WO2015046716A1

WO2015046716A1 - Catalyst for glycerin dehydration reaction, preparation method therefor, and acrolein preparation method

Info

Publication number: WO2015046716A1
Application number: PCT/KR2014/005485
Authority: WO
Inventors: 조왕래; 최준선; 김지연; 천주영
Original assignee: 주식회사 엘지화학
Priority date: 2013-09-30
Filing date: 2014-06-20
Publication date: 2015-04-02

Abstract

The present invention relates to a catalyst for a glycerin dehydration reaction, a preparation method therefor, and an acrolein preparation method. More specifically, the catalyst for the glycerin dehydration reaction can improve acrolein selectivity by minimizing the generation of by-products and can maintain a high catalytic activity during a reaction.

Description

【Specification】

[Name of invention]

Glycerin dehydration reaction catalyst, preparation method thereof and preparation method of acrolein [technical field]

The present invention relates to a catalyst for glycerin dehydration, a method for preparing the same, and a method for preparing acrolein, a catalyst having high selectivity for acrolein and minimizing the generation of by-products, and a highly active glycerin dehydration reaction catalyst, a method for preparing the same. And to a process for producing acrolein.

[Technique to become background of invention]

Acrolein is a simple unsaturated aldehyde compound that has high reactivity, including incomplete reactors, and is used as a major intermediate for the synthesis of various compounds. In particular, acrolein has been widely used as an intermediate for the synthesis of acrylic acid, acrylic esters, superabsorbent resins, animal feed supplements, or food supplements.

Such acrolein has been produced through the selective gas phase oxidation reaction with atmospheric oxygen mainly using propylene synthesized in the petroleum process as a starting material. However, as environmental problems such as the reduction of fossil fuels and the greenhouse effect are gradually raised, a great deal of research has been conducted on how to synthesize acrolein using renewable raw materials that are not based on fossil fuels.

Accordingly, glycerin, which can be obtained as a by-product of the process of synthesizing biodiesel as a natural product, has received much attention as a raw material for producing acrolein. In particular, the market size of glycerin is increasing according to the production of biodiesel, and the method of applying it industrially due to the price drop of glycerin is being studied.

For example, a method for obtaining acrolein by dehydrating glycerin in the presence of a catalyst is known, and it is known to be carried out using an acid catalyst such as zeolite, phosphate, tungstophosphoric acid (H ₃ PW ₁₂ 0 ₄ ). have. However, previous catalysts used to make acrolein produced byproducts such as hydroxy acetone, hydroxy propane, polycondensation products of propane aldehyde, acetaldehyde, acetone, and glycerin to synthesize high purity acrolein. There was a limit to use in the process. Accordingly, there is a need to develop a highly active catalyst system capable of minimizing the formation of by-products to increase the selectivity and purity of acrolein, and to improve the conversion and reaction yield of glycerin.

[Content of invention]

Problem to be solved

The present invention can improve the selectivity and purity of acrolein prepared by minimizing the production of by-products, and to provide a catalyst for glycerin dehydration that is highly active.

The present invention also provides a method for preparing the catalyst for glycerin dehydration.

The present invention also relates to a method for producing acrolein using the catalyst for glycerin dehydration reaction.

[Measures of problem]

The present invention is selected from the group consisting of phosphorus (P) and silicon (Si)

Provided is a catalyst for glycerin dehydration comprising at least one element and a heteropolyacid compound comprising copper (Cu) and tungsten (W).

In addition, the present invention includes a step of sequentially reacting a heteropolyacid compound containing tungsten (W) with at least one element selected from the group consisting of phosphorus (P) and silicon (Si) with a barium compound and a copper compound, and glycerin dehydration. It provides a method for producing a catalyst for reaction.

In addition, the present invention provides a method for producing acrolein comprising the step of reacting glycerin in the presence of the catalyst for glycerin dehydration reaction. Hereinafter, a glyc _{, a} serine dehydration catalyst, a method for preparing the same, and a method for preparing acrolein according to a specific embodiment of the present invention will be described in more detail. In the present specification, "glycerine dehydration reaction" means the whole process of the reaction in which water is separated in the glycerin molecule, and glycerin can be converted into acrolein through such glycerin dehydration.

