.g., -0.5 bar, 1 bar, 3 bar, 5 bar, 7 bar, 9 bar or 10 bar), preferably 1 to 5 bar.

[0054] According to the present invention, in some embodiments, the refining conditions include: an operating temperature of less than 50°C, preferably 30-45°C.

[0055] A second aspect of the present invention provides acetone obtained by the above purification method.

[0056] According to the present invention, the content of reducing impurities in the acetone is less than or equal to 2 ppm, preferably less than 1 ppm; and / or the purity of the acetone is greater than 99.998%.

[0057] According to the present invention, it is understood that reducing impurities are components with reducing properties, such as alcohols, aldehydes, ketones, esters, ethers and alkenes.

[0058] The third aspect of this invention provides the use of acetone obtained by the above purification method in the production of isopropanol and / or its use in integrated circuits after deionization and departiculation.

[0059] The present invention will be described in detail below through embodiments.

[0060] In the following embodiments, the metal oxygen-containing complex has the structure shown in formula (I).

[0061]

[0062] Example 1

[0063] Preparation of metal oxygen-containing complexes: In an inert atmosphere, a ligand solution providing the ligand and a metal salt solution providing the central atom are mixed at a molar ratio of metal salt to ligand of 1:1. After the coordination reaction is carried out under magnetic stirring at room temperature for 5 hours, an oxidant (potassium permanganate, with a molar ratio of 1.5:1 to the metal salt) is added to carry out an oxidation reaction for 2 hours. After desolvation, extraction, and drying, the product is obtained.

[0064] Using industrial-grade acetone (99.5%) as raw material, the raw material is pressurized by a raw material pump and then fed into a reactor containing a pre-oxidized metal oxygen-containing complex (M is Mn, two R1s are methyl, four R2s are H, n is 0, and X is Cl). The effluent after contact is then sequentially introduced into a dehydration tower and a plate purification tower containing 4A molecular sieves for dehydration and purification to obtain purified acetone. During contact, the amount of metal oxygen-containing complex added is 0.02% by weight of the acetone raw material; the flow rate of industrial-grade acetone is 0.5 mL / min at room temperature and pressure.

[0065] During dehydration: the flow rate of the effluent is 30 L / h;

[0066] During refining: reflux ratio is 0.5, operating pressure is 1 bar, and operating temperature is 30°C.

[0067] The purity of the purified acetone and the content of reducing impurities in the acetone are shown in Table 1.

[0068] Example 2

[0069] The method according to Example 1 differs in that:

[0070] Metal oxygen-containing complex (M is Co, two R1 are methyl groups, four R2 are H, n is 1, X is OAc);

[0071] The oxidizing agent is hydrogen peroxide;

[0072] The purity of the purified acetone and the content of reducing impurities in the acetone are shown in Table 1.

[0073] Example 3

[0074] The method according to Example 1 differs in that:

[0075] Metal oxygen-containing complex (M is Mo, two R1 are methyl groups, four R2 are H, n is 0, X is Cl);

[0076] The oxidizing agent is peracetic acid;

[0077] The purity of the purified acetone and the content of reducing impurities in the acetone are shown in Table 1.

[0078] Example 4

[0079] The method of Example 1 differs in that the metal oxygen-containing complex is not treated with an oxidizing agent;

[0080] Preparation of metal oxygen-containing complexes: In an inert atmosphere, a ligand solution providing the ligand and a metal salt solution providing the central atom are mixed at a molar ratio of metal salt to ligand of 1:1. The complexation reaction is carried out under magnetic stirring at room temperature for 5 hours, followed by desolvation, extraction, and drying to obtain the final product.

[0081] The structure of the metal oxygen-containing complex is shown in formula (II).

[0082]

[0083] In formula (II), M is Mn, the two R1s are methyl groups, the four R2s are H groups, n is 0, and X is Cl.

[0084] The purity of the purified acetone and the content of reducing impurities in the acetone are shown in Table 1.

[0085] Example 5

[0086] The method according to Example 1 differs in that:

[0087] Metal oxygen-containing complex (M is Mn, two R1s are H, four R2s are methylphenyl, n is 0, X is Cl).

[0088] The purity of the purified acetone and the content of reducing impurities in the acetone are shown in Table 1.

[0089] Example 6

[0090] The method according to Example 1 differs in that:

[0091] The raw material is analytical grade acetone (purity 99.9%).

[0092] The purity of the purified acetone and the content of reducing impurities in the acetone are shown in Table 1.

[0093] Example 7

[0094] Metal oxygen-containing complex (M is Mn, two R1s are methyl groups, four R2s are heptyl groups, n is 0, X is Cl).

[0095] Example 8

[0096] Metal oxygen-containing complex (M is Mn, two R1 are methyl groups, four R2 are H, n is 6, X is Cl).

