Acetone composition as well as preparation method and application thereof

Abstract

The invention relates to the field of reagent purification, in particular to an acetone composition and a preparation method and application thereof. In the composition, the content of acetone is more than 99.99%, the total content of olefin is less than 1ppm, the total content of alcohol compounds is less than 10ppm, the total content of aldehyde compounds is less than 2ppm, and the content of water is less than 100ppm. The acetone composition also has high acetone purity and low impurity content, and can be applied to preparation of high-end ultrapure reagents for integrated circuits.

Description

Technical Field

[0001] The invention relates to the field of reagent purification, and in particular to an acetone composition and a preparation method and application thereof. Background Art

[0002] Acetone is a very common high-purity solvent. It is colorless and has stable chemical properties. Acetone has good solubility and is mainly used in the production of epoxy resins, polycarbonates, organic glass, medicines, pesticides, etc. It is also a good solvent for coatings, adhesives, acetylene cylinders, etc. It is also used as a diluent, cleaning agent, and extractant.

[0003] Acetone is produced in a variety of ways, most of which produce acetone solutions containing additional undesirable byproducts or impurities. The acetone raw material often contains impurities such as hydrocarbons, aldehydes, alcohols, etc. There are many methods for purifying acetone in the prior art, but each method has its disadvantages. For example, crude acetone can be processed by using simple distillation. However, using distillation alone is not completely effective because impurities (especially fatty aldehydes, olefins and a series of other impurities) remain in the processed acetone product, which reduces its purity and quality.

[0004] That is, the purified acetone obtained by the general purification treatment method cannot meet the requirements of high-end applications, and some existing methods also cause the loss of acetone raw materials and produce many by-products while purifying acetone. Summary of the invention

[0005] The purpose of the present invention is to overcome the problems of low acetone purity and high impurity content in the acetone composition in the prior art, and to provide an acetone composition and a preparation method and application thereof. The acetone composition has high acetone content and low impurity content.

[0006] In order to achieve the above-mentioned object, the first aspect of the present invention provides an acetone composition, wherein the acetone content in the composition is above 99.99%, the total olefin content is below 1 ppm, the total alcohol compound content is below 10 ppm, the total aldehyde compound content is below 2 ppm, and the water content is below 100 ppm.

[0007] The second aspect of the present invention provides a method for preparing an acetone composition, the method comprising: dehydrating the reaction product of a mixture of an acetone raw material and an auxiliary agent after a catalytic reaction with a catalyst, and distilling the reaction product to obtain the acetone composition; the catalyst is a porous material that has been oxidatively modified.

[0008] The third aspect of the present invention provides use of the composition described in the first aspect and / or the composition prepared by the preparation method described in the second aspect in the preparation of high-purity reagents.

[0009] Through the above technical solution, the present invention has the following advantages:

[0010] The acetone composition of the invention has high acetone purity and low impurity content, and can be applied to the preparation of high-end ultrapure reagents for integrated circuits.

[0011] According to the preparation method of the present invention, the oxidation of impurities in the acetone raw material is catalyzed by the porous material modified by the oxidant, so that an acetone composition with high acetone purity and low impurity content can be prepared, and the operation is convenient and the acetone loss rate is low. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 It is the infrared spectra of oxidatively modified activated carbon and unmodified activated carbon. DETAILED DESCRIPTION

[0013] The endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0014] The invention provides an acetone composition, wherein the acetone content of the composition is above 99.99%, the total olefin content is below 1 ppm, the total alcohol compound content is below 10 ppm, the total aldehyde compound content is below 2 ppm, and the water content is below 100 ppm.

[0015] The acetone composition of the invention has high acetone purity and low impurity content, and can be applied to the preparation of high-end ultrapure reagents for integrated circuits.

[0016] According to a preferred embodiment of the present invention, the olefin comprises C2-C3 olefin, and preferably the content of C2-C3 olefin is below 0.5 ppm.

[0017] According to a preferred embodiment of the present invention, the aldehyde compound comprises C2-C3 aldehydes, and preferably the content of C2-C3 aldehydes is below 1 ppm.

[0018] The invention provides a method for preparing an acetone composition, which comprises: a mixture of an acetone raw material and an auxiliary agent is subjected to a catalytic reaction by a catalyst, a reaction product is dehydrated, and a distillation is performed to obtain the acetone composition; the catalyst is a porous material that has been oxidatively modified.

[0019] According to the preparation method of the present invention, the oxidation of impurities in the acetone raw material is catalyzed by the porous material modified by the oxidant, so that an acetone composition with high acetone purity and low impurity content can be prepared, and the operation is convenient and the acetone loss rate is low.

