KR20240086011A - Apparatus and method for manufacturing methyl formate - Google Patents

Abstract

Disclosed is a methyl formate production device that can effectively remove catalyst poison and water generated in the methyl formate production process. The methyl formate manufacturing apparatus includes a container body having a certain volume; A stirrer with stirring blades installed inside the container body for mixing the methanol and catalyst contained in the container body; A carbon monoxide inlet installed to inject carbon monoxide gas into the interior of the container body; A separation membrane is installed on the inner peripheral surface of a cylindrical dewatering filter case with a certain volume, high-temperature dried zeolite powder is accommodated inside the separation membrane, and inlets and outlets communicating with the inside of the container body are arranged at the inlet and outlet of the dehydration filter case. and a dewatering filter means installed on one side of the container body so that the inside of the dewatering filter case is maintained in a vacuum state; and a carbon dioxide removal means including a cylindrical carbon dioxide discharge pipe installed on one upper side of the container body and receiving activated carbon inside the carbon dioxide discharge pipe. It may be configured to include.

Description

Efficient catalyst poison removal device and method for producing high purity methyl formate {Apparatus and method for manufacturing methyl formate}

This invention relates to an efficient catalyst poison removal device and method for producing high purity methyl formate. More specifically, it relates to high purity methyl formate production that enables catalyst poison and water generated in the methyl formate production process to be effectively removed. It relates to an efficient catalyst poison removal device and method.

Methyl formate is an important intermediate in the production of formic acid and is known to be industrially produced by continuous carbonylation of methanol in the liquid phase in the presence of sodium methoxide or potassium methoxide as a catalyst at a temperature range of about 50 to 150°C. This reaction is a homogeneously catalyzed equilibrium reaction in which the equilibrium shifts toward methyl formate as the partial pressure of carbon monoxide increases and the temperature decreases.

Meanwhile, methyl formate is synthesized directly from synthesis gas, in addition to the metalol carbonylation process, in the metalol dehydrogenation reaction process, in the metalol oxidative dehydrogenation reaction process, in the dimerization process of formic acid aldehyde, and in the process using the metalol carbonylation reaction. It is known that it can be manufactured by a process such as a process such as hydrogenation and condensation of carbon dioxide and metalol.

However, in most methyl formate production processes, including the metalol carbonylation reaction as described above, high purity methyl formate is produced due to a decrease in yield due to failure to completely remove water or moisture mixed with the raw materials. There was a difficult problem.

In addition, carbon dioxide gas generated in the methyl formate production process also acts as a catalyst poison, which has been pointed out as a problem that must be solved in producing high purity methyl formate.

Korea Intellectual Property Office Registered Patent Publication No. 10-0974123 (announced on August 4, 2010) Republic of Korea Intellectual Property Office Public Patent Publication No. 10-2015-0089010 (published on August 4, 2015) U.S. Patent and Trademark Office Registration No. 9,944,587 (announced on April 17, 2018)

This invention was created to solve the problems of the prior art as described above, and is an efficient catalyst poison removal device for high purity methyl formate production that allows catalyst poison and water generated in the methyl formate production process to be effectively removed. The purpose is to provide methods and methods.

This invention can be configured as follows as a means to achieve the purpose of the invention as described above.

An efficient catalyst poison removal device for producing high purity methyl formate according to a preferred embodiment of the present invention includes a container body having a certain volume in which methanol and a catalyst are accommodated therein so that a continuous carbonylation reaction of methanol occurs; A stirrer with stirring blades installed inside the container body for mixing the methanol and catalyst contained in the container body; A carbon monoxide inlet installed to inject carbon monoxide gas into the interior of the container body; A separation membrane is installed on the inner peripheral surface of a cylindrical dewatering filter case with a certain volume, high-temperature dried zeolite powder is accommodated inside the separation membrane, and inlets and outlets communicating with the inside of the container body are arranged at the inlet and outlet of the dehydration filter case. and a dewatering filter means installed on one side of the container body so that the inside of the dewatering filter case is maintained in a vacuum state; and a carbon dioxide removal means including a cylindrical carbon dioxide discharge pipe installed on one upper side of the container body and receiving activated carbon inside the carbon dioxide discharge pipe. It may be configured to include.

In the methyl formate production apparatus according to a preferred embodiment of the present invention, the zeolite powder contained in the dehydration filter means may be calcined and dried at a temperature of 600 to 650° C. for 4 to 5 hours.

