KR20110032841A - The purification method of hbr and apparatus thereof - Google Patents

Abstract

PURPOSE: An ultra high pure hydrobromide purifier and a method thereof are provided to recover ultra high pure hydrobromide with the purity greater than 99.7%(mol) compare to a conventional device. CONSTITUTION: A purifying method of hydrobromide comprises the following steps: removing the moisture from the hydrobromide containing impurities, by transferring the hydrobromide inside a raw material tank(110) to an absorption tower(120); liquefying the hydrobromide using a heat exchanger(130); and removing air containing oxygen and nitrogen from the liquefied hydrobromide using a distillation tower(140) including a condenser(141), a separator(142), and a re-heater(143).

Description

Hydrogen bromide purification method and purification apparatus

The present invention relates to a method for purifying hydrogen bromide and a purifying apparatus, and more particularly, to a method and apparatus for purifying hydrogen bromide with high purity by removing impurities, moisture, and gaseous components such as oxygen and nitrogen from crude hydrogen bromide. The present invention also relates to an ultra-high purity hydrogen bromide purification method and apparatus for increasing the purity and maximizing the yield by using a distillation column to remove impurities remaining by the difference in boiling point of the gas.

Hydrogen bromide is widely used in cooling, pharmaceuticals, chemical fibers, etc. It is also used in the synthesis of pharmaceuticals such as sedatives and anesthetics. Recently, it is often used in major processes of semiconductor, LCD, and LED industries. In particular, when used as an etching solution, it is required to supply as high purity as possible in order to exhibit excellent performance. Therefore, technologies for increasing purity are constantly being developed.

Impurities of hydrogen bromide are mainly water (H ₂ O), oxygen, nitrogen, and the like, and adsorption is mainly used to remove such impurities, and the method of purifying hydrides such as hydrogen chloride and hydrogen bromide (HBr) using adsorption is mainly used. US Pat. No. 6,461,411 describes a method for removing SiH ₄ , H ₂ S, GeH _4, etc. using alumina. US Pat. Nos. 6,395,070 and 6,110,258 dehydrate and superheat zeolites having high silica content. A method of removing trace amounts of water is described. US Pat. Nos. 6,241,955 and 6,221,132 describe methods for purifying hydrides such as hydrogen chloride and hydrogen bromide using adsorbents such as metal oxides such as MnO _X and MoO _X or MgX ₂ supported on activated carbon.

In addition, U. S. Patent No. 4,925, 646 discloses drying of gaseous hydrogen halides, which supplies a scavenger precursor composition comprising a support in which some or all alkylated metal alkyl compounds or pendent groups are associated to remove water from gaseous halides. The method is described.

However, even though high purity hydrogen bromide can be obtained through such techniques, the yield of hydrogen bromide obtained is not so high. Therefore, there has been a demand for the development of a technology capable of recovering high purity hydrogen bromide at high yield.

Accordingly, an object of the present invention is to provide a hydrogen bromide purification device capable of obtaining ultra-high purity hydrogen bromide.

Another object of the present invention is to provide an ultra-high purity hydrogen bromide purification apparatus using a distillation column to further increase the purity and maximize the purification yield.

It is another object of the present invention to provide a method for purifying ultra high purity hydrogen bromide in high yield.

In order to achieve the above object, the present invention provides a water removal step of removing moisture by (a) transferring the hydrogen bromide containing impurities present in the raw material tank to an adsorption tower filled with a moisture adsorbent, and (b) water content. Liquefaction step of transferring the removed hydrogen bromide to the heat exchanger, (c) to transfer the liquefied hydrogen bromide to the distillation column having a condenser at the top and a reheater at the bottom to remove air components containing oxygen and nitrogen It provides a method for purifying hydrogen bromide comprising the step of removing the air component, and (d) transferring the purified ultra-high purity hydrogen bromide to the storage tank through a pump.

Preferably, the adsorption tower of the present invention is composed of two adsorption towers, one of which alternately performs a water removal function and the other of the adsorption regeneration function, and the direction of the compressed air supplied to each of the adsorption towers through a directional valve. It switches and controls the operation of this directional valve via a control panel with integrated solenoid valve and timer. This can greatly improve the water removal capacity.

The heat exchanger uses an expansion valve and a freezer to liquefy the dehydrogenated hydrogen bromide and lower the temperature. Through this, high purity hydrogen bromide can be obtained in high yield.