As used herein, "heteropolyacid" refers to a multi-nucleic acid multi-acid formed by combining two or more different elements of oxo acid as a component and forming these molecules, and having different valence soccer ball shapes based on a central atom. (Keggin type) may be combined form. According to an embodiment of the present invention, a catalyst for glycerin dehydration comprising one or more elements selected from the group consisting of phosphorus (P) and silicon (Si) and a heteropolyacid compound including copper (Cu) and tungsten (W) Can be provided.

The present inventors recognize that the conventional method of producing acrolein through gas phase oxidation using propylene as a starting material is limited due to the reduction of fossil fuel storage and the rise of environmental problems such as greenhouse effect. Research was conducted on the production of acrolein using environmentally friendly and renewable raw materials. Accordingly, when dehydration of glycerin in the presence of a catalyst comprising a heteropolyacid compound containing copper and tungsten with at least one element selected from the group consisting of phosphorus and silicon, high yields of acrolein can be achieved while minimizing the formation of by-products. It was confirmed through experimentation that the high conversion was made to complete the invention.

The heteropolyacid compound is a form in which oxygen atoms and tungsten atoms are bonded in a soccer ball shape (Keggin type) around phosphorus or silicon atoms, and copper and / or hydrogen ions are bonded between the bonded molecules. May exist. In particular, the heteropolyacid compound of the above type The amount and strength of Brönsted or Lewis acid points can be controlled, thus allowing the glycerin to dehydrate more efficiently.

Particularly, the catalyst for glycerin dehydration is a cation such as Cs, Rb, Ca, Fe, Zr, La, Hf, Bi, etc. of H ⁺ cations of heteropolyacids having a structure of ¾PW ₁₂ 0 ₄ or H ₄ SiW ₁₂ 0 ₄ . Compared with the substituted catalyst, it can show high acrolein selectivity and low byproducts.

The molar ratio of copper and tungsten in the heteropolyacid compound included in the glycerin dehydration reaction catalyst may be 1: 5 to 1: 10,000. In addition, the content of oxygen in the heteropolyacid compound may be appropriately adjusted according to the content and ratio of one or more elements selected from the group consisting of phosphorus and silicon, tungsten, and components which may be further included, but preferably phosphorus and silicon. The ratio of the number of moles of oxygen to the total number of moles of one or more elements selected from the group consisting of copper and tungsten may be 2 to 5, preferably 2 to 4. If the content of oxygen is too small or too large, a soccer ball shape (eg, Keggin type) heteropoly acid structure cannot be formed, and it is preferable to include oxygen in the above-described content.

In addition, the heteropolyacid compound is selected from the group consisting of Zr, Ti, Ce, V, Nb, Cr, Mo, Mn, Zn, B, and Cu in addition to at least one element selected from the group consisting of phosphorus and silicon and copper and tungsten It may further comprise at least one second metal. The expression "second" is a term used to distinguish the metals from phosphorus, silicon, copper, and tungsten, and does not indicate a reaction order or importance.

The second metal may be in a state in which the oxygen is shared with one or more elements selected from the group consisting of phosphorus and silicon, copper, and / or tungsten and oxygen in the heteropolyacid compound. The heteropolyacid compound may further improve the selectivity of acrolein by further including the second metal, and may act to inhibit the production of by-product hydroxy acetone, hydroxy propanone, and the like.

The second metal may be included in an amount of 0.1 mol to 10 mol relative to tungsten, respectively. When the second metal is included too little, The effect of improving the selectivity of acrolein may be insignificant, and if it is included too much, the catalytic activity or the selectivity improving effect due to the increase of the content of the metal may be insignificant, resulting in low economic efficiency.

On the other hand, such a heteropoly acid compound may be represented by the following formula (1).

[Formula 1]

(Cu) _x (H) _y AW (i ₂ - _Z) Bz04o

In Formula 1, A is phosphorus (P) or silicon (Si), B is selected from the group consisting of Zr, Ti, Ce, V, Nb, Cr, Mo, Mn, Zn, B and Cu, x is 0. (31-5, y is 0-5, z is 0-12.

