KR101790223B1 - High Quality CO generating apparatus using recycle process and CO generating method - Google Patents

Abstract

The present invention relates to an apparatus and method for producing high-purity carbon monoxide by using a recycle process. According to the present invention, the apparatus for producing carbon monoxide (CO) comprises: a first vaporizer which vaporizes formic acid (HCOOH), introduced in a liquid phase as a raw material, and supplies the same as a first source gas; a first decomposition reactor which has a structure filled with a zeolite catalyst as a decomposition catalyst, and by using the decomposition catalyst, decomposes the first source gas supplied from the first vaporizer into a first reaction gas containing carbon monoxide-containing gas mixture, steam, and unreacted formic acid; a first condenser which cools the first reaction gas to separate condensed water and an unreacted formic acid (HCOOH) condensate from the first reaction gas; a first catalyst reactor which conducts a reaction of the first reaction gas, passed through the first condenser, in the presence of a Pd catalyst with a controlled activity to remove hydrogen gas (H_2) therefrom; and a first adsorption module which, by using an adsorbent, removes gaseous impurities containing carbon dioxide (CO_2), steam (H_2O), and unreacted formic acid (HCOOH) from the first reaction gas from which hydrogen gas has been removed through the first catalyst reactor, and isolates carbon monoxide from the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a high-purity carbon monoxide producing apparatus,

More particularly, the present invention relates to an apparatus and a method for producing high purity carbon monoxide, and more particularly, to a method and apparatus for producing high purity carbon monoxide by producing an environmentally friendly high purity carbon monoxide by lengthening the lifetime of a catalyst used through an eco-friendly process using sulfuric acid, nitric acid, And more particularly, to a carbon monoxide manufacturing apparatus and a manufacturing method thereof.

Generally, there are various techniques for producing carbon monoxide (CO). For example, a method of producing a disproportionation reaction (Boudouard reaction), a method of producing synthesis gas from natural gas or hydrocarbon fuel, a method of producing carbon monoxide (CO) using metal oxide and carbon, A method of producing carbon monoxide (CO) by decomposing acetic acid (CH ₃ COOH), methyl formate (HCOOCH ₃ ) or the like is known.

In particular, it is known that when carbon monoxide (CO) is produced using an MCOOM compound (M: hydrogen or methyl group), high purity carbon monoxide (CO) having a low metal impurity level can be produced. It is known that it is simple and suitable for producing with high purity without any other complicated impurities.

As a method for producing high purity carbon monoxide (CO) using formic acid (HCOOH), a method of producing carbon monoxide (CO) by decomposing formic acid (HCOOH) into CO and H ₂ O using sulfuric acid and a method of using zeolite Thereby producing carbon monoxide (CO).

The production of carbon monoxide (CO) using sulfuric acid is disadvantageous in that sulfuric acid, which is a strong acid, is heated to 180 ° C, so expensive materials that can withstand acids are used and that waste sulfuric acid is generated in an environment.

Even in the case of the method using zeolite, the addition of sulfuric acid to zeolite having a low reactivity increases the conversion rate and lowers the reaction temperature to suppress side reaction (H ₂ and CO ₂ ) generation. Therefore, An expensive glass coating is needed for the reactor and the inside of the pipe to prevent it. In addition, since zeolite is immersed in sulfuric acid, aluminum is escaped by sulfuric acid and the skeletal structure of the zeolite is destroyed, so that the catalyst life is low and the catalyst must be replaced in a short period of time.

Therefore, in the case of the conventional method of producing high purity carbon monoxide (CO) using formic acid (HCOOH), expensive problems such as environmental problems due to spent sulfuric acid and expensive materials such as reactors and pipes must be used, There is a problem in that the production cost is excessive.

Korean Patent Publication No. 10-2014-0138193 (Dec. 23, 2014)

Accordingly, it is an object of the present invention to provide a high-purity carbon monoxide manufacturing apparatus and a manufacturing method which can overcome the above-mentioned problems of the prior art.

Another object of the present invention is to provide a process for producing carbon monoxide which is low in production cost and capable of producing a high purity carbon monoxide because it does not require a strong acid such as sulfuric acid, nitric acid, hydrochloric acid, The present invention provides a carbon monoxide producing device and a manufacturing method thereof.

It is still another object of the present invention to provide a high-purity carbon monoxide producing apparatus and a manufacturing method using a recycling process which can be used for a semiconductor process or other precise industrial processes due to a low level of gaseous impurities or metal impurities.

According to an embodiment of the present invention to achieve some of the above-mentioned technical problems, the apparatus for producing carbon monoxide (CO) according to the present invention vaporizes raw liquid formic acid (HCOOH) supplied as a raw material and supplies it as a first raw material gas A first vaporizer; Wherein the decomposition catalyst is used to decompose the first raw material gas supplied from the first vaporizer to produce a first reaction in the form of a carbon monoxide mixture gas, steam, and unreacted formic acid mixture A first decomposition reactor for generating a gas; A first condenser for cooling the first reaction gas to separate condensate of condensed water and unreacted formic acid (HCOOH) from the first reaction gas; A first catalytic reactor for reacting the first reaction gas passing through the first condenser under an active control Pd catalyst to remove hydrogen gas (H ₂ ); The gaseous impurities including carbon dioxide (CO ₂ ), water vapor (H ₂ O) and unreacted formic acid (HCOOH) are removed from the first reaction gas from which hydrogen gas has been removed through the first catalytic reactor by using an adsorbent A first adsorption module for separating carbon monoxide; A second vaporizer for supplying condensed water separated from the first condenser and condensed unreacted formic acid (HCOOH) from the first condenser and vaporizing the condensed water to supply the second raw material gas; And a decomposition catalyst for decomposing the second source gas supplied from the second vaporizer using the catalyst for decomposition to generate a carbon monoxide mixed gas and a second reaction gas in the form of a steam mixture A second decomposition reactor; A second condenser for cooling the second reaction gas to separate the condensed water from the second reaction gas; A second catalytic reactor for reacting the second reaction gas passing through the second condenser under an active control Pd catalyst to remove hydrogen gas (H ₂ ); The gaseous impurities including carbon dioxide (CO ₂ ), water vapor (H ₂ O) and unreacted formic acid (HCOOH) are removed from the second reaction gas from which the hydrogen gas has been removed through the second catalytic reactor by using an adsorbent And a second adsorption module for separating carbon monoxide.

