KR101148995B1 - Method for Preparing Acrolein via Dehydration of Glycerol - Google Patents

Abstract

The present invention relates to a method for producing acrolein, and more particularly to a method for producing acrolein with high yield and selectivity over a wide reaction temperature range by gas phase dehydration reaction in the presence of water-containing glycerol in the presence of a zeolite catalyst having a specific structure It is about.

Description

Acrolein through the gas phase dehydration reaction of glycerol and its preparation method {Method for Preparing Acrolein via Dehydration of Glycerol}

The present invention relates to acrolein showing a high yield and selectivity by a vapor phase dehydration reaction in the presence of a zeolite catalyst having a H-ferrierite structure and a method for producing the same.

Acrolein is also known as 2-propenal, acrylaldehyde or acrylaldehyde. Acrolein is highly reactive due to the incomplete reactor with simple unsaturated aldehydes. In particular, it is an intermediate for the synthesis of synthetic proteins, such as acrylic acid, acrylic esters, superabsorbents, polymers, animal feed supplements, methionine. Acrolein is a synthetic intermediate, because of the high toxicity that companies are trying to avoid storing and transporting the chemical.

In commercial processes, the production of acrolein can be produced through selective gas phase oxidation with atmospheric oxygen using propylene synthesized in the petroleum process as starting material. However, with the reduction of fossil fuels and the greenhouse effect and environmental issues, methods for synthesizing acrolein using renewable raw materials that are not based on fossil fuels should be developed.

Glycerol can be produced as a byproduct of the process of synthesizing biodiesel as a natural product. The market size of glycerol is increasing according to the production of biodiesel. Due to the price drop of glycerol, a method for industrial application of it has been studied.

For example, a study of preparing acrolein using glycerol was performed as in Scheme 1 below. Specifically, glycerol is dehydrated to obtain it in the form of a mixture of acrolein.

Scheme 1

CH ₂ OH-CHOH-CH ₂ OH ↔ CH ₂ = CH-CHO + 2H ₂ O

In Scheme 1, the reaction should proceed in an acidic state. Also, the hydration reaction prefers low temperature while the dehydration reaction prefers high temperature as endothermic reaction. In addition, the development of a catalyst system that improves reactivity and selectivity to acrolein through sufficient temperature, pressure and / or concentration of glycerol, as the various functional groups of the reactants and products may impede the yield of acrolein with side reaction products. This is required.

Thus, the dehydration of glycerol to acrolein can be prepared using mineral acids or acid catalysts in liquid and gaseous phases. When acrolein is synthesized using an acid catalyst in the liquid phase, low glycerol conversion must be maintained to obtain high acrolein selectivity. Disadvantages of the liquid phase reaction can be compensated when the reaction proceeds in the high temperature and supercritical region, but the corrosion of the reactor in the process conditions and the stability of the process requires improvement in the commercial process.

As a solution to the above-mentioned problem, Japanese Laid-Open Patent Publication No. 2008-290815 discloses a method for synthesizing acrolein using a batch reaction reactor using an aqueous solution of glycerol at various pressures (potassium sulfate, hydrogenosulfate) as a catalyst. . Synthesis method proposed in the patent is a method of recovering in the aqueous solution of the hydroquinone, a polymerization inhibitor by vaporizing the synthesized acrolein. Using this process can improve the acrolein selectivity up to 82% at a conversion rate of 97%, but there are disadvantages in the process being too complex and not a continuous process for commercial application.

US Pat. No. 2,042,224 shows a yield of about 49% when the aqueous solution of glycerol is dehydrated using a sulfuric acid solution as a mineral acid catalyst.

Japanese Patent Application Laid-Open No. 2007-268363 discloses a phosphoric acid catalytic compound supported on silica (SiO ₂ ) in the gas phase, specifically P, P-Mn, P-Zr, P-Cu, P-Fe, P-Al, or MnP ₂ . Supported silica (SiO ₂ ) is illustrated.

Japanese Laid-Open Patent Publication No. 2007-268364 exemplifies a phosphoric acid catalytic compound supported on silica (SiO ₂ ) in the gas phase, specifically P-Na, P-Cs, and PK.

