KR101827626B1 - Method for manufacturing formaldehyde from methanol and formaldehyde manufactured by the same - Google Patents

Abstract

The present invention relates to a process for the production of formaldehyde from methanol and a process for the production of formaldehyde from methanol according to an embodiment of the present invention comprises the step of dehydrogenating methanol in the presence of a catalyst and carbon dioxide .

Description

METHOD FOR MANUFACTURING FORMALDEHYDE FROM METHANOL AND FORMALDEHYDE MANUFACTURED BY THE SAME, PROCESS FOR PRODUCING FORMALDEHYDES FROM METHANOL AND METHOD FOR PRODUCING THE SAME,

The following examples relate to a process for the production of formaldehyde from methanol and formaldehyde prepared by the process.

Since formaldehyde has high reactivity, it is used in various fields of daily life such as melamine resin, paper, and paint. Most formaldehyde is synthesized through the dehydrogenation reaction of methanol, and the amount of methanol used and the amount of formaldehyde generated through the dehydrogenation reaction of methanol are increasing year by year.

There are various types of catalysts used for the dehydrogenation reaction of methanol, such as the Dynea process using silver (Ag) catalyst and the Formox AB process using molybdenum oxide (MoO) containing iron (Fe). Silver catalysts have a disadvantage in that the yield of formaldehyde reaches about 95%, which is very high. However, since the reaction proceeds at a high temperature of more than 600 ° C, catalyst activity is easily lowered and the lifetime is short. On the other hand, the process using iron-containing molybdenum oxide catalysts accounts for about 70% of the currently known formaldehyde production process. Molybdenum oxide catalysts containing iron have a problem of excessive energy use and explosion risk because they require a high oxygen partial pressure although the reaction proceeds at a relatively low temperature (350 ° C. to 450 ° C.) The risk of explosion of the formaldehyde-generating plant can be identified. Because the dehydrogenation process of methanol is an exothermic reaction, the sublimation of molybdenum metal species used in the Formox AB process is still a drawback.

In order to solve this problem, various industrial and academic methods have been tried. The Santacesaria research team tried to overcome the problems of the existing process by using a relatively low-cost and highly reactive metal catalyst such as copper (Cu) or zinc (Zn) instead of expensive metals such as silver (Ag) or palladium (Pd) Deng researchers succeeded in increasing the yield of formaldehyde by modifying the shape of the catalyst or the shape of the catalyst carrier. However, it is known that the acid sites of catalyst metal species that produce byproducts with the instability of these catalysts are still to be overcome. To date, the reaction conditions of high reaction temperature or high oxygen partial pressure in the dehydrogenation reaction of methanol have been improved, There has been no attempt to introduce a process for suppressing the generation of the process.

According to U.S. Patent No. 6,958,427, the effect of increasing the selectivity of the product can be confirmed by using carbon dioxide in the process of producing a styrene monomer from ethylbenzene. At this time, it has been experimentally proven that carbon dioxide can reduce the by-products resulting from low oxidizing power through the role of soft oxidant. In the case of the domestic patent KR 10-2015-0088668, even when carbon dioxide was introduced into the aromaticization process of isobutanol, the yield of the aromatic compound was improved and the effect of reducing the production of coke during the reaction was obtained. In other words, these two examples suggest that carbon dioxide can play a particular role in chemical reactions.

However, introduction of formaldehyde generation process through introduction of a catalyst system suppressing the acidic point of the metal species and having basicity has not yet been attempted with the use of carbon dioxide for the dehydrogenation reaction.

One embodiment relates to a process for the production of formaldehyde from methanol and a process for the production of formaldehyde which is capable of increasing the methanol conversion, formaldehyde selectivity and formaldehyde yield by dehydrogenating the methanol at a relatively low reaction temperature to provide.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

According to one embodiment, there is provided a process for the production of formaldehyde from methanol comprising the step of dehydrogenating methanol in the presence of a catalyst and carbon dioxide.