The zeolite catalyst has an acid site and has pores of 8 to 10-membered rings, and the molecular ratio of Si / Al can be 2 to 150.

The zeolite catalyst may have any of the structural types selected from FER, CHA, MWW, HEU, STI, AFX, DDR, LEV, RHO and MFI.

The decomposition catalyst does not contain a strong acid including sulfuric acid, nitric acid, and hydrochloric acid.

Wherein the first decomposition reactor or the second decomposition reactor comprises: a heater for maintaining a reaction temperature; The first raw material gas or the second raw material gas, and the opposite surface of the inlet is closed and has a hollow cylindrical structure and has a plurality of through holes in the circumferential surface thereof, A gas distributor for dispersing the first source gas or the second source gas into the reactor; And a catalyst support member having a mesh structure having mesh holes smaller than the particle size of the decomposition catalyst and supporting the decomposition catalyst may be provided in the reactor.

The active control Pd catalyst controls the activity by adsorbing or reacting 0.05 to 5.0 wt% of a halogen compound with a Pd catalyst having a Pd loading of 0.2 to 5.0 wt% based on the weight of the support, and the support is composed of alumina, silica, silicon oxide, magnesium An oxide, a cerium oxide, and a carbon material.

Wherein the first catalytic reactor or the second catalytic reactor comprises: a heater for maintaining a reaction temperature; The first reaction gas or the second reaction gas, and the opposite surface of the inlet is closed, and the plurality of through holes are formed in the circumferential surface of the hollow cylindrical structure, A gas distributor for dispersing the first reaction gas or the second reaction gas into the reactor; And a catalyst support for supporting the active control Pd catalyst, the catalyst support being provided in the reactor and having a mesh structure having mesh holes smaller than the particle size of the active control Pd catalyst.

The adsorbent may be at least one selected from silica, alumina, Molecular Sieve 5A, and Molecular Sieve 13X.

The carbon monoxide production apparatus includes a compression system for compressing carbon monoxide separated from the first adsorption module and the second adsorption module; A buffer tank for storing carbon monoxide compressed through the compressor; And a charging system for charging carbon monoxide stored in the buffer tank into the cylinder.

According to another embodiment of the present invention, there is provided a method for producing carbon monoxide (CO) according to the present invention, which comprises vaporizing a liquid raw formic acid (HCOOH) supplied as a raw material, A first vaporization step of supplying the vaporized gas; A first decomposition reaction step of decomposing and reacting the first source gas using a zeolite catalyst as a decomposition catalyst to produce a first reaction gas in the form of a carbon monoxide mixed gas, steam and unreacted formic acid mixture; A first condensing step of cooling the first reaction gas to separate condensate of condensed water and unreacted formic acid (HCOOH) from the first reaction gas; A first catalytic reaction step of reacting the first reaction gas in which the condensate is separated under an active control Pd catalyst to remove hydrogen gas (H ₂ ); In the first reaction gas from which the hydrogen gas has been removed through the first catalytic reaction step, impurities of the gas phase including carbon dioxide (CO ₂ ), water vapor (H ₂ O) and unreacted formic acid (HCOOH) And a first adsorption step of removing carbon monoxide by removing the carbon monoxide.

Wherein the condensate in the first condensation step is introduced into a recycle process to further separate carbon monoxide, wherein the recycling step includes: a second vaporization step of vaporizing the condensate and supplying it as a second source gas; A second decomposition reaction step of decomposing and reacting the second source gas using a zeolite catalyst as a decomposition catalyst to produce a carbon monoxide mixed gas and a second reaction gas in the form of steam vapor; A second condensing step of cooling the second reaction gas to separate condensed water from the second reaction gas; A second catalytic reaction step of catalytically reacting a second reaction gas in which condensed water is separated under an active control Pd catalyst to remove hydrogen gas (H ₂ ); Removing a gas phase impurity including carbon dioxide (CO ₂ ), water vapor (H ₂ O) and unreacted formic acid (HCOOH) using the adsorbent in the second reaction gas from which hydrogen gas has been removed, Step.

CHA, MWW, HEU, STI, AFX, DDR, and LEV (having a molecular weight ratio of 2 to 150) having a pore of 8 to 10-membered rings in the form of an acid site. , RHO, and MFI.

In the first vaporization step or the second vaporization step, the vaporization temperature of the formic acid (HCOOH) or the condensate is 105 to 150 ° C., and the reaction temperature in the first decomposition reaction step or the second decomposition reaction step is 130 to 150 ° C., 200 ° C, and the reaction temperature in the first catalytic reaction step or the second catalytic reaction step may be 100-150 ° C.

In the first decomposition reaction step or the second decomposition reaction step, the process pressure may be 0 to 5 bar (not including 0).

 In the first decomposition reaction step or the second decomposition reaction step, the contact time of the first source gas or the second source gas with the decomposition catalyst may be 5 to 70 seconds.

The active control Pd catalyst controls the activity by adsorbing or reacting 0.05 to 5.0 wt% of a halogen compound with a Pd catalyst having a Pd loading of 0.2 to 5.0 wt% based on the weight of the support, and the support is composed of alumina, silica, silicon oxide, magnesium An oxide, a cerium oxide, and a carbon material.

The adsorbent may be at least one selected from silica, alumina, Molecular Sieve 5A, and Molecular Sieve 13X.

The method for producing carbon monoxide includes: a compression step of compressing carbon monoxide separated in the first adsorption step and the second adsorption step; A storage step of storing carbon monoxide compressed through the compression step in a buffer tank; And a charging step of charging the cylinder with carbon monoxide stored in the buffer tank.

According to the present invention, since a strong acid such as sulfuric acid, nitric acid, and hydrochloric acid is not used, it is possible to prolong the period of catalyst replacement without requiring an eco-friendly, expensive reactor or piping, and to produce carbon monoxide at a low production cost and high purity There is an advantage. In addition, a recycle process is formed by recycling process to increase the conversion rate, which is advantageous in the case of replacing the catalyst and the lifetime of the catalyst can be extended, thereby improving the efficiency. The low levels of gaseous impurities and metal impurities make it possible to produce high purity carbon monoxide that can be used in semiconductor processes and other precision industrial processes.

