KR100976372B1 - Reaction equipment for hi nitrogen monoxide production - Google Patents

Abstract

PURPOSE: A reaction apparatus for manufacturing hi nitrogen monoxide is provided to maintain a reaction temperature of a liquid over than 30L a creation temperature and reduce the concentration of water in nitrogen oxide to less than 50ppm. CONSTITUTION: In a reaction apparatus for manufacturing hi nitrogen monoxide, ammonia and air are mixed a mixing filter(32) are heated by a heater(35). The mixing filter comprised of a first and second filters which include a plurality of penetration holes. The rector includes an external body, an internal body, a Pt-Rh catalyst installed on the internal body, and the heater controlled by a temperature sensor.

Description

Reaction equipment for Hi nitrogen monoxide production

The present invention relates to a high purity nitrogen monoxide production reactor for producing nitrogen monoxide gas by oxidation of high purity ammonia (NH ₃ ) gas and air.

Nitrogen monoxide is a material used to deposit an oxide film in a semiconductor process, and the demand of nitrogen monoxide is increasing due to the activation of the semiconductor industry. In addition, with the development of the semiconductor industry, the purity of nitrogen monoxide is also increasingly required.

In general, nitrogen monoxide is prepared by contacting metal copper with dilute nitric acid. However, this method does not facilitate continuous processing in large-scale synthesis. Nitrogen monoxide produced by this method contains many impurities as well as wastewater. And because the production cost is very expensive, it is not suitable for the production of large-capacity nitrogen monoxide.

As another method for producing nitrogen monoxide, a method for producing NO ₂ -free nitrogen monoxide using a sulfur-containing polymer of Korean Patent Publication No. 1997-003275 is provided. Another method for preparing nitrogen monoxide includes ammonia and ammonia. Oxygen can be prepared by reacting at a high temperature, and these methods are also not suitable for the mass synthesis method of nitrogen monoxide due to the high content of impurities or the possibility of explosion due to an increase in reaction temperature.

Therefore, in order to synthesize nitrogen monoxide in a large amount, a different synthesis method needs to be invented, the production cost is low, the reaction temperature is easy to be maintained constant, and most of the impurities are generated by water or nitrogen, which is easy to purify the ammonia gas. A method of producing nitrogen monoxide by reacting with air is suitable.

High purity ammonia gas is required to produce high purity nitrogen monoxide by reacting the ammonia gas and air.

Therefore, in order to increase the purity of nitrogen monoxide, it is necessary to reduce the concentration of N ₂ O (nitrous oxide) contained therein to 50 ppm or less, and the high purity nitrogen monoxide having the concentration of N ₂ O (nitrous oxide) of 50 ppm or less. In order to prepare a high purity 99.99995% or more of ammonia is required, the high purity 99.99995% or more of ammonia can be prepared by a large-capacity purification method of high purity ammonia of the Korean Patent Publication No. 10-0584686 proposed by the applicant of the present invention. .

It is an object of the present invention to provide a reaction apparatus for producing high-purity nitrogen monoxide, which is capable of obtaining nitrogen monoxide by reacting ammonia and air suitable for a large-capacity manufacturing method at a high temperature, rather than a conventional method for producing nitrogen monoxide.

That is, the technical problem to be achieved by the present invention is to present a structure of a reactor most suitable for a method of producing nitrogen monoxide by reacting ammonia gas and air at a high temperature, and presenting a reactor having such a reactor structure, based on the mass synthesis of nitrogen monoxide. The purpose is to provide a reaction apparatus.

In order to achieve the above object, the present invention provides a high purity nitrogen monoxide production apparatus,

Mixing / pre-heating at equipped with a high-purity ammonia (NH ₃₎ supplies the air supplying ammonia from the apparatus (20) (NH ₃₎ and the mixture passed through the filter and the pre-heating heaters made of a four-stage receives the air supply to scale mixer and The mixed gas mixed in the mixer is heat treated to produce nitrogen monoxide, and the produced nitrogen monoxide is cooled to a low temperature below zero to pass a cooling separator separating water, thereby producing high purity nitrogen monoxide.

High-purity ammonia (NH ₃₎ supply and the ammonia out of the air supply (NH ₃₎ and receives the air supplied by a percentage mixed in a mixer, and the mixed gas mixed in the mixing reactor is heat-treated produced nitrogen monoxide, wherein The produced nitrogen monoxide is cooled to a low temperature below zero to pass through a cooling separator that separates moisture to produce high purity nitrogen monoxide,

The reactor has a cylindrical outer body formed with an inlet and an outlet for discharging nitrogen monoxide, which is a mixed gas reacted with a mixed gas, respectively, at both ends thereof, and an inner side of the cylindrical body disposed to form an air cooling port spaced apart from an inner surface of the outer body. A body, a plurality of catalyst support plates fixed to the inner body and a plurality of Pt-Rh catalysts spaced from the catalyst support, a plurality of temperature sensors for measuring the temperature in the inner body, and a heater controlled by the temperature sensor Characterized in that configured to include.