According to one aspect, the step of dehydrogenating methanol in the presence of the catalyst and carbon dioxide comprises: injecting the methanol into the reactor; Injecting the carbon dioxide into the reactor; Reacting the methanol with the carbon dioxide in the presence of the catalyst to produce formaldehyde; And recovering the resultant formaldehyde.

According to one aspect, the molar ratio of the carbon dioxide to the methanol may be 0.001 to 0.2.

According to one aspect, the reaction may be performed at a reaction temperature of 300 ° C or more and less than 600 ° C.

According to one aspect, the reaction may be performed at a reaction pressure of 0.1 atm to 2 atm.

According to one aspect, the reaction may be such that the weight hourly space velocity (WHSV) of the methanol per weight of the catalyst per hour is from 0.01 h ^-1 to 0.7 h ^-1 .

According to one aspect, the catalyst may be a metal or a metal oxide supported on a carrier.

According to one aspect, the carrier may comprise at least one selected from the group consisting of silica, alumina, titania, barium titania, ceria, germania, manganese, magnesia, zirconia and niobia.

According to one aspect, the specific surface area of the carrier may be 200 m ² / g to 1,200 m ² / g.

According to one aspect, the carrier may be one which comprises mesopores of 5 nm to 200 nm in size.

According to one aspect, the metal or metal oxide may be at least one selected from the group consisting of cesium, sodium, barium, magnesium, palladium, platinum, silver, nickel, (V), molybdenum (Mo), tin (Sn), lithium (Li), potassium (K), ruthenium (Ru), calcium (Ca), lanthanum (La), praseodymium (Pr) and cerium And at least one metal or metal oxide selected from the group consisting of metal oxides.

According to one aspect, the metal or metal oxide in the catalyst may be 0.1 wt% to 30 wt%.

According to another embodiment, formaldehyde prepared by the process for the production of formaldehyde from methanol according to one embodiment is provided.

According to one aspect, the formaldehyde may have a selectivity of at least 30%.

In one embodiment, through the introduction of carbon dioxide into the formaldehyde production process using methanol, the methanol conversion, formaldehyde selectivity and yield can be increased in the dehydrogenation reaction system, and formaldehyde Production can be further improved. In addition, the production cost can be lowered through the use of an inexpensive metal catalyst used industrially, and carbon dioxide, which is higher in atmospheric concentration due to global warming, can be used to produce more effective formaldehyde, thereby securing economical efficiency. In addition, the use of carbon dioxide with low oxidizing power can increase the stability in the formaldehyde production process where the possibility of explosion is remarkable.

1 is a flow chart illustrating a process for producing formaldehyde from methanol according to one embodiment.
Figure 2 is a second embodiment of magnesium according to - the inert gas helium (He) in accordance with the silica (Mg-SiO ₂₎ When using carbon dioxide (CO ₂₎ at a reaction temperature of 400 ℃ by using the catalyst in a flow of gas and Comparative Example 2 And the methanol conversion rate when used as a flow gas.

Hereinafter, embodiments according to the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to or limited by the embodiments. In addition, the same reference numerals shown in the drawings denote the same members.

Also, terminologies used herein are terms used to properly represent preferred embodiments of the present invention, which may vary depending on the viewer, the intention of the operator, or the custom in the field to which the present invention belongs. Therefore, the definitions of these terms should be based on the contents throughout this specification.

Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise.

Hereinafter, the method for producing formaldehyde from methanol of the present invention and the formaldehyde prepared by the method will be described in detail with reference to examples and drawings. However, the present invention is not limited to these embodiments and drawings.

According to one embodiment, there is provided a process for the production of formaldehyde from methanol comprising the step of dehydrogenating methanol in the presence of a catalyst and carbon dioxide.

The method for producing formaldehyde from methanol according to an embodiment of the present invention is a method for converting formaldehyde into formaldehyde by conducting a dehydrogenation reaction between methanol and a catalyst in a flow gas of carbon dioxide to convert methanol into formaldehyde. Partial removal can improve the selectivity of formaldehyde. By applying carbon dioxide in the methanol dehydrogenation reaction, the equilibrium conversion of the dehydrogenation reaction can be improved and increased activity can be obtained.

