阅读说明：本技术 一种溴化氢纯化方法 (A kind of hydrogen bromide purification process ) 是由 金向华 栗鹏伟 齐相前 侯倩 王亚亮 孙猛 王新喜 于 2019-10-14 设计创作，主要内容包括：本发明公开了一种溴化氢纯化方法,包括如下步骤：将溴化氢进行部分汽化；汽化后的溴化氢进入Nafion干燥器,深度去除溴化氢中的水分；去除水分后的溴化氢气体进入脱轻精馏塔；脱除轻组分的溴化氢进入脱重精馏塔,脱除溴化氢中的重组分；脱除重组分的溴化氢从脱重精馏塔的塔顶出料,进入溴化氢存储单元,得到电子级溴化氢产品。本发明在新型干燥剂的使用下,在简单高效的去除溴化氢中的水分的同时,不需要使用镍基合金等贵重材料加工设备,使用316L等材料便可,大大减低了设备投入。(The invention discloses a kind of hydrogen bromide purification process, include the following steps: hydrogen bromide carrying out part vaporization；Hydrogen bromide after vaporization enters Nafion drier, and depth removes the moisture in hydrogen bromide；Bromination hydrogen after removing moisture removal enters de-light rectification column；The hydrogen bromide for removing light component enters de- heavy distillation column, removes the heavy constituent in hydrogen bromide；The hydrogen bromide for removing heavy constituent discharges from the tower top of de- heavy distillation column, into hydrogen bromide storage unit, obtains electron level bromination hydrogen production.The present invention while moisture removed in hydrogen bromide being simple and efficient, does not need to greatly reduce equipment investment using materials such as 316L using the precious materials process equipment such as nickel-base alloy under the use of novel drier.)

1. a kind of hydrogen bromide purification process, which comprises the steps of:

(1) hydrogen bromide is subjected to part vaporization, vapourizing temperature is controlled at 0 DEG C to 30 DEG C；

(2) hydrogen bromide after vaporizing enters Nafion drier, and depth removes the moisture in hydrogen bromide；

(3) the bromination hydrogen after removing moisture removal enters de-light rectification column from the middle and upper part of de-light rectification column, de-light rectification column At -18 DEG C to 10 DEG C, the voltage-controlled system of the tower of de-light rectification column removes light group in hydrogen bromide in 0.7MPa to 1.8MPa for tower temperature control Point；

(4) hydrogen bromide for removing light component discharges from the tower bottom of de-light rectification column, enters de- weight from the middle and lower part of de- heavy distillation column Rectifying column, take off heavy distillation column tower temperature control at -18 DEG C to 10 DEG C, take off heavy distillation column tower it is voltage-controlled system 0.65MPa extremely 1.75MPa removes the heavy constituent in hydrogen bromide；

(5) hydrogen bromide for removing heavy constituent discharges from the tower top of de- heavy distillation column, into hydrogen bromide storage unit, obtains electron level Bromination hydrogen production.

2. hydrogen bromide purification process as described in claim 1, which is characterized in that in step (1), hydrogen bromide steel cylinder is heated Part vaporizes afterwards.

3. hydrogen bromide purification process as described in claim 1, which is characterized in that in step (2), Nafion drier is by bromination Moisture in hydrogen is reduced to 10ppb or less.

4. hydrogen bromide purification process as described in claim 1, which is characterized in that in step (3), the tower top of de-light rectification column is cold - 25 DEG C to -30 DEG C of condenser temperature, the light component condensed out generates motive force through gravity and the temperature difference, receives steel into lighter component Bottle, the quality of light component are the 1/5 to 1/12 of rectifying material, in step (4), take off the tower reactor of heavy distillation column through pressure difference gravity and temperature Difference, which produces motive force, makes the stable discharging of the tower reactor of de- heavy distillation column to heavy component receive steel cylinder, and the quality of heavy constituent is rectifying material 1/5 to 1/12, in step (5), the overhead condenser temperature for taking off heavy distillation column is -25 DEG C to -30 DEG C, and the product condensed out passes through Gravity and the temperature difference generate motive force and obtain electron level bromination hydrogen production, electron level bromination hydrogen production into hydrogen bromide storage unit Total impurities be less than 5ppm.