[0097] Comparative Example 1

[0098] The method according to Example 1 differs in that:

[0099] Analytical grade acetone (99.9% purity) was used as raw material. After being pressurized by a raw material pump, it was sequentially introduced into a dehydration tower and a plate purification tower equipped with 4A molecular sieve for dehydration and purification to obtain purified acetone. The dehydration and purification conditions were the same as in Example 1.

[0100] The purity of the purified acetone and the content of reducing impurities in the acetone are shown in Table 1.

[0101] Comparative Example 2

[0102] The method according to Example 1 differs in that,

[0103] Replace the metal oxygen-containing complex with 5 wt% Pd / SiO2, while keeping the other treatment conditions unchanged.

[0104] The purity of the purified acetone and the content of reducing impurities in the acetone are shown in Table 1.

[0105] Comparative Example 3

[0106] The method according to Example 1 differs in that,

[0107] Replace the metal oxygen-containing complex with a bis(triphenylphosphine) palladium chloride complex, while keeping the other treatment conditions unchanged.

[0108] The purity of the purified acetone and the content of reducing impurities in the acetone are shown in Table 1.

[0109] Table 1

[0110] Example 1 99.9990 0 Example 2 99.9988 0 Example 3 99.9985 0 Example 4 99.91 35 Example 5 99.9989 0 Example 6 99.9992 0 Example 7 99.97 2 Example 8 99.94 2 Comparative Example 1 99.99 40 Comparative Example 2 99.85 40 Comparative Example 3 99.89 38

[0111] As can be seen from the results in Table 1, Examples 1-8, which use the acetone raw material of the present invention to contact with metal oxygen-containing complexes, can effectively improve the purity of acetone products and reduce the content of reducing impurities in purified acetone.

[0112] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for purifying acetone, characterized in that, The method includes contacting acetone raw material with a metal oxygen-containing complex, and optionally dehydrating and purifying the effluent after contact. The metal oxygen-containing complex has the structure shown in formula (I). Equation (I), In formula (I), R1 and R2 are each independently selected from H, C1-C3 alkyl, benzyl, C1-C2 alkyl-substituted phenyl, and C1-C2 alkyl-substituted naphthyl; M includes at least one of Group VIB, Group VIIB and Group VIII metals; X includes an element or group that provides a nonmetallic anion, wherein the element or group that provides the nonmetallic anion includes at least one of chloride, iodine and acetate. n is an integer between 0 and 3; The group VIB metal elements include Mo; The group VIIB metallic elements include Mn; The Group VIII metallic elements include one or more of Fe, Co, and Ni.

2. The purification method according to claim 1, wherein, The method for preparing the metal oxygen-containing complex includes: performing a coordination reaction between a ligand solution providing the ligand and a metal salt solution providing the central atom, followed by adding an oxidant to perform an oxidation reaction; optionally, after the oxidation reaction is completed, the metal oxygen-containing complex is obtained by desolvation, extraction, and drying.

3. The purification method according to claim 2, wherein, The coordination and / or oxidation reactions are carried out in an inert atmosphere.

4. The purification method according to claim 2, wherein, The molar ratio of metal salt to ligand is 1:(1-1.2).

5. The purification method according to claim 2, wherein, The oxidant includes one or more of air, oxygen, hydrogen peroxide, cumene peroxide, peracetic acid, perchlorate, permanganate, and dichromate.

6. The purification method according to claim 1, wherein, The acetone raw material includes one or more of industrial-grade acetone, analytical-grade acetone, and electronic-grade acetone; and / or The contact conditions include: The amount of metal oxygen-containing complex added is greater than 0.01% based on the weight of acetone raw material; and / or At room temperature and pressure.

7. The purification method according to claim 6, wherein, The amount of metal oxygen-containing complex added is greater than or equal to 0.02% based on the weight of acetone raw material.

8. The purification method according to claim 7, wherein, The amount of metal oxygen-containing complex added is 0.03-0.08% based on the weight of acetone raw material.

9. The purification method according to claim 1, wherein, The dehydration conditions include: Dehydrating agents include one or more of molecular sieves, silica gel, membranes, resins, and salts that can form crystalline hydrates; and / or The refining conditions include: Refining equipment includes plate distillation columns or packed distillation columns; and / or The reflux ratio is 0.1-10; and / or Operating pressure is -0.5 to 10 bar; and / or The operating temperature is less than 50℃.

10. The purification method according to claim 9, wherein, The refining conditions include: The reflux ratio is 0.5-5; and / or Operating pressure is 1-5 bar; and / or The operating temperature is 30-45℃.

11. The purification method according to any one of claims 1-10, wherein, The content of reducing impurities in the acetone is less than or equal to 2 ppm; and / or The acetone has a purity greater than 99.998%.

12. The purification method according to claim 11, wherein, The content of reducing impurities in the acetone is less than 1 ppm.

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