According to one aspect, the step of dehydrogenating methanol in the presence of the catalyst and carbon dioxide comprises the steps of: injecting the methanol into the reactor with a flow gas; Injecting the carbon dioxide into the reactor; Reacting the methanol with the carbon dioxide in the presence of the catalyst to produce formaldehyde; And recovering the resultant formaldehyde.

1 is a flow chart illustrating a process for producing formaldehyde from methanol according to one embodiment. Referring to FIG. 1, a process for preparing formaldehyde from methanol according to an embodiment includes a methanol injection step (S110), a carbon dioxide injection step (S120), a formaldehyde generation step (S130), and a formaldehyde recovery step (S140) .

According to one aspect, the methanol injection step (S110) injects the methanol into the reactor with a flow gas. The methanol may be pure methanol, industrial methanol, crude methanol produced by the high-pressure or low-pressure process, or a mixture of these and water. For aqueous mixtures, the methanol concentration in the aqueous mixture may be from 60% to 95% by weight. For example, the crude methanol may be subjected to the removal of the low boiling fraction according to the process described in DE-B-12 77 834, DE-C-12 35 881 and DE-C 11 36 318, or to the oxidation and / .

According to one aspect, the carbon dioxide injection step (S120) injects the carbon dioxide into the reactor and mixes the carbon dioxide with the methanol. The carbon dioxide may be used directly without purifying the high purity product or the carbon dioxide by-product discharged from the petrochemical oxidation reaction process. The carbon dioxide can be recycled without further purification, which is advantageous in securing economical efficiency.

According to one aspect, the molar ratio of the carbon dioxide to the methanol may be 0.001 to 0.2. If the molar ratio is less than 0.001, the dehydrogenation reaction due to the methanol and the carbon dioxide does not sufficiently occur. If the molar ratio is more than 0.2, the side reaction due to the dehydrogenation reaction easily occurs, and the selectivity of formaldehyde is lowered.

According to one aspect, in the formaldehyde generating step (S130), formaldehyde is produced by reacting the flow gas methanol with the carbon dioxide in the presence of the catalyst. In this case, the reaction is a dehydrogenation reaction, and methanol may be converted to formaldehyde from the dehydrogenation reaction.

According to one aspect, the reaction may be performed at a reaction temperature of 300 ° C or more and less than 600 ° C. If the reaction temperature is lower than 300 ° C, methanol and carbon dioxide are not activated, resulting in no catalytic activity. When the reaction temperature is higher than 600 ° C, the catalyst activity is low and a side reaction such as cracking reaction tends to occur. There is a problem of lowering the selectivity of aldehyde. The dehydrogenation reaction temperature of methanol can exhibit sufficient catalytic activity even at a low reaction temperature as compared with the conventional method.

According to one aspect of the present invention, the carbon dioxide can prolong the lifetime of the catalyst by removing the coke accumulated on the catalyst surface in the dehydrogenation reaction, and induce the reaction with hydrogen to be released from methanol, so that, as in an oxidative dehydrogenation reaction using oxygen, So that the equilibrium conversion rate can be greatly improved. Therefore, when the reaction is carried out together with the catalyst promoting the dehydrogenation reaction in the presence of carbon dioxide, formaldehyde can be produced in an energy saving mode, and the lifetime of the catalyst can be increased. In addition, carbon dioxide emissions from petrochemical processes can be recycled when used in a hydrocarbon dehydrogenation reaction, and the stability of formaldehyde generation process, in which the possibility of explosion is prominent through the use of low-oxidizing carbon dioxide, is increased .

According to one aspect, the reaction may be performed at a reaction pressure of 0.1 atm to 2 atm. If the reaction pressure is less than 0.1 atm, the conversion to formaldehyde decreases. If the reaction pressure exceeds 2 atm, the temperature in the reactor rises and the catalyst activity decreases.

