KR102035846B1 - Surface modified catalyst for dehydration of 2,3-butanediol and method of preparing the same - Google Patents

Surface modified catalyst for dehydration of 2,3-butanediol and method of preparing the same Download PDF

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KR102035846B1
KR102035846B1 KR1020130155926A KR20130155926A KR102035846B1 KR 102035846 B1 KR102035846 B1 KR 102035846B1 KR 1020130155926 A KR1020130155926 A KR 1020130155926A KR 20130155926 A KR20130155926 A KR 20130155926A KR 102035846 B1 KR102035846 B1 KR 102035846B1
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butanediol
catalyst
dehydration
preparing
acid
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KR20150069477A (en
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김우영
신우균
이고르
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지에스칼텍스 주식회사
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/12—Alkadienes
    • C07C11/16—Alkadienes with four carbon atoms
    • C07C11/167—1, 3-Butadiene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/10—Methyl-ethyl ketone

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  • Engineering & Computer Science (AREA)
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Abstract

The present invention relates to a catalyst for dehydration of 2,3-butanediol having a surface modified and a method for preparing the same. Specifically, an acid point is added to the surface to modify an acid-base balance by modifying the surface. It relates to a catalyst having high activity in the dehydration reaction of, 3-butanediol and a preparation method thereof.

Description

Catalyst for dehydration of surface-modified 2,3-butanediol and its preparation method {SURFACE MODIFIED CATALYST FOR DEHYDRATION OF 2,3-BUTANEDIOL AND METHOD OF PREPARING THE SAME}

The present invention relates to a catalyst for dehydration of 2,3-butanediol having a surface modified and a method for preparing the same, and specifically, 2,3-butanediol by adjusting an acid-base balance on the surface by modifying the surface. It relates to a catalyst having high activity in the dehydration reaction of and a preparation method thereof.

Methyl ethyl ketone, called 2-butanone, methyl acetone, etc., is a colorless liquid with a strong vapor and a sweet smell. Gasoline is widely used in the manufacture of celluloid, artificial leather, photographic film, and the like as an organic synthetic intermediate.

On the other hand, 1,3-butadiene is a colorless, odorless, flammable gas, which is a very important base oil which is a raw material of synthetic rubber. As an industrial method for obtaining 1,3-butadiene using petrochemical base oil as a raw material, a method of extracting butadiene from C4 oil produced by steam cracking naphtha, and dehydrogenating butane or butene, There is a method for oxidative dehydrogenation of butenes.

The method of synthesizing the methyl ethyl ketone and 1,3-butadiene at the same time is typical of the dehydration reaction of 2,3-butanediol.

Dehydration of 2,3-butanediol can be carried out by reacting with a strong acid such as sulfuric acid at a high temperature. However, in this case, there was a problem that the yield of the reaction product methyl ethyl ketone, 1.3-butadiene is not high.

Therefore, it was urgent to develop a catalyst that can increase the reaction yield.

An object of the present invention is to solve the problem of low yield of 1,3-butadiene and methyl ethyl ketone as reaction products in the dehydration of 2,3-butanediol as described above. In the present invention to provide a catalyst for the dehydration reaction of surface-modified 2,3-butanediol, and a method for producing the same, which can increase the yield of 1,3-butadiene relative to methyl ethyl ketone.

The catalyst for dehydration of 2,3-butanediol according to an embodiment of the present invention for achieving the above object is characterized in that the surface is modified to adjust the acid-base balance on the surface.

On the other hand, the method for producing a catalyst for dehydration of 2,3-butanediol according to an embodiment of the present invention for achieving the above object comprises the steps of: a) preparing a first solution containing an acid-providing compound; b) preparing a mixed solution by adding lithium phosphate to the first solution; c) heating the mixed solution under reflux conditions; And d) cooling the heated mixed liquid, filtration, washing and drying and baking the same.

When the catalyst according to the present invention is used for dehydration of 2,3-butanediol, the conversion of 2,3-butanediol to 1,3-butadiene and methyl ethyl ketone is high, resulting in the above-mentioned product in high yield. have. In particular, 1,3-butadiene can be prepared in high yield compared to methyl ethyl ketone from 2,3-butanediol.

1 is a diagram showing the results of ammonia, carbon dioxide TPD analysis of the surface-modified lithium phosphate catalyst prepared in Example 1.
2 is a diagram showing the results of ammonia and carbon dioxide TPD analysis on the catalyst prepared in Comparative Example 1.

