CN104973573B - A kind of preparation method of the preparation method and high-pure hydrofluoric acid of high-purity hydrogen fluoride - Google Patents
A kind of preparation method of the preparation method and high-pure hydrofluoric acid of high-purity hydrogen fluoride Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of the preparation method and high-pure hydrofluoric acid of high-purity hydrogen fluoride, the preparation method of high-purity hydrogen fluoride is comprised the following steps：1) under conditions of isolation air, 1～17 DEG C, 0.1～0.2MPa, barium compound and/or calcium compound are added in liquid fluorinated hydrogen feedstock and are reacted, obtain mixture；2) fluorine nitrogen mixed gas are passed through into step 1) obtained by carry out oxidation reaction in mixture, obtain thick hydrogen fluoride；3) thick hydrogen fluoride carries out negative pressure and slightly evaporates, and obtains mixed gas；4) mixed gas carry out negative pressure rectifying, obtain final product high-purity hydrogen fluoride.High-purity hydrogen fluoride obtains high-pure hydrofluoric acid through allotment.The present invention is different from the boiling point of impurity in industrial hydrofluoric acid raw material using hydrogen fluoride, and the different solubility in hydrogen fluoride and industrial hydrofluoric acid raw material after impurity conversion in acid removes various impurity, especially anionic impurity and fluosilicic acid component, high-purity hydrogen fluoride is obtained, and then obtains high-pure hydrofluoric acid.
Description
Technical field
The invention belongs to super clean, high purified hydrofluoric acid preparing technical field, and in particular to a kind of preparation method of high-purity hydrogen fluoride
And the preparation method of high-pure hydrofluoric acid.
Background technology
High-pure hydrofluoric acid, molecular formula HF, molecular weight 20.01；Colourless transparent liquid, relative density 1.15～1.18, boiling point
112.2 DEG C, smoke in atmosphere, irritant smell, severe toxicity；Can react with common metal, metal oxide and hydroxide
Generate various salt；Its corrosivity is stronger, can attack glass and the gaseous ocratation of silicate generation；Soluble in water, alcohol, indissoluble
In other organic solvents.
High-pure hydrofluoric acid is highly acid cleaning, corrosive agent, can be with nitric acid, glacial acetic acid, hydrogen peroxide, sulfuric acid, hydrochloric acid and hydrogen-oxygen
Change ammonium etc. and prepare use, be mainly used in the cleaning and corruption of integrated circuit (IC) and super large-scale integration (VLSI) chip
Erosion, is one of key foundation chemical materials in microelectronic industry manufacturing process, it may also be used for makes analytical reagent and prepares high
The fluorine-containing chemical of purity.At present, substantially it is used for microelectronic industry as etchant and cleaning agent at home.
International SEMI (Semiconductor Equipment and Materials International) standardization group
The practical development situation worldwide according to high purity reagent is knitted, is classified by kind, each kind merger refers to for one
The standard of the property led, including multiple grades for different process technology.The high-pure hydrofluoric acid of external existing production meets SEMI-
Grade5 is required, is required suitable for the making less than 0.09 μm of IC technology, but the high-pure hydrofluoric acid of domestic enterprise's production is current
It is only applicable to mostly SEMI-C7 (Grade2) requirements, it is adaptable to which the making of 0.8-1.2 μm of IC technology is required, and product quality ginseng
Difference is uneven.
Impurity in commercial fluorided hydrogen feedstock is mainly derived from fluorite and sulfuric acid, and the fluorite impurity component of different sources is each
It is different, with regard to the removal of impurity, relate generally to the cation impurities such as arsenic, magnesium, calcium, chromium, chloride, nitrate, sulfate, phosphate
Deng anionic impurity, and fluosilicic acid (H2SiF6) composition.
Domestic existing hydrofluoric acid purification technique mainly has three kinds of malleation rectifying, negative pressure rectifying and sub-boiling distillation, its Central Asia
Boiling distillation is only suitable for laboratory and prepares in a small amount, is difficult industrial applications.Malleation rectifying and negative pressure rectifying are most widely used hydrogen
Fluoric acid method of purification.Most cation impurities all can be removed by rectifying means, but AsF3It is more or less the same with hydrofluoric acid boiling point, only
Unsatisfactory by rectifying separating effect, the method for adopting at present is that volatility trivalent arsenic is changed into nonvolatile five by oxidant
Valency arsenic, is then removed by washing, rectifying.The method of oxidant arsenic removal include hydrogen oxide method, permanganimetric method, fluorine gas method,
PtF6Method and high-molecular chelating agent and mixed bed zwitterion system absorption method etc., these methods only focused on arsenic etc. sun from
The removal of sub- impurity, anionic impurity and fluosilicic acid (H2SiF6) removal of composition seldom refers to, as anionic impurity is in water phase
The stable components such as middle formation sulfate, phosphate, fluosilicic acid (H2SiF6) composition stable existence in water phase, anionic impurity and
Fluosilicic acid (H2SiF6) composition remove difficulty it is very big.