The distillation column is provided with a tray or a filling material therein, and preferably further includes a separator at the top to be discharged to the top of the distillation column to separate the condensed material through the condenser to discharge the waste water, and return the remaining water except the waste water to the distillation column. To recycle. The distillation column can further increase the yield by recovering hydrogen bromide lost in the liquefaction process cooled by the heat exchanger, and can further remove oxygen and nitrogen, which are residual impurities, by using the difference in boiling point of the gas from the liquefied hydrogen bromide. Since purity can also be improved, ultra high purity hydrogen bromide can be recovered in high yield.

In addition, the present invention, (a) a raw material tank containing hydrogen bromide containing impurities, (b) an adsorption tower filled with a moisture adsorbent for removing the water of hydrogen bromide transported from the raw material tank, (c) the moisture through the adsorption tower A heat exchanger for liquefying the removed hydrogen bromide, (d) a device for transferring liquefied hydrogen bromide through the heat exchanger to remove air constituents containing oxygen and nitrogen, including a condenser at the top and a reheater at the bottom; Provided is a hydrogen bromide purification device consisting of a distillation column consisting of a stage, (e) a pump for transferring the hydrogen bromide from which the air component from the distillation column is removed to a storage tank, and a storage tank for storing the hydrogen bromide transferred from the pump.

Preferably, the adsorption column of the present invention is an activated alumina, silica gel, alumina silica gel, molecular sieves, bouxite, zeolite as a water adsorbent. Adsorbents such as

The distillation column includes a tray or a filling material therein, and further includes a separator for discharging the condensed material through the condenser to discharge the waste water and recycling the remaining water except the waste water to the distillation column for recycling.

Therefore, through the hydrogen bromide purification method and purification apparatus of the present invention, it is possible to recover ultra-high purity hydrogen bromide having a higher purity than the prior art with a maximum purification yield of 99.5% (mol) or more.

In order to achieve the above object, the present invention is a device for purifying hydrogen bromide with ultra high purity, the raw material tank for storing crude hydrogen bromide containing water, oxygen and nitrogen, the water of hydrogen bromide from the raw material tank The adsorption tower to remove (H ₂ O), the nitrogen contained in the hydrogen bromide from which the water from the adsorption tower was removed, the heat exchanger to cool and liquefy hydrogen bromide to remove oxygen, and the difference in boiling point of gas from the liquefied hydrogen bromide. By removing the residual air components such as oxygen and nitrogen and recovering the hydrogen bromide that can be lost in the liquefaction step to transfer ultra-high purity hydrogen bromide recovered from the distillation column, distillation column to obtain ultra-high purity hydrogen bromide in high yield to the storage tank It is characterized by consisting of a storage tank for storing the pump and conveyed ultra-high purity hydrogen bromide .

Metal materials that can be used in the refiner of the present invention are aluminum and its alloys, copper, copper-zinc alloys, copper-nickel alloys, copper-tin alloys, iron, carbon steel, stainless steel, nickel-chromium alloys, silver and the like. Alloys, tantalum, tin, and the like, preferably copper-zinc alloy, copper-nickel alloy, copper-tin alloy, carbon steel, stainless steel, nickel-chromium alloy, silver and alloys thereof, tantalum, and more preferably. Are copper-nickel alloys, copper-tin alloys, stainless steels, nickel-chromium alloys, tantalum. Sealing materials include Buna S ®, Buna N ®, Viton ®, Neoprene ®, Kel-F ®, Teflon ®, preferably Viton ®, Neoprene ®, Kel-F ®, Teflon ® and more preferably Kel -F ®, Teflon ®.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

1 is a view schematically showing a purification apparatus for purifying hydrogen bromide according to the present invention with high purity. Hydrogen bromide purification apparatus 100 of the present invention is a raw material tank 110, the hydrogen bromide mixed with water, oxygen and nitrogen is stored, the adsorption tower 120 for removing water from the hydrogen bromide from the raw material tank 110, the moisture is Heat exchanger 130 for cooling and liquefying to remove oxygen and nitrogen as air components contained in the removed hydrogen bromide, liquefied hydrogen bromide further removes oxygen and nitrogen by using the boiling point difference of the gas, and ultra-high purity bromination Distillation column 140 for recovering hydrogen in a high yield, the storage tank 160 for storing the purified ultra-high-purity hydrogen bromide from the distillation column via the pump 150.

Preferably, the adsorption tower 120 is configured by at least two or more when the water removal ability is reduced is configured to switch to perform alternately to significantly improve the water removal ability. Moisture removal is necessarily due to the adsorbent because water and hydrogen bromide are eutectic compounds (see Fig. 2) because it is impossible to remove by a phase separator or a liquefaction method, so it is safe to remove with a moisture adsorbent.