In the methyl formate production apparatus according to a preferred embodiment of the present invention, the dehydration filter means may be installed so that the internal temperature is maintained at 100° C. or higher and the internal pressure is maintained at 50 bar or higher during the dehydration reaction.

An efficient catalyst poison removal method for producing high-purity methyl formate according to a preferred embodiment of the present invention includes: a container body having a certain volume in which methanol and a catalyst are accommodated therein so that a continuous carbonylation reaction of methanol occurs; A stirrer with stirring blades installed inside the container body for mixing the methanol and catalyst contained in the container body; A carbon monoxide inlet installed to inject carbon monoxide gas into the interior of the container body; A separation membrane is installed on the inner peripheral surface of a cylindrical dewatering filter case with a certain volume, high-temperature dried zeolite powder is accommodated inside the separation membrane, and inlets and outlets communicating with the inside of the container body are arranged at the inlet and outlet of the dehydration filter case. and a dewatering filter means installed on one side of the container body so that the inside of the dewatering filter case is maintained in a vacuum state; and a carbon dioxide removal means in which a cylindrical carbon dioxide discharge pipe is installed on one upper side of the container body and activated carbon is accommodated inside the carbon dioxide discharge pipe. In the process of producing methyl formate using a methyl formate production device consisting of: , a dehydration reaction process in which methanol present in a gaseous state in the container body in the continuous carbonylation reaction of methanol passes through a dehydration filter means, moisture is discharged by vacuum pressure, and methanol is recovered into the container body, and the cycle is repeated; A catalyst poison removal process in which carbon dioxide existing in a gaseous state in the container body in the continuous carbonylation reaction of methanol is removed by passing through activated carbon of the carbon dioxide removal means; It can be done including.

In the efficient catalyst poison removal method for producing high-purity methyl formate according to a preferred embodiment of the present invention, the zeolite powder contained in the dehydration filter means is calcined and dried at a temperature of 600 to 650 ° C. for 4 to 5 hours, and the dehydration is performed. The filter means may be set to maintain an internal temperature of 100° C. or higher and an internal pressure of 50 bar or higher during the dehydration reaction.

In the efficient catalyst poison removal method for producing high-purity methyl formate according to a preferred embodiment of the present invention, the catalyst for the continuous carbonylation reaction of methanol is a metal selected from one or more of sodium methoxide, potassium methoxide, and nitium methoxide. It could be a catalyst.

In the efficient catalyst poison removal method for producing high-purity methyl formate according to a preferred embodiment of the present invention, for the continuous carbonylation reaction of methanol, the stirrer is operated at a speed of 600 to 750 rpm while methanol and catalyst are placed in the vessel body. While rotating, carbon monoxide is injected into the container body through the carbon monoxide inlet, and the methanol and carbon monoxide supplied into the container body are each 1:0.5 to 1.5 based on weight ratio, and the amount of catalyst can be set to 0.1 to 0.3 mol/L. .

In the high-purity methyl formate production device according to this invention, the water component generated in the process of producing methyl formate through the methanol carbonylation reaction is effectively removed by the zeolite powder and the separation membrane, and the catalyst poison is removed through the carbon dioxide removal means. There is a great effect in obtaining higher purity methyl formate by effectively removing carbon dioxide.

Figure 1 is a diagram for explaining the configuration of a methyl formate production apparatus according to an embodiment of the present invention.
Figure 2 is a diagram for explaining the structure of the dewatering filter of the methyl formate production device according to an embodiment of the present invention.

Hereinafter, an efficient catalyst poison removal device and method for producing high-purity methyl formate according to a preferred embodiment of the present invention will be described in detail with reference to the attached drawings.

Figure 1 is a diagram for explaining the structure of a methyl formate production device according to an embodiment of the present invention, and Figure 2 is a diagram for explaining the structure of a dehydration filter of the methyl formate production device according to an embodiment of the invention. . Reference numeral 100 shown in the drawing indicates a methyl formate production apparatus according to an embodiment of the present invention.

As shown in FIG. 1, the methyl formate production apparatus 100 according to a preferred embodiment of the present invention includes a container body 110 and a stirrer 120 installed to mix methanol and catalyst contained in the container body 110. , a carbon monoxide inlet 130 installed in the container body 110 to inject carbon monoxide gas into the container body 110, and a container to remove water components generated during the carbonylation process of methanol in the container body 110. A dehydration filter means 140 installed in the main body 110, and a carbon dioxide removal means 150 installed in the container body 110 to remove carbon dioxide gas generated during the carbonylation process of methanol in the container body 110. It can be configured to include.

