KR20190053339A - Method of producing methanol - Google Patents

Abstract

A method for manufacturing methanol according to the present invention comprises steps of: providing a first reaction gas containing methane to a reactor in which a copper-containing zeolite is disposed, to make contact of the copper-containing zeolite and methane; providing a second reaction gas comprising water vapor to the reactor; and obtaining methanol at the time when the second reaction gas is discharged from the reactor. According to the present invention, methanol can be directly obtained from methane using the copper-containing zeolite as a catalyst.

Description

[0001] METHOD OF PRODUCING METHANOL [0002]

The present invention relates to a method for producing methanol, and more particularly, to a method for producing methanol with improved productivity in methanol production.

Methanol itself is widely used as a chemical product, and it can be converted to basic fuels such as dimethyl ether, gasoline and ethylene or propylene through additional chemical processes. At present, methanol is produced from synthesis gas, which is a mixture of carbon monoxide and hydrogen, through a high pressure reaction using a catalyst containing copper (Cu). Syngas is produced by a gasification reaction such as coal or biomass Or a steam reforming reaction in which methane is reacted with water vapor at a high temperature. Therefore, methanol has a disadvantage in that a large amount of energy costs are incurred because it is subjected to various high-temperature / high-pressure processes in order to produce methanol.

In addition, there is a technique of selectively oxidizing methane in a temperature range of 350 ° C to 550 ° C in the vapor phase using silicon metallate molecular sieve containing iron (Fe), but using nitrogen oxide (N ₂ O) which is an expensive oxidizer And there is a disadvantage in that the selectivity and yield are very low when oxygen is directly used. However, the use of oxygen (O ₂ ) as an oxidizing agent makes it difficult to control the complexity of the process which requires alternating gas / oxygen / methane / water vapor at high temperature. Lt; / RTI >

In addition, there is a technology for producing methanol by oxidizing methane by using hydrogen peroxide in a liquid phase using zeolite containing copper or iron, but disadvantage of using expensive hydrogen peroxide and low yield are disadvantageous.

It is an object of the present invention to provide a method for producing methanol which can improve productivity in methanol production by directly converting methane to methanol through a gas phase reaction under a low temperature condition without using an oxidizing agent .

The method for producing methanol for one purpose of the present invention comprises the steps of: providing a first reaction gas comprising methane to a reactor in which a copper containing zeolite is disposed, thereby contacting the copper containing zeolite with methane; Providing a second reaction gas comprising water vapor to the reactor; And obtaining methanol at the time when the second reaction gas is discharged from the reactor.

In one embodiment, the first reaction gas may further comprise a saturated hydrocarbon compound having 2 to 6 carbon atoms.

In one embodiment, the second reaction gas may further include at least one of oxygen, carbon dioxide, and nitrogen.

In one embodiment, each of the steps of the method for producing methanol may be performed at 200 ° C to 450 ° C, and each of the steps may be performed at a pressure of from atmospheric pressure to 30 atmospheres.

A method for producing methanol for one purpose of the present invention comprises the steps of: providing a third reaction gas containing both methane and water vapor to a reactor in which a copper-containing zeolite is disposed; And contacting the copper-containing zeolite with the third reaction gas to produce methanol.

In one embodiment, the third reaction gas may further include at least one of a saturated hydrocarbon compound having 2 to 6 carbon atoms, oxygen, carbon dioxide, and nitrogen.

In one embodiment, each of the steps of the method for producing methanol may be performed at 200 ° C to 350 ° C, and each of the steps may be performed at a pressure of from atmospheric pressure to 30 atmospheres.

According to the present invention described above, methanol can be directly obtained from methane using a copper-containing zeolite as a catalyst. In addition, the process of converting methane to methanol can produce methanol at a high selection through a gas phase reaction at a low temperature, which is advantageous in that the production of methanol can be improved more than that used in a conventional high temperature process.