[0020] In the present invention, as long as the purpose of the present invention can be achieved, there is no particular limitation on the modification method. According to a preferred embodiment of the present invention, the modification method comprises: contacting the porous material with an oxidant, washing, and drying. By adopting the above preferred scheme, the obtained catalyst can be more suitable for purifying acetone, further improving the purity of acetone and further reducing the impurity content.

[0021] According to a preferred embodiment of the present invention, the modification method includes: removing fine powder and attachments on the surface of the catalyst, for example, washing the fine powder and attachments on the surface of the catalyst such as activated carbon with deionized water, and then drying for later use.

[0022] According to a preferred embodiment of the present invention, the contacting is carried out in a rotating pot, and the specific contacting method includes adding an oxidant to the porous material in the rotating pot.

[0023] In the present invention, as long as the purpose of the present invention can be achieved, there is no particular requirement for the concentration of the oxidant. According to a preferred embodiment of the present invention, the mass concentration of the oxidant is 0.1%-20%, preferably 0.5%-8%. By adopting the above preferred scheme, the purity of acetone can be further improved and the impurity content can be further reduced.

[0024] In the present invention, the type of the oxidant can be a conventional choice in the art. According to a preferred embodiment of the present invention, the oxidant is selected from at least one of nitric acid, sulfuric acid, hydrogen peroxide, permanganate, peracetic acid, cumene peroxide and meta-chloroperbenzoic acid.

[0025] According to a preferred embodiment of the present invention, the oxidant is one of a combination of permanganate and nitric acid, permanganate and sulfuric acid, dichromate and nitric acid, and dichromate and sulfuric acid. By adopting the above preferred embodiment, the purity of acetone can be further improved and the impurity content can be further reduced.

[0026] In the present invention, the contact and drying conditions may be conventionally selected in the art.

[0027] According to a preferred embodiment of the present invention, the contacting conditions include a temperature of 20-50° C. and a time of 0.5-2 h.

[0028] According to a preferred embodiment of the present invention, the drying conditions include: inert atmosphere, temperature of 100-630° C., preferably 400-630° C.; time of 0.5-5 h, preferably 2-4 h.

[0029] According to a preferred embodiment of the present invention, the inert atmosphere may be at least one of a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere.

[0030] In the present invention, there is no particular restriction on the selection of the acetone raw material. According to a preferred embodiment of the present invention, based on the GC analysis result, the acetone content in the acetone raw material is 99.93-99.98%, the total olefin content is 1-50 ppm, the total content of alcohol compounds is 10-180 ppm, the total content of aldehyde compounds is 1-50 ppm, and the water content is 1000-5000 ppm.

[0031] In the present invention, the auxiliary agent is an oxidizing substance, and the type of the oxidizing substance can be a conventional choice in the art. According to a preferred embodiment of the present invention, the oxidizing substance is selected from a liquid oxidant and / or an acetone-soluble non-liquid oxidant, preferably at least one of air, oxygen, hydrogen peroxide, permanganate, peracetic acid, cumene peroxide and meta-chloroperbenzoic acid, preferably permanganate. By adopting the above preferred embodiment, the purity of acetone can be further improved and the impurity content can be further reduced.

[0032] In the present invention, the type of the porous material can be a conventional choice in the art. According to a preferred embodiment of the present invention, the porous material comprises at least one of molecular sieves, alumina, silica, diatomaceous earth and carbon-based materials.

[0033] According to a preferred embodiment of the present invention, the porous material is a carbon-based material, preferably the carbon-based material is selected from at least one of activated carbon, carbon nanotubes, graphite, and graphene oxide. In this case, the oxidatively modified carbon-based material has a unique infrared spectrum. For example, when the carbon-based material is activated carbon, the catalyst has a wavelength of 3450 cm -1 The OH stretching vibration peaks near 2820 and 2910 cm -1 The stretching vibration peak of CH on C connected to the oxygen-containing functional group appears nearby. By adopting the above preferred embodiment, the purity of acetone can be further improved and the impurity content can be further reduced.

[0034] In the present invention, the reaction conditions can be selected conventionally in the art.

[0035] According to a preferred embodiment of the present invention, the reaction conditions include: by weight, the amount of the auxiliary agent added is 0.001-10% by weight of the acetone raw material, preferably 0.005-5% by weight of the acetone raw material, and more preferably 0.01-0.1% by weight of the acetone raw material.

[0036] According to a preferred embodiment of the present invention, the conditions for the first contact include: a temperature of 30-80° C. The reaction time is determined according to the reaction temperature, for example, it can be 3-5 hours.

[0037] According to a preferred embodiment of the present invention, the conditions for the first contact include: a pressure of 0.1-0.7 MPa.

[0038] According to a preferred embodiment of the present invention, the washing method is dehydration using a dehydrating agent.