A drain port may be further installed between the reactor and the cooling separator.

Four pass filters are formed in the mixer, and the pass filters are formed of two first pass filters formed in the form of perforated plates with a plurality of pass holes formed therein, and two second pass filters formed with pass holes in the center thereof. The first pass filter and the second pass filter is characterized in that the installation is crossed with each other.

The catalyst support fixing plate is characterized in that it is fixed by a fixing spring installed on one side.

The catalyst support is installed on both sides of the Pt-Rh catalyst, characterized in that consisting of a frame and a mesh network.

According to the reactor for producing high-purity nitrogen monoxide according to the present invention made as described above, even if the reaction flow rate into the reactor is 30L or more, the reaction temperature is kept constant, and the concentration of moisture in nitrogen monoxide is also reduced to less than 50 ppm.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms or words used in the specification and claims should not be construed as having a conventional or dictionary meaning, and the inventors should properly explain the concept of terms in order to best explain their own invention. Based on the principle that can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention.

Therefore, the embodiments described in the specification and the drawings shown in the drawings are only the most preferred embodiment of the present invention and do not represent all of the technical idea of the present invention, various modifications that can be replaced at the time of the present application It should be understood that there may be equivalents and variations.

Figure 1 is a schematic diagram of a high purity nitrogen monoxide production reactor showing a preferred embodiment of the present invention.

As shown in FIG. 1, the reactor for producing high purity nitrogen monoxide includes an ammonia supply device 10 for supplying high purity ammonia (NH ₃ ) of 99.99995% or more at a constant flow rate, an air supply device 20 for supplying air at a constant flow rate, and A mixer provided with a mixing pass filter 32 and a preheating heater 35 having four stages of mixing and preheating high purity ammonia and air from the ammonia supply device 10 and the air supply device 20 at a predetermined ratio. 30 and a reactor 40 in which a plurality of Pt-Rh catalysts are installed to heat-treat the mixed gas mixed in the mixer 30 at a high temperature, and the nitrogen monoxide generated by the heat treatment in the reactor 40 is supplied with impurities. Drain port (50, Drain Port) for removing the phosphorus moisture, and the cooling separator (60, for separating the moisture by cooling the nitrogen monoxide passed through the drain port 50 to a low temperature (-30 ~ 0 ℃) Cold Trap) All.

The ammonia (NH ₃ ) supply device 10 is an ammonia (NH ₃ ) tank that stores a high purity ammonia (NH ₃ ) gas of 99.99995% or more, and a flow regulator for controlling the amount of ammonia supplied from the ammonia (NH ₃ ) tank It is configured to include an on / off valve to supply and block ammonia (NH ₃ ) at a constant flow rate.

The air supply device 20 is configured to include an air tank in which air is stored, a flow regulator for controlling the amount of air supplied from the air tank, and an opening / closing valve 23 to supply and block air at a constant flow rate.

The mixing chamber 30 has an inlet 31a through which ammonia and air are supplied at one end, and an outlet 31b through which a mixed gas mixed with ammonia and air is discharged at the other end of the inlet 31a. Is formed of a housing 31, a four-stage mixing passage filter 32 installed inside the housing 31, and a heater 35 for preheating the mixed gas to be mixed.

The mixed filter 32 is formed with a plurality of through holes as shown in FIG. 3 and two first through filters 33 formed in the form of a perforated plate, and two second through filters with a through hole formed in the center as shown in FIG. 34, the first pass filter 33 and the second pass filter 34 are installed to cross each other as shown in Figure 2 to mix the ammonia and air flowing into the inlet (31a).

The mixed gas of ammonia and air mixed through the mixed passage filter 32 is preheated by the heater 35.

The mixed gas is preheated to 120 ~ 130 ℃, when preheating the mixed gas in this way it is possible to remove the moisture contained in the air (AIR) gas. If the preheating temperature is less than 100 ° C., it is difficult to completely remove moisture, and thus it is preferable to maintain the above range.

The reactor 40, in which the plurality of Pt-Rh catalysts are installed, receives a mixed gas from the mixer 30 and heat-treats it to generate nitrogen monoxide, as shown in FIG.