1 is a schematic view of an apparatus for producing carbon monoxide according to the present invention,
FIG. 2 is a schematic view of the decomposition reactor or the catalytic reactor of FIG. 1,
Figure 3 is a schematic view of the gas distributor of Figure 2,
4 is a graph of GC-TCD (Gas Chromatograph-Thermal Conductivity Detector) analysis results of high purity carbon monoxide gas produced according to embodiments of the present invention,
5 is a GC-DID (Discharge Ionization Detector) analysis result table of carbon monoxide standard gas and high purity carbon monoxide gas produced according to the embodiments of the present invention,
6 is an ICP-MS analysis result table of metal impurities of the high purity carbon monoxide gas produced according to the embodiments of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings without intending to intend to provide a thorough understanding of the present invention to a person having ordinary skill in the art to which the present invention belongs.

1 is a schematic view of an apparatus for producing carbon monoxide according to the present invention.

1, an apparatus 100 for producing carbon monoxide (CO) according to the present invention includes a first vaporizer 110, a first decomposition reactor 120, a first condenser 130, a first catalytic reactor 140). And a first adsorption module (150). In addition, the second vaporizer 210, the second decomposition reactor 220, the second condenser 230, and the second catalytic reactor 240 for the recycle process. And a second adsorption module 250 may be provided.

The first vaporizer 110 vaporizes raw liquid formic acid (HCOOH) supplied as raw material for carbon monoxide production and supplies it to the first decomposition reactor 120 as a first raw material gas.

The raw formic acid (HCOOH) is supplied to the first vaporizer 110 through a raw material feeder (not shown). The raw material feeder may include a liquid pump or the like for supplying a stable raw material.

The raw formic acid (HCOOH) is usually supplied in the form of a mixture of formic acid (HCOOH) and water (H ₂ O) in an amount of about 50 wt% to 85 wt%. The raw formic acid (HCOOH) may be supplied to the first vaporizer 110 at a rate of 1.5 to 100 ml / min, and preferably at a rate of 30 ml / min.

In the first vaporizer 110, the raw formic acid (HCOOH) is heated to 105 to 150 ° C, which is higher than the vaporization temperature of the raw formic acid (HCOOH), to be supplied to the first decomposition reactor 120 as a first raw material gas. 1 vaporization process is performed. If the gasification temperature is lower than 105 ° C, the boiling point of the raw formic acid (HCOOH) is 100.5 ° C, and thus the gasification can not be sufficiently performed. If the gasification temperature exceeds 150 ° C, There is a problem that a side reaction occurs before being introduced into the reactor.

Since the first source gas is highly corrosive in a vaporized state, the piping from the first vaporizer 110 to the first decomposition reactor 120 should be protected by Teflon or a ceramic coating. A ceramic ball or the like may be filled in the first vaporizer 110 to increase the heat transfer area.

In the first decomposition reactor 120, the first raw material gas supplied from the first vaporizer 110 is decomposed and reacted to form carbon monoxide (CO), water vapor (H ₂ O), and unreacted formic acid (HCOOH) 1 < / RTI > reaction gas.

At this time, as the catalyst for decomposition in the first decomposition reactor 120, a zeolite catalyst having pores of 8 to 10-membered ring (MR) may be used.

However, in the present invention, since strong acid such as sulfuric acid is not used, the dealumination of the zeolite catalyst does not occur, so that the structure of the zeolite catalyst The problem of collapse is not caused at the origin.

In the case of the present invention, the conversion rate may be lowered due to the absence of strong acid, but in order to increase the conversion rate, the first decomposition reactor 120, the first catalytic reactor 140, and the recycle process described below, It is possible to produce high purity carbon monoxide by adjusting the reaction temperature and the process pressure appropriately to realize the optimum combination to increase the conversion ratio.

Wherein the zeolite catalyst has pores of 8 to 10-membered ring (MR), wherein the zeolite catalyst is selected from the group consisting of FER, CHA, MWW, HEU, STI, AFX, DDR, LEV, RHO and MFI Lt; / RTI >

Generally, in the case of formic acid (HCOOH), the pore has a kinetic diameter (Å) of 4.0 and a critical diameter and a maximum diameter (Å) of 4.6.

Here, the zeolite catalyst may be used in the form of an acid site, and the molecular ratio of Si / Al may range from 2 to 150. When the molecular weight ratio of Si / Al is less than 2, it is not structurally stable in the presence of the above-mentioned formic acid (HCOOH). When the molecular weight ratio is more than 150, the conversion point becomes too low.

In the first decomposition reactor 120, since strong acids such as sulfuric acid, nitric acid, and hydrochloric acid are not used, eco-friendly production is possible and the lifetime of the catalyst can be extended by prevention of dialumination.

The first reaction gas generated in the first decomposition reactor 120 is the result of the main reaction in the following reaction formula 1, and the first raw material gas, formic acid (HCOOH), is decomposed and generated, and carbon monoxide (CO), water vapor H ₂ O) and an unreacted formic acid mixture. Here, the decomposition catalyst serves to suppress the side reaction of the reaction formula 2 in which side reaction impurities such as carbon dioxide and hydrogen gas are generated and helps the main reaction of the reaction formula 1 to occur.

[Reaction Scheme 1]

HCOOH → CO + H ₂ O Primary reaction

[Reaction Scheme 2]

HCOOH → CO ₂ + H ₂ side reaction

The first decomposition reactor 120 has a reaction temperature of 130 to 200 ° C., a process pressure of 0 to 5 bar (not including 0), and a contact time of the first source gas with the decomposition catalyst is 5 to 30 ° C., 150 seconds, and preferably 10 to 70 seconds.

When the reaction temperature is higher, the side reaction is more likely to occur than the main reaction, and hydrogen gas is generated more frequently. Therefore, the reaction temperature may be 130 to 200 ° C, which is a higher reaction temperature than the side reaction.

Also, even in the case of the process pressure, if the pressure is generally applied, the reverse reaction may occur. However, if a certain range of process pressure (reaction pressure) is applied in the presence of the catalyst for decomposition, it is experimentally confirmed that the conversion is increased I could. As a result, it is possible to achieve the highest conversion rate and main reaction with a reaction temperature of 130 to 200 ° C and a process pressure of 0 to 5 bar (not including 0). When the process pressure is 5 bar or more, the reverse reaction takes place so that the reaction conversion rate is lowered.

In addition, if the process pressure is appropriately applied, the probability that the formic acid (HCOOH) contacts the acid sites of the decomposition catalyst is increased, the conversion rate is increased, and the reaction stabilization of the process rapidly progresses and the efficiency of the process operation is improved.