[0039] In the present invention, the type of the dehydrating agent can be a conventional choice in the art. According to a preferred embodiment of the present invention, the dehydrating agent is selected from at least one of molecular sieves, silica gel, resins and salts that can form crystalline hydrates.

[0040] By adopting the preferred embodiment of the aforementioned reaction conditions, the purity of acetone can be further improved and the impurity content can be further reduced.

[0041] In the present invention, the distillation conditions may be conventionally selected in the art.

[0042] According to a preferred embodiment of the present invention, the distillation conditions include: a pressure of 0.05-0.2 MPa.

[0043] According to a preferred embodiment of the present invention, the distillation conditions include: collecting fractions with a distillation range of 54-58°C.

[0044] In the present invention, the reaction can be carried out in any reaction bed. According to a preferred embodiment of the present invention, the reaction is carried out in at least one of a fixed bed reactor, a basket reactor, and a tubular reactor.

[0045] The present invention provides an application of the composition and / or the composition prepared by the preparation method of the present invention in the preparation of high-purity reagents, preferably in the preparation of high-purity isopropanol as a raw material.

[0046] The present invention will be described in detail below through examples. In the following examples, the purity and organic impurity content parameters are measured by GC and GC-MS, and the water content is measured by Karl Fischer method; the raw materials used in the examples and comparative examples, if not particularly limited, are all disclosed in the prior art, for example, can be directly purchased or prepared according to the preparation method disclosed in the prior art.

[0047] Example 1

[0048] Wash the fine powder and attachments on the surface of the activated carbon with deionized water, and dry it for later use; take 100g of the dried activated carbon and place it in a rotating pot, add an equal volume of 0.5wt% potassium permanganate aqueous solution while rotating, rotate for 1h, wash it with deionized water 3 times, and dry it at 550℃ in a nitrogen atmosphere for 3h. Figure 1 The infrared characterization results show that the activated carbon after oxidation modification has a wavelength of 3450cm -1The OH stretching vibration peaks near 2820 and 2910 cm -1 The stretching vibration peak of CH on C connected to the oxygen-containing functional group appears nearby.

[0049] Industrial-grade acetone (according to GC analysis results, acetone 99.93%, C2-C3 olefins 12ppm, C2-C3 aldehydes 31ppm, alcohols 152ppm, water 2800ppm) is used as a raw material, acetone and hydrogen peroxide are uniformly mixed in a premixer, and the mixed material enters a fixed bed reactor, and the effluent from the fixed bed reactor is sequentially introduced into a dehydration tower equipped with 4A molecular sieves, and then purified acetone is obtained by distillation;

[0050] Reaction conditions: the weight ratio of acetone raw material and hydrogen peroxide (based on the weight of hydrogen peroxide) is 100:0.05; feed flow rate is 0.5 ml / min, 30°C, normal pressure, and reaction time is 3 h;

[0051] During dehydration: the flow rate of the effluent is 30L / h;

[0052] During distillation: normal pressure, collect the fraction at 54-58℃.

[0053] The composition of the purified acetone composition is shown in Table 1, which has very few impurities and high acetone purity. At the same time, the acetone loss during the purification process is small and the recovery rate is high.

[0054] Example 2

[0055] Same as Example 1, except that the porous material is carbon nanotubes, the modified oxidant is 1% nitric acid, the mixture is dried at 400° C. for 3 h in a nitrogen atmosphere, and the dehydrating agent is silica gel.

[0056] Reaction conditions: the weight ratio of acetone raw material to cumene peroxide is 100:0.1.

[0057] The composition of the purified acetone composition is shown in Table 1.

[0058] Example 3

[0059] Same as Example 1, except that the porous material is graphene oxide, the modified oxidant is 5% potassium dichromate; the mixture is dried at 630° C. for 2 h in a nitrogen atmosphere; and the dehydrating agent is resin;

[0060] Reaction conditions: the weight ratio of acetone raw material and peracetic acid is 100:0.01.

[0061] The composition of the purified acetone composition is shown in Table 1.

[0062] Example 4

[0063] Same as Example 3, except that the acetone was dried at 100° C. in a nitrogen atmosphere. The composition of the purified acetone composition is shown in Table 1.

[0064] Example 5

[0065] Same as Example 3, except that the auxiliary agent (cumene peroxide) is replaced by potassium permanganate. The composition of the purified acetone composition is shown in Table 1.

[0066] Example 6

[0067] Same as Example 3, except that the oxidant (potassium dichromate) is replaced by a composition of potassium permanganate and sulfuric acid in a mass ratio of 1:1. The composition of the purified acetone composition is shown in Table 1.

[0068] Example 7

[0069] Same as Example 3, except that the porous material is silicon dioxide. The composition of the purified acetone composition is shown in Table 1.