In particular, in the heteropolyacid compound represented by Formula 1, X may vary depending on the substitution amount of hydrogen ions to a value corresponding to 0.01 to 5. When the value of X is large, the amount of scattering points is reduced, and when the value of X is small, the amount of scattering points is increased.

And when A is (P), y is 3-2x, X is 0.01 to

1.5 and y may be 0 to 2.98.

Or, A is the silicon (S ^'i) when, and y is 4-2x, X = 0.01 to 2, y can be 0 to 3.98.

The heteropolyacid represented by Formula 1 is a form in which H + positive ions are substituted with copper silver in a heteropolyacid of ¾PW ₁₂ 0 ₄ or H ₄ SiW ₁₂ 0 ₄ , and prepared according to a method for preparing a glycerin dehydration catalyst, which will be described later. In particular, the copper ions can increase the amount of distribution of the weak acid point and decrease the strong acid point, thereby controlling the acid strength to a strength suitable for the production reaction of acrolein, so that hydrogen ions are reduced to Cs, Compared with a catalyst substituted with elements of Rb, Ca, Fe, Zr, La, Hf and Bi, higher arc selectivity can be exhibited.

Meanwhile, specific examples of the heteropolyacid compound represented by Chemical Formula 1 may include Cu ₀ . ₂₅ H ₂ . ₅ PW ₁₂ 0 ₄₀ , Cuo. ₅ H ₂ .oPW ₁₂ 0 ₄₀ , CU0.75H1.5PW12O40, CLU.OHI.OPWA, CU1.5PW12O40, CU0.75H2.5S1W12O40, CU0.75H1.5PM012O40, CU0.75H2.5S1M012O40, Cuo.75H1.5PWe Mo ₆ 0 ₄₀ etc. are mentioned. In addition, the glycerin dehydration reaction catalyst may further include a carrier to which the heteropolyacid compound is fixed. The carrier can be used without any significant limitation as long as it is known that it can be used in a conventional catalyst. Specific examples of such a carrier include silica, alumina, silica-alumina, titania, zeolite, activated carbon, clay, zirconia, magnesia, magnesium aluminate, calcium aluminate, silicon carbide, zirconium phosphate, or a combination thereof. Preferably, silica having a pore size of 20 nm or more may be used.

The carrier serves to fix a heteropolyacid compound containing copper and tungsten with at least one element selected from the group consisting of phosphorus and silicon, and the heteropolyacid compound is fixed in a form of sharing oxygen to a carrier having a large surface area. There may be. When the heteropolyacid compound is prepared in a form fixed to the carrier as described above, it can be stored and transported more easily, and due to the large surface area, a large amount of glycerin can be efficiently reacted.

And, the carrier may have a specific surface area of 10 to 500 mVg, preferably 50 to 200 mVg. In particular, the catalyst for glycerin dehydration prepared by supporting the heteropolyacid compound on a carrier having a large specific surface area in the above range has an appropriate pore size so that coke deposition may be reduced and sufficient catalyst activity may be provided. .

The catalyst for glycerin dehydration may include 1 to 50 parts by weight of a heteropolyacid compound containing one or more elements selected from the group consisting of phosphorus and silicon and copper and tungsten based on 100 parts by weight of the carrier. Meanwhile, according to another embodiment of the present invention, a heteropolyacid compound including tungsten (W) and at least one element selected from the group consisting of phosphorus (P) and silicon (Si) may be sequentially converted to a barium compound and a copper compound. It can be provided a method for producing a catalyst for glycerin dehydration comprising the step of reacting. According to this production method, a catalyst for glycerin dehydration of an embodiment of the present invention described above may be provided. As described above, this catalyst can minimize the formation of by-products in the dehydration reaction of glycerin to produce acrolein with high selectivity.

More specifically, the glycerin dehydration catalyst is represented by the formula

By reacting a barium compound with a heteropolyacid compound represented by 2,

Preparing a compound of 3; And reacting the prepared compound of Chemical Formula 3 with a copper compound to prepare a compound represented by Chemical Formula 1 below.