More specifically, the air is contacted with the solid adsorbent to be adsorbed into the micropores of the adsorbent to remove moisture. This is in terms of thermal efficiency. Although lower than the method, it is higher than the hygroscopic method in terms of water removal efficiency. This adsorption process can be accomplished through two adsorption towers with adsorbents, one of which switches the direction of the compressed air supplied to the two adsorption towers to alternately perform the water removal function and the other regeneration of the adsorbent. It consists of a control panel with a built-in directional valve and a solenoid valve and timer to control the operation of the directional valve.

The adsorption tower 120 has activated alumina, silica gel, alumina silica gel, molecular sieves, bouxite, zeolite, zeolite, etc. as a moisture adsorbent therein. The same adsorbent is filled.

Nitrogen or oxygen in the air is not mixed with HBr (see Fig. 3). In case of batch purification, the air component can be removed by theoretical means.

Preferably, the heat exchanger 130 includes an expansion valve for reducing the pressure of the hydrogen bromide and a freezer for liquefying the hydrogen bromide at a low temperature. Since the hydrogen bromide passed through the adsorption tower 120 contains air components such as oxygen and nitrogen, the hydrogen bromide is a device for purifying hydrogen bromide of high purity by removing them. The freezer uses a 1.3 horsepower freezer with a safety factor of 1.13 horsepower used for liquefaction.

Distillation column 140 for further increasing the purity of the recovered high-purity hydrogen bromide and further improve the yield is preferably, the reheater 143 is provided at the bottom in consideration of the relative efficiency of the distillation column efficiency due to the viscosity of the fluid, The condenser 141 is provided. In addition, the theoretical stages are calculated and applied, preferably eight stages. Between the reheater 143 and the condenser 141 is provided a common tray or other irregular filling material as the filling in the required position. In addition, the upper part of the distillation column 140 to separate the condensation of the gas from the top of the distillation column 140 by the condenser 141 to discharge the waste water from the bottom and the fluid discharged from the upper back to the distillation column to recirculate the separator ( 142 is provided.

Hereinafter, a method for purifying ultra high purity hydrogen bromide according to the present invention will be described.

Moisture from the raw material tank 110 and the crude hydrogen bromide containing oxygen, nitrogen is transferred to the adsorption tower 120 to remove the moisture. Hydrogen bromide from which moisture is removed using the adsorption tower 120 is transferred to the heat exchanger 130 to remove oxygen and nitrogen, which are impurities, to open the expansion valve, drop the pressure, and lower the temperature through the freezer to liquefy. The liquefied hydrogen bromide is transferred to the distillation column 140 using the heat exchanger 130 to further remove oxygen and nitrogen by using the difference in boiling point of the gas, and to recover the hydrogen bromide lost in the liquefaction step. Purify the hydrogen bromide. Ultra-high purity hydrogen bromide purified using the distillation column 140 is stored in the storage tank 160 via the pump 150.

The present invention will be described in more detail with reference to the following Examples.

Purity HBr raw material present in 98%, 0.1% moisture, 0.05% nitrogen, 0.05% oxygen, 20kg / hr, 25 degrees, 24Bar of production was transferred from the raw material tank 110 to the adsorption tower 120 to remove water. Hydrogen bromide from which water was removed through the adsorption tower 120 was transferred to the heat exchanger 130 to undergo liquefaction to remove oxygen and nitrogen.

Hydrogen bromide from which the water transferred to the heat exchanger 130 was removed was liquefied when the pressure was reduced from 24Bar to 15Bar when the expansion valve and the refrigerator were used, and the temperature was cooled from 25 ° C to 5 ° C. Table 1 is shown. When water-removed hydrogen bromide (S1 in Table 1) was flowed at a fluid rate of 0.2473 kg-mol / hr, the fluid velocity of high-purity hydrogen bromide (S3 in Table 1) recovered in a liquid state was 0.2132 kg-mol / It can be seen that the hr is recovered in a yield of 86.2% (mol).

TABLE 1

The liquefied hydrogen bromide was transferred to the distillation column 140 to further increase the purity and further improve the yield through the heat exchanger 130. Hydrogen bromide containing air components such as oxygen and nitrogen through the distillation column 140 is distilled by using a difference in boiling point, and the hydrogen bromide, which is a high boiling point material, is recovered at a high purity from the bottom and stored in a storage tank through the pump 150. Transfer to the 160, and discharge the oxygen and nitrogen as a low boiling point to the upper and condensate it through the condenser 141 and then discharge the waste water from the separator 142, the remaining fluid except the waste water to the distillation column 140 Recycled.

Table 2 shows experimental data of hydrogen bromide purified to ultra high purity through the distillation column 140.