According to one aspect, the reaction may be such that the weight hourly space velocity (WHSV) of the methanol per weight of the catalyst per hour is from 0.01 h ^-1 to 0.7 h ^-1 . When the weight hourly space velocity (WHSV) is less than 0.01 hr <" ¹ >, there is a problem that the selectivity of formaldehyde is lowered due to an atmosphere in which the cracking reaction in which the product is transferred to the secondary reaction, If it exceeds 0.7 hr < ^{-1 &} gt ;, there is a problem that it is easily produced as a component having a low molecular weight.

According to one aspect of the present invention, a catalyst having no acid sites can be used in order to ignore the diffusion resistance in the dehydrogenation reaction, since the catalyst can be selected to enable the dehydrogenation reaction using the carbon dioxide. A basic catalyst may be used for increasing the activity and stability of the catalyst.

According to one aspect, the catalyst may be a metal or a metal oxide supported on a carrier. The catalyst may have an active component such as a metal or a metal oxide supported on a meshed structure having a large surface area. When the metal or the metal oxide is supported on the support, the alkali acts as an active component in the catalyst, neutralizes the active site, and can generate a base point. It can also act as an electronic factor.

According to one aspect, the carrier may comprise at least one selected from the group consisting of silica, alumina, titania, barium titania, ceria, germania, manganese, magnesia, zirconia and niobia. Preferably, silica having no diffusion resistance and little acid point can be used as the carrier.

According to one aspect, the carrier may have a crystal lattice having all crystal structures such as gamma, theta and alpha. The carrier is excellent in the ability to adsorb metals or metal oxides, and is excellent in conversion and selectivity. The carrier may be in the form of an aerosol.

According to one aspect, the specific surface area (Brunauer, Emmett and Teller; BET) of the carrier may be 200 m ² / g to 1,200 m ² / g. When the specific surface area of the support is less than 200 m ² / g, it is difficult to exhibit the performance as a catalyst because it can not support a large amount of active components such as metal or metal oxide. In the case of more than 1,200 m ² / g, A metal or a metal oxide is supported, and the speed of caulking is very fast. For example, the silica support has a high specific surface area of 200 m ² / g or more even after the heat treatment at 1,000 ° C, and such a high specific surface area can have a high dispersion degree when the metal or metal oxide is supported. The volume and pore size of the support can be a key factor in determining the mass transfer coefficient of reactants and products.

According to one aspect, the carrier may be one which comprises mesopores of 5 nm to 200 nm in size. Since the diffusion resistance of a substance determines the overall reaction rate in the case of a high chemical reaction rate, a structure having a large pore size is advantageous in maintaining the activity of the catalyst high. When the size of the mesopores of the support is less than 5 nm, the mass transfer rate is lowered by Knudsen diffusion and the reaction activity is decreased. In addition, when a carrier having a large pore size is used, it is insensitive to the accumulation of coke and thus is advantageous for maintaining catalytic activity. However, when the size of mesopores of the carrier exceeds 200 nm, There is a problem of lowering.

According to one aspect, the metal or metal oxide may be at least one selected from the group consisting of cesium, sodium, barium, magnesium, palladium, platinum, silver, nickel, (V), molybdenum (Mo), tin (Sn), lithium (Li), potassium (K), ruthenium (Ru), calcium (Ca), lanthanum (La), praseodymium (Pr) and cerium And at least one metal or metal oxide selected from the group consisting of metal oxides.

According to one aspect, the metal or metal oxide may include one metal or metal oxide, or may include two or more metals or metal oxides in a composite form. In the case of containing one kind of metal, a catalyst in which barium is supported on a silica support (Ba-SiO ₂ ) and a catalyst in which magnesium is supported on a silica support (Mg-SiO ₂ ) are exemplified. When two kinds of metals are contained in the form of a composite, a catalyst (Cu-Cs-SiO ₂ ) carrying copper and cesium on a silica carrier, and a catalyst (V-Ce-SiO ₂ ) carrying vanadium and cerium have. When the above two or more complexes are included, there is an effect of having high methanol conversion and formaldehyde selectivity.

