KR20120099818A - Cesium oxide-silica composite, method of preparing the same and method of preparing methylethyl ketone and 1,3-butadiene from 2,3-butanediol using the same - Google Patents

Abstract

Cesium oxide-silica complex catalyst according to an embodiment of the present invention can be easily separated from the product, it may have a high activity. In addition, the cesium oxide-silica composite catalyst may be adjusted to the acid / base ratio according to the amount of cesium oxide to selectively obtain the desired product. Furthermore, when preparing methyl ethyl ketone (MEK) and 1,3-butadiene using cesium oxide-silica composite catalyst according to an embodiment of the present invention, selectivity and yield of methyl ethyl ketone and 1,3-butadiene This can be improved.

Description

Cesium oxide-silica composite, method for preparing the same, and method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol AND 1,3―BUTADIENE FROM 2,3―BUTANEDIOL USING THE SAME}

A cesium oxide-silica composite, a method for producing the same, and a method for producing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol using the same are disclosed. More specifically, a cesium oxide-silica composite that can be used as an acid / base complex catalyst, a method for preparing the same, and a method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol using the same are disclosed.

2,3-butanediol is an example of a compound that can be produced from a clean source of biomass. In 1906, Harden and Walpole, through fermentation of xylose and glucose, Since the production of 3-butanediol, research is being actively carried out to produce it using biotechnology. In particular, since 2,3-butanediol is used as a precursor of various compounds such as synthetic rubbers, plasticizers, antifreezes and fuel additives, the production of 2,3-butanediol by bioprocessing is expected to continue to increase. There is also a growing need for technology that can be valuable.

1,3-butadiene is a key material used in the manufacture of industrial materials, such as tires, fuel lines, automobile parts, shoes, and electronics parts. It is a representative chemical product amounting to KRW 22 trillion / year. Commercial production of 1,3-butadiene is carried out through the extraction and purification process of ethylene production by steam cracking, and dehydration of some n-butane or n-butene It is obtained through the digestion reaction. Since 1,3-butadiene is obtained as a by-product of ethylene production, the production of 1,3-butadiene is linked to ethylene production, which makes it difficult to control the production of butadiene according to market conditions.

Meanwhile, methyl ethyl ketone (MEK) is a representative solvent used in large quantities in various process fields, but since there are no companies in Korea, it relies on imports. In particular, MEK is not only used as a solvent such as nitrocellulose, vinyl resin, cellulose acetate, etc., but is also consumed in many industries such as polyurethane, paint, magnetic tape, ink, synthetic leather, adhesives and coatings. .

Existing commercial processes for producing MEK have been carried out from 400 to 2-butanol obtained through hydration of 1-butene or 2-butene, the naphtha C4 fraction. MEK is manufactured by dehydrogenation using a zinc (Zn), copper (Cu) or tin (Sn) catalyst at a high temperature of 500 ° C. and a high pressure of about 4 bar. However, high oil prices continue to be around the world, and the demand for C4 oil is increasing for olefin production or ethylene decomposition, causing a lot of inconveniences in the supply and demand of raw materials and continuing price instability.

2,3-butanediol can be converted to MEK and 1,3-butadiene via dehydration, which requires a dehydration catalyst. Homogeneous inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid are known to exhibit high activity in the dehydration reaction of 2,3-butanediol, but they are difficult to corrode, difficult to handle, and costly to separate them from the product. Therefore, in order to effectively produce MEK and 1,3-butadiene from 2,3-butanediol, it is necessary to develop a catalyst having a high activity and a reaction process using the same, which is easy to separate from a product.

Cesium oxide-silica composite, a method for producing the same, and a method for producing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol using the same are provided.

Cesium oxide-silica composite according to an embodiment of the present invention, cesium oxide (cesium oxide) and silica (silica).

In the cesium oxide-silica composite according to one side of the present invention, the weight of cesium oxide may be 10% by weight to 40% by weight.