The container body 110 of the methyl formate production apparatus 100 according to a preferred embodiment of the present invention has a cylindrical structure with a certain volume in which methanol and a catalyst are accommodated therein to enable a continuous carbonylation reaction of methanol. can be formed.

Meanwhile, a stirrer 120 is installed to ensure that the methanol and catalyst contained within the container body 110 of the methyl formate production apparatus 100 according to a preferred embodiment of the present invention are smoothly mixed. The stirrer 120 includes a drive motor 122 fixed to the outside of the container body 110, and a stirring blade 124 installed inside the container body 110 via a shaft connected to the drive motor 122. It can be configured.

And a carbon monoxide inlet (130) for injecting carbon monoxide gas into the container body (110) of the methyl formate production device (100) according to a preferred embodiment of the present invention to ensure that the methanol carbonylation reaction is continuously and smoothly performed. ) is installed. A carbon monoxide pressure gauge 132 to measure the pressure of carbon monoxide is installed on the gas supply pipe connected to the carbon monoxide inlet 130.

That is, while methanol and catalyst are placed in the container body 110 so that the continuous carbonylation reaction of methanol proceeds smoothly within the container body 110, the stirrer 120 is rotated at a constant speed within the range of 600 to 750 rpm. It is configured to inject carbon monoxide at a certain pressure level into the container body 110 through the carbon monoxide inlet 130.

In particular, in the methyl formate production apparatus 100 according to a preferred embodiment of the present invention, the water component flowing into or generated inside the container body 110 is removed during the process of producing methyl formate through the methanol carbonylation reaction. A dewatering filter means 140 is installed for this purpose.

The dewatering filter case 142 of the dewatering filter means 140 may be installed inside or outside the container body 110, and a separation membrane 144 is installed on the inner peripheral surface of the dehydration filter case 142, and the separation membrane 144 ) Inside, high-temperature dried zeolite powder 146 is accommodated.

In addition, an inlet 142a and an outlet 142b communicating with the inside of the container body 110 are arranged at the inlet and outlet of the dehydration filter case 142, and the inside of the dehydration filter case 142 is maintained in a vacuum state. A vacuum pressure line is connected for this purpose.

The dehydration filter means 140 according to a preferred embodiment of the present invention is configured to maintain an internal temperature of 100° C. or higher and an internal pressure of 50 bar or higher during the dehydration reaction.

In addition, the zeolite powder 146 accommodated in the dehydration filter means 140 is preferably calcined and dried at a temperature of 600 to 650° C. for 4 to 5 hours.

After a certain usage time of the dewatering filter means 140 according to this invention has elapsed, the zeolite powder can be dried again under the temperature conditions described above and used again.

Meanwhile, a carbon dioxide removal means (150) for removing carbon dioxide, which is one of the catalyst poisons, in the process of producing methyl formate through a methanol carbonylation reaction in the methyl formate production apparatus (100) according to a preferred embodiment of the present invention. This is installed.

The carbon dioxide removal means 150 according to this invention may be composed of a cylindrical carbon dioxide discharge pipe 152 installed on one upper side of the container body, and activated carbon 154 accommodated inside the carbon dioxide discharge pipe 152.

On one side of the container body 110 of the methyl formate production device 100 according to a preferred embodiment of the present invention, a thermometer 160 and a pressure gauge 170 are provided for measuring the temperature and pressure inside the container body 110. ) can be installed.

Hereinafter, the process of producing methyl formate through a methanol carbonylation reaction using the methyl formate production apparatus 100 according to a preferred embodiment of the present invention will be described in detail.

A certain amount of methanol, carbon monoxide, and catalyst are introduced into the container body 110 of the methyl formate production apparatus 100 according to a preferred embodiment of the present invention. That is, in a preferred embodiment of the present invention, for the continuous carbonylation reaction of methanol, methanol and catalyst are placed in the container body 110, and the stirrer 120 is rotated at a speed of 600 to 750 rpm while the carbon monoxide inlet 130 ) Carbon monoxide is injected into the container body 110 through.