According to one aspect, the metal or metal oxide in the catalyst may be 0.1 wt% to 30 wt%. If the amount of the metal or the metal oxide is less than 0.1 wt%, the catalytic activity is poor. If the amount of the metal or metal oxide is more than 30 wt%, the durability of the catalyst may be increased, but the dehydrogenation efficiency may be low.

According to one aspect, the formaldehyde recovery step (S140) is to recover the formaldehyde generated through the dehydrogenation reaction. Formaldehyde, a product of dehydrogenation of methanol, and dimethyl ether, a product of dehydrogenation, can be separated from each other through a condensation-separation process and purified through a distillation process. The dehydrogenation reaction can continuously produce formaldehyde by maintaining the initial activity even after a long period of reaction.

Through the introduction of carbon dioxide into the process for the production of formaldehyde using methanol in accordance with the process for the production of formaldehyde from methanol according to one embodiment, the conversion of methanol, selectivity and yield of formaldehyde in the dehydrogenation reaction can be increased So that it is possible to develop the production of formaldehyde, which is synthesized by a cyclic process. In addition, it is possible to reduce the production cost through the use of an inexpensive metal catalyst which is industrially used, and it is possible to secure economical efficiency by making it possible to manufacture more effective formaldehyde by utilizing carbon dioxide which is higher in atmospheric concentration due to global warming Can be proved. In addition, the use of carbon dioxide with low oxidizing power can increase the stability in the formaldehyde production process where the possibility of explosion is remarkable.

According to another embodiment, formaldehyde prepared by the process for the production of formaldehyde from methanol according to one embodiment is provided.

The formaldehyde prepared by the process for the production of formaldehyde from methanol according to an embodiment can have a high methanol conversion, formaldehyde selectivity and formaldehyde yield.

The methanol conversion can be calculated by the following equation (1).

[Equation 1]

In the above formula (1), A is the concentration (wt%) of the methanol to be injected and B is the concentration (wt%) of the methanol remaining after the reaction.

According to one aspect, the formaldehyde may have a selectivity of at least 30%.

The formaldehyde selectivity can be calculated by the following equation (2).

&Quot; (2) "

Wherein B is the concentration (% by weight) of methanol remaining after the reaction and C is the concentration (% by weight) of the formaldehyde produced through the reaction .

The formaldehyde yield can be calculated by the following equation (3).

&Quot; (3) "

In the above formula (3), A is the concentration (wt%) of the methanol to be injected and C is the concentration (wt%) of the formaldehyde produced through the reaction.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the technical idea of the present invention is not limited or limited thereto.

[Example 1]

A mesoporous silica catalyst (Ba-SiO ₂ ) carrying a barium metal oxide was prepared by supporting a barium (Ba) ion precursor on the prepared mesoporous silica (SiO ₂ ) and firing at 550 ° C. Methanol was vaporized and injected into the prepared barium-silica (Ba-SiO ₂ ) catalyst to maintain a weight hourly space velocity (WHSV) of 0.22 h ^-1 . The reaction was pre-treated at 500 ° C for 30 minutes in an inert gas (He) atmosphere before the reaction, and the reaction temperature was kept constant at 400 ° C, 425 ° C, 450 ° C and 475 ° C, respectively. During the reaction, fresh carbon dioxide (a mixture of carbon dioxide and helium, expressed as CO ₂ ) was flowed as a flow gas and the selectivity of each formaldehyde was confirmed. The gas after the reaction was analyzed by gas chromatography (GC).

[Example 2]

A mesoporous silica catalyst (Mg-SiO ₂ ) carrying a magnesium metal oxide was prepared by supporting a magnesium (Mg) ion precursor on a prepared mesoporous silica (SiO ₂ ) catalyst and firing at 550 ° C. The reaction and reaction analysis were carried out under the same conditions as in Example 1, except that the mesoporous silica catalyst (Mg-SiO ₂ ) carrying magnesium metal oxide was used.