Cesium oxide-silica composite manufacturing method according to an embodiment of the present invention, dissolving a cesium oxide source (cesium oxide source) in a solvent to prepare a first solution, by impregnating silica in the first solution a second solution Preparing a, and drying and calcining the second solution.

In the cesium oxide-silica composite manufacturing method according to one aspect of the present invention, the cesium oxide source may be cesium carbonate (Cs ₂ CO ₃ ), cesium chloride (CsCl), or cesium nitrate (CsNO ₃ ).

In the cesium oxide-silica composite manufacturing method according to one aspect of the present invention, the weight of cesium oxide in the cesium oxide-silica composite may be 10% to 40% by weight.

In the cesium oxide-silica composite manufacturing method according to one side of the present invention, the firing step may be carried out at 450 ℃ ~ 650 ℃.

Method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol according to an embodiment of the present invention, the step of vaporizing 2,3-butanediol, inert gas to the vaporized 2,3-butanediol Mixing to form a mixture and reacting the mixture with the cesium oxide-silica composite catalyst.

In the method for producing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol according to one aspect of the present invention, the weight of the cesium oxide in the cesium oxide-silica composite catalyst may be 10% to 40% by weight have.

In the method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol according to one side of the present invention, the reaction temperature in the reaction step may be 320 ℃ ~ 480 ℃.

In the method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol according to one aspect of the present invention, the total yield of methyl ethyl ketone and 1,3-butadiene may be 95% or more.

In the method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol according to one aspect of the present invention, the selectivity of 1,3-butadiene may be 40% to 65%.

Cesium oxide-silica complex catalyst according to an embodiment of the present invention can be easily separated from the product, it may have a high activity. In addition, the cesium oxide-silica composite catalyst may be adjusted to the acid / base ratio according to the amount of cesium oxide to selectively obtain the desired product.

Furthermore, when preparing methyl ethyl ketone (MEK) and 1,3-butadiene using cesium oxide-silica composite catalyst according to an embodiment of the present invention, selectivity and yield of methyl ethyl ketone and 1,3-butadiene This can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a schematic diagram of a continuous gas phase reaction for producing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol.

Hereinafter, a cesium oxide-silica composite catalyst according to an embodiment of the present invention, a preparation method thereof, and a method of preparing methyl ethyl ketone (methyl ethyl ketone, MEK) and 1,3-butadiene will be described in detail.

The cesium oxide-silica composite according to the embodiment of the present invention includes cesium oxide and silica. The cesium oxide-silica complex is a complex in which the cesium oxide, which can act as a base catalyst, and the silica, which can act as a weak acid catalyst as well as a support, are structurally bound.

Cesium oxide acts as a base catalyst by providing oxygen atoms or electrons. More specifically, the oxygen atom on the cesium oxide surface is able to bind very strongly to the protons around it and acts as a basic site, thereby providing an oxygen atom or an electron and acting as a base catalyst.

Silica not only acts as a support that serves to disperse cesium oxide and keep the catalyst in a stable structure, and can also receive electrons and thus function as a weak acid catalyst.

Proper control of the acid / base ratio in the catalytic reaction is important for selectively obtaining the desired product. The cesium oxide-silica composite according to an embodiment of the present invention may act as an acid / base complex catalyst by including cesium oxide which may act as a base catalyst and silica which may act as a weak acid catalyst. In addition, by adjusting the amount of cesium oxide in the cesium oxide-silica composite catalyst, it is possible to control the acid / base ratio, thereby selectively obtaining the desired product.

In the cesium oxide-silica composite catalyst according to one side of the present invention, the amount of cesium oxide may be 10% by weight to 40% by weight. When the amount of cesium oxide is less than 10%, the activity of the cesium oxide-silica complex catalyst is lowered, and when the amount of cesium oxide is more than 40%, it is disadvantageous to disperse the cesium oxide, and the amount of cesium oxide is increased so that economic efficiency is low. Therefore, by adjusting the amount of cesium oxide 10% to 40% by weight can increase the selectivity of the desired product.