[Formula 1]

(Cu) _x (H) _y AW ₍ i2-z) B _z 0 ₄ o

[Formula 2]

[Formula 3]

(Ba) _x (H) _y AW (i ₂ - _z ) B _z 0 ₄ o

In Formulas 1 to 3, A is phosphorus (P) or silicon (Si), B is selected from the group consisting of Zr, Ti, Ce, V, Nb, Cr, Mo, Mn, Zn, B and Cu, X is each independently O. Oi to 5, y is each independently 0 to 5, z is 0 to 12, and a is 0.01 to 5.

And, when A in Formulas 1 and 3 is (P), y is 3-2x, x is

0.01 to 1.5, and y may be 0 to 2.98. When A is silicon (Si), y may be 4 × 2x, X may be 0.01 to 2, and y may be 0 to 3.98. The preparing of the compound of Formula 3 and the preparing of the compound of Formula 1 may be performed in the presence of a solvent. That is, the compound of Formula 2 and the barium compound may be reacted under a solvent, and the compound of Formula 3 and the copper compound prepared above may be reacted under a solvent. Examples of the solvent include water, alcohols or a mixture thereof.

As the barium compound, Ba (0H) ₂ , BaS0 ₄ , Ba (N0 ₃ ) ₂ , BaC0 ₃ , BaC.l _2, or a mixture thereof may be used, and in particular, by-products when Ba (0H) ₂ is used. Because of the production of water rather than strong acids such as sulfuric acid and nitric acid. It does not affect the activity, and since the purification process of the catalyst is not necessary, it is possible to prepare the catalyst for glycerin dehydration reaction more easily.

In addition, as the copper compound, CuS0 ₄ , Cu (N0 ₃ ) ₂ , CuC0 ₃ , CuCl _2, or a mixture thereof may be used. In particular, the case of using the CuS0 ₄ Of these copper compounds, BaS0 ₄ occurs as substitution is precipitated rather insoluble in water, it is easy to remove the precipitate.

In addition, the method for preparing a glycerin dehydration reaction catalyst may further include drying and calcining the compound of Chemical Formula 1 produced by sequentially reacting the heteropolyacid compound with a barium compound and a copper compound.

More specifically, in the drying step, after reacting the heteropoly acid with a copper compound, it may be dried for 10 minutes to 24 hours at a temperature of 100 ^° C or more before firing to remove the solvent. In this drying process, a drying method and a drying apparatus known to be commonly used may be used. For example, drying may be performed using a heat source such as a hot air fan, an oven, a heating plate, and the like.

In addition, the step of firing means a series of processes for making the curable material by heating the semi-coated water at a high temperature, it may be made in a temperature range of 100 to 900 ^° C, preferably 200 to 5 (xrc. If less than, the organic matter remaining in the catalyst may not be properly removed, thereby reducing the activity of the reaction catalyst, and in the case of exceeding the silver range, the structure of the heteropoly acid may collapse and lose its inherent acid properties. _^ The drying and firing steps may be performed for 10 minutes to 10 hours, respectively.If the drying and firing time is too short, the catalyst may not be completely dried and calcined, and the drying and firing time is too long. In the long case, various side reactions such as carbonization of the catalyst can occur.

Meanwhile, before the drying and calcining of the compound of Formula 1, the method may further include separating the precipitate of the barium compound generated by sequentially reacting the compound of Formula 2 with the barium compound and the copper compound. Separation of the precipitate is a compound of formula 2 to a barium compound and a copper compound In order to remove the barium precipitate, which is a by-product of substitution, in a solution in which the compound of Chemical Formula 1 produced by sequentially reacting is dissolved, it may be separated and removed by filtration or centrifugation.

In addition, the method for preparing a glycerin dehydration reaction catalyst of one embodiment may further include supporting the compound of Formula 1 on a carrier. The step of supporting the compound on the carrier can be used without limitation methods known in the art, for example, impregnation method or powder mixing method can be used. In addition, the specific examples and the mixing ratio of the carrier can be applied to the above-described content without limitation.

In the impregnation method, the carrier is used as it is, or is produced in the form of a sphere or pellet, and then aged and calcined together with the mixed solution in which the precipitate in the gel form is formed. The powder ^mixing method is It is a process of baking and supporting the powder obtained by mixing with a powder support | carrier the powdery result obtained through the aging and drying process in the manufacturing process of an oxide catalyst.