The reactor 40 has a cylindrical outer body 41 having an inlet 41a and an outlet 41b for discharging nitrogen monoxide, which is a mixed gas reacted with the mixed gas, respectively, corresponding to both ends, and the outer body 41. A cylindrical inner body 42 installed to be spaced apart from an inner surface of the c), and an air cooling port 43 formed therein, a plurality of Pt-Rh catalysts 44 spaced apart from the inner body 42, and the Pt- A catalyst support 45 provided on both sides of the Rh catalyst 44 and a catalyst support fixing plate 46 for fixing the catalyst support 45 to maintain a gap therebetween, and for fixing the catalyst support 46. A fixed spring 46 ', a plurality of temperature sensors 47 for measuring the internal temperature, a heater 48 controlled by the temperature sensor 47, and a purge helium (He) supply pipe 49 Is done.

As shown in FIG. 8, the catalyst support fixing plate 46 is inserted into the inner body 42, the Pt-Rh catalyst 44 having the catalyst support 45 installed at both sides is inserted, and the catalyst support fixing plate 46 is inserted again. The inner body 42 by inserting the Pt-Rh catalyst 44 having the catalyst support 45 on both sides, inserting the catalyst support fixing plate 46, and inserting the fixed spring 46 '. Pt-Rh catalyst 44 is installed at regular intervals.

This installation method is characterized in that the installation position control and replacement of the catalyst of the Pt-Rh catalyst 44 is easy.

The catalyst support 45 is composed of a frame 45a and a mesh network 45b as shown in FIG.

The Pt-Rh catalyst 44 is usually composed of 2 to 5 stages, Nitro-Lok catalyst form as shown in Figure 7 (a), Pro-Lok catalyst form as shown in (b), Hi- as shown in (c) It is in the form of Lok catalyst.

The temperature sensor 45 is preferably installed to correspond to the Pt-Rh catalyst 44 to measure the internal temperature of the portion where the Pt-Rh catalyst 44 is installed.

The reactor for producing high-purity nitrogen monoxide by reacting ammonia gas and air of the present invention made as described above to produce high-purity nitrogen monoxide comprises passing ammonia (NH ₃ ) and air (AIR) through respective flow controllers at a constant ratio. 30, supplying and mixing into a mixing chamber; Generating nitrogen monoxide by passing the mixed gas mixed in the step through the catalytic reactor 40 at a high temperature (550 ° C. to 650 ° C.); Nitrogen monoxide produced in the step is passed through the drain port (50, the drain port) and the cooling separator 60 and cooled to remove the moisture as impurities.

When described in more detail the reaction apparatus for producing high purity nitrogen monoxide according to the present invention as follows.

1. Mixing in Mixing Chamber

99.99995% or more of high purity ammonia (NH ₃ ) made by refining metal impurities, gaseous impurities, moisture and oil contained in the raw material ammonia and air (AIR) is mixed at a constant ratio when using it as a raw material.

The ammonia (NH ₃ ) and air (AIR) is to be sufficiently mixed in a uniform ratio using a mixer, the volume ratio (Vol) of the high-purity ammonia and air as the raw material is 1: 1 to 15, preferably 1 It is good to mix in a ratio of 10.

At the time of mixing the ammonia (NH ₃ ) and air (AIR) to create a mixed gas by using a mixer after preheating to 120 ~ 130 ℃ to create an atmosphere.

2. Oxidation reaction in catalytic reactor

The mixed gas mixed in the mixing step is supplied to a high temperature (catalyst) reactor 40 and heat treated.

The temperature of the catalytic reactor is maintained at 550 ~ 650 ℃ heat treatment of the supplied mixed gas.

The catalytic reactor used for the heat treatment is not particularly limited, but in the present invention, an electric furnace having a Pt-Rh catalyst was used, and designed to adjust the position of the catalyst inside the reactor. If the temperature is less than 550 ℃ it is preferable to maintain the above range because a large amount of nitrogen monoxide is not synthesized and the content of impurities is increased.

In order to withstand the high temperature oxidation reaction, the material of the catalytic reactor is made of Sus 316L and the inner body is made of Hasteloy. If the inner body is made of Sus 316L, sus material corroded by high temperature oxidation is introduced into the gas and generated as metal impurities. Both the cost- and gas-efficient ones were fabricated from Hasteloy and Sus 316L from the outside of the reactor.

The heat treatment time is not particularly limited, but heat treatment may be performed continuously or discontinuously depending on the catalyst.

3. Cooling to remove moisture

The product obtained after the heat treatment in the step of oxidizing in the catalytic reactor is cooled by passing through a low-temperature cooling separator 60 to separate moisture as impurities.