Cesium oxide-silica composite manufacturing method according to an embodiment of the present invention, dissolving a cesium oxide source (cesium oxide source) in a solvent to prepare a first solution, by impregnating silica in the first solution a second solution Preparing a, and drying and calcining the second solution.

In the method of manufacturing cesium oxide-silica composite according to one aspect of the present invention, the cesium oxide source includes cesium halides such as cesium carbonate (Cs ₂ CO ₃ ), cesium nitrate (CsNO ₃ ), or cesium chloride (CsCl). This is not restrictive. Preferably, the cesium oxide source may be cesium carbonate (Cs ₂ CO ₃ ). Silica that can act as a support and a weak acid catalyst is not particularly limited, for example, Davisil? 35-60 mesh materials can be used, and the solvent can be water or alcohol.

First, the amount of cesium carbonate, which is a cesium oxide source, is adjusted to dissolve in water to form a first solution, and then the first solution is impregnated with silica to form a second solution. Thereafter, the second solution is dried at room temperature or below 100 ° C., preferably 70 ° C. to 90 ° C., and then calcined to prepare cesium oxide-silica composite. In the cesium oxide-silica composite manufacturing method according to one side of the present invention, the firing step may be carried out at 450 ℃ ~ 650 ℃. Preferably, the firing step may be performed at 530 ℃ ~ 620 ℃. More preferably, the firing step can be carried out at 600 ° C. In addition, the firing step may be performed for about 4 hours.

As a result, cesium oxide-silica composites having various composition ratios can be prepared through this process. Preferably, the composite may be prepared in which the weight of cesium oxide in the cesium oxide-silica composite is 10% by weight to 40% by weight.

In addition, the specific surface area and pore structure of the cesium oxide-silica composite catalyst according to one embodiment of the present invention may vary depending on the silica used, and are not limited to a specific specific surface area and pore structure.

Hereinafter, an embodiment of preparing a cesium oxide-silica composite catalyst will be described. In the present specification, normal temperature means about 20 ° C. to 25 ° C., and normal pressure means about 1 atmosphere.

Example 1

A first solution was prepared by dissolving 0.038 moles of Cs ₂ CO _{3 in 3} moles of water. A second solution was prepared by impregnating 100 g of silica (Davisil 35-60 mesh) in the first solution. The second solution obtained was dried at 80 ° C. for 24 hours. The dried sample was calcined at 600 ° C. for 4 hours under air conditions.

Example 2

A first solution was prepared by dissolving 0.075 moles of Cs ₂ CO _{3 in 3} moles of water. A second solution was prepared by impregnating 100 g of silica (Davisil 35-60 mesh) in the first solution. The second solution obtained was dried at 80 ° C. for 24 hours. The dried sample was calcined at 600 ° C. for 4 hours under air conditions.

Example 3

0.113 mol of Cs ₂ CO ₃ was dissolved in 3 mol of water to prepare a first solution. A second solution was prepared by impregnating 100 g of silica (Davisil 35-60 mesh) in the first solution. The second solution obtained was dried at 80 ° C. for 24 hours. The dried sample was calcined at 600 ° C. for 4 hours under air conditions.

Example 4

0.143 mol of Cs ₂ CO ₃ was dissolved in 3 mol of water to prepare a first solution. A second solution was prepared by impregnating 100 g of silica (Davisil 35-60 mesh) in the first solution. The second solution obtained was dried at 80 ° C. for 24 hours. The dried sample was calcined at 600 ° C. for 4 hours under air conditions.

Comparative Example 1 (Bulk Silica)

Bulk silica was purchased from Aldrich, Davisil 35-65 mesh (commercial silica).

Table 1 shows the amount of cesium oxide in the cesium oxide-silica composite catalyst prepared according to Examples 1 to 4.

% By weight of cesium oxide in the catalyst prepared according to Examples 1-4 Example 1 Example 2 Example 3 Example 4 Amount of cesium oxide (% by weight) 11 21 32 40

In the cesium oxide-silica composite catalyst prepared according to Examples 1 to 4 it can be seen that the amount of cesium oxide is in the range of 10% by weight to 40% by weight.