In particular, the catalyst for glycerin dehydration reaction of the embodiment is more preferably used by impregnation because the heteropolyacid compound is easy to disperse on a carrier, and in this impregnation method, alcohol, such as water and methanol, is preferably used. And polar solvents such as acetone, THF, acetone and acetonitrile. In particular, when alcohols such as water or methanol are used as a supporting solvent, the produced glycerin dehydration reaction catalyst may exhibit higher catalytic activity. On the other hand, according to another embodiment of the present invention, there may be provided a method for producing acrolein comprising the step of reacting the glycerin in the presence of the above-mentioned catalyst for glycerin dehydration reaction.

As described above, by using the catalyst for glycerin dehydration of the embodiment of the present invention, it is possible to perform dehydration of glycerin having a high acrolein selectivity, and in particular, by-products compared to other catalysts previously known. The production can be minimized. The amount of the catalyst for glycerin dehydration reaction can be appropriately adjusted according to the amount and concentration of glycerin as a reactant, for example, the catalyst can be layered at a weight space velocity of 10 to 300 kPa ol / h · g _cat , preferably Preferably it can be filled at a weight space velocity of 10 to lOOmmol l / h · g _cat .

In addition, the step of reacting the glycerin may be carried out at a temperature of 200 to 4 (xrc. It is preferable to carry out the reaction.

According to the present invention, by minimizing the production of by-products, a high selectivity of acrolein, a highly active catalyst for glycerin dehydration, a method for preparing the same, and a method for preparing acrolein using the same can be provided. [Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples. EXAMPLES AND COMPARATIVE EXAMPLES: Preparation of Glycerin Dehydration Anticoagulant Catalyst

Example 1

4 g of tungstophosphoric acid (H ₃ PW ₁₂ 0 ₄₀ , WAK0) was diluted in 30 ml of distilled water to prepare an aqueous solution of tungstoic acid. 109 g of barium hydroxide (Ba (0H) ₂ 8¾0, purity 98%, KANT0) was added to an aqueous tungstoic acid solution. The barium hydroxide is completely substituted to a transparent Ba ₀ . ₂₅ H ₂ . After waiting for ₅ PW ₁₂ 0 ₄₀ aqueous solution, 0.087 g of copper sulfide (CuS0 ₄ 5¾0, purity 99%, manufactured by DAEJUNG) was dissolved in 10 ml of distilled water to prepare an aqueous solution of copper sulfide. Then, the prepared copper sulfide aqueous solution was Ba ₀ . ₂₅ H ₂ . Slowly add ₅ PW ₁₂ 0 _{40 to the} aqueous solution and stir to CLI ₀ . ₂₅ H ₂ . _{A 5} PW ₁₂ 0 ₄₀ aqueous solution and a BaS0 ₄ precipitate were obtained. The produced BaS0 ₄ was separated and removed by centrifugation, and the remaining Cu ₀ . ₂₅ H ₂ . ₅ PW ₁₂ 0 _{40 The} aqueous solution is heated to distilled water After removing, drying at 110 ° C. oven for 12 hours, and calcined at 300 ° C. for 4 hours Cu ₀ . ₂₅ H ₂ . ₅ PW ₁₂ 0 ₄₀ catalyst was prepared.

Example 2

In the same manner as in Example 1, except that 0.219 g of barium hydroxide and 0.17¾ copper sulfide were used, Cu ₀ . ₅ H ₂ . ₀ PW ₁₂ 0 ₄₀ catalyst was prepared.

Example 3

In the same manner as in Example 1, except that 0.329 g of barium hydroxide and 0.260 g of copper sulfide were used, Cu ₀ . ₇₅ H _L5 PW ₁₂ 0 ₄₀ catalyst was prepared.

Example 4

A CULOHLOPW ^ C ^ O catalyst was prepared in the same manner as in Example 1 except that 0.438 g of barium hydroxide and 0.347 g of copper sulfide were used.

Example 5

A CULSP ^ O ^ catalyst was prepared in the same manner as in Example 1 except that 0.657 g of barium hydroxide and 0.520 g of copper sulfide were used.