[Example 3]

Copper (Cu) and cesium (Cs) ion precursor mesoporous silica prepared a (SiO ₂₎ is supported on the catalyst, and copper are then fired at 550 ℃ - cesium metal oxide-carrying the mesoporous silica catalyst (Cu-Cs-SiO ₂₎ Were prepared. Reaction and reaction analysis were carried out under the same conditions as in Example 1, except that a mesoporous silica catalyst (Cu-Cs-SiO ₂ ) carrying copper-cesium metal oxide was used.

[Example 4]

Vanadium (V) and cerium (Ce) ion mesoporous silica prepared precursors (SiO ₂₎ and supported on the catalyst, and calcined at 550 ℃ vanadium-cerium metal oxide is impregnated mesoporous silica catalyst (V-Ce-SiO ₂₎ Were prepared. Methanol was vaporized and injected into the prepared vanadium-cerium-silica (V-Ce-SiO ₂ ) catalyst to maintain a weight hourly space velocity (WHSV) of 0.53 h ^-1 . The catalysts were pre-treated at 500 ° C. for 30 minutes in an inert gas (He) atmosphere. The reaction temperature was maintained at 375 ° C., 400 ° C., 425 ° C. and 450 ° C., respectively. During the reaction, fresh carbon dioxide (99.9% CO ₂ ) was flowed as a flow gas and the selectivity of formaldehyde was confirmed. The gas after the reaction was analyzed by gas chromatography (GC).

[Comparative Example 1]

Except that inert gas helium (He) was used instead of carbon dioxide (CO ₂ ) as a flow gas during the reaction.

[Comparative Example 2]

Except that inert gas helium (He) was used instead of carbon dioxide (CO ₂ ) as a flow gas during the reaction.

[Comparative Example 3]

Except that inert gas helium (He) was used instead of carbon dioxide (CO ₂ ) as a flow gas during the reaction.

[Comparative Example 4]

Except that inert gas helium (He) was used instead of carbon dioxide (CO ₂ ) as a flow gas during the reaction.

Table 1 below shows the selectivities of formaldehyde and dimethyl ether of Examples 1 to 4 and Comparative Examples 1 to 4. Table 1 compares the selectivities of formaldehyde and dimethyl ether in the case of using carbon dioxide (CO ₂ ) as a flow gas and the case of using an inert gas (He) as a flow gas, -SiO ₂₎ a catalyst at a reaction temperature of 425 ℃, magnesium-silica (Mg-SiO2) catalyst and a copper-cesium-silica (Cu-Cs-SiO ₂₎ catalyst at 400 ℃ reaction temperature, vanadium-cerium-silica (V -Ce-SiO ₂ ) catalyst showed that methanol and carbon dioxide (CO ₂ ) were in contact with each other at a reaction temperature of 375 ° C. Formaldehyde, a product of dehydrogenation of methanol, and hydrocarbons, including dimethyl ether and other by-products, are products of dehydration.

catalyst
(Reaction temperature) Formaldehyde selectivity (%) Dimethyl ether selectivity (%) CO ₂ He CO ₂ He Ba-SiO ₂
(425 DEG C) 73.4
(Example 1) 63.4
(Comparative Example 1) 2.9
(Example 1) 2.5
(Comparative Example 1) Mg-SiO ₂
(400 ° C) 53.7
(Example 2) 49.1
(Comparative Example 2) 32.0
(Example 2) 28.9
(Comparative Example 2) Cu-Cs-SiO ₂
(400 ° C) 43.6
(Example 3) 24.8
(Comparative Example 3) 11.7
(Example 3) 1.9
(Comparative Example 3) V-Ce-SiO ₂
(375 DEG C) 32.7
(Example 4) 23.7
(Comparative Example 4) 5.4
(Example 4) 5.1
(Comparative Example 4)