Specific details of other embodiments are included in the following detailed description and drawings.

Advantages and / or features of the present invention and methods of achieving them will be apparent with reference to the embodiments and drawings described below. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, only the present embodiments to make the disclosure of the present invention complete, and common knowledge in the art to which the present invention pertains. It is provided to fully inform the person having the scope of the invention, so that the invention is defined only by the scope of the claims.

Hereinafter, a catalyst for dehydration of 2,3-butanediol having a surface modified according to the present invention and a method for preparing the same will be described in detail.

Surface Modified  2,3- Butanediol  Dehydration Catalyst

The catalyst according to an embodiment of the present invention is characterized in that the acid-base balance is adjusted by adding acid points to the surface by modifying the surface.

Preferably, the catalyst is a lithium phosphate in which one or more lithium ions in the structure are replaced with an acid point.

In the catalyst of the present invention, the catalytic activity is improved by improving the weak acid / weak base property of the surface. As shown in Equation 1, acidity is increased and basicity is decreased by increasing acidity than before the partial replacement of lithium ions with hydrogen ions is improved. The proportion of base is controlled. Lithium phosphate Li 3 PO 4 is a strong base, Li ion is a strong acid, the base acid is a weak acid, PO 4 ions, a weak base is a strong base. At this time, when Li ions are replaced with hydrogen ions, the acidity is increased and basicity is weakened to achieve an acid-base balance suitable for the reaction.

[Equation 1]

Figure 112013114549024-pat00001

Surface Modified  2,3- Butanediol  Process for preparing catalyst for dehydration reaction

On the other hand, the method for producing a catalyst for dehydration of 2,3-butanediol according to an embodiment of the present invention for achieving the above object comprises the steps of: a) preparing a first solution containing an acid-providing compound; b) preparing a mixed solution by adding lithium phosphate to the first solution; c) heating the mixed solution under reflux conditions; And d) cooling the heated mixed liquid, filtration, washing and drying and baking the same.

First, a) a first solution containing an acid-imparting compound is prepared.

Here, the acid point granting compound may be at least one compound selected from the group consisting of a mixture of LiH 2 PO 4 , NaH 2 PO 4 , H 3 PO 4 and NaNO 3 , a mixture of H 3 PO 4 and NaNO 3 May be present as NaH 2 PO 4 or the like and the modification conditions may be slightly acidic. The compounds are preferred because of the similar composition to lithium phosphate, which facilitates bonding and maintains a similar structure after modification.

The first solution is prepared by dissolving each acid-providing compound in a common solvent such as distilled water.

Next, b) lithium phosphate is added to the first solution to prepare a mixed solution. That is, lithium phosphate (Li 3 PO 4 ), which is the target of surface modification, and the prepared first solution for surface modification are mixed.

At this time, it is preferable that pH of a liquid mixture is 3-8, More specifically, it is a weakly acidic condition of 3-5. When the pH is less than 3, there is a problem in that the composition of lithium in the lithium phosphate is too low to lose the activity of the catalyst, when the pH is greater than 8 there is a problem that the effect of improving the activity of the catalyst is low due to the slight substitution of hydrogen ions.

C) The mixed solution is then heated under reflux conditions. The heating time is not particularly limited but may be 12 to 24 hours since it must be sufficiently heated.

Next, d) the mixed solution of which the heating is completed is cooled, filtered, washed, dried and calcined.

Specifically, for example, after the heating of the mixed solution is cooled to room temperature, the precipitate is filtered, and the precipitate is washed with distilled water, and the washed precipitate is washed for 6 to 18 hours at 80 to 150 ° C. (primary drying), After drying for 6 to 18 hours (secondary drying) at 200 to 300 ° C, firing is performed at 550 to 700 ° C for 1 to 4 hours.

The present invention includes a method for producing 1,3-butadiene and methylethylketone using the above-described surface-modified catalyst for dehydration of 2,3-butanediol.

Specifically, the method for producing 1,3-butadiene and methyl ethyl ketone through dehydration of 2,3-butanediol of the present invention comprises the steps of: (a) vaporizing 2,3-butanediol to obtain a vapor; And (b) reacting the vaporizer with a catalyst, wherein the catalyst has a surface modified to add an acid point to the acid-base balance.