Example 6

4 g of tungstosilicate (H ₄ SiW ₁₂ 0 ₄₀ , WAK0) was distilled off in 30 ml of distilled water to prepare an aqueous tungstosilicate solution. 0.286 g of barium hydroxide (Ba (0H) ₂ 8¾0, purity 98%, KANT0) was added to an aqueous tungstosilicate solution. Barium hydroxide is completely substituted for transparent Ba ₀ . ₇₅ ¾. ₅ SiW ₁₂ 0 ₄₀ wait until the aqueous solution, 0.226g of a separate beaker, copper sulfide (CuS0 _4. 5¾0, purity 99%, DAEJUNG g) copper sulfide receiving dissolved in 10ml distilled ^water. I made a liquid. Then the mixture was stirred and then added slowly to the copper sulfate aqueous solution prepared in Bao.7 H2.5SiW ₅ ₁₂ 0 ₀ ₄ o aqueous solution of Cu. ₇₅ H ₂ . _{A 5} SiW ₁₂ 0 ₄₀ aqueous solution and a BaS0 ₄ precipitate were obtained. The produced BaS0 ₄ was separated and removed by centrifugation, and the remaining Cu ₀ . ₇₅ H ₂ . ₅ SiW ₁₂ 0 ₄₀ Aqueous solution was heated to remove distilled water, dried for 12 hours at 110 ° C. oven, calcined at 30 CTC for 4 hours, Cu ₀ . ₇₅ H ₂ . ₅ SiW ₁₂ 0 ₄₀ catalyst was prepared.

Example 7

0.2 g of the catalyst prepared in Example 3 was dissolved in 7 ml of distilled water to form an aqueous solution, and then 1.8 g of silica (Q30, FUJI Co., Ltd.) was added thereto to prepare a silica slurry, which was then stirred. After that, the moisture of the silica slurry is Removed. Then dry in a no ^° c oven for 12 hours ，

It was calcined at 300 ^° C. for 4 hours and loaded at 10 weight ratio of 0. ₇₅ ¾. ₅ 1¾ ₂ 0 ₄ 0 / ^ 0 ₂ (030) catalyst was prepared.

Example 8

The same method as in Example 7 was carried out except that Si — A1 ₂ 0 ₃ (ALDRICH) was used as a carrier instead of silica (Q30, FUJ I). TOHL

A1 ₂ 0 ₃ supported catalyst was prepared.

Example 9

A Cuo ^ HuPW ^ to / ST supported catalyst was prepared in the same manner as in Example 7, except that ST31116 (Ti0 ₂ from SAINT GOBAIN) was used as a carrier instead of silica (Q30, FUJ I).

Comparative Example 1

H ₃ PW ₁₂ 0 ₄₀ purchased from WM0 was used.

Comparative Example 2

H ₄ SiW ₁₂ 0 ₄₀ purchased from WAK0 was used.

Comparative Example 3

Similar to Example 1 except that cesium nitrate was used, Cs ₂ . ₅ . A catalyst of ₅ PW ₁₂ 0 ₄₀ was prepared.

[Comparative Example 4]

Cu ₀ .75Hi. ₅ PWi ₂ 0 ₄ o instead. A H ₃ PW ₁₂ 0 ₄₀ / Si0 ₂ catalyst was prepared in the same manner as in Example 7, except that ¾PW ₁₂ 0 ₄₀ (K0) was used.

[Comparative Example 5]

Cu ₀ .75Hi. _A H ₄ SiW ₁₂ 0 ₄₀ / Si0 ₂ -Al ₂ 0 ₃ catalyst was prepared in the same manner as in Example 8 except that H ₄ SiW ₁₂ 0 ₄₀ (KO) was used instead of ₅ PWi ₂ 04o.

Comparative Example 6

A H ₄ SiW ₁₂ 0 ₄₀ / Ti0 ₂ catalyst was prepared in the same manner as in Comparative Example 5 except that Ti0 ₂ (DEGUSSA) was used as the carrier.