Nitrogen monoxide, which is a product obtained after the heat treatment, is passed through a cooling separator 60 and cooled to minus 30 (−) 30 ° C. to separate moisture generated during synthesis, thereby lowering the impurity content of nitrogen monoxide. The temperature in the cold separator is preferably maintained in the above range.

The reaction apparatus for preparing high-purity nitrogen monoxide made as described above may maintain the reaction temperature even if the reaction flow rate into the reactor is increased, and reduce the concentration of moisture in nitrogen monoxide to less than 50 ppm, thereby producing nitrogen monoxide.

Hereinafter, an optimized reactor according to various embodiments of the reactor for producing high purity nitrogen monoxide as described above is invented.

[ Example  1] to [ Example  9]

Mix more than 99.99995% high purity ammonia (NH ₃ ) 2.3L, air (AIR) 20L, but mix the air (AIR) and ammonia (NH 3) in a mixer (30, Mixing Chamber) to preheat to 120 ℃ to create an atmosphere .

The mixed gas is supplied to an electric furnace which is a reactor to react (heat treatment) at a synthesis temperature of 600 ° C., and the reacted product (gas) is passed through a cooling separator 60 maintained at -30 ° C. to remove moisture as impurities. Removed to prepare high purity nitrogen monoxide.

When passing through the electric furnace which is the reactor 40, the inside of the reactor 30 is divided into three parts, but the positions are called 1, 2, and 3 from the inlet 41a side in the drawing (see FIG. 5), and the positions and numbers of the catalysts are different. The conversion efficiency of nitrogen monoxide according to the position and number of catalysts was measured and shown in Table 1 below.

The reactor size used in the experiment was 460mm, the outer diameter was 76mm, and the inner diameter was 60mm.

TABLE 1

division NH ₃
(L) AIR
(L) Reactor
Temperature (℃) Pt-Rh catalyst location and number NO efficiency
(%) One 2 3 Example 1 2.3 20 600 1 piece 1 piece 89.7 Example 2 2.3 20 600 1 piece 66.6 Example 3 2.3 20 600 1 piece 73.9 Example 4 2.3 20 600 1 sheet 74.4 Example 5 2.3 20 600 1 piece 1 sheet 82.8 Example 6 2.3 20 600 1 sheet 1 piece 77 Example 7 2.3 20 600 2 sheets 86.3 Example 8 2.3 20 600 1 sheet 1 piece 1 sheet 81.4 Example 9 2.3 20 600 3 sheets 85.5

[ Example 10] to [ Example 13]

After optimizing the position and number of catalysts in the reactor 40 through Examples 1 to 9, the ammonia gas and air were reacted under the same conditions, but the cooling separator 60 and the drain port 50 (Dain Port) were passed. The difference in water concentration was measured and shown in Table 2.

TABLE 2

division Catalyst location and number Passed H ₂ O (ppm) Cooling separator Drain port Example 10 1 sheet in position 1, 1 sheet in position 2 Passed Passed 50 Example 11 1 sheet in position 1, 1 sheet in position 2 Do not pass Do not pass 3700 Example 12 1 sheet in position 1, 1 sheet in position 2 Passed Do not pass 153 Example 13 1 sheet in position 1, 1 sheet in position 2 Do not pass Passed 1650

[ Example 14] to [ Example 16]

After optimizing the position and number of catalysts in the reactor 40 through Examples 1 to 9 are shown in Table 3 the difference in the conversion efficiency of nitrogen monoxide gas according to the structure of the catalyst under the same conditions.

[Table 3]

division NH ₃ (L) AIR (L) Reactor temperature (℃) Catalyst type NO efficiency (%) Example 14 2.3 20 600 Nitro-lok 70.2 Example 15 2.3 20 600 Pro-Lok 78.4 Example 16 2.3 20 600 Hi-lok 89.7

As shown in Table 1, when producing nitrogen monoxide gas by oxidizing 2.3L of ammonia gas flow rate and 20L of air at the reactor temperature of 600 ° C, the position and number of catalysts in the reactor were 1 position, 1 position, 2 positions, 1 sheet. The conversion efficiency of nitrogen monoxide was found to be the highest.

In addition, as shown in [Table 2], when the nitrogen monoxide gas generated by installing the cooling separator and the drain port at the rear of the reactor was allowed to pass through the cooler and the drain port, it was confirmed that water impurities generated during the synthesis process could be removed to 50 ppm or less. It was.