Hereinafter, a method of preparing MEK and 1,3-butadiene from 2,3-butanediol using a cesium oxide-silica composite catalyst prepared according to an embodiment of the present invention will be described.

Method for producing methyl ethyl ketone from 2,3-butanediol according to an embodiment of the present invention, the step of vaporizing 2,3-butanediol, nitrogen, helium, argon gas, etc. in the vaporized 2,3-butanediol Mixing an inert gas to form a mixture and reacting the mixture with a cesium oxide-silica composite catalyst according to one embodiment of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a schematic diagram of a continuous gas phase reaction for producing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol.

Referring to FIG. 1, 2,3-butanediol may be converted into methyl ethyl ketone and 1,3-butadiene through a continuous gas phase reaction. Specifically, 2,3-butanediol solution is injected into the evaporation zone at a constant rate via a pump. The evaporation zone can be maintained at 200-250 ° C. to allow 2,3-butanediol to evaporate completely.

The 2,3-butanediol vaporized in the evaporation zone is mixed with nitrogen as one of the carrier gases and then fed from the top of the stainless steel reactor or the quartz reactor to the bottom to react through the catalyst bed. do.

At this time, the reaction temperature may be 300 ~ 500 ℃. If the reaction temperature is less than 300 ℃ has a disadvantage of low activity, if it exceeds 500 ℃ can be maintained at 300 ~ 500 ℃ because the energy consumption is large, economic efficiency is low. The reaction pressure may be atmospheric pressure (about 1 atmosphere), but is not particularly limited.

In the process for preparing methylethylketone and 1,3-butadiene from 2,3-butanediol, the amount of catalyst, reactant injection rate, reactant concentration and carrier gas injection rate are not particularly limited and can be appropriately adjusted by those skilled in the art.

In the method for preparing methyl ethyl ketone from 2,3-butanediol according to one aspect of the present invention, the weight of cesium oxide in the cesium oxide-silica composite catalyst used may be 10% to 40% by weight. As such, by adjusting the amount of cesium oxide in the cesium oxide-silica composite catalyst, the acid / base ratio can be adjusted, thereby selectively obtaining the desired product.

As described below, when methyl ethyl ketone and 1,3-butadiene are prepared from 2,3-butanediol according to an embodiment of the present invention, the total yield of methyl ethyl ketone and 1,3-butadiene may be 95% or more. . In addition, the selectivity of 1,3-butadiene may be 40% to 65%.

Hereinafter, embodiments of preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol using the cesium oxide-silica composite catalyst described above will be described.

Reaction results for the examples were analyzed via a gas chromatography instrument (using Aglient's HP6890 Model GC and HP-5 columns) connected to the bottom of the reactor.

Example 5

The catalyst prepared in Example 1 was reacted under the conditions shown in Table 2 below.

Reaction Experimental Conditions in Example 5 Amount of catalyst 5 g Reaction temperature 400 ° C Reactant Supply 5 mL / min Carrier Gas (N ₂ ) Supply 100 mL / min

Example 6

The reaction was carried out in the same manner as in Example 5, except that the catalyst prepared in Example 2 was used.

Example 7

The reaction was carried out in the same manner as in Example 5, except that the catalyst prepared in Example 3 was used.

Example 8

The reaction was carried out in the same manner as in Example 5, except that the catalyst prepared in Example 4 was used.

Comparative Example 2

The reaction was carried out in the same manner as in Example 5, except that the catalyst prepared in Example 4 was used and the reaction temperature was 300 ° C.

Comparative Example 3

The reaction was carried out in the same manner as in Example 5, except that the catalyst prepared in Example 4 was used and the reaction temperature was 500 ° C.

Comparative Example 4

The reaction was carried out in the same manner as in Example 5, except that the catalyst prepared in Comparative Example 1 was used.

Table 3 shows the reaction test results in Examples 5 to 8 and Comparative Examples 2 to 4.