1 is a view for explaining a method for producing methanol according to the present invention.
Fig. 2 is a view for explaining a reaction occurring in the reactor of Fig. 1; Fig.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the term " comprises " or " having ", etc. is intended to specify that there is a feature, step, operation, element, part or combination thereof described in the specification, , &Quot; an ", " an ", " an "

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

1 is a view for explaining a method for producing methanol according to the present invention.

Referring to FIG. 1 (a), a method for producing methanol according to an embodiment of the present invention includes providing a first reaction gas containing methane to a reactor in which a copper-containing zeolite is disposed, ; Providing a second reaction gas comprising water vapor to the reactor; And obtaining methanol at the time when the second reaction gas is discharged from the reactor. At this time, the first reaction gas may further include a saturated hydrocarbon compound having 2 to 6 carbon atoms in addition to methane. The second reaction gas may further include at least one of oxygen, carbon dioxide, and nitrogen in addition to steam.

Referring to FIG. 1 (b), a method for producing methanol according to another embodiment of the present invention includes the steps of: providing a third reaction gas containing both methane and steam in a reactor in which copper-containing zeolite is disposed; And contacting the copper-containing zeolite with the third reaction gas to produce methanol. At this time, the third reaction gas may further include at least one of a saturated hydrocarbon compound having 2 to 6 carbon atoms, oxygen, carbon dioxide, and nitrogen.

The copper-containing zeolite used for the production of methanol in the present invention means a zeolite carrying copper on a zeolite having a structure such as MOR, EON, MAZ, MEI, BPH, FAU, LTL MFI, HEU, FER, SZR and CHA , Where the metal cation of the zeolite may be obtained by ion exchange with copper ions.

In one embodiment, the copper containing zeolite may be Cu-SSZ-13 or Cu-MOR (Cu-mordenite). Such a copper-containing zeolite is advantageous in that it can be economically advantageous compared with the use of a noble metal because the copper-containing zeolite is cheaper than the noble metal and has a high catalytic activity for methanol production.

The temperature of the reactor in which the first reaction gas and the second reaction gas are provided or the reactor in which the third reaction gas is provided may be performed at a low temperature condition of 200 ° C to 500 ° C. Accordingly, the reaction temperature at which methanol is produced may be a low temperature condition of 200 ° C to 500 ° C. When the reaction temperature is lower than 200 ° C, there is a problem that the amount of methanol to be obtained is insufficient due to low reaction yield. In order to convert methane directly to methanol as in the present invention, the reaction is preferably carried out at a temperature of at least 200 ° C Do. When the reaction temperature is higher than 500 ° C, the effect of the high-temperature energy on the conversion of methane to methanol is insignificant, so there is a limit to the yield of methanol that can be obtained with respect to the cost of the process, Is preferably set to 500 DEG C or less. That is, setting the reaction temperature to 200 to 500 ° C can maximize the effect of improving economical efficiency in the production of methanol.

In one embodiment, when the first reaction gas and the second reaction gas are used, the reaction temperature may be 200 ° C to 450 ° C.

In one embodiment, when the third reaction gas is used, the reaction temperature may be 200 ° C to 350 ° C.

In one embodiment, the reaction temperature at which methane is converted to methanol and the extraction temperature at which methanol is extracted may be substantially the same.

In one embodiment, the pressure conditions during the reaction in which methane is converted to methanol may be atmospheric pressure and 30 atmospheres (atm).

Fig. 2 is a view for explaining a reaction occurring in the reactor of Fig. 1; Fig.

Referring to FIG. 2, the limited size of the pores of the copper-containing zeolite (Cu-SSZ-13) used in the method for producing methanol according to the present invention and well-defined ion exchange sites stabilize bivalent copper ions. This copper ion reacts with methane to generate methoxy (methodxy) and hydrogen (hydrogen). Methanol is produced from methoxy by the supplied water (H ₂ O). According to the results of the X-ray analysis, it was confirmed that the coordination of oxygen around the copper metal was 3, and the bivalent copper ion stably existed in the process of methanol formation by the reaction of methane and water.