Dehydration of glycerol with acid catalysts includes alcohols, aldehydes, ketones, aromatic compounds, specifically hydroxypropanone, propanealdehyde, acetaldehyde, acetone, allyl alcohol, acrolein, methanol and glycerol oligomer adducts, glycerol multicondensation products And cyclic glycerol ethers and the like and cause side reactions with substances such as phenols and polyaromatic compounds. This not only reduces the selectivity of the target but also causes deactivation of the catalyst due to carbon deposition.

As such, various processes have been developed to increase the yield, selectivity, and stability of high products. However, in order to simplify the process, a catalyst system showing high activity should be developed first. Therefore, there is an urgent need for measures to overcome these limitations.

The present inventors have continued to develop a catalyst system focusing on overcoming the limitations of the prior art, and as a result, a zeolite catalyst having a specific structure using glycerol as a starting material, in particular, an H-peririte structure It was found that the gas phase dehydration reaction in the presence of the catalyst of the zeolite having a zeolite can exhibit high yield and selectivity over a wide temperature range.

Accordingly, it is an object of the present invention to provide an acrolein prepared by gas phase dehydration reaction in the presence of a catalyst of a zeolite having an H-peririte structure using glycerol as a starting material.

It is an object of the present invention to provide a process for producing acrolein which exhibits high acrolein yield and selectivity over a wide range of reaction temperature ranges.

Another object of the present invention is to provide a method for preparing acrolein that can minimize the production of by-products during the reaction process.

It is still another object of the present invention to provide a method for producing acrolein which is economical by confirming that high selectivity can be achieved using a catalyst system effective for acrolein synthesis.

The present inventors have previously reported the use of a zeolite having a specific silica-alumina molar ratio to prepare acrolein by reacting a glycerol containing water as a starting material with a zeolite catalyst having an H-peririte structure, and thus using the catalyst. Zeolite catalysts such as H-ZSM-5, Hb, HY, and H-mordernite and low-silica-alumina (SiO ₂ -Al ₂ O ₃ ) molar ratios with acid content and gamma alumina (g-Al ₂ O ₃ ), amorphous Compared to using silica-alumina (SiO ₂ -Al ₂ O ₃ ) and silica (SiO ₂ ) as catalysts, it is possible to achieve high acrolein yield and selectivity over a wide range of reaction temperature ranges, and in particular to minimize the formation of by-products during the reaction process. It was confirmed that it shows an improved effect, and the like, showing a high acrolein yield and selectivity, to complete the present invention based on this.

The method for producing acrolein according to the present invention is H- having a low silica-alumina mole ratio having a high acid content, which has been reported in the past by using a catalyst having a zeolite having an H-peririte structure having a specific silica-alumina mole ratio in the zeolite catalyst. Zeolite catalysts such as ZSM-5, Hb, HY, H-mordernite and gamma alumina (g-Al ₂ O ₃ ), amorphous silica-alumina (SiO ₂ -Al ₂ O ₃ ), silica (SiO ₂ ) as catalyst It has been found that improved acrolein yields and selectivities can be achieved over a wide range of reaction temperature ranges compared to those used, and in particular, improved effects such as minimizing the production of by-products during the reaction process, high acrolein yields and selectivities. Therefore, it is expected that the method of the present invention can effectively replace the conventional acrolein manufacturing process in the gas phase.

Hereinafter, the present invention will be described in more detail.

The present invention relates to acrolein prepared by dehydration reaction of glycerol in the presence of a catalyst comprising a zeolite having an H-ferrierite structure.

        The present invention also relates to a method for producing acrolein comprising the step of subjecting glycerol to a gas phase dehydration reaction in the presence of a catalyst comprising a zeolite having an H-ferrierite structure.

The silica-alumina mole ratio of the catalyst including the zeolite having the H-ferrierite structure is adjusted to a level of about 1000: 1 to 10: 1, preferably about 150: 1 to 25: 1. It is advantageous in terms of the surface, and a target product of acrolein can be obtained at a high production rate. When the molar ratio of silica-alumina exceeds 1000: 1, there is a problem in that the reactivity is lower, whereas when less than 10: 1, acrolein selectivity due to side reactions may be lowered.

In addition, the content of the catalyst including the zeolite having the H-peririte structure of the present invention may be included in 1 to 100% by weight of the total catalyst. In order to achieve the effects of the present invention, the higher the content of the zeolite having the structure of H-peririte, the more advantageous, but alumina, silica, or other layered inorganic materials may be further included for catalyst molding. However, if the content of the zeolite having the structure of H- ferrierite is less than 1% by weight of the total catalyst, the reactivity required by the present invention is greatly lowered, which is not preferable.