The first decomposition reactor 120 may be designed such that the ratio of the height of the decomposition catalyst to the diameter of the reactor is 3 to 10, preferably 5.

In the first decomposition reactor 120, carbon dioxide and hydrogen gas are generated by the side reaction of the reaction formula 2, but a first reaction gas mainly containing carbon monoxide (CO), water vapor (H ₂ O) and unreacted formic acid mixture is generated . Specifically, the first reaction gas contains carbon monoxide (CO), water vapor (H ₂ O), and unreacted formic acid, carbon dioxide, and hydrogen, so that the first reaction gas has a mixed gas form. Here, a gas in which carbon monoxide, carbon dioxide, and hydrogen gas are mixed is referred to as a carbon monoxide mixture gas. The conversion in the first decomposition reactor is about 70 to 90%.

The first condenser 130 is configured to cool the first reaction gas generated in the first decomposition reactor 120 to separate condensed water and condensed water of unreacted formic acid HCOOH from the first reaction gas, The condensation process is performed. Accordingly, the water vapor (H ₂ O) and the unreacted formic acid constituting the first reaction gas are partially or wholly removed. In the case of water vapor (H ₂ O) and unreacted formic acid, since the boiling point is about 100 ° C. (water vapor has a boiling point of 100 ° C. and formic acid has a boiling point of 100.5 ° C.), when the first reaction gas is cooled to 100 ° C. or less, H ₂ O) and unreacted formic acid are condensed and discharged to the condensate.

Here, the first reaction gas separated from the condensate through the first condenser 130 is supplied to the first catalytic reactor 140. The condensate separated through the first condenser 130 and the condensate in the form of unreacted formic acid (HCOOH) is supplied to the second vaporizer 210 for recycling.

The first reaction gas supplied to the first catalytic reactor 140 contains most of carbon monoxide, some carbon dioxide and hydrogen gas, some steam and unreacted formic acid (HCOOH).

The first catalytic reactor 140 performs a first catalytic reaction process in which a first reaction gas having passed through the first condenser 130 is reacted under an active control Pd catalyst to remove hydrogen gas (H ₂ ). At this time, the first catalytic reactor 140 may be configured to have the same or similar structure as that of the first decomposition reactor 120, except for the catalyst.

The hydrogen gas (H ₂ ) is a side reaction impurity produced by the side reaction of the reaction formula ( ₂ ), and is about 50 to 3000 ppm, and can be removed through the first catalytic reactor (140). The first catalytic reactor 140 in the first catalytic reactor 140, the reaction temperature is in filling the active control Pd catalyst state 100 ~ 150 ℃ in, and the space velocity of the first reaction gas 5 ~ 300h ^{- 1} So that the reaction can proceed. When the reaction temperature is less than 100 ° C, the reaction is not performed well and moisture can not be desorbed. When the reaction temperature exceeds 150 ° C, hydrogen gas (H ₂ ) is generated by WGS (Water Gas Shift) reaction.

The oxygen gas (O ₂ ) for removing the hydrogen gas (H ₂ ) is supplied to the first catalytic reactor (140) so as to correspond to the equivalence ratio of the hydrogen gas. Approximately 40 to 2700ppm or so will be supplied. Most of the supplied oxygen gas is used to react with the hydrogen gas, and the excess oxygen gas that is supplied in excess reacts with carbon monoxide (CO).

Herein, the active control Pd catalyst controls the activity by adsorbing or reacting a halogen compound (F, Cl, Br, I) with a Pd catalyst having a Pd loading of 0.2 to 5.0 wt% The support is supported and fired such that the amount of the support is 0.05 to 5.0 wt% based on the weight of the support.

The support of the active control Pd catalyst may be composed of at least one selected from alumina, silica, silicon oxide, magnesium oxide, cerium oxide, and carbon, irrespective of the acid point.

In the first adsorption module 150, carbon dioxide (CO ₂ ), water vapor (H ₂ O), and water (H ₂ O) are removed using the adsorbent in the first reaction gas in which the hydrogen gas is purified through the first catalytic reactor A first adsorption step of removing gas phase impurities including reaction formic acid (HCOOH) and separating carbon monoxide is performed.

The first adsorption module 150 is provided with a pair of adsorption towers. When one adsorption tower performs an adsorption process, the other adsorption tower has a valve for alternately performing a regeneration process, and includes a heater. At this time, helium (He) or high purity carbon monoxide (CO) produced by the first adsorption module 150 may be used as the regeneration gas for the regeneration process.

The first adsorption module 150 may include at least one selected from the group consisting of silica, alumina, molecular sieve 5A, and molecular sieve 13X as the adsorbent. The first reaction unit 140, Gas-phase impurities including carbon dioxide (CO ₂ ), water vapor (H ₂ O) and trace amounts of unreacted formic acid (HCOOH) are removed from the gas to separate and generate high purity carbon monoxide (CO).

Meanwhile, the condensed water separated through the first condenser 130 and the unreacted condensed HCOOH are supplied to the second vaporizer 210 for the recycle process. Thus, the recycling process is performed.

At this time, the condensate separated through the first condenser 130 may be supplied to the second vaporizer 210 after being stored in a separate raw material supplier (not shown). The raw material feeder may include a liquid pump or the like for supplying a stable raw material.

The second vaporization process of vaporizing the condensate and supplying the vaporized second raw material gas to the second decomposition reactor 220 is performed in the second vaporizer 210.

Since most of the water (H ₂ O) (for example, about 80 wt%) and a small amount of formic acid (HCOOH) (for example, about 20 wt%) are present in the condensed product in the first decomposition reaction through the first decomposition reactor 120, Degree).

In the second vaporizer 210, the condensate is heated to 105 to 150 ° C, which is equal to or higher than the vaporization temperature, and is supplied to the second decomposition reactor 220 as a second source gas. When the gasification temperature is less than 105 ° C, the boiling point of the raw formic acid HCOOH is 100.5 ° C, and thus the vaporization is not sufficiently performed. When the vaporization temperature exceeds 150 ° C, the second source gas is introduced into the second decomposition reactor 220, There is a problem that a side reaction occurs before being introduced into the reactor. The condensate may be supplied to the second vaporizer 210 at a rate of 1.5 to 100 ml / min, and preferably at a rate of 30 ml / min.