Patent CN103086327A discloses a kind of preparation method of super clean, high purified hydrofluoric acid, and which is fluorinated with technical grade dry state
Hydrogen is raw material, and derived hydrogen fluoride gas pass through molecular sieve adsorption, 0.01 μm of filter element filtering, barium fluoride and silver fluoride aqueous solution
Afterwards, absorbed with ultra-pure water, and add hydrogen peroxide reaction, after carrying out rectifying, be prepared for high-pure hydrofluoric acid.The cation impurity of product
In below 0.01ppb, anionic impurity is less than 20ppb, but fluosilicic acid (H to content2SiF6) composition at least 13000ppb with
On, single fluosilicic acid (H2SiF6) the too high manufacturing process that can equally affect microelectronic industry of component content.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the preparation method and high-pure hydrofluoric acid of high-purity hydrogen fluoride, not only
The cation impurities such as arsenic removal, magnesium, calcium, chromium can be effectively removed, anionic impurity and fluosilicic acid (H can also be further removed2SiF6)
Composition, so as to greatly improve product purity, with suitable for microelectronics industry technology, especially super large-scale integration.
In order to realize object above, the technical solution adopted in the present invention is：A kind of preparation method of high-purity hydrogen fluoride, bag
Include the following steps：
1) under conditions of isolation air, 1～17 DEG C, 0.1～0.2MPa, barium compound and/or calcium compound are added
Reacted in liquid fluorinated hydrogen feedstock, obtained mixture；
2) to step 1) obtained by be passed through fluorine nitrogen mixed gas in mixture and carry out oxidation reaction, obtain thick hydrogen fluoride；
3) by step 2) obtained by thick hydrogen fluoride carry out negative pressure and slightly evaporate, obtain mixed gas；
4) by step 3) obtained by mixed gas carry out negative pressure rectifying, obtain final product high-purity hydrogen fluoride.
The present invention step 1) (removal of impurities) reaction and step 2) oxidation reaction process in be fluorinated hydrogen feedstock with liquid shape
Formula is present, and the impurity such as barium compound and/or calcium compound and silicon, phosphorus, sulphur, arsenic is combined generates barium fluosilicate, barium sulfate, fluosilicic acid
The difficulty soluble salts such as calcium, calcium sulfate or barium phosphate, so as to utilize the different of solubility in hydrofluoric acid to remove.Prior art is more with gaseous state
Form carries out removal of impurities and oxidizing process to commercial fluorided hydrogen feedstock, easily introduces introduced contaminants, and the purity to reagent treatment will
Ask very high, inevitably introduce other impurities ion in many cases.
Lower boiling arsenide is converted into high boiling arsenide by fluorine nitrogen mixed gas by the present invention, and then by thick
Evaporate, distillation process, remove low boiling impurity and high-boiling-point impurity respectively, and further remove the anionic impurities such as sulphur removal, silicon.
The present invention solves the anionic impurities such as silicon, sulphur, phosphorus, arsenic by the conversion of liquid phase impurity and oxidizing process
With fluosilicic acid (H2SiF6) composition is difficult the difficult problem that removes, using thick, rectifying so that product purity is further lifted.
Directly can take out after the purified process of the fluorochemical of by-product in process of the present invention, after thick, smart gold-plating, bottom of towe is residual
Sour (the generally mixture of hydrofluoric acid, fluosilicic acid) can be used to produce ice crystal, and what this invented alleviates environmental protection pressure, reduces
Consume, saved cost.
Step 1) in, isolation air, 1～17 DEG C, the environmental condition of 0.1～0.2MPa, it is ensured that liquid fluorinated hydrogen feedstock
It is stable, it is that impurity conversion and the oxidation reaction of next stage is ready.
Step 1) mechanism of action of the barium compound is using containing in barium compound and industrial liquid fluorination hydrogen feedstock
A large amount of ocratations or fluosilicate, sulfur dioxide, sulfur trioxide, sulfate, phosphate reaction generate be insoluble in hydrofluoric acid
Material, so as to be easily removed.Barium compound can meet above-mentioned requirements, preferably, barium compound be barium fluoride,
At least one of barium chloride, brium carbonate.
Step 1) calcium compound is identical with the mechanism of action of barium compound, and preferably, calcium compound is fluorine
Change at least one of calcium, calcium carbonate.