At this time, methanol and carbon monoxide supplied into the container body 110 may be set to 1:0.5 to 1.5, respectively, based on the weight ratio.

For example, if it is desired to produce 1 ton of methyl formate, 0.58 ton of methanol and 450 ㎥ of carbon monoxide can be injected into the container body 110.

Meanwhile, a metal catalyst selected from potassium methoxide, sodium methoxide, and nitium methoxide may be used as the catalyst. Preferably, the sodium methoxide metal catalyst may be used alone, or two or more selected metal catalysts may be used in combination.

Meanwhile, the amount of catalyst introduced into the container body 110 may be added on the basis of 0.1 to 0.3 mol/L. It is desirable to set the catalyst dosage as 0.2 mol/L.

As described above, a certain amount of methanol, carbon monoxide, and catalyst are placed inside the container body 110 of the methyl formate production device 100 according to a preferred embodiment of the present invention, and then stirred with a stirrer at a speed of about 600 to 750 rpm. Make sure the ingredients are well mixed.

Additionally, the temperature inside the container body 110 is set to be maintained at about 60 to 120°C, and the pressure is set to be maintained at about 20 to 70 bar.

Meanwhile, the methanol that has passed through the dehydration filter means 140 according to an embodiment of the present invention is injected back into the container body 110, and the cycle is repeated, making it possible to produce high purity methyl formate. That is, in the continuous carbonylation reaction of methanol, methanol present in a gaseous state in the container body 110 passes through the dehydration filter means 140, moisture is discharged by vacuum pressure, and methanol is recovered into the container body 110. A dehydration reaction process in which the cycle is repeated is performed. In this process, methanol, which has relatively large particles compared to water molecules, is recovered back to the container body 110, and the water component is separated by the zeolite powder 146 and the separation membrane 144 of the dehydration filter means 140. are discharged separately.

Example 1

To produce 1 ton of methyl formate, 0.58 ton of methanol and a certain amount of sodium methoxide as a metal catalyst were added into the container body 110, and then the stirrer 120 was rotated at a speed of 600 rpm and 450 ㎥ of methyl formate was added. Carbon monoxide was injected. At this time, the dosage of sodium methoxide was set at 0.2 mol/L, which corresponds to 0.014% of methanol. The internal temperature of the container body 110 was maintained at 100°C, and the pressure was maintained at 800 psig. Through the process according to this example, methyl formate with a purity of 97% was produced. It was confirmed that the methanol content in the product was 2.95% by weight, the moisture content was 0.03% by weight, and the content of other impurities was 0.02% by weight.

Through the dehydration reaction process as described above, the water component generated in the process of producing methyl formate through the methanol carbonylation reaction in the methyl formate production device according to the present invention is effectively removed by the zeolite powder and the separation membrane.

In addition, carbon dioxide, one of the catalyst poisons, is effectively removed through the carbon dioxide removal means 150 of the methyl formate production apparatus 100 according to an embodiment of the present invention. That is, in the continuous carbonylation reaction of methanol, carbon dioxide existing in a gaseous state in the container body 110 passes through the activated carbon 154 of the carbon dioxide removal means 150 and is removed, thereby performing a catalyst poison removal process.

Therefore, the water component and carbon dioxide, which is one of the catalyst poisons, generated in the process of producing methyl formate are effectively removed by the efficient catalyst poison removal device and method for producing high purity methyl formate according to a preferred embodiment of the present invention. Production of high purity methyl formate becomes possible.

In particular, the efficient catalyst poison removal device and method for producing high-purity methyl formate according to a preferred embodiment of the present invention does not fill or empty the interior of the container body 110 during the reaction, thereby producing higher purity methyl formate. Production of mates becomes possible.

In addition, the efficient catalyst poison removal device and method for producing high-purity methyl formate according to a preferred embodiment of the present invention produces high-purity methyl formate as the reaction occurs inside the container body 110 in a high temperature and high pressure environment. This becomes possible.

In addition, the high-purity methyl formate produced by the efficient catalyst poison removal device and method for producing high-purity methyl formate according to an embodiment of the present invention can be used as a foaming agent for foaming foam materials used for construction, shipbuilding, etc. there is.

In the above, an efficient catalyst poison removal device and method for producing high purity methyl formate according to a preferred embodiment of the present invention has been described with reference to the attached drawings. These embodiments are included in the technical idea described in the claims of this invention. Additionally, the above-described embodiments are merely illustrative and should not be construed as limited.