Since the second source gas is highly corrosive in a vaporized state, the piping from the second vaporizer 210 to the second decomposition reactor 220 should be protected by Teflon or a ceramic coating. A ceramic ball or the like may be filled in the second vaporizer 210 to increase the heat transfer area.

The second decomposition reactor 220 may have the same structure as that of the first decomposition reactor 120. The second decomposition reactor 220 decomposes and reacts the second source gas supplied from the second vaporizer 210 to generate carbon monoxide (H ₂ O) and an unreacted formic acid (HCOOH) mixed type.

At this time, a zeolite catalyst having 8 to 10-membered ring (MR) pores may be used as the decomposition catalyst in the second decomposition reactor 220, as in the case of the first decomposition reactor 120. The zeolite catalyst may have any of the structural types selected from FER, CHA, MWW, HEU, STI, AFX, DDR, LEV, RHO and MFI.

Generally, in the case of formic acid (HCOOH), the pore has a kinetic diameter (Å) of 4.0 and a critical diameter and a maximum diameter (Å) of 4.6.

Here, the zeolite catalyst may be used in the form of an acid site, and the molecular ratio of Si / Al may range from 2 to 150. When the molecular weight ratio of Si / Al is less than 2, it is not structurally stable in the presence of the above-mentioned formic acid (HCOOH). When the molecular weight ratio is more than 150, the conversion point becomes too low.

In the second decomposition reactor 220, as described above, strong acids such as sulfuric acid, nitric acid, and hydrochloric acid are not used, eco-friendly production is possible, and the lifetime of the catalyst can be extended due to prevention of dialumination.

The reaction temperature of the second decomposition reactor 220 is in the range of 130 to 200 ° C. The contact time of the second source gas with the decomposition catalyst may be 5 to 150 seconds, and preferably 10 to 70 seconds. When the reaction temperature is higher, the side reaction is more likely to occur than the main reaction, and hydrogen gas is generated more frequently. Therefore, the reaction temperature may be 130 to 200 ° C, which is a higher reaction temperature than the side reaction.

Also, even in the case of the process pressure, if the pressure is generally applied, the reverse reaction may occur. However, if a certain range of process pressure (reaction pressure) is applied in the presence of the catalyst for decomposition, it is experimentally confirmed that the conversion is increased I could. As a result, with a reaction temperature of 150-200 ° C and a process pressure of 0-5 bar (not including 0), it is possible to achieve the highest conversion and main reaction. If the process pressure exceeds 5 bar, the reverse reaction occurs and the reaction conversion rate becomes low.

In addition, if the process pressure is suitably applied, the probability that the formic acid (HCOOH) will contact the acid point of the decomposition catalyst increases to increase the conversion rate, and the reaction stabilization of the process rapidly progresses, thereby improving the efficiency of the process operation.

The second decomposition reactor 220 may be designed such that the ratio of the height of the decomposition catalyst to the diameter of the reactor is 3 to 10, preferably 5.

The second reaction gas generated according to the second decomposition reaction process in the second decomposition reactor 220 is the product of the main reaction in the reaction formula 1, and the second source gas, HCOOH, Carbon monoxide (CO), water vapor (H ₂ O), and unreacted formic acid mixture. Here, the decomposition catalyst serves to suppress the side reaction of the reaction formula 2 in which side reaction impurities such as carbon dioxide and hydrogen gas are generated and helps the main reaction of the reaction formula 1 to occur. Since the conversion of formic acid in the second source gas (reaction rate) passes through the second decomposition reactor 220 in a state in which it has already passed through the first decomposition reactor 120, the converted conversion rate %.

In the second decomposition reactor 220, carbon dioxide and hydrogen gas are generated by the side reaction of the reaction scheme 2, but a second reaction gas mainly composed of carbon monoxide (CO), water vapor (H ₂ O) and unreacted formic acid mixture is generated . Specifically, the second reaction gas contains carbon monoxide (CO), water vapor (H ₂ O), and unreacted formic acid, carbon dioxide, and hydrogen, and has a mixed gas form. Here, a gas in which carbon monoxide, carbon dioxide, and hydrogen gas are mixed is referred to as a carbon monoxide mixture gas.

The second condenser 230 is configured to cool the second reaction gas generated in the second decomposition reactor 220 to separate the condensed water and condensed water of the unreacted formic acid HCOOH from the second reaction gas, The condensation process is performed. Most of the formic acid is decomposed through the second decomposition reactor 220, so that most of water (H ₂ O) is condensed through the second condenser 230, and some unreacted formic acid is condensed and removed.

Here, the second reaction gas separated from the condensate through the second condenser 230 is supplied to the second catalytic reactor 240.

The second reaction gas supplied to the second catalytic reactor 240 contains most of carbon monoxide, some carbon dioxide and hydrogen gas, some water vapor (H ₂ O), and unreacted formic acid (HCOOH).

In the second catalytic reactor 240, a second catalytic reaction process is performed in which a second reaction gas, which has passed through the second condenser 230, is reacted under an active control Pd catalyst to remove hydrogen gas (H ₂ ). At this time, the second catalytic reactor 240 may have the same structure as the first catalytic reactor 140.

The hydrogen gas (H ₂ ) is a side reaction impurity generated by a side reaction of Reaction Scheme 2 in the recycle process. The hydrogen gas (H ₂ ) is generated in an amount of about 50-2500 ppm and can be removed through the second catalytic reactor 240. The second catalyst reactor 240 in the second catalytic reactor 240. The reaction temperature in filling the active control Pd catalyst state 100 ~ 150 ℃ in, and the space velocity of the second reaction gas 5 ~ 300h ^{- 1} So that the reaction can proceed. At this time, in order to remove the hydrogen gas, the oxygen gas (O ₂ ) is supplied to the second catalytic reactor 240 so as to correspond to the equivalence ratio of the hydrogen gas. Approximately 30 to 1800 ppm or so will be supplied.

Herein, the active control Pd catalyst controls the activity by adsorbing or reacting a halogen compound (F, Cl, Br, I) with a Pd catalyst having a Pd loading of 0.2 to 5.0 wt% The support is supported and fired such that the amount of the support is 0.05 to 5.0 wt% based on the weight of the support.

The support of the active control Pd catalyst may be composed of at least one selected from alumina, silica, silicon oxide, magnesium oxide, cerium oxide, and carbon.