According to the present invention, a copper-containing zeolite is provided as a catalyst based on the principle described in FIG. 2 as a catalyst to provide a first reaction gas containing methane, and then a second reaction gas containing water vapor is provided. Methanol can be obtained constantly through contact with the catalyst. The same principle, methane and water vapor can be provided simultaneously for the copper-containing zeolite to easily obtain methanol.

The above-described method for producing methanol according to the present invention will be described in more detail with reference to the following specific examples. It is to be noted, however, that the present invention is not limited to the following embodiments.

Production Example 1: Preparation of Catalyst 1 (Cu-SSZ-13)

After dissolving NaOH in distilled water, zeolite USY containing aluminum oxide and silica (in this case, SiO ₂ / Al ₂ O ₃ molar ratio = 30) was added and mixed until a homogeneous solution was obtained. Benzyltrimethylammonium hydroxide (SDA1) was added to the mixed solution and mixed until a homogeneous solution was obtained. Thus, a hydrogel (hydrogel) having a molar ratio of SiO ₂ : NaOH: SDA 1: H ₂ O = 1: 0.2: 0.2: ).

The hydrogel was hydrothermally synthesized for 4 to 10 days while rotating at 140 ° C at 20 to 60 rpm. The sample was recovered by centrifugal separation, air was flown and maintained at 400 ° C for 3 hours to obtain a catalyst (Na-SSZ- 13).

Thereafter, ion exchanging was performed in a liquid phase using 1 M ammonium chloride aqueous solution, and air was flowed thereinto and kept at 400 ° C for 3 hours to obtain a catalyst (H-SSZ-13).

After dissolving 2.7667 g of Copper (Ⅱ) acetate monohydrate (Cu (Ac) ₂ H ₂ O, Junsei Chem.) In 1365 mL of distilled water, 17.5 g of H-SSZ-13 was added and the copper was stirred for 24 hours at 450 rpm -SSZ-13. ≪ / RTI > After vacuum filtration without additional distilled water, it was dried at about 110 ° C for more than 12 hours. This process was repeated two more times and three times of ion exchange was performed. In the last filtration, 750 ml of distilled water was used for vacuum filtration. Thereafter, air was flown and maintained at 400 DEG C for 3 hours to obtain a catalyst. The content of copper in the catalyst was about 2 wt%.

Production Example 2: Preparation of Catalyst 2 (Cu-MOR)

The catalyst was prepared by aqueous ion exchange (Aqueous ion-exchage). 2.7667 g of Copper (Ⅱ) acetate monohydrate (Cu (Ac) ₂ H ₂ O, Junsei Chem.) Was dissolved in 1365 mL of distilled water and mordenite (Cation type H, SiO ₂ / Al ₂ O ₃ , Tosoh Cor.), And the copper was ion-exchanged into mordenite for 24 hours at 450 rpm in a stirrer. After vacuum filtration without additional distilled water, it was dried at about 110 ° C for more than 12 hours. This process was repeated two more times and three times of ion exchange was performed. In the last filtration, 750 ml of distilled water was used for vacuum filtration. Thereafter, air was flown and maintained at 400 DEG C for 3 hours to obtain a catalyst. The content of copper in the catalyst was about 3.1 wt% and the molar ratio of copper per mol of aluminum was about 0.30.

Example 1-1

0.3 g of the catalyst 1 (Cu-SSZ-13) prepared according to Preparation Example 1 was charged into a fixed bed tubular reactor. Methanol was obtained by contacting 30 mL of high purity methane gas at 300 ° C. under atmospheric pressure at a flow rate of 30 mL per minute, and then passing 300 mL of 90% steam and 10% nitrogen per minute on a molar basis. The produced methanol was recovered by condensing using a cooler maintained at a temperature of -10 DEG C at the bottom of the reactor. The product was analyzed by gas chromatography equipped with a flame ion detector. At this time, the yield of methanol constantly obtained through contact with water vapor was 22 μmol / g _cat .