In the present invention, the H-ferrierite may be used by itself, and typically includes a step of heat-treating (pretreatment) NH ₄ -ferrierite, the heat treatment process is not limited to a special gas composition but helium , Nitrogen, or air is preferred, but the heat treatment temperature may be performed in the range of about 200 to 900 ℃.

In the present invention, alkali metal, alkaline earth metal or lanthanum-based metal may be ion-exchanged in order to enhance the performance of H-ferrierite.

Specifically, the element is potassium (K), lithium (Li), sodium (Na), rubidium (Rb), cesium (Cs), Fr (franium), beryllium (Be), magnesium (Mg), calcium ( Ca), Strontium (Sr), Barium (Ba), Radium (Ra), Lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (TM), ytterbium (Yb), and lutetium (Lu) One or more kinds, preferably potassium (K), may be used as a catalyst by ion exchange.

In the present invention, the catalyst can not only broaden the reaction temperature range compared to the prior art, but also can be used to prepare the target product in high yield and high selectivity over the reaction temperature range.

On the other hand, preferred specifications in the application of the method for producing acrolein according to the present invention are as follows. However, the present invention is not limited thereto.

In general, in order to maximize the yield of acrolein, by-product alcohols, aldehydes, ketones, aromatic compounds, preferably hydroxypropanone, acetaldehyde, propanealdehyde, acetone, allyl alcohol, methanol and glycerol oligomer adducts, and glycerol multicondensation The reaction may proceed while removing products such as products, cyclic glycerol ethers, and the like, phenols and polyaromatic compounds, out of the reaction system. Due to the high toxicity of acrolein, companies are trying to avoid direct storage and transport of this chemical, increasing the equilibrium constant in Scheme 1 (see Background of the Invention), which is a known method, and proceeding to equilibrium to produce acrolein. It is possible to apply the method in the present invention. In this case, the affinity for water can be more effectively increased by improving affinity for water in the reaction system using the aforementioned H-peririte catalyst. In addition, the carbon deposited zeolites during the reaction are easy to regenerate the catalyst with high thermal stability.

Therefore, when the above reaction process is applied in the present invention, high selectivity to acrolein can be obtained, and the catalyst can be used as a production method for easy catalyst regeneration.

In a preferred embodiment of the present invention, the reaction for dehydration in the starting material glycerol may be carried out in a continuous gas phase, fluidized bed gas phase or batch liquid phase, preferably a continuous gas phase reaction, but is not limited thereto.

In addition, in the present invention, the addition ratio of the starting material glycerol and water can be determined according to the desired product, in a ratio of about 1: 0.5 to 1: 100, preferably about 1: 9 to 1:12 on a molar basis. Can be added. In particular, adjusting to a level of about 1:11 is advantageous for improving the yield and selectivity, and the target acrolein can be obtained at a high production rate.

The addition ratio of glycerol: water may increase the content of water to increase the selectivity of acrolein, but when the addition ratio of glycerol: water exceeds 1: 12, a problem of energy consumption for vaporizing water may occur. have. This problem can be overcome by using a fluidized bed reactor, and the heat recovered due to the combustion of carbon deposited on the catalyst can be used for vaporization of the liquid phase.

In addition, in the present invention, the hydrophobicity of the catalyst can control the reaction rate of the rate step of the glycerol dehydration reaction,

In view of the above, the space velocity (mol _{glycerol ?} G _cat . ⁻¹ _? H ⁻¹ ) of _glycerol is controlled in the range of 10 to 10,000, preferably 100 to 5,000. The space velocity of glycerol is determined by the amount of catalyst and the flow rate. If the space velocity of glycerol is less than 10, there is a problem that the reactor becomes too large. If the space velocity of glycerol is greater than 10,000, the conversion ratio of glycerol is too low and the recycle ratio is low. Too high can cause problems with low economic efficiency.

In the present invention, the reaction temperature may be carried out at a temperature of about 220 to 380 ℃, preferably about 260 to 350 ℃.

When the reaction temperature is less than 220 ℃ the reaction activity is low, the reaction time or contact time also increases, so the yield of acrolein is lowered, if it exceeds 380 ℃ the by-products can be increased to increase the carbon deposition, the above range It is advantageous to carry out the reaction in the production of the desired acrolein with high yield and high selectivity.