TABLE 2

High-purity hydrogen bromide (liquefied through the heat exchanger 130) and recovered in a liquid state when flowing hydrogen bromide (S1 in Table 2) at a fluid rate of 0.2473 kg-mol / hr mixed with gas and liquid (Table 2 The flow rate of S3) was 0.2460 kg-mol / hr, indicating a yield of 99.5% (mol). This can be seen that the yield of high purity hydrogen bromide is significantly improved as compared with the yield of 86.2% (mol) derived from the results shown in the experimental data <Table 1> only through the heat exchanger (130).

In addition, the amount of oxygen and nitrogen to be removed is also 2.3528 × 10 ⁻⁴ kg-mol / hr in Table 2, when compared to 2.1418 × 10 ⁻⁴ kg-mol / hr in Table 1. It can be seen that the ultra-high purity hydrogen bromide is further refined.

Each of the devices may additionally include a power source, a temperature sensor, a humidity sensor, a pressure sensor, various types of valves, a panel displaying a current state of each device, and the like, necessary to control the device. It is obvious to those skilled in the art. In addition, if necessary, additional heat exchangers, surge tanks, boilers, condensers, feed pumps, compressors, etc. may be further included.

1 is a process diagram schematically showing a purification apparatus for purifying hydrogen bromide according to the present invention with high purity.

2 is a graph of the vapor / liquid molar fraction of HBr in water and HBr.

3 is a graph of the vapor / liquid molar fraction of HBr in air and HBr.

<Explanation of symbols for the main parts of the drawings>

100: hydrogen bromide purification device

110: raw material tank, 120: adsorption tower,

130: heat exchanger, 140: distillation column,

141: condenser, 142: separator,

143: reheater, 150: pump,

160: storage tank

Claims (11)

(a) a water removal step of removing water by transferring hydrogen bromide containing impurities present in the raw material tank to an adsorption tower; (b) liquefaction step of liquefied by transferring the removed hydrogen bromide to a heat exchanger; And (c) purifying the hydrogen bromide comprising the air component removal step of removing the air component containing oxygen and nitrogen by transferring the liquefied hydrogen bromide to the distillation column having a condenser and separator at the top and a reheater at the bottom . The method for purifying hydrogen bromide according to claim 1, wherein the water removal is performed using any one or more moisture adsorbents of activated alumina, silica gel, molecular sieve, alumina silica gel, bauxite and zeolite. The method of claim 1, wherein the adsorption tower is composed of two adsorption towers, one of which removes moisture and the other of alternately performing adsorbent regeneration. The method for purifying hydrogen bromide according to claim 1, wherein the material discharged to the upper part of the distillation column and condensed through the condenser is separated from the separator to discharge waste water, and the remaining water except the waste water is recycled to the distillation column for recycling. . (a) a raw material tank containing hydrogen bromide containing impurities; (b) an adsorption tower filled with a moisture adsorbent for removing moisture of hydrogen bromide transferred from the raw material tank; (c) a heat exchanger for liquefying hydrogen bromide from which water is removed through the adsorption tower, and (d) Hydrogen bromide purification apparatus comprising a distillation column comprising a condenser at the top and a reheater at the bottom to transfer the liquefied hydrogen bromide through the heat exchanger to remove air components including oxygen and nitrogen. 6. The hydrogen bromide purification apparatus according to claim 5, further comprising a pump for transferring the hydrogen bromide from which the air component from the distillation column is removed to the storage tank and a storage tank for storing the hydrogen bromide transferred from the pump. The hydrobromide purification apparatus according to claim 5, wherein the water adsorbent of the adsorption tower comprises any one or more of activated alumina, silica gel, molecular sieve, alumina silica gel, bauxite and zeolite. The method according to claim 5 or 7, wherein the adsorption tower is composed of two adsorption towers alternately performing a water removal function on one side and an adsorbent regeneration function on the other side, and the direction of compressed air supplied to the two adsorption towers. Hydrogen bromide purification apparatus comprising a control panel with a built-in direction switching valve for switching the operation, the solenoid valve for controlling the operation of the direction switching valve and a timer. 6. The hydrogen bromide refining apparatus according to claim 5, wherein the heat exchanger includes an expansion valve for depressurizing the dehydrogenated hydrogen bromide and a freezer for making it at a low temperature. 6. The hydrogen bromide refining apparatus according to claim 5, wherein the distillation column is composed of eight stages. The method of claim 5 or 10, wherein the distillation column is discharged to the top to separate the condensed material through the condenser to discharge the waste water, and further comprising a separator for recirculating the remaining water except the waste water to the distillation column. Hydrogen bromide refining apparatus.

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