In the second adsorption module 250, carbon dioxide (CO ₂ ), water vapor (H ₂ O), and unreacted formic acid are adsorbed to the second reaction gas from which hydrogen gas has been removed through the second catalytic reactor 240 (HCOOH), and performs a second adsorption process for separating the carbon monoxide.

The second adsorption module 250 includes a pair of adsorption towers having the same structure as that of the first adsorption module 150. When one adsorption tower performs the adsorption process, And a heater, respectively. At this time, helium (He) or high purity carbon monoxide (CO) produced by the second adsorption module 250 may be used as a regeneration gas for the regeneration process.

The second adsorption module 250 may include at least one selected from the group consisting of silica, alumina, molecular sieve 5A, and molecular sieve 13X as the adsorbent. The second reaction unit 240, which has passed through the second catalytic reactor 240, Gas-phase impurities including carbon dioxide (CO ₂ ), water vapor (H ₂ O) and trace amounts of unreacted formic acid (HCOOH) are removed from the gas to separate and generate high purity carbon monoxide (CO).

The high purity carbon monoxide (CO) generated through the first adsorption module 150 and the second adsorption module 250 is compressed through a compressor or a compression system 160 to 90 to 200 atm, The carbon monoxide stored in the buffer tank 170 is charged into the cylinder or sent to the charger or the charging system 180 to be used for charging the carbon monoxide stored in the buffer tank 170 through the storage process of storing the carbon monoxide compressed through the compression process in the buffer tank 170, Process.

FIG. 2 illustrates the structure of the first decomposition reactor 120 or the second decomposition reactor 220 of FIG. 1, and FIG. 3 illustrates the structure of a gas distributor of the decomposition reactor 120 or 220 of FIG.

2 and 3, the decomposition reactors 120 and 220 include a heater 122 for maintaining a reaction temperature, a gas distributor 124, and a catalyst support 126.

The heater 122 is provided around the reactor to maintain the reaction at a high temperature. The heater 122 raises the temperature for the reaction. In particular, the first raw material gas or the second raw material gas is raised to a reaction temperature of 105 to 400 ° C so that the first raw material gas or the second raw material gas can be reacted.

The gas distributor 124 is provided at an inlet through which the raw material gas is introduced into the decomposition reactor 120 and 220. The gas distributor 124 has a hollow cylindrical structure in which the inlet for introducing the raw material gas is opened and the opposite side of the inlet is closed, and a plurality of through holes 124a are formed in the circumferential surface of the gas distributor 124, The gas is uniformly dispersed in the decomposition reactors 120 and 220, so that the raw material gas is uniformly contacted with the catalyst. That is, the raw material gas is dispersed in the plurality of through holes 124a on the circumferential surface (side surface) to distribute the raw material gas evenly to the catalyst distributed over a wide area.

The catalyst support table 126 is provided at a position (well-communicated position) for accurately receiving the heat of the heater 122 in the decomposition reactor 120 or 220. The catalyst support 126 has a mesh structure having mesh holes of a size smaller than the particle size of the decomposition catalyst.

2 and 3 may be used as the first catalytic reactor 140 and the second catalytic reactor 240 with different reaction gases from the raw gas, the catalyst, and the reaction temperature.

FIG. 4 is a graph showing a GC-TCD (Gas Chromatograph-Thermal Conductivity Detector) analysis result of the high purity carbon monoxide gas produced according to the present invention.

4, the high-purity carbon monoxide (CO) generated through the first adsorption module 150 and the second adsorption module 250 is analyzed through the analysis system, and only the carbon monoxide (CO) is measured .

5 is a GC-DID (Discharge Ionization Detector) analysis result of carbon monoxide standard gas and high purity carbon monoxide (CO) generated through the first adsorption module 150 and the second adsorption module 250, 6 is an ICP-MS analysis result of metal impurities of the high purity carbon monoxide gas produced according to the embodiments of the present invention.

As shown in FIG. 5, the high purity carbon monoxide according to the present invention has impurities of H ₂ , O ₂ + Ar, N ₂ , CH ₄ and CO ₂ , and each impurity is in the range of 0.2 to 2 ppm , It can be seen that as shown in FIG. 6, the high purity carbon monoxide produced according to the present invention exhibits impurities of less than a few ppb, indicating that high purity carbon monoxide is produced.

Each embodiment will be described below.

≪ Example 1 >

The raw formic acid (HCOOH) was mixed with 85 wt% of formic acid and the remainder with water or the like. The raw formic acid was supplied to the first vaporizer 110 at a rate of 1.5 to 100 mL / min, preferably 30 mL / . In the first vaporizer 110, the raw formic acid was heated to 110 DEG C and vaporized. The vaporized formic acid is introduced into the first decomposition reactor 120 through a heating pipe, and the reaction temperature of the first decomposition reactor 120 is 180 ° C. The zeolite catalytic reaction in the first decomposition reactor 120 is designed so that the contact time is 10 to 50 seconds, preferably about 25 seconds, and the catalyst height / reactor diameter ratio is 3 to 10, preferably 5 . A zeolite H-FER with 10 MR or 8 MR and a molecular weight ratio of Si / Al of 10 was used as the decomposition catalyst.

The decomposition conversion ratio (reaction rate) of formic acid in the first decomposition reactor 120 is about 70 to 90%. The process pressure was 0.1 to 2.0 bar, preferably 0.5 bar. Unreacted formic acid (HCOOH) condensed through the first condenser 130 is sent to the second vaporizer 210 together with condensed water (H ₂ O). The carbon monoxide mixed gas generated from the first decomposition reactor 120 is transferred to the first catalytic reactor 140 via the first condenser 130.

The first catalytic reactor 140 was filled with 0.1 wt% of Cl, 0.5 wt% of Pd / Al ₂ O ₃ , and a reaction temperature of 110 ° C for hydrogen (H ₂ ) removal. The space velocity of the carbon monoxide mixed gas for the active control Pd catalytic reaction is 10-100 h ^-1 . The supply of oxygen (O ₂ ) was supplied according to the equivalent ratio of generated hydrogen (H ₂ ), and preferably 100 to 1300 ppm of the flow rate of the carbon monoxide (CO) mixed gas was supplied. The carbon monoxide (CO) mixed gas from which the hydrogen (H ₂ ) has been removed is sent to the first adsorption module 150 and the carbon dioxide (CO ₂ ) and water vapor (H ₂ O) Formic acid (HCOOH) and the like are removed and carbon monoxide of high purity is produced.