Step 1) generation such as barium compound and/or calcium compound and silicon, sulphur, phosphorus, arsenic removal of impurities reaction preferred reaction time
For 1～3h.The addition of barium compound and/or calcium compound is determined according to commercial fluorided hydrogen feedstock impurity content, it is ensured that barium
Compound and/or calcium compound are somewhat excessive, preferably, in terms of commercial fluorided hydrogen feedstock quality, barium compound and/or calcium
The addition of compound is 0.5～2%.
Step 2) using fluorine nitrogen mixed gas, react excessively fierce after can avoiding being passed through pure fluorine gas, easily cause security incident
Disadvantage, preferably, fluorine gas accounts for the 5%～20% of fluorine nitrogen mixed gas quality, and the consumption of fluorine nitrogen mixed gas is liquid fluorine
Change the 0.005～0.03% of hydrogen feedstock quality.The strong oxidizing property of fluorine gas by industrial liquid be fluorinated hydrogen feedstock in sulfur dioxide and
Arsenic trifluoride is oxidized to sulfur trioxide and arsenic pentafluoride, so as to be easily removed.To ensure fully carrying out for oxidation reaction, during reaction
Between be preferably 1～5h.
According to the content of impurities of commercial fluorided hydrogen feedstock, step 2) after oxidation reaction terminates, can be according to actual conditions
Carry out filtering and impurity removing.Removal of impurities can be carried out using various filter plants, removal of impurities is carried out preferably by 5 μm of filters.
Step 3) slightly evaporate process for negative pressure, by step 2) obtained by thick hydrogen fluoride be passed through topping still bottom, at 10～22 DEG C
At a temperature of raw material acid is continuously increased, control reflux ratio, make in tower air-liquid two-phase close contact repeatedly, remove lower boiling miscellaneous
Matter, such as SO2、SiF4Deng, it is to ensure slightly to evaporate efficiency and product quality, 10～22 DEG C of the bottom temperature that control slightly evaporates, outlet temperature
For -5～-10 DEG C, pressure is less than 0.1Mpa.
Step 4) for negative pressure distillation process, step 3) obtained by mixed gas be passed through rectifier bottoms, in 40～65 DEG C of temperature
Raw material acid is continuously increased under degree, control reflux ratio, remove high boiling impurity, such as H2SO4、H2O and metal ion etc., are guarantor
Card rectification efficiency and product quality, the bottom temperature for controlling rectifying are 40～65 DEG C, and outlet temperature is 15～20 DEG C, and pressure is less than
0.1Mpa。
The preparation method of the high-pure hydrofluoric acid that the present invention is provided, comprises the following steps：
1) under conditions of isolation air, 1～17 DEG C, 0.1～0.2MPa, barium compound and/or calcium compound are added
Reacted in liquid fluorinated hydrogen feedstock, obtained mixture；
2) to step 1) obtained by be passed through fluorine nitrogen mixed gas in mixture and carry out oxidation reaction, obtain thick hydrogen fluoride；
3) by step 2) obtained by thick hydrogen fluoride carry out negative pressure and slightly evaporate, obtain mixed gas；
4) by step 3) obtained by mixed gas carry out negative pressure rectifying, obtain final product high-purity hydrogen fluoride；
5) by step 4) obtained by high-purity hydrogen fluoride add water and allocated, obtain high-pure hydrofluoric acid.
When high-purity hydrogen fluoride is allocated, high purity water is selected to be deployed into a certain proportion of hydrofluoric acid solution.Allocation process
For prior art, can allocate to proper ratio according to needs.Preferably, the gas for rectifying column being exported is from spray-absorption
Tower bottom is passed through, the high purity water lower with tower top spray mixing preparation in proportion, prepared 48%～49% high-pure hydrofluoric acid finished product.
According to the impurity content and each enterprise practical condition of production of commercial fluorided hydrogen feedstock, can according to need select microporous barrier
Filtering technique is controlling granule foreign content.Microporous membrane filter techniques can adopt the phase of patent CN101570318B record inside the Pass
Hold, in step 4) derived from after the allotment of high-purity hydrogen fluoride, first obtain thick hydrofluoric acid solution, High Purity Hydrogen obtained Jing after micro-pore-film filtration
Fluoric acid finished product.Preferably, thick hydrofluoric acid solution, Jing after the micro-pore-film filtration of 0.1 μm and two grades 0.02 μm of one-level automatically
It is filling make 48%～49% high-pure hydrofluoric acid finished product.Filtered by two-stage mocromembrane, can further reduce granule foreign and contain
Amount, can solve the problems, such as that some domestic high-pure hydrofluoric acid producer particles are not up to standard.