Examples 1-2

Methanol was obtained in substantially the same manner as in Example 1-1 except that the temperature of the reactor was changed to 350 캜. At this time, the yield of methanol constantly obtained through contact with water vapor was 40 μmol / g _cat .

Example 1-3

Methanol was obtained in substantially the same manner as in Example 1-1 except that the temperature of the reactor was changed to 400 캜. At this time, the yield of methanol constantly obtained through contact with water vapor was 41 μmol / g _cat .

Examples 1-4-a to 1-4-c

Methanol was obtained in substantially the same manner as in Example 1-2 except that the pressure condition of the reactor was 10 bar (Example 1-4-a). Methanol was also obtained by substantially the same method as in Example 1-2 with reactor pressure conditions of 20 bar and 30 bar, respectively (Examples 1-4-b and 1-4-c).

The yields of methanol uniformly obtained through contact with the vapors in Examples 1-4-a, 1-4-b and 1-4-c were 41, 57 and 56 μmol / g _cat , respectively.

Examples 1-5-a to 1-5-c

Substantially the same method as in Example 1-1 except that 0.3 g of the catalyst 2 (Cu-MOR) prepared according to Preparation Example 2 was used, the pressure condition of the reactor was set to 37 bar, and the temperature was set to 250 ° C (Example 1-5-a). Further, methanol was obtained in the same manner as in Example 1-5-a (Examples 1-5-b and 1-5-c), except that the reaction temperatures were 300 캜 and 350 캜.

The yields of methanol uniformly obtained through contact with the vapors in Examples 1-5-a, 1-5-b and 1-5-c, respectively, were 75, 84 and 49 μmol / g _cat .

Examples 2-1 to 2-3

0.3 g of the catalyst 1 (Cu-SSZ-13) prepared according to Preparation Example 1 was charged into a fixed bed tubular reactor, and 3 쨉 l of water was periodically injected while flowing high purity methane gas at 30 째 C at a given atmospheric pressure at 300 째 C To obtain methanol (Example 2-1). The produced methanol was analyzed by mass spectrometer. At this time, the yield of methanol constantly obtained through contact with water vapor was 11 μmol / g _cat .

Methanol was obtained in substantially the same manner as in Example 2-1 except that the amounts of water injected periodically were 5 占 퐇 and 10 占 퐇, respectively. The yields of methanol uniformly obtained through contact with the vapors in Examples 2-2 and 2-3 were 14 and 17 μmol / g _cat , respectively.

Examples 3-1 to 3-3

0.3 g of the catalyst 1 (Cu-SSZ-13) prepared in Preparation Example 1 was charged into a fixed bed tubular reactor, and 6 mL of steam was simultaneously injected at a rate of 30 mL of high purity methane gas at 200 ° C. under atmospheric pressure, (Example 3-1). The produced methanol was analyzed by mass spectrometer. At this time, the yield of methanol was 10 μmol / g _cat per hour.

Methanol was also obtained in substantially the same manner as in Example 3-1, except that the reaction temperature was 250 ° C and 300 ° C, respectively. The methanol obtained in each of Examples 3-2 and 3-3 was 15 and 17 μmol / g _cat per hour.

Comparative Example 1

Under atmospheric pressure, the catalyst 1 (Cu-SSZ-13) was pretreated by keeping air at 350 ° C for 30 minutes while flowing air 10 mL / minute, and helium was sifted for 20 minutes. Then, the reaction was carried out at 350 DEG C for 30 minutes while flowing 60 mL of high purity methane gas at a rate of 60 mL / min, and the product was obtained by flowing water vapor and helium at the same temperature. As a result, the yield of methanol per constant catalyst mass was 40 μmol / g _cat .