In Table 3, NO efficiency was tested according to the structure of the catalyst. As shown in [Table 3], even when the Pt-Rh catalyst had a Hi-Lok structure, the conversion efficiency of NO was determined to be the best.

Figure 1 is a schematic diagram of a high purity nitrogen monoxide production reactor showing a preferred embodiment of the present invention.

2 is a cross-sectional view of the mixer used in the reactor for producing high purity nitrogen monoxide.

3 is a front view of a first mixing pass filter of the mixing pass filter of the mixer;

4 is a front view of a second mixed pass filter of the mixing pass filter of the mixer;

5 is a cross-sectional view of a reactor used in the reactor for producing high purity nitrogen monoxide.

6 is a front view of the catalyst support installed in the reactor to support the catalyst.

Figure 7 is an enlarged view showing the Pt-Rh catalyst morphology showing the type of Pt-Rh catalyst.

8 is an exploded perspective view in which the Pt-Rh catalyst is installed on the inner body of the reactor.

9 is a graph of [Table 1] showing the efficiency of high purity nitrogen monoxide prepared by the method of Examples 1 to 9 of the present invention.

10 is a graph of Table 2 showing the measurement of the concentration of water in high purity nitrogen monoxide prepared by the method of Examples 10 to 13 of the present invention.

[Explanation of symbols on the main parts of the drawings]

10: ammonia (NH ₃ ) supply device 20: air supply device

30: mixer 31: housing

32, 33, 34: mixed pass filter 35: heater

40: reactor 41, 42: body

43: air cooling port 44: Pt-Rh catalyst

45: catalyst support 46: catalyst support fixed plate

50: drain port 60: cooling separator

Claims (5)

A high-purity ammonia (NH ₃ ) supply unit 10 and the air supply unit 20 receives ammonia (NH ₃ ) and air at a constant ratio, the four-pass mixing filter 32 and the preheating heater 35 Mixing / preheating in the mixer 30 is provided, the mixed gas mixed in the mixer 30 is heat-treated to generate nitrogen monoxide, the nitrogen monoxide is cooled to sub-zero temperatures to cool the moisture Passing through the separation of the cooling separator 60 to produce high-purity nitrogen monoxide, The mixed pass filter 32 is composed of two first pass filters 33 having a plurality of through holes formed in the form of perforated plates, and two second pass filters 34 having pass holes formed in the center thereof. The first pass filter 33 and the second pass filter 34 are installed to cross each other, The reactor 40 has a cylindrical outer body 41 having an inlet and an outlet for discharging nitrogen monoxide, which is a mixed gas reacted with the mixed gas, respectively, at both ends thereof, and spaced apart from the inner surface of the outer body 41. Cylindrical inner body 42 installed to form a cooling port 43 and a plurality of Pt-Rh catalysts spaced apart from the plurality of catalyst support fixing plates 46 and the catalyst support 45 on the inner body 42. (44), a plurality of temperature sensors (47) for measuring the internal temperature, and a heater (48) for producing a high purity nitrogen monoxide, characterized in that it comprises a heater controlled by the temperature sensor (47). A high-purity ammonia (NH ₃ ) supply unit 10 and the air supply unit 20 receives ammonia (NH ₃ ) and air at a constant ratio, the four-pass mixing filter 32 and the preheating heater 35 Mixing / preheating in the mixer 30 is provided, the mixed gas mixed in the mixer 30 is heat-treated to generate nitrogen monoxide, the nitrogen monoxide is cooled to sub-zero temperatures to cool the moisture Passing through the separation of the cooling separator 60 to produce high-purity nitrogen monoxide, The reactor 40 has a cylindrical outer body 41 having an inlet and an outlet for discharging nitrogen monoxide, which is a mixed gas reacted with the mixed gas, respectively, at both ends thereof, and spaced apart from the inner surface of the outer body 41. A cylindrical inner body 42 installed to form a cooling port 43, and a plurality of Hi-Lok spaced apart from the plurality of catalyst support fixing plate 46 and the catalyst support 45 on the inner body 42 High purity monoxide, characterized in that it comprises a Pt-Rh catalyst 44 in the form, a plurality of temperature sensors 47 for measuring the internal temperature, and a heater 48 controlled by the temperature sensor 47 Reactor for producing nitrogen. The method according to claim 1 or 2, Reactor device for producing high purity nitrogen monoxide, characterized in that the drain port 50 is further installed between the reactor 40 and the cooling separator (60). The method according to claim 1 or 2, The catalyst support fixing plate 46 is a high purity nitrogen monoxide production reactor, characterized in that fixed to the fixing spring 49 is installed on one side. delete

Images