On the other hand, a mixed liquid of unreacted formic acid (HCOOH) and condensed water (H ₂ O), which is a condensate sent to the second vaporizer 210, is heated for a recycling process and heated to 110 ° C. in the second vaporizer 210 and vaporized. The vaporized formic acid (HCOOH) is introduced into the second decomposition reactor 220 through a heating pipe and heated to a reaction temperature of 180 ° C. The second decomposition reactor 220 has the same structure as the first decomposition reactor 120, and the same catalyst is used. The catalytic reaction was designed to have a contact time of 25 to 70 seconds, preferably 35 seconds.

The conversion ratio (reaction rate) of formic acid (HCOOH) in the second decomposition reactor 220 is 99.8% or more. The generated carbon monoxide (CO) mixed gas is sent to the second catalytic reactor 240 via the second condenser 230. As in the first catalytic reactor 140, the second catalytic reactor 240 is also filled with 0.1% by weight of Cl, 0.5% by weight of Pd / Al ₂ O ₃ , and the reaction for removing hydrogen (H ₂ ) The temperature was 110 캜. The supply of oxygen (O ₂ ) was supplied according to the equivalence ratio of hydrogen (H ₂ ) generated, and preferably 100 to 1300 ppm of the flow rate of carbon monoxide (CO) mixed gas was supplied. The space velocity of the carbon monoxide (CO) mixed gas was set to 10-100 h ^-1 for the reaction through the active control Pd catalyst. The carbon monoxide (CO) mixed gas from which the hydrogen (H ₂ ) has been removed is transferred to the second adsorption module 250 to remove carbon dioxide (CO ₂ ), water vapor (H ₂ O) and trace amounts of formic acid (HCOOH) Carbon monoxide is produced.

The high purity carbon monoxide (CO) produced through the first adsorption module 150 and the second adsorption module 250 has a purity of 99.995% or more and is passed through the compressor or compression system 160 at a rate of about 10 and the compressed carbon monoxide is stored in the buffer tank 170 through the compression process and the carbon monoxide stored in the buffer tank 170 is supplied to the cylinder And then goes through a charging process to the charger or charging system 180 for charging or use.

The carbon monoxide (CO) gas produced by the above-described method has a few impurities and does not use a strong acid such as sulfuric acid, so that it can be used for a long time and has an advantage of being an environmentally friendly process in which no sulfuric acid is generated.

≪ Example 2 >

Catalyst for decomposition: SAPO-34 (CHA, 8 MR)

Active control Pd catalyst: 0.1 wt% Cl, 0.5 wt% Pd / Al ₂ O ₃ catalyst

The same procedure as in Example 1 was carried out except that SAPO-34 (CHA, 8 MR) catalyst was used as a decomposition catalyst used in the first decomposition reactor 120 and the second decomposition reactor 220 Respectively. The high purity carbon monoxide (CO) gas produced according to Example 2 was analyzed for gas impurities and metal impurities and purified to a purity of 99.9% to 99.99995%.

≪ Example 3 >

 Catalyst for decomposition: H-CHA (CHA, 8 MR)

Active control Pd catalyst: 0.1 wt% Cl, 0.5 wt% Pd / Al ₂ O ₃ catalyst

 The same procedure as in Example 1 was carried out except that H-CHA (CHA, 8 MR) catalyst was used as the decomposition catalyst used in the first decomposition reactor 120 and the second decomposition reactor 220 Respectively. The high purity CO gas produced according to Example 3 was analyzed for gas impurities and metal impurities and purified to a purity of 99.9% to 99.99995%.

As described above, according to the present invention, since a strong acid such as sulfuric acid, nitric acid, and hydrochloric acid is not used, an eco-friendly, expensive reactor or piping is not required and the catalyst replacement period can be lengthened, There is an advantage that carbon monoxide can be produced. In addition, a recycle process is formed by recycling process to increase the conversion rate, which is advantageous in the case of replacing the catalyst and the lifetime of the catalyst can be extended, thereby improving the efficiency. The low levels of gaseous impurities and metal impurities make it possible to produce high purity carbon monoxide that can be used in semiconductor processes and other precision industrial processes.

The foregoing description of the embodiments is merely illustrative of the present invention with reference to the drawings for a more thorough understanding of the present invention, and thus should not be construed as limiting the present invention. It will be apparent to those skilled in the art that various changes and modifications may be made without departing from the basic principles of the present invention.

110: first vaporizer 120: first decomposition reactor
130: first condenser 140: first catalytic reactor
150: first adsorption module
210: Second vaporizer 220: Second decomposition reactor
230: second condenser 240: second catalytic reactor
250: second adsorption module

Claims (18)