The present invention can be more clearly understood by the following examples, which are only intended to illustrate the present invention and are not intended to limit the scope of the invention.

Example 1

1-1 Catalyst Pretreatment

A quartz tubular reactor having a length of 23.5 cm and an inner diameter of 9.5 mm was charged to the catalyst under atmospheric pressure and used to carry out the reaction. This reactor is located perpendicular to the furnace maintained at the reaction temperature. Of 0.3g NH ₄ - ferrierite (NH ₄ -ferrierite) of 600 ℃ to the catalyst loaded in the reactor Pretreatment was carried out with a helium at a flow rate of 30 ml / min at the reaction temperature to obtain H-ferrilite.

1-2 glycerol Dehydration

In the presence of helium, 8.3 mol% glycerol and 76.0 mol% moisture were allowed to pass through the reactor. The reaction was evaporated at a temperature of at least 265 ° C. before passing through the reactor to prevent partial condensation of the reactants. The average flow rate of the liquid glycerol was maintained to 23.4 mmol / h. The product obtained was recovered during the initial 2 hours after the start of the reaction. The product was subjected to the dehydration reaction of glycerol through the process of recovering through a trap maintained at a temperature of -5 ℃, the experimental results are shown in Table 1 below.

catalyst Silica-alumina molar ratio Reaction temperature (℃) Glycerol
Conversion rate
(%) Selectivity (%) Acrolein 1-hydroxy
Acetone Acet
Aldehyde H-ferrierite 20 315 42.0 40.7 6.9 2.7 H-ferrierite 55 315 45.6 59.0 4.9 2.5

As shown in Table 1, when H-ferrilite was used as a catalyst, as the silica-alumina mole ratio was increased, the acrolein selectivity increased to 19% (40.7% → 59.0%). In particular, when a zeolite having an H-peririte structure having a silica-alumina ratio of 55 according to the present invention was used as a catalyst, it was found that high acrolein selectivity was shown in gas phase dehydration reaction.

Example 2

2-1 Catalyst Pretreatment

A quartz tubular reactor having a length of 23.5 cm and an inner diameter of 9.5 mm was charged to the catalyst under atmospheric pressure and used to carry out the reaction. This reactor is located perpendicular to the furnace maintained at the reaction temperature. Of 0.3g NH ₄ - ferrierite (NH ₄ -ferrierite) of 600 ℃ to the catalyst loaded in the reactor Pretreatment was carried out with a helium at a flow rate of 30 ml / min for 1 hour at the reaction temperature to obtain H-perilite having a silica-alumina molar ratio of 55.

2-2 glycerol Dehydration

The molar concentration of 8.3 mol% glycerol was fixed in the presence of helium and the water content was varied to allow it to pass through the reactor. The reaction was allowed to evaporate at a temperature of at least 265 ° C. before passing through the reactor to prevent partial condensation of the reactants. The average flow rate of the liquid glycerol was maintained to 23.4 mmol / h. The product obtained was recovered during the initial 2 hours after the start of the reaction. The product was subjected to a dehydration reaction of glycerol through the process of recovering through a trap maintained at a temperature of -5 ℃, the results are shown in Table 2 below.

catalyst Silica-alumina molar ratio Water content
(mole%)
Reaction temperature (℃) Glycerol
Conversion rate
(%) Selectivity (%) Acrolein 1-hydroxy
Acetone Acet
Aldehyde H-ferrierite 55 91.7 315 51.5 76.8 6.8 4.2

As shown in Table 2 above, when H-ferrilite having a silica-alumina mole ratio of 55 was used as a catalyst and the experiment was performed at a water content of 91.7%, high acrolein selectivity was exhibited. Accordingly, the selectivity of the acrolein was confirmed to increase significantly as the water content increases.

Example 3

3-1 Catalyst Pretreatment

A quartz tubular reactor having a length of 23.5 cm and an inner diameter of 9.5 mm was charged to the catalyst under atmospheric pressure and used to carry out the reaction. This reactor is located perpendicular to the furnace maintained at the reaction temperature. 0.3g of NH ₄ - ferrierite (NH ₄ -ferrierite) and to the catalyst loaded in the reactor, performing the pre-processing at a flow rate of helium to 30ml / min each for 1 hour at 600 ℃, silica - alumina molar ratio of 55 Perry H- I got an Alight.