Experimental Example: Conversion of Glycerin, Selectivity of Acrolein and By-products Arc from glycerine using a high-throughput screening (HTS) device manufactured to evaluate the performance of the catalyst in a short time under the conditions shown in Table 1 using the catalyst prepared by the above Examples and Comparative Examples Relane was produced and the product was analyzed by GC in in-s i tu state to calculate conversion, selectivity and yield. The conversion of glycerin and the selectivity of acrolein are shown in Tables 2 and 3 below.

Herein, the conversion rate of glycerin represents the ratio of glycerin to another compound, and the selectivity of acrolein represents the ratio of acrolein to the converted compound.

In addition, Comparative selectivity 1 shows the comparison of the selectivity of the hydroxy acetone with respect to the selectivity of the acrolein and the compound of molecular weight 130, Comparative selectivity 2 is the selectivity of the compound of molecular weight 130 A comparison of the selectivity of by-products against selectivity is shown. In the comparative selectivity 1 and 2, hydroxy acetone is the main by-product of glycerin dehydration reaction, the by-product is hydroxy acetone, aryl alcohol, ace, propionic acid, 1, 2- propanediol, 1, 3-propanedi, Cyclic acetal compounds produced through depolymerization between intermolecular glycerin, or acer and glycerin, and the like. In addition, the compound having a molecular weight of 130 in the molecular weight 130 compound selectivity is a cyclic acetal compound produced by dehydration of acrolein and glycerin and is a by-product produced by heating to 2oo ^° C. ^{at the} rear of the reactor.

Table 1 Glycerin Dehydration Conditions

TABLE 2 Formula, glycerin conversion and selectivity of catalysts prepared in Examples and Comparative Examples

TABLE 3 Selectivity and Comparative Selectivity of Hydroxy Acetone

Comparative Example 3 21.31 1.21 3.92 Comparative Example 4 19.51 1.41 5.33

Comparative Example 5 24.60 2. 15 7. 11

Comparative Example 6 24.36 1.75 5.66

* Comparative selectivity 1 = selectivity of hydroxy acetone I (selectivity of acrolein + selectivity of 130 molecular weight compounds)

Comparative selectivity 2 = selectivity I of the by-product (selectivity of acrolein + selectivity of 130 molecular weight compounds), as shown in Table 2 and Table 3, containing the phosphorus and / or silicon, copper and tungsten When glycerin was reacted using the catalyst of the example, the glycerin conversion and the acrolein selectivity were higher than those of the catalyst of the comparative example. In addition, the comparative selectivity 1 and 2, which is the ratio of the selectivity of the byproduct to the selectivity of the target main product, acrolein, were lower than those of the catalyst of the comparative example.

In particular, the catalyst prepared in Examples from the above experimental results has a higher selectivity of acrolein compared to a heteropolyacid compound of H ₃ PW ₁₂ 0 ₄ and Comparative Example 3 prepared by substituting hydrogen of the heteropolyacid compound with Cs, and by-products. It can be seen that the selectivity of is low.

That is, it can be seen from the above results that the catalyst for glycerin dehydration reaction of the embodiment can generate acrolein with high selectivity and high purity from glycerin, and can suppress the formation of by-products such as hydroxy acetone.

Claims

【Patent Claims】

【Claim 1】

A catalyst for glycerin dehydration reaction, comprising one or more elements selected from the group consisting of phosphorus (P) and silicon (Si), and a heteropoly acid compound containing copper (Cu) and tungsten (W).

【Claim 2】

In clause 1,

The molar ratio between copper and tungsten is 1:5 to 1:10,000, glycerin dehydration banungyong catalyst.

【Claim 3】

In clause 1,

The heteropoly acid compound further contains at least one second metal selected from the group consisting of Zr, Ti, Ce, V, Nb, Cr, Mo, Mn, Zn, B and Cu, a catalyst for glycerin dehydration banung .

【Claim 4】

In clause 3,

A catalyst for glycerin dehydration reaction, wherein the second metal is contained in an amount of 0.1 mole to 10 mole relative to the tungsten.