100: Methyl formate manufacturing device 110: Container body
120: stirrer 124: stirring wing
130: Carbon monoxide inlet 140: Dehydration filter means
142: Dewatering filter case 144: Separation membrane
146: Zeolite powder 150: Carbon dioxide removal means

Claims (7)

A container body having a certain volume in which methanol and a catalyst are accommodated therein to enable a continuous carbonylation reaction of methanol, a stirrer in which stirring blades for mixing the methanol and catalyst contained in the container body are installed inside the container body, In the methyl formate production device comprising a carbon monoxide inlet installed to inject carbon monoxide gas into the interior of the container body,
A separation membrane is installed on the inner peripheral surface of a cylindrical dewatering filter case with a certain volume, high-temperature dried zeolite powder is accommodated inside the separation membrane, and the inlet and outlet of the dehydration filter case have an inlet and an outlet that communicate with the inside of the container body. A dewatering filter means is arranged and installed on one side of the container body so that the inside of the dewatering filter case is maintained in a vacuum state; and
A carbon dioxide removal means including a cylindrical carbon dioxide discharge pipe installed on one upper side of the container body and receiving activated carbon inside the carbon dioxide discharge pipe; An efficient catalyst poison removal device for producing high purity methyl formate, comprising:
According to paragraph 1,
An efficient catalyst poison removal device for producing high-purity methyl formate, characterized in that the zeolite powder contained in the dehydration filter means is calcined and dried at a temperature of 600 to 650 ° C. for 4 to 5 hours.
According to claim 1 or 2,
An efficient catalyst poison removal device for producing high-purity methyl formate, characterized in that the dehydration filter means is installed to maintain an internal temperature of 100 ℃ or more and an internal pressure of 50 bar or more during the dehydration reaction.
A container body having a certain volume in which methanol and a catalyst are accommodated therein so that a continuous carbonylation reaction of methanol occurs; A stirrer with stirring blades installed inside the container body for mixing methanol and the catalyst contained in the container body; a carbon monoxide inlet installed to inject carbon monoxide gas into the interior of the container body; A separation membrane is installed on the inner peripheral surface of a cylindrical dewatering filter case with a certain volume, high-temperature dried zeolite powder is accommodated inside the separation membrane, and the inlet and outlet of the dehydration filter case have an inlet and an outlet that communicate with the inside of the container body. A dewatering filter means is arranged and installed on one side of the container body so that the inside of the dewatering filter case is maintained in a vacuum state; And a cylindrical carbon dioxide discharge pipe installed on one upper side of the container body, and a carbon dioxide removal means in which activated carbon is accommodated inside the carbon dioxide discharge pipe. Producing methyl formate using a methyl formate production device consisting of a. In the process,
In the continuous carbonylation reaction of methanol, a dehydration reaction in which methanol present in a gaseous state in the container body passes through the dehydration filter means, moisture is discharged by vacuum pressure, and methanol is recovered into the container body is repeated. process;
A catalyst poison removal process in which carbon dioxide existing in a gaseous state in the container body in the continuous carbonylation reaction of methanol is removed by passing through activated carbon of the carbon dioxide removal means; An efficient catalyst poison removal method for producing high purity methyl formate, comprising:
According to paragraph 4,
The zeolite powder accommodated in the dehydration filter means is calcined and dried at a temperature of 600 to 650°C for 4 to 5 hours, and the internal temperature of the dehydration filter means is 100°C or higher during the dehydration reaction, and the internal pressure An efficient catalyst poison removal method for producing high purity methyl formate, characterized in that the conditions are set to be maintained above 50 bar.
According to clause 5,
An efficient catalyst poison removal method for producing high purity methyl formate, wherein the catalyst for the continuous carbonylation reaction of methanol is selected from one or more of sodium methoxide, potassium methoxide, and nitium methoxide.
According to any one of claims 4 to 6,
For the continuous carbonylation reaction of methanol, carbon monoxide is injected into the container body through the carbon monoxide inlet while the stirrer is rotated at a speed of 600 to 750 rpm with methanol and a catalyst placed in the container body. An efficient catalyst poison removal method for producing high-purity methyl formate, characterized in that the supplied methanol and carbon monoxide are each 1:0.5 to 1.5 based on weight ratio, and the amount of catalyst is set to 0.1 to 0.3 mol/L.

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