The high-pure hydrofluoric acid of gained of the invention reaches semiconductor SEMI-Grade5 standards, meets the demand of semicon industry,
Especially needs of super large-scale integration.Finished product index：Cation≤0.01ppb, fluosilicic acid (H2SiF6), sulfate (with
SO4Meter), phosphate is (with PO4Meter) anion-content is all not more than 10ppb.
Description of the drawings
Preparation method schematic flow sheets of the Fig. 1 for the high-pure hydrofluoric acid of the embodiment of the present invention 2～4.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
The preparation method of the high-purity hydrogen fluoride of the present embodiment, comprises the following steps：
1) Nitrogen gas purifying system is used, air in removal system maintains 22.5 DEG C of room temperature, and the temperature of operating position is 22.5
DEG C, humidity is maintained at 40%；The liquid fluorinated hydrogen feedstock of 300kg is added into the pretreatment reaction kettle with heat exchanger, temperature is controlled
For 17 DEG C, in kettle, pressure is 0.1MPa；Barium fluoride and calcium chloride are added, its total addition is that 4.50kg (accounts for liquid hydrogen fluoride former
Material quality 1.5%), with liquid fluorinated hydrogen feedstock in ocratation, sulfur dioxide, sulfur trioxide, sulfate, phosphate etc.
Reaction generates calcium fluosilicate, barium sulfate and barium phosphate of indissoluble etc., and the above-mentioned reaction time is 1 hour, obtains mixture；
2) to step 1) obtained by be passed through the fluorine nitrogen mixed gas that fluorine gas accounts for 15wt% in mixture, intake is 0.025kg, instead
Answer 3 hours and lower boiling arsenide is converted into into high boiling arsenide, obtain thick hydrogen fluoride about 304kg；
3) by step 2) obtained by thick hydrogen fluoride be passed through topping still bottom, in control kettle, pressure is less than 0.1MPa, at 22 DEG C
Material is continuously increased, control reflux ratio, make in tower air-liquid two-phase close contact repeatedly, entirely slightly evaporate process control top of tower
Outlet temperature is -5 DEG C, removes lower boiling impurity, such as SO2、SiF4Deng mixed gas are obtained from the top of topping still；
4) by step 3) obtained by mixed gas be passed through rectifier bottoms, in control kettle, pressure is less than 0.1MPa, at 40 DEG C
At a temperature of material is continuously increased, control reflux ratio and top of tower outlet temperature remove high boiling impurity, such as at 15 DEG C
H2SO4、H2O and metal ion etc., obtain high-purity hydrogen fluoride.
The preparation method of the present embodiment high-pure hydrofluoric acid, comprises the following steps：
1) Nitrogen gas purifying system is used, air in removal system maintains 22.5 DEG C of room temperature, and the temperature of operating position is 22.5
DEG C, humidity is maintained at 40%；The liquid fluorinated hydrogen feedstock of 300kg is added into the pretreatment reaction kettle with heat exchanger, temperature is controlled
For 17 DEG C, in kettle, pressure is 0.2MPa；Barium fluoride and calcium chloride are added, its total addition is that 4.50kg (accounts for liquid hydrogen fluoride former
Material quality 1.5%), with liquid fluorinated hydrogen feedstock in ocratation, sulfur dioxide, sulfur trioxide, sulfate, phosphate etc.
Reaction generates calcium fluosilicate, barium sulfate and barium phosphate of indissoluble etc., and the above-mentioned reaction time is 1 hour, obtains mixture；
2) to step 1) obtained by be passed through the fluorine nitrogen mixed gas that fluorine gas accounts for 15wt% in mixture, intake is 0.025kg, instead
Answer 3 hours and lower boiling arsenide is converted into into high boiling arsenide, obtain thick hydrogen fluoride about 304kg；
3) by step 2) obtained by thick hydrogen fluoride be passed through topping still bottom, in control kettle, pressure is less than 0.1MPa, at 22 DEG C
Material is continuously increased, control reflux ratio, make in tower air-liquid two-phase close contact repeatedly, entirely slightly evaporate process control top of tower
Outlet temperature is -5 DEG C, removes lower boiling impurity, such as SO2、SiF4Deng mixed gas are obtained from the top of topping still；
4) by step 3) obtained by mixed gas be passed through rectifier bottoms, in control kettle, pressure is less than 0.1MPa, at 40 DEG C
At a temperature of material is continuously increased, control reflux ratio and top of tower outlet temperature remove high boiling impurity, such as at 15 DEG C
H2SO4、H2O and metal ion etc., obtain high-purity hydrogen fluoride；
5) by rectifying column export high-purity hydrogen fluoride from spray-absorption tower bottom be passed through with tower top spray under high purity water by
Ratio mixing preparation, is obtained 48.7% high-pure hydrofluoric acid finished product 585kg.