5. hydrogen bromide purification process as claimed in claim 4, which is characterized in that in step (3), light component receives steel cylinder and carries out Cold insulation processing, -25 DEG C to -30 DEG C of cold insulation temperature, in step (5), the progress cold insulation processing of bromination hydrogen production steel cylinder, cold insulation temperature - 25 DEG C to -30 DEG C.

6. hydrogen bromide purification process as claimed in claim 4, which is characterized in that in step (3), the tower top of de-light rectification column is not Solidifying gas enters alkali liquid washing tower, is vented after cleaning of off-gas, and in step (5), the tower top on-condensible gas of de- heavy distillation column enters alkali Liquid scrubbing tower is vented after cleaning of off-gas.

7. hydrogen bromide purification process as claimed in claim 4, which is characterized in that in step (3), the quality of light component is rectifying The 1/7 to 1/10 of material, in step (4), the quality of heavy constituent is the 1/7 to 1/10 of rectifying material.

8. hydrogen bromide purification process as described in claim 1, which is characterized in that all pipelines use EP grades of clean pipes.

9. hydrogen bromide purification process as described in claim 1, which is characterized in that the tower pressure of de-light rectification column is higher than de- rectifying again The tower pressure of tower.

10. hydrogen bromide purification process as described in claim 1, which is characterized in that hydrogen bromide storage unit is hydrogen bromide steel cylinder.

Technical field

The present invention relates to gas purification fields, and in particular to a kind of hydrogen bromide purification process.

Background technique

High-purity hydrogen bromide (HBr) is for the N-shaped polysilicon of semiconductor p-doped, the monocrystalline silicon of p-doped or two-dimensional semiconductor Etching, is the first choice of fluorine carbon gas instead product.It can pass through using hydrogen bromide as the plasma etching technology of etching gas The temperature for controlling the substance that is etched, which reaches, accurately controls the taper etch of vertical etch or the coning angle for having setting.Therefore, high Pure electron level HBr is mainly used for the etching polysilicon in 8 cun and 12 cun of chip manufacturing process, is the core gas of chip advanced process One of body.Furthermore hydrogen bromide is widely used due to having the ability as catalyst or reactant.It is pure in bromination hydrogen The problem of being most difficult to during changing is how to remove moisture therein, and moisture content is high, extremely strong to metallic material corrosion, while also Foreign gas is generated, product purity is influenced, this also becomes the most important restraining factors of high-purity bromination hydrogen preparation.Typically now Purification or dry common method to hydrogen bromide have freezing separation method, physisorphtion and chemical de-moisture method.Freezing separation, but Energy consumption is high, is difficult to control, industrial production has little significance.Physisorphtion, adsorbent include molecular sieve, silica gel, activated alumina Deng.Such as Matheson TRI Gas, Inc patent WO00/20101 (using the method for the water in superheated zeolites removal gas), Pu Lai Ke Si Technology Co., Ltd. patent WO2003/027581 (method and apparatus of purification hydrogen bromide), uses molecular sieve, silica gel, work Property the adsorbents such as aluminium oxide purify hydrogen bromide, easily part reaction and heat release, when especially water content is higher, while causing part bromine Change hydrogen loss, absorption method uses in the case that preferably moisture content is low in hydrogen bromide.Chemical de-moisture method, using to steam ten Divide sensitive or is easily reacted with water electrode but do not pass through chemical reaction dehydration with the substance of reaction of hydrogen bromide.Such as the bright chemical research of middle sky Co., Ltd, designing institute patent CN103318843 A (a kind of method of drying hydrogen bromide), these chemicals generally include Silicon bromide, phosphorus tribromide, lithium bromide etc., these chemical attacks are active, are to be difficult to control in large-scale production process, there are larger Security risk, be not suitable for so large-scale production.The production technology of hydrogen bromide has much room for improvement under industrial condition.