[0070] Example 8

[0071] Same as Example 3, except that the acetone raw material is synthetic grade acetone (according to GC analysis results, acetone 99.98%, C2-C3 olefins 7ppm, C2-C3 aldehydes 28ppm, alcohols 76ppm, water 1820ppm). The composition of the purified acetone composition is shown in Table 1.

[0072] Example 9

[0073] Same as Example 3, except that the reactor is a basket-type reactor. The composition of the purified acetone composition is shown in Table 1.

[0074] Comparative Example 1

[0075] The same as Example 1, except that the fixed bed reactor is filled with untreated activated carbon.

[0076] The composition of the purified acetone composition is shown in Table 1.

[0077] Comparative Example 2

[0078] Same as Example 3, except that inert filler glass beads were added to the fixed bed reactor. The composition of the purified acetone composition is shown in Table 1.

[0079] Comparative Example 3

[0080] Same as Example 3, except that no auxiliary agent (hydrogen peroxide) was added. The composition of the purified acetone composition is shown in Table 1.

[0081] Table 1

[0082]

[0083]

[0084] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An acetone composition, characterized in that The composition has an acetone content of more than 99.99%, a total olefin content of less than 1 ppm, a total alcohol compound content of less than 10 ppm, a total aldehyde compound content of less than 2 ppm, and a water content of less than 100 ppm.

2. The composition according to claim 1, wherein The olefins include C2-C3 olefins, preferably the C2-C3 olefin content is below 0.5 ppm; and / or The aldehyde compound comprises C2-C3 aldehyde, and preferably the content of C2-C3 aldehyde is below 1 ppm.

3. A method for preparing an acetone composition, characterized in that: The method comprises: a mixture of an acetone raw material and an auxiliary agent is subjected to a catalytic reaction, and a reaction product thereof is dehydrated and distilled to obtain an acetone composition; The catalyst is a porous material that has been oxidatively modified.

4. The preparation method according to claim 3, wherein The modification method comprises: contacting the porous material with an oxidant, washing, and drying; preferably, The mass concentration of the oxidant is 0.1%-20%, preferably 0.5%-8%; The contact conditions include: temperature of 20-50°C, time of 0.5-2h; and / or The drying conditions include: inert atmosphere, temperature of 100-630°C, preferably 400-630°C; time of 0.5-5h, preferably 2-4h; and / or The oxidant is selected from at least one of nitric acid, sulfuric acid, hydrogen peroxide, permanganate, dichromate, peracetic acid, cumene peroxide and m-chloroperbenzoic acid, preferably a combination of permanganate and nitric acid, permanganate and sulfuric acid, dichromate and nitric acid, and dichromate and sulfuric acid.

5. The preparation method according to claim 3 or 4, wherein According to the GC analysis results, the acetone content in the acetone raw material is 99.93-99.98%, the total olefin content is 1-50 ppm, the total content of alcohol compounds is 10-180 ppm, the total content of aldehyde compounds is 1-50 ppm, and the water content is 1000-5000 ppm.

6. The preparation method according to any one of claims 3 to 5, wherein: The auxiliary agent is an oxidizing substance, preferably selected from at least one of air, oxygen, hydrogen peroxide, permanganate, peracetic acid, cumene peroxide and m-chloroperbenzoic acid, preferably permanganate.

7. The preparation method according to any one of claims 3 to 6, wherein: The porous material comprises at least one of molecular sieves, alumina, silica, diatomaceous earth and carbon-based materials, preferably a carbon-based material, and more preferably the carbon-based material is selected from at least one of activated carbon, carbon nanotubes, graphite and graphene oxide.

8. The preparation method according to any one of claims 3 to 7, wherein: The reaction conditions include: In terms of weight, the additive is added in an amount of 0.001-10% of the weight of the acetone raw material, preferably 0.005-5% of the weight of the acetone raw material, and more preferably 0.01-0.1% of the weight of the acetone raw material; and / or Temperature of 30-80°C, and / or The pressure is 0.1-0.7MPa; and / or The washing method is to use a dehydrating agent for dehydration, preferably, the dehydrating agent is selected from at least one of molecular sieves, silica gel, resins and salts that can form crystalline hydrates; and / or The conditions of the distillation include: The pressure is 0.05-0.2MPa; and / or The fractions with a distillation range of 54-58°C were collected.

9. The preparation method according to any one of claims 3 to 8, wherein: The reaction is carried out in at least one of a fixed bed reactor, a basket kettle reactor and a tubular reactor.

10. Use of the composition according to claim 1 or 2 and / or the composition prepared by the preparation method according to any one of claims 3 to 9 in the preparation of high-purity reagents, preferably in the preparation of high-purity isopropanol as a raw material.

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