Here, the catalyst is characterized in that the lithium phosphate in which one or more lithium ions in the structure is substituted with hydrogen ions, a detailed description thereof will be omitted here.

In the present invention, the catalyst is advantageous for obtaining 1,3-butadiene and methyl ethyl ketone when using the catalyst treated at 300 to 600 ° C under inert gas conditions.

According to the above, when the catalyst according to the present invention is used for the production reaction of 1,3-butadiene and methyl ethyl ketone of 2,3-butanediol, the surface is modified to add an acid point to the surface, thereby adjusting the acid-base balance. The reaction activity increases due to the catalyst of the present invention, and thus the conversion of 2,3-butanediol to 1,3-butadiene and methyl ethyl ketone is increased, resulting in 1,3-butadiene and methyl ethyl ketone in high yield. have. In particular, 1,3-butadiene can be prepared in high yield compared to methyl ethyl ketone from 2,3-butanediol.

Hereinafter, the catalyst of the present invention and its preparation method will be described in more detail with reference to Examples, but the following Examples are illustrative to explain the present invention in more detail, and the contents of the present invention are limited to the following Examples. It is not.

Example

Example  One

17.67 g of LiH 2 PO 4 was added to 200 mL of distilled water to make Solution 1, and 19.69 g of Li 3 PO 4 was added to Solution 1 to make Mixture 1. At this time, pH of the liquid mixture was five. The mixture 1 was boiled under reflux for 24 hours, and the mixture was cooled to room temperature and the precipitate was filtered off. After washing the precipitate with 1 L of distilled water, the washed precipitate was dried at 100 ° C. for 10 hours, at 250 ° C. for 10 hours, and calcined at 650 ° C. for 2 hours to prepare a surface-modified lithium phosphate catalyst. Was used for the dehydration of 2,3-butanediol.

Example  2

A surface-modified lithium phosphate catalyst was prepared in the same manner as in Example 1, except that 28.52 g of NaH 2 PO 4 was used instead of 17.67 g of LiH 2 PO 4 . The prepared catalyst was used for dehydration of 2,3-butanediol.

Example  3

NaH 2 PO 4 to a 28.95g and 5g NaOH was added to 300ml of distilled water to create a solution 1, by the addition of Li 3 PO 4 28.95g was added to a mixture made of 1: 1. At this time, pH of the liquid mixture was eight. The mixture 1 was boiled under reflux for 24 hours, and the mixture was cooled to room temperature and the precipitate was filtered off. The precipitate was washed with 1 L of distilled water, and then the washed precipitate was dried at 100 ° C. for 10 hours, at 250 ° C. for 10 hours, and calcined at 650 ° C. for 2 hours to prepare a surface-modified lithium phosphate catalyst. The prepared catalyst was used for dehydration of 2,3-butanediol.

Example  4

16.67 g of H 3 PO 4 and 14.45 g of NaNO 3 were added to 300 ml of distilled water to make Solution 1, and 39.37 g of Li 3 PO 4 was added to Solution 1 to make Mixture 1. At this time, pH of the liquid mixture was 6.5. The mixture 1 was boiled under reflux for 24 hours, and the mixture was cooled to room temperature and the precipitate was filtered off. The precipitate was washed with 1 L of distilled water, and then the washed precipitate was dried at 100 ° C. for 10 hours, at 250 ° C. for 10 hours, and calcined at 650 ° C. for 2 hours to prepare a surface-modified lithium phosphate catalyst. The prepared catalyst was used for dehydration of 2,3-butanediol.

Example  5

A surface-modified lithium phosphate catalyst was prepared in the same manner as in Example 1, but after preparing a mixed solution 1, the mixture was further prepared using H 3 PO 4 under a condition of pH 3 of the mixed solution. It was used for dehydration of the prepared 2,3-butanediol.

Comparative example  One

A surface-modified lithium phosphate catalyst was prepared in the same manner as in Example 1, but after preparing the mixed solution 1, the mixture was further prepared under NaOH using a pH of 8.5. The prepared catalyst was used for dehydration of 2,3-butanediol.

Comparative example  2

A conventional lithium phosphate (Li 3 PO 4 ) catalyst was used for dehydration of 2,3-butanediol.