Referring to Table 1, when the inert gas helium (He) was used as the flow gas in the barium-silica (Ba-SiO2) catalyst system in Comparative Example 1, the selectivity of formaldehyde was 63.40% CO ₂ ) was used as the flow gas, the selectivity of formaldehyde was as high as 73.4%. It can be confirmed that the dehydrogenation reaction of methanol shows a selectivity increase of about 10% when carbon dioxide (CO ₂ ) is used as the flow gas. The increase in the selectivity of formaldehyde in the above-mentioned carbon dioxide (CO ₂ ) is due to the increase in the selectivity of magnesium-silica (Mg-SiO ₂ ), copper-cesium-silica (Cu-Cs-SiO ₂ ), vanadium- Ce-SiO ₂ ) catalysts, showing an increase of 4.5%, 18.8% and 8.97%, respectively. It can be seen that when using the same catalyst at the same reaction temperature, the selectivity is better when carbon dioxide (CO ₂ ) is used than when inert gaseous helium (He) is used as the flow gas.

Figure 2 is a second embodiment of magnesium according to - the inert gas helium (He) in accordance with the silica (Mg-SiO ₂₎ When using carbon dioxide (CO ₂₎ at a reaction temperature of 400 ℃ by using the catalyst in a flow of gas and Comparative Example 2 And the methanol conversion rate when used as a flow gas. At this time, it can be seen that the conversion rate of methanol is increased when carbon dioxide (CO ₂ ) is injected than in the case of inert gas helium (He).

Through the comparative experiments of Examples 1 to 4 and Comparative Examples 1 to 4, it was confirmed that the selectivity of formaldehyde was greatly increased when carbon dioxide (CO ₂ ) was injected into the flow gas, (Ba-SiO ₂ ) catalyst, the selectivity of formaldehyde was remarkably excellent at 73.4%.

While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined by the equivalents of the claims, as well as the claims.

Claims (14)

Catalyst and dehydrogenation reaction of methanol in the presence of carbon dioxide
Lt; / RTI >
The catalyst is a metal or metal oxide supported on a carrier,
The metal or metal oxide may be at least one selected from the group consisting of cesium, sodium, barium, magnesium, palladium, platinum, silver, nickel, vanadium, Selected from the group consisting of molybdenum (Mo), tin (Sn), lithium (Li), potassium (K), ruthenium (Ru), calcium (Ca), lanthanum (La), praseodymium (Pr) and cerium At least one metal or metal oxide,
The reaction is carried out at a reaction temperature of 300 ° C or more and less than 600 ° C
Wherein the molar ratio of the carbon dioxide to the methanol is 0.001 to 0.2,
Wherein the step of reacting comprises:
Reacting the methanol with the carbon dioxide in the presence of the catalyst to produce formaldehyde having a selectivity of at least 30%.
The method according to claim 1,
The dehydrogenation reaction of methanol in the presence of the catalyst and carbon dioxide comprises:
Injecting the methanol into the reactor;
Injecting the carbon dioxide into the reactor;
Reacting the methanol with the carbon dioxide in the presence of the catalyst to produce formaldehyde; And
Recovering the resultant formaldehyde;
≪ / RTI > wherein the reaction is carried out in the presence of formaldehyde.
delete delete The method according to claim 1,
Wherein the reaction is carried out at a reaction pressure of from 0.1 atm to 2 atmospheres.
The method according to claim 1,
The reaction process for producing formaldehyde from the methanol to a weight space velocity (WHSV) of the weight per hour of methanol per the catalyst is carried out at 0.01 h ^-1 to 0.7 h ^-1.
delete The method according to claim 1,
Wherein the carrier comprises at least one selected from the group consisting of silica, alumina, titania, barium titania, ceria, germania, manganese, magnesia, zirconia and niobia.
The method according to claim 1,
Wherein the specific surface area of the carrier is 200 m ² / g to 1,200 m ² / g.
The method according to claim 1,
Wherein the carrier comprises mesopores of a size between 5 nm and 200 nm.
delete The method according to claim 1,
Wherein the metal or metal oxide in the catalyst is from 0.1 wt% to 30 wt%.
delete delete

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