3-2 Glycerol Dehydration

The reactor was passed through a concentration of 8.3 mol% glycerol and 91.7 mol% moisture. The reaction was evaporated at a temperature of at least 265 ° C. before passing through the reactor to prevent partial condensation of the reactants. The average flow rate of the liquid glycerol was maintained to 23.4 mmol / h. The product obtained was recovered during the initial 2 hours after the start of the reaction. The product was subjected to a dehydration reaction of glycerol through a process of recovering through a trap maintained at a temperature of -5 ℃, the results are shown in Table 3 below.

catalyst Silica-alumina molar ratio Water content
(mole%) Reaction temperature (℃) Glycerol
Conversion rate
(%) Selectivity (%) Acrolein 1-hydroxy
Acetone Acet
Aldehyde H-ferrierite 55 91.7 290 40.2 71.4 5.2 3.4 H-ferrierite 55 91.7 340 70.9 77.1 7.8 6.7

As shown in Table 3, when the experiment was performed using a zeolite catalyst having an H-peririte structure having a silica-alumina mole ratio of 55, it was found that the selectivity of acrolein increased with increasing temperature.

Example 4

Acrolein was synthesized by dehydrating glycerol in the same manner as in Example 1, except that 8 mol% K was used as a catalyst in a zeolite catalyst having an H-peririte structure having a silica-alumina molar ratio of 20. The method was carried out. The results are shown in Table 4 below.

catalyst Silica-alumina molar ratio Reaction temperature (℃) Glycerol
Conversion rate
(%) Selectivity (%) Acrolein 1-hydroxy
Acetone Acet
Aldehyde 8mol% K / ferrierite 20 315 38.2 53.4 6.9 2.9

As shown in Table 4 above, Example 1? When compared with the results of the zeolite catalyst having an H-peririte structure having a silica-alumina molar ratio of Table 1, it was confirmed that the acrolein selectivity was greatly increased. On the other hand, it was confirmed that the selectivity of by-product 1-hydroxyacetone and acetaldehyde did not differ.

Comparative Example 1

A reaction of synthesizing acrolein by dehydrating glycerol in the same manner as in Example 1, except that H-ZSM-5, Hb, H-mordenite, and HY showing different structures among the zeolite catalysts were used as catalysts. It was. The results are shown in Table 5 below.

catalyst Silica-alumina molar ratio Reaction temperature (℃) Glycerol
Conversion rate
(%) Selectivity (%) Acrolein 1-hydroxy
Acetone Acet
Aldehyde H-b 25 315 76.4 45.8 4.9 5.8 H-ZSM-5 23 315 36.3 45.8 11.0 4.2 H-Y 5.1 315 29.7 29.7 8.1 3.7 H-mordenite 20 315 49.5 40.5 8.1 2.2

As shown in Table 5, when using the Hb, HY, H-ZSM-5 and H-mordenite as a catalyst when comparing the acrolein selectivity, all catalysts are H- ferrierite structure of 55 silica-alumina mole ratio The selectivity was lower than that of the zeolite catalyst having (Example 1-Table 1).

Comparative Example 2

In the same manner as in Example 1, except that silica (SiO ₂ ), alumina (g-Al ₂ O ₃ ), and amorphous silica alumina (SiO ₂ -Al ₂ O ₃ ) forming a framework of zeolite were used as a catalyst. Dehydration of glycerol was carried out to synthesize acrolein. The results are shown in Table 6 below.

catalyst Silica-alumina molar ratio Reaction temperature (℃) Glycerol
Conversion rate
(%) Selectivity (%) Acrolein 1-hydroxy
Acetone Acet
Aldehyde g-Al ₂ O ₃ - 315 71.3 36.3 12.7 2.7 SiO ₂ - 315 9.6 1.0 n.d. n.d. SiO ₂ -Al ₂ O ₃ 7.4 315 93.6 37.8 9.9 9.1

As shown in Table 6, when using the silica (SiO ₂ ) as a catalyst it showed a low glycerol conversion. When gamma alumina (g-Al ₂ O ₃ ) and amorphous silica-alumina (SiO ₂ -Al ₂ O ₃ ) were used as catalysts, reactions using H-ferrilite having a silica-alumina molar ratio of 55 as a catalyst (execution) Low acrolein selectivity compared to Example 1).