Comparative example  3

A surface-modified lithium phosphate catalyst was prepared in the same manner as in Example 1, but after preparing the mixed solution 1, the mixture was further prepared under NaOH using a pH of 10. It was used for dehydration of the prepared 2,3-butanediol.

evaluation

One. Ammonia, Carbon Dioxide of Prepared Catalysts TPD  Analysis

Ammonia and carbon dioxide TPD analysis were performed on the surface modified lithium phosphate catalyst prepared in Example 1 and the lithium phosphate catalyst of Comparative Example 1, and the results are shown in FIGS. 1 and 2, respectively.

1 is a result of ammonia and carbon dioxide TPD analysis of the surface modified lithium phosphate catalyst prepared in Example 1, the ammonia TPD peak is increased compared to the catalyst of Comparative Example 1 of FIG. It could be confirmed that appeared. This means that both the acid and base points are evenly distributed on the surface of the lithium phosphate catalyst of the present invention.

2. 2,3- using the prepared catalyst From butanediol  Preparation of 1,3-butadiene and methyl ethyl ketone

(1) manufacturing method

First, 1, 2-butadiene and methyl ethyl ketone were prepared by vaporizing 2,3-butanediol to obtain a vaporized product, and reacting the vaporized material with the lithium phosphate catalysts of the examples and comparative examples. At this time, after the inert gas is mixed with the 2,3-butanediol vapor to form a mixture, the mixture may be reacted with the prepared lithium phosphate supported catalyst.

Specifically, 2,3-butanediol solution was injected into the evaporation zone at a constant rate via a pump. The evaporation zone was maintained at 200-250 ° C. to allow 2,3-butanediol to evaporate completely. 2,3-butanediol vaporized in the evaporation zone, or a mixed gas in which an inert gas such as nitrogen, helium or argon gas is mixed with the 2,3-butanediol vaporized from top to bottom of the stainless steel reactor or the quartz reactor The reaction was carried out by passing through a catalyst layer supplied with the catalysts of Examples and Comparative Examples of the present invention.

(2) results

The ratio of 1,3-butadiene and methyl ethyl ketone obtained by the above method, the yield of 1,3-butadiene and methyl ethyl ketone are shown in Table 1 below.

Ratio of 1,3-butadiene (BD) and methyl ethyl ketone (MEK) (BD / MEK) Yield (%) of 1,3-butadiene and methyl ethyl ketone Example 1 0.68 90 Example 2 1.00 93 Example 3 0.61 90 Example 4 0.80 92 Example 5 0.82 76 Comparative Example 1 0.4 32 Comparative Example 2 0.2 9 Comparative Example 3 0.19 10

From the results shown in Table 1 above, when the catalyst of the present invention is used for the production reaction of 1,3-butadiene and methyl ethyl ketone of 3-butanediol, the surface is modified and an acid point is added to the surface to adjust the acid-base balance. The reaction activity increases due to the catalyst of the present invention, and thus the conversion of 2,3-butanediol to 1,3-butadiene and methyl ethyl ketone is increased, resulting in 1,3-butadiene and methyl ethyl ketone in high yield. It could be confirmed. In particular, it is possible to prepare a relatively high ratio of 1,3-butadiene to methyl ethyl ketone from 2,3-butanediol.

As described above, although the present invention has been described by way of limited embodiments, the present invention is not limited to the above-described embodiments, which can be variously modified and modified by those skilled in the art to which the present invention pertains. It is possible. Accordingly, the spirit of the present invention should be understood only by the claims set forth below, and all equivalent or equivalent modifications thereof will belong to the scope of the present invention.

Claims (9)

delete delete a) preparing a first solution containing an acid-imparting compound;
b) preparing a mixed solution by adding lithium phosphate to the first solution;
c) heating the mixed solution under reflux conditions; And
d) cooling, filtration, washing and drying the heated mixed solution, followed by baking;
Method for preparing a catalyst for dehydration of surface-modified 2,3-butanediol.
The method of claim 3,
The acid point imparting compound is LiH 2 PO 4 , NaH 2 PO 4 , H 3 PO 4 And the production method characterized in that at least one compound selected from the group consisting of NaNO 3 .
The method of claim 3,
PH of the mixed solution in step b) is characterized in that 3 to 8.
The method of claim 3,
The firing temperature is a manufacturing method, characterized in that 550 ~ 700 ℃.
delete delete delete
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KR101740058B1 (en) * 2011-02-14 2017-05-25 지에스칼텍스 주식회사 - 23 13 cesium oxide-silica composite method of preparing the same and method of preparing methylethyl ketone and 13butadiene from 23butanediol using the same

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