It essentially reacts, adsorb in existing hydrogen bromide purifying process, the way of purification such as rectifying.Teisan K.K. patent CN 1138314A prepares the method and apparatus of high purity hydrogen bromide, purifies the hydrogen bromide containing low boiling impurity, does not solve to remove The scheme of weight boiling contaminants, especially water in hydrogen bromide.107352511 A (bromination of Lv Ling Electron Material Co., Ltd patent CN Hydrogen purifying technique), hydrogen bromide is purified by the method for rectifying plus absorption and obtains electron level hydrogen bromide, but uses nickel in rectifier unit Based alloy etc., equipment investment is excessive, while aqueous bromination hydrogen is also to have corrosion to nickel-base alloy, corrodes to pure nickel outstanding Very, filling process is that heating pressurization fills, and the use of heating equipment, there are some potential safety problemss, propose more to safety High requirement.

Summary of the invention

The object of the present invention is to provide a kind of hydrogen bromide purification process, under the use of novel drier, are being simple and efficient Removal hydrogen bromide in moisture while, do not need to greatly reduce and set using the precious materials process equipment such as nickel-base alloy Standby investment.

In order to achieve the above objectives, the technical solution adopted by the present invention is that: a kind of hydrogen bromide purification process, including walk as follows It is rapid:

(1) hydrogen bromide is subjected to part vaporization, vapourizing temperature is controlled at 0 DEG C to 30 DEG C；

(2) hydrogen bromide after vaporizing enters Nafion drier, and depth removes the moisture in hydrogen bromide；

(3) the bromination hydrogen after removing moisture removal enters de-light rectification column from the middle and upper part of de-light rectification column, takes off light rectifying At -18 DEG C to 10 DEG C, the voltage-controlled system of the tower of de-light rectification column removes in hydrogen bromide in 0.7MPa to 1.8MPa for the tower temperature control of tower Light component；

(4) hydrogen bromide for removing light component discharges from the tower bottom of de-light rectification column, enters from the middle and lower part of de- heavy distillation column De- heavy distillation column, the tower temperature for taking off heavy distillation column control taken off at -18 DEG C to 10 DEG C the voltage-controlled system of tower of heavy distillation column 0.65MPa extremely 1.75MPa removes the heavy constituent in hydrogen bromide；

(5) hydrogen bromide for removing heavy constituent discharges from the tower top of de- heavy distillation column, into hydrogen bromide storage unit, obtains electricity Sub- grade bromination hydrogen production.

Further, in step (1), hydrogen bromide steel cylinder partially vaporizes after being heated.

Further, in step (2), the moisture in hydrogen bromide is reduced to 10ppb or less by Nafion drier.

Further, in step (3), -25 DEG C to -30 DEG C of the overhead condenser temperature of de-light rectification column is condensed out Light component generates motive force through gravity and the temperature difference, receives steel cylinder into lighter component, the quality of light component be rectifying material 1/5 to 1/12, in step (4), the tower reactor of de- heavy distillation column, which produces motive force through pressure difference gravity and the temperature difference, stablizes the tower reactor of de- heavy distillation column Discharging to heavy component receives steel cylinder, and the quality of heavy constituent is the 1/5 to 1/12 of rectifying material, in step (5), takes off heavy distillation column Overhead condenser temperature is -25 DEG C to -30 DEG C, and the product condensed out generates motive force through gravity and the temperature difference, into hydrogen bromide Storage unit, obtains electron level bromination hydrogen production, and the total impurities of electron level bromination hydrogen production are less than 5ppm.

Further, in step (3), light component receives steel cylinder and carries out cold insulation processing, -25 DEG C to -30 DEG C of cold insulation temperature, walks Suddenly in (5), the progress cold insulation processing of bromination hydrogen production steel cylinder, -25 DEG C to -30 DEG C of cold insulation temperature.