[Claim 5]

In clause 1,

The heteropoly acid compound is a catalyst for glycerin dehydration reaction, represented by the following formula Ί:

[Formula 1]

(Cu) _x (H) _y AW ₍ i2- _z )B _z 0 ₄ o

In Formula 1,

A is phosphorus (P) or silicon (Si), B is selected from the group consisting of Zr, Ti, Ce, V, Nb, Cr, Mo, Mn, Zn, B and Cu,

X is 0.01 to 5,

y is 0 to 5,

z is 0 to 12. ᅳ

[Claim 6]

In clause 5,

When A is phosphorus (P), y is 3-2x,

【Claim 7】

In clause 5,

When A is silicon (Si), y is 4—2x, x is 0.01 to 2, and y is 0 to 3.98, a catalyst for glycerin dehydration banung.

【Claim 8】

In clause 1,

A catalyst for glycerin dehydration banung, further comprising a carrier on which the heteropoly acid compound is fixed.

【Claim 9】

In clause 8,

The carrier is glycerin dehydrated, selected from the group consisting of silica, alumina, silica-alumina, titania, zeolite, activated carbon, clay, zirconia, magnesia, magnesium aluminate, calcium aluminate, silicon carbide, zirconium phosphate and mixtures thereof. Catalyst for reaction.

[Claim 10]

In clause 8, The carrier has a specific surface area (BET) of 10 to 500 mVg, and is a catalyst for glycerin dehydration reaction.

【Claim 11】

In clause 8,

A catalyst for glycerin dehydration banungyong, comprising 1 to 50 parts by weight of the heteropoly acid compound based on 100 parts by weight of the carrier.

[Claim 12]

'Glycerin dehydration banungyong catalyst comprising the step of sequentially reacting a heteropoly acid compound containing one or more elements selected from the group consisting of phosphorus (P) and silicon (Si) and tungsten (W) with a barium compound and a copper compound. Manufacturing method.

【Claim 13】

In clause 12,

Preparing a compound of formula 3 by reacting a heteropoly acid compound represented by formula 2 and a barium compound; and

A method for producing a glycerin dehydration Banungyong catalyst, comprising the step of reacting the prepared compound of Chemical Formula 3 with a copper compound to prepare a compound of Chemical Formula 1:

[Formula 1]

(Cu) _x (H) _y AW ₍ i2-z)B _z 0 ₄ o

[Formula 2]

[Formula 3]

(Ba) _x (H) _y AW( i2- ₂ )B _z 0 ₄ o

In Formulas 1 to 3,

X is each independently within 0. to 5,

y is each independently 0 to 5, z is 0 to 12,

a is 0.01 to 5.

【Claim 14】

According to clause 12,

The barium compound is Ba(0H) ₂ , BaS0 ₄₎ Ba(N0 ₃ ) ₂ , BaC0 ₃ , and BaCl _2. A method for producing a glycerin dehydration banungyong catalyst comprising at least one selected from the group consisting of.

【Claim 15】

According to clause 12,

The copper compound is CuS0 ₄ , Cu(N0 ₃ ) ₂ , CuCOs, or CuCl _2. Method for producing a catalyst for glycerin dehydration reaction.

【Claim 16】

In clause 13,

The step of preparing the compound of Formula 3 and the step of preparing the compound of Formula 1 are performed in the presence of a solvent. Method for producing a glycerin dehydration banungyong catalyst.

[Claim 17]

In clause 13,

A method for producing a catalyst for glycerin dehydration reaction, further comprising drying and calcining the compound of Formula 1.

【Claim 18】

In clause 17 The calcination step is performed in a temperature range of loo to 9 (xrc). A method for producing a catalyst for glycerin dehydration reaction.

[Claim 19]

In clause 13,

A method for producing a catalyst for glycerin dehydration, further comprising the step of supporting the compound of Formula 1 on a carrier.

【Claim 20】

A method for producing arclaine, comprising the step of reacting glycerin in the presence of the glycerin dehydration reaction catalyst of claim 1.

[Claim 21]

According to clause 20,

A method for producing arclaine, wherein the catalyst for the glycerin dehydration reaction advances at a weight space velocity of 10 to 300 ol / h · g _cat .

【Claim 22】

In clause 20,

The step of reacting glycerin is performed at a temperature of 200 to 400 ^° C, a method for producing arclein.