A carbon monoxide (CO) production apparatus comprising:
A first vaporizer for vaporizing raw formic acid (HCOOH) in a liquid state to be supplied as a raw material and supplying it as a first source gas;
Wherein the decomposition catalyst is used to decompose the first raw material gas supplied from the first vaporizer to produce a first reaction in the form of a carbon monoxide mixture gas, steam, and unreacted formic acid mixture A first decomposition reactor for generating a gas;
A first condenser for cooling the first reaction gas to separate condensate of condensed water and unreacted formic acid (HCOOH) from the first reaction gas;
A first catalytic reactor for reacting the first reaction gas passing through the first condenser under an active control Pd catalyst to remove hydrogen gas (H ₂ );
The gaseous impurities including carbon dioxide (CO ₂ ), water vapor (H ₂ O) and unreacted formic acid (HCOOH) are removed from the first reaction gas from which hydrogen gas has been removed through the first catalytic reactor by using an adsorbent A first adsorption module for separating carbon monoxide;
A second vaporizer for supplying condensed water separated from the first condenser and condensed unreacted formic acid (HCOOH) from the first condenser and vaporizing the condensed water to supply the second raw material gas;
And a decomposition catalyst for decomposing the second source gas supplied from the second vaporizer using the catalyst for decomposition to generate a carbon monoxide mixed gas and a second reaction gas in the form of a steam mixture A second decomposition reactor;
A second condenser for cooling the second reaction gas to separate the condensed water from the second reaction gas;
A second catalytic reactor for reacting the second reaction gas passing through the second condenser under an active control Pd catalyst to remove hydrogen gas (H ₂ );
The gaseous impurities including carbon dioxide (CO ₂ ), water vapor (H ₂ O) and unreacted formic acid (HCOOH) are removed from the second reaction gas from which the hydrogen gas has been removed through the second catalytic reactor by using an adsorbent And a second adsorption module for separating carbon monoxide from the carbon monoxide. The method according to claim 1,
Wherein the zeolite catalyst has a pore of 8 to 10-membered rings in the form of an acid site, and the molecular ratio of Si / Al is 2 to 150. The method of claim 2,
Wherein the zeolite catalyst has any of the structural types selected from among FER, CHA, MWW, HEU, STI, AFX, DDR, LEV, RHO and MFI. The method of claim 3,
Wherein the decomposition catalyst contains no strong acid including sulfuric acid, nitric acid, and hydrochloric acid. The method according to claim 1,
Wherein the first decomposition reactor or the second decomposition reactor comprises:
A heater for maintaining the reaction temperature;
The first raw material gas or the second raw material gas, and the opposite surface of the inlet is closed and has a hollow cylindrical structure and has a plurality of through holes in the circumferential surface thereof, A gas distributor for dispersing the first source gas or the second source gas into the reactor;
Wherein the catalyst supporting unit comprises a mesh structure having mesh holes smaller than the granule size of the decomposition catalyst, and the catalyst support supporting the decomposition catalyst is provided inside the reactor. The method according to claim 1,
The active control Pd catalyst controls the activity by adsorbing or reacting 0.05 to 5.0 wt% of a halogen compound with a Pd catalyst having a Pd loading of 0.2 to 5.0 wt% based on the weight of the support, and the support is composed of alumina, silica, silicon oxide, magnesium An oxide, a cerium oxide, and a carbonaceous material. The method according to claim 1,
Wherein the first catalytic reactor or the second catalytic reactor comprises:
A heater for maintaining the reaction temperature;
The first reaction gas or the second reaction gas, and the opposite surface of the inlet is closed, and the plurality of through holes are formed in the circumferential surface of the hollow cylindrical structure, A gas distributor for dispersing the first reaction gas or the second reaction gas into the reactor;
And a catalyst support for supporting the active control Pd catalyst, the catalyst support being disposed in the reactor and having a mesh structure having mesh holes smaller than the particle size of the active control Pd catalyst. The method according to claim 1,
Wherein the adsorbent is at least one selected from silica, alumina, Molecular Sieve 5A, and Molecular Sieve 13X. The apparatus for producing carbon monoxide according to claim 1,
A compression system for compressing carbon monoxide separated from the first adsorption module and the second adsorption module;
A buffer tank for storing carbon monoxide compressed through the compression system;
Further comprising a charging system for charging carbon monoxide stored in the buffer tank into the cylinder. A method for producing carbon monoxide (CO) comprising:
A first vaporization step of vaporizing raw formic acid (HCOOH) in a liquid state supplied as a raw material and supplying it as a first source gas;
A first decomposition reaction step of decomposing and reacting the first source gas using a zeolite catalyst as a decomposition catalyst to produce a first reaction gas in the form of a carbon monoxide mixed gas, steam and unreacted formic acid mixture;
A first condensing step of cooling the first reaction gas to separate condensate of condensed water and unreacted formic acid (HCOOH) from the first reaction gas;
A first catalytic reaction step of reacting the first reaction gas in which the condensate is separated under an active control Pd catalyst to remove hydrogen gas (H ₂ );
In the first reaction gas from which the hydrogen gas has been removed through the first catalytic reaction step, impurities of the gas phase including carbon dioxide (CO ₂ ), water vapor (H ₂ O) and unreacted formic acid (HCOOH) And separating the carbon monoxide from the carbon monoxide. The method of claim 10,
The condensate in the first condensation step is introduced into the recycling process to further separate carbon monoxide,
In the recycling step,
A second vaporization step of vaporizing the condensate and supplying it as a second source gas;
A second decomposition reaction step of decomposing and reacting the second source gas using a zeolite catalyst as a decomposition catalyst to produce a carbon monoxide mixed gas and a second reaction gas in the form of steam vapor;
A second condensing step of cooling the second reaction gas to separate condensed water from the second reaction gas;
A second catalytic reaction step of catalytically reacting a second reaction gas in which condensed water is separated under an active control Pd catalyst to remove hydrogen gas (H ₂ );
Removing a gas phase impurity including carbon dioxide (CO ₂ ), water vapor (H ₂ O) and unreacted formic acid (HCOOH) using the adsorbent in the second reaction gas from which hydrogen gas has been removed, Wherein the carbon monoxide production step comprises the steps of: The method of claim 11,
CHA, MWW, HEU, STI, AFX, DDR, and LEV (having a molecular weight ratio of 2 to 150) having a pore of 8 to 10-membered rings in the form of an acid site. , RHO, and MFI. ≪ / RTI > The method of claim 11,
In the first vaporization step or the second vaporization step, the vaporization temperature of the formic acid (HCOOH) or the condensate is 105 to 150 ° C., and the reaction temperature in the first decomposition reaction step or the second decomposition reaction step is 130 to 150 ° C., 200 ° C, and the reaction temperature in the first catalytic reaction step or the second catalytic reaction step is 100-150 ° C. 14. The method of claim 13,
Wherein in the first decomposition reaction step or the second decomposition reaction step, the process pressure is 0 to 5 bar (not including 0). 15. The method of claim 14,
Wherein the contact time of the first source gas or the second source gas with the decomposition catalyst in the first decomposition reaction step or the second decomposition reaction step is 5 to 70 seconds. The method of claim 11,
The active control Pd catalyst controls the activity by adsorbing or reacting 0.05 to 5.0 wt% of a halogen compound with a Pd catalyst having a Pd loading of 0.2 to 5.0 wt% based on the weight of the support, and the support is composed of alumina, silica, silicon oxide, magnesium An oxide, a cerium oxide, and a carbonaceous material. The method of claim 11,
Wherein the adsorbent is at least one selected from silica, alumina, Molecular Sieve 5A, and Molecular Sieve 13X. The method according to claim 11,
A compression step of compressing the carbon monoxide separated in the first adsorption step and the second adsorption step;
A storage step of storing carbon monoxide compressed through the compression step in a buffer tank;
And filling the cylinder with carbon monoxide stored in the buffer tank.

Images