Further, in step (3), the tower top on-condensible gas of de-light rectification column enters alkali liquid washing tower, after cleaning of off-gas It is vented, in step (5), the tower top on-condensible gas of de- heavy distillation column enters alkali liquid washing tower, is vented after cleaning of off-gas.

Further, in step (3), the quality of light component is the 1/7 to 1/10 of rectifying material, in step (4), heavy constituent Quality be rectifying material 1/7 to 1/10.

Further, all pipelines use EP grades of clean pipes.

Further, the tower pressure of de-light rectification column is higher than the tower pressure of de- heavy distillation column.

Further, hydrogen bromide storage unit is hydrogen bromide steel cylinder.

Due to the above technical solutions, the present invention has the following advantages over the prior art:

1) hydrogen bromide purification process disclosed by the invention, under the use of novel drier, in the removal bromine being simple and efficient While changing the moisture in hydrogen, do not need using the precious materials process equipment such as nickel-base alloy, using materials such as 316L, greatly Equipment investment is reduced greatly；

2) hydrogen bromide purification process disclosed by the invention, is filled by low temperature, improves the safety filled；

3) hydrogen bromide purification process disclosed by the invention, it is contemplated that the cleanliness of electron level hydrogen bromide, pipeline use EP grades Cleaning pipe, it is ensured that product quality.

4) hydrogen bromide purification process disclosed by the invention carries out de-light rectification column by pressure difference and feeds to de- heavy distillation column, Without also subtracting on the basis of reducing equipment simultaneously using dynamic equipment such as pump or compressors in the purification system of entire hydrogen bromide The low contaminated probability of hydrogen bromide, improves the operability and stability of technique；

5) hydrogen bromide purification process disclosed by the invention, is applied in combination by de-light rectification column and de- heavy distillation column, is taken off light Tower removes H₂、N₂、CO、Ar、O₂、CH₄、C₂H₆、HCl、CO₂Equal low boiling impurities, weight-removing column remove H₂S、HI、H₂The heavy components such as O, Also metal bromide, solid particulate matter etc. are removed simultaneously, weight-removing column tower top obtains bromination hydrogen production；

6) hydrogen bromide purification process disclosed by the invention, select -25 to -30 degrees Celsius between refrigerant, avoid using at The refrigerants such as this higher liquid nitrogen, also lower the requirement to equipment material, reduce the cost；

7) hydrogen bromide purification process disclosed by the invention produces the hydrogen bromide of a small amount of production capacity, directly hydrogen bromide original Expect that steel cylinder is used when head tank, reduces equipment investment；Such as the device of the larger demand of production capacity, vaporizer is installed additional after device.

Detailed description of the invention

Fig. 1 is the composition schematic diagram of bromination hydrogen purification devices disclosed by the invention.

Wherein, 11, hydrogen bromide raw material steel cylinder；12, heating blanket；21, Nafion drier；31, de-light rectification column；32, it takes off Heavy distillation column；33, light component receives steel cylinder；34, the second cold insulation mechanism；35, heavy constituent receives steel cylinder；36, third cold insulation mechanism； 41, bromination hydrogen production steel cylinder；42, the first cold insulation mechanism.

Specific embodiment

In conjunction with accompanying drawings and embodiments, the invention will be further described:

Referring to Fig. 1, as shown in legend therein, a kind of bromination hydrogen purification devices, comprising:

Raw material feed unit comprising two hydrogen bromide raw material steel cylinders 11, the outside of every hydrogen bromide raw material steel cylinder 11 are set There is heating blanket 12；

Drying unit comprising Nafion drier 21, the feed inlet and hydrogen bromide raw material steel cylinder of Nafion drier 21 11 outlet connection, desiccant use polytetrafluoroethylene (PTFE) (Teflon) and perfluor -3,6- diepoxy -4- methyl -7- decene-sulfuric acid Copolymer；