Comparative Example 2

Under atmospheric pressure, the catalyst 1 (Cu-SSZ-13) was pretreated by holding 10 mL of helium at 350 캜 for 30 minutes while flowing 10 mL per minute. The product was then reacted with high purity methane gas at 350 ° C. for 30 minutes while flowing 60 mL per minute. The product was obtained by flowing water vapor and helium at the same temperature. The yield of methanol per constant mass of the catalyst was 38 μmol / g _cat .

Comparative Example 3

Methanol was obtained in substantially the same manner as in Example 1-1, except that the reaction was carried out at 250 ° C under atmospheric pressure. At this time, the yield of methanol constantly obtained through contact with water vapor was 8 μmol / g _cat .

Comparative Example 4

Methanol was obtained in substantially the same manner as in Example 1-1 except that the reaction was carried out at 350 DEG C of 37 bar. At this time, the yield of methanol constantly obtained through contact with water vapor was 47 μmol / g _cat .

Comparative Examples 5-1 and 5-2

Except that catalyst 2 (Cu-MOR) was used at 200 ° C (Comparative Example 5-1) and 450 ° C (Comparative Example 5-2) of 37 bar, respectively, in substantially the same manner as in Example 1-1 Methanol. At this time, the yields of methanol uniformly obtained through contact with water vapor in Comparative Examples 5-1 and 5-2 were 1.3 and 1.2 μmol / g _cat , respectively.

Comparative Example 6

Methanol was obtained in substantially the same manner as in Example 2-1, except that 1 占 퐇 of water was periodically injected while flowing high-purity methane gas at 30 mL per minute. At this time, the yield of methanol constantly obtained through contact with water vapor was 4 μmol / g _cat .

Comparative Examples 7-1 to 7-3

Substantially the same method as in Example 3-1 except that the reaction temperature was 150 ° C (Comparative Example 7-1), 350 ° C (Comparative Example 7-2), and 400 ° C (Comparative Example 7-3) Methanol was obtained. At this time, the methanol obtained in Comparative Example 7-1 was 4 μmol / g _cat per hour, the methanol obtained in Comparative Example 7-2 was 5 μmol / g _cat per hour, and the methanol was not obtained in Comparative Example 7-3.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims. It can be understood that it is possible.

Claims (9)

Providing a first reaction gas comprising methane to the reactor in which the copper containing zeolite is disposed to contact the copper containing zeolite with methane;
Providing a second reaction gas comprising water vapor to the reactor; And
And obtaining methanol at the time when the second reaction gas is discharged in the reactor.
≪ / RTI >
The method according to claim 1,
Wherein the first reaction gas further comprises a saturated hydrocarbon compound having 2 to 6 carbon atoms.
≪ / RTI >
The method according to claim 1,
Wherein the second reaction gas further comprises at least one of oxygen, carbon dioxide, and nitrogen.
≪ / RTI >
The method according to claim 1,
Characterized in that each of the steps is carried out at a temperature of 200 < 0 > C to 450 &
≪ / RTI >
The method according to claim 1,
Characterized in that each of the steps is carried out under atmospheric pressure to 30 atmospheric pressure.
≪ / RTI >
Providing a third reaction gas comprising both methane and water vapor to a reactor in which a copper-containing zeolite is disposed; And
Containing zeolite is contacted with a third reaction gas to produce methanol.
≪ / RTI >
The method according to claim 6,
The third reaction gas
A saturated hydrocarbon compound having 2 to 6 carbon atoms, at least one of oxygen, carbon dioxide, and nitrogen.
≪ / RTI >
The method according to claim 6,
Characterized in that each of the steps is carried out at a temperature of 200 [deg.] C to 350 [
≪ / RTI >
The method according to claim 6,
Characterized in that each of the steps is carried out under atmospheric pressure to 30 atmospheric pressure.
≪ / RTI >

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