Reaction Experiment Results in Examples 5 to 10 and Comparative Example 2 2,3-butanediol conversion (%) MEK + 1,3-butadiene yield (%) MEK selectivity (%) 1,3-butadiene selectivity (%) Example 5 100 95 44 51 Example 6 100 95 39 56 Example 7 100 95 37 58 Example 8 100 95 33 62 Comparative Example 2 50 48 46 2 Comparative Example 3 100 42 9 33 Comparative Example 4 10 6 One 5

As shown in Table 3, Examples 5 to 8 using the cesium oxide-silica complex prepared in Examples 1 to 4 showed a high activity in the production of methyl ethyl ketone (MEK) and butadiene from 2,3-butanediol . That is, the methyl ethyl ketone and 1,3-butadiene prepared according to Examples 5 to 8 had a total yield of more than 95%, and the selectivity of 1,3-butadiene was also high as 51% to 62%.

However, from the results of Comparative Example 2 and Comparative Example 3, it can be seen that the reaction temperature directly affects the catalytic reaction, when the reaction temperature is 320 ℃ or less, the reaction activity dropped sharply, at 480 ℃ or more side reactions are excessive I could confirm that it happened.

In addition, the bulk silica used in Comparative Example 4 showed a very low conversion rate of 10% and methyl ethyl ketone and 1,3-butadiene yield of 6%, and it can be seen that the yield and selectivity are much lower than those of the examples. .

Cesium oxide-silica composite prepared according to one embodiment of the present invention, by adjusting the amount of cesium oxide used to 10% to 40% by weight to adjust the properties of the acid / base complex catalyst to obtain a desired product selectively can do. Furthermore, when methyl ethyl ketone (MEK) and 1,3-butadiene are prepared using cesium oxide-silica composite catalyst according to an embodiment of the present invention, the total yield of methyl ethyl ketone and 1,3-butadiene is also improved. Can be.

Therefore, when using the cesium oxide-silica complex catalyst according to an embodiment of the present invention, it is possible to control the yield and production rate of methyl ethyl ketone and 1,3-butadiene produced from 2,3-butanediol, which is a market situation It is evaluated economically because it can control the production amount of each substance.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, It will be understood that various modifications and applications are possible. For example, each component specifically shown in the embodiment can be modified. It is to be understood that all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (11)

Cesium oxide-silica composite comprising cesium oxide and silica.
The method of claim 1,
The cesium oxide is the cesium oxide-silica composite of 10% by weight to 40% by weight.
Dissolving a cesium oxide source in a solvent to prepare a first solution;
Preparing a second solution by impregnating silica into the first solution; And
Method of producing a cesium oxide-silica composite comprising the step of drying and calcining the second solution.
The method of claim 3,
Wherein the cesium oxide source is cesium carbonate (Cs ₂ CO ₃ ), cesium chloride (CsCl), or cesium nitrate (CsNO ₃ ).
The method of claim 3,
The cesium oxide in the cesium oxide-silica composite is a method for producing a cesium oxide-silica composite is 10% by weight to 40% by weight.
The method of claim 3,
The firing step is a method for producing a cesium oxide-silica composite is carried out at 450 ℃ ~ 650 ℃.
Vaporizing 2,3-butanediol;
Mixing an inert gas with the vaporized 2,3-butanediol to form a mixture; And
A method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol comprising reacting the mixture with the cesium oxide-silica complex catalyst of claim 1.
The method of claim 7, wherein
Method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol of the cesium oxide in the cesium oxide-silica composite catalyst has a weight of 10% to 40% by weight.
The method of claim 7, wherein
In the reaction step, the reaction temperature is 320 to 480 ℃ to prepare methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol.
The method of claim 7, wherein
A method for producing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol wherein the total yield of methyl ethyl ketone and 1,3-butadiene is 95% or more.
The method of claim 10,
Method for producing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol having a selectivity of 1,3-butadiene 40% ~ 65%.

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