Rectification cell comprising de-light rectification column 31 and de- heavy distillation column 32, the middle and upper part feed inlet of de-light rectification column 31 It is connect with the discharge port of Nafion drier 21, the middle and lower part feed inlet of de- heavy distillation column 32 and the tower bottom of de-light rectification column 31 go out Material mouth connection, the liquid-phase outlet of the overhead condenser of de-light rectification column 31 receive steel cylinder 33 with light component and connect, and light component receives The outside of steel cylinder 33 is equipped with the second cold insulation mechanism 34, and the second cold insulation mechanism 34 includes surrounding light component to receive the second cold of steel cylinder 33 But pipe and the second muff on the outside of the second cooling tube, the liquid-phase outlet and heavy constituent for taking off the tower reactor of heavy distillation column 32 receive Steel cylinder 35 connects, and the outside that every heavy constituent receives steel cylinder 35 is equipped with third cold insulation mechanism 36, and third cold insulation mechanism 36 includes ring The third cooling tube and the third muff on the outside of third cooling tube for receiving steel cylinder 35 around heavy constituent, de-light rectification column 31 The incoagulable gas of overhead condenser exports and the fixed gas gas vent of the overhead condenser of de- heavy distillation column 32 is separately connected To the entrance of alkali liquid washing tower 37；

Product receiving unit, including two bromination hydrogen production steel cylinders 41, bromination hydrogen production steel cylinder 41 and de- heavy distillation column 32 Overhead condenser liquid-phase outlet connection, the outside of every bromination hydrogen production steel cylinder 41 is equipped with the first cold insulation mechanism 42, first Cold insulation mechanism 42 includes surrounding the first cooling tube of bromination hydrogen production steel cylinder 41 and the first heat preservation on the outside of the first cooling tube Set.

Preferred embodiment in this implementation, all pipelines use EP grades of clean pipes.

It is below hydrogen bromide purification process, hydrogen bromide raw material steel cylinder carries out heating and carries out part vaporization, controls vapourizing temperature It is 10 degrees Celsius；Gas enters Nafion drier after vaporization, and depth removes moisture in hydrogen bromide；Bromination hydrogen after purification It into de-light rectification column, is fed from the middle and upper part of tower, the control of tower temperature degree is at 10 degrees Celsius, and for the voltage-controlled system of tower in 1.73MPa, tower top is cold - 25 to -30 degrees Celsius of condenser temperature, when de-light rectification column rectifying, removes H₂、N₂、CO、Ar、O₂、CH₄、C₂H₆、HCl、CO₂Etc. low Boiling contaminants, the quality of low boiling component are rectifying material 1/10, and the lighter component condensed out generates promotion through gravity and the temperature difference Power receives steel cylinder into lighter component, and lighter component receives steel cylinder and carries out cold insulation processing, -25 degrees Celsius of cold insulation temperature.De-light rectification column Tower top on-condensible gas enter alkali liquid washing tower, be vented after cleaning of off-gas.Heavy distillation column is taken off in the tower bottom discharging of de-light rectification column, It is fed from the middle and lower part of tower, the control of tower temperature degree is at 0 degree Celsius, and for the voltage-controlled system of tower in 1.28MPa, overhead condenser temperature -25 is Celsius Degree takes off hydrogen bromide liquid of the heavy distillation column tower reactor discharging containing heavy component, removes the heavy components such as H2S, HI, H2O, also remove gold simultaneously Belong to bromide, solid particulate matter etc.；The quality of weight boiling point component is rectifying material 1/10, and tower reactor is generated through pressure difference gravity and the temperature difference The discharging that motive force keeps the tower reactor of de- heavy distillation column stable to heavy component receives steel cylinder, -25 degrees Celsius of overhead condenser temperature, tower It pushes up the product condensed out and generates motive force through gravity and the temperature difference, into bromination hydrogen production steel cylinder, obtain the production of electron level hydrogen bromide Product, total impurities are less than 5ppm, and bromination hydrogen production steel cylinder carries out cold insulation processing, -25 degrees Celsius of cold insulation temperature.De- heavy distillation column Tower top on-condensible gas enters alkali liquid washing tower, is vented after cleaning of off-gas.

The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one The widest scope of cause.