Comparative Example 3

Acrolein was synthesized by dehydrating glycerol in the same manner as in Example 1 using Hb having a high conversion ratio of silica-alumina in zeolite structure and H-ZSM-5 catalyst having silica-alumina mole ratio of 150. Reaction was carried out. However, in order to compare the selectivity, by adjusting the amount of catalyst, the conversion rate was fixed in the same manner as the conversion rate of the zeolite catalyst having the H-peririte structure shown in Table 1. The catalyst amount was 0.1 g for H-b and 0.03 g for H-ZSM-5 and the average flow rate of glycerol was maintained at 23.4 mmol / h. The results are shown in Table 7 below.

catalyst Silica-alumina molar ratio Reaction temperature (℃) Glycerol
Conversion rate
(%) Selectivity (%) Acrolein 1-hydroxy
Acetone Acet
Aldehyde H-b 25 315 32.2 36.6 6.7 8.3 H-ZSM-5 150 315 32.1 38.7 3.6 0.8

As shown in Table 7, Hb and silica-alumina having a silica-alumina mole ratio of 25 compared to the reaction using a zeolite having a H-peririte structure having a silica-alumina mole ratio of 55 as a catalyst (see Example 1). When H-ZSM-5 with a molar ratio of 150 was used as a catalyst, it showed low acrolein selectivity.

Comparative Example 4

Using a H-b having a high silica-alumina mole ratio of 25 in the zeolite catalyst as a catalyst, a reaction of synthesizing acrolein by dehydration of glycerol was carried out in the same manner as in Example 3. The results are shown in Table 8 below.

catalyst Silica-alumina molar ratio Water content
(mole%) Reaction temperature (℃) Glycerol
Conversion rate
(%) Selectivity (%) Acrolein 1-hydroxy
Acetone Acet
Aldehyde H-b 25 91.7 290 60.1 48.6 4.2 2.4 H-b 25 91.7 340 95.2 46.9 8.3 18.9

As shown in Table 8, compared with the reaction using a zeolite having an H-peririte structure having a silica-alumina mole ratio of 55 as a catalyst (see Example 3), Hb having a silica-alumina mole ratio of 25 was used as a catalyst. In the case of low acrolein selectivity, it was confirmed that the acrolein selectivity decreases with increasing temperature.

From the results of the above examples and comparative examples, in the case of using a zeolite having an H-peririte structure having a specific silica-alumina molar ratio in the zeolite compound as a catalyst, conventionally known H-ZSM-5, Hb, H-mordenite, HY Shows higher acrolein selectivity over a wider range of reaction temperature ranges compared to the use of, gamma alumina (g-Al ₂ O ₃ ), silica-alumina (SiO ₂ -Al ₂ O ₃ ), and silica (SiO ₂ ) as catalysts can confirm.

All simple modifications and variations of the present invention fall within the scope of the present invention, and the specific scope of the present invention will be apparent from the appended claims.

Claims (10)

delete A method for producing acrolein comprising a step of dehydrating a glycerol in the presence of a catalyst comprising a zeolite having an H-peririte structure. The method of claim 2,
The zeolite having the H- ferrierite structure is a molar ratio of silica: alumina 1000: 1 to 10: 1 method for producing acrolein. The method of claim 2,
The content of the zeolite having the H- ferrierite structure is 1 to 100% by weight of the total catalyst is acrolein production method. The method of claim 2,
The zeolite having the H- ferrierite structure additionally comprises the step of heat treatment (pretreatment) NH ₄ -ferrilite at a reaction temperature of 200 to 900 ℃. The method of claim 2,
The H-ferrierite is acrolein production method is one or more selected from the group consisting of alkali metals, alkaline earth metals and lanthanide metals are ion-exchanged. The method of claim 6, wherein the alkali metal is at least one selected from the group consisting of potassium (K), lithium (Li), sodium (Na), rubidium (Rb), cesium (Cs) and Fr (franzium), The alkaline earth metal is at least one selected from the group consisting of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra), and the lanthanum-based metal is lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), erbium (Er), thulium (TM), ytterbium (Yb), and lutetium (Lu) at least one selected from the group consisting of acrolein. The method of claim 2, wherein the dehydration reaction is carried out in a continuous gas phase, fluidized bed gas phase or batch liquid phase mode. The method of claim 2, wherein the dehydration reaction is a molar ratio of glycerol: water of 1: 0.5 to 1: 100. The method of claim 2, wherein the dehydration reaction is carried out at a temperature of 220 to 380 ℃ acrolein production method.