Embodiment 2
The preparation method of the high-purity hydrogen fluoride of the present embodiment, comprises the following steps：
1) Nitrogen gas purifying system is used, air in removal system maintains 22.5 DEG C of room temperature, and the temperature of operating position is 22.5
DEG C, humidity is maintained at 40%；The liquid fluorinated hydrogen feedstock of 300kg is added into the pretreatment reaction kettle with heat exchanger, temperature is controlled
For 1 DEG C, in kettle, pressure is 0.1MPa；Brium carbonate, its addition is added (to account for liquid hydrogen fluoride material quality for 5.05kg
1.7%) ocratation, in liquid fluorinated hydrogen feedstock, sulfur dioxide, sulfur trioxide, sulfate, phosphate etc. and barium compound
Reaction generates barium fluosilicate, barium sulfate and barium phosphate of indissoluble etc., and the above-mentioned reaction time is 2 hours, obtains mixture；
2) to step 1) obtained by be passed through the fluorine nitrogen mixed gas that fluorine gas accounts for 15wt% in mixture, intake is 0.025kg, instead
Answer 2 hours and lower boiling arsenide is converted into into high boiling arsenide, gas is entered by 5 μm of filter after terminating by reaction
Row is removed by filtration bulky grain mechanical admixture, obtains thick hydrogen fluoride about 305kg.
3) by step 2) obtained by thick hydrogen fluoride be passed through topping still bottom, in control kettle, pressure is less than 0.1MPa, at 10 DEG C
Material is continuously increased, control reflux ratio, make in tower air-liquid two-phase close contact repeatedly, entirely slightly evaporate process control top of tower
Outlet temperature is -10 DEG C, removes lower boiling impurity, such as SO2、SiF4Deng mixed gas are obtained from the top of topping still；
4) by step 3) obtained by mixed gas be passed through rectifier bottoms, in control kettle, pressure is less than 0.1MPa, at 65 DEG C
At a temperature of material is continuously increased, control reflux ratio and top of tower outlet temperature remove high boiling impurity, such as at 20 DEG C
H2SO4、H2O and metal ion etc., obtain high-purity hydrogen fluoride.
The preparation flow schematic diagram of the present embodiment high-pure hydrofluoric acid is as shown in figure 1, comprise the following steps：
Step 1)～step 4) it is identical the step of prepare high-purity hydrogen fluoride with the present embodiment；
5) by rectifying column export high-purity hydrogen fluoride from spray-absorption tower bottom be passed through with tower top spray under high purity water by
Ratio mixing preparation, is obtained 49.5% thick hydrofluoric acid solution, is filled Jing after the micro-pore-film filtration of 0.1 μm and 0.02 μm of one-level automatically
Dress makes 49.5% high-pure hydrofluoric acid finished product 573kg.
Embodiment 3
The preparation method of the high-purity hydrogen fluoride of the present embodiment, comprises the following steps：
1) Nitrogen gas purifying system is used, air in removal system maintains 22.5 DEG C of room temperature, and the temperature of operating position is 22.5
DEG C, humidity is maintained at 40%；The liquid fluorinated hydrogen feedstock of 300kg is added into the pretreatment reaction kettle with heat exchanger, temperature is controlled
For 10 DEG C, in kettle, pressure is 0.15MPa；Calcirm-fluoride, its addition is added (to account for liquid hydrogen fluoride material quality for 2.12kg
0.7%) ocratation, in liquid fluorinated hydrogen feedstock, sulfur dioxide, sulfur trioxide, sulfate, phosphate etc. are anti-with calcirm-fluoride
The compounds such as calcium fluosilicate, calcium sulfate and the calcium phosphate of indissoluble should be generated, the above-mentioned reaction time is 2.5 hours, obtains mixture；
2) to step 1) obtained by be passed through the fluorine nitrogen mixed gas that fluorine gas accounts for 5wt% in mixture, intake is 0.075kg, instead
Answer 4 hours and lower boiling arsenide is converted into into high boiling arsenide, gas is entered by 5 μm of filter after terminating by reaction
Row is removed by filtration bulky grain mechanical admixture, obtains thick hydrogen fluoride about 302kg；
3) by step 2) obtained by thick hydrogen fluoride be passed through topping still bottom, in control kettle, pressure is less than 0.1MPa, at 22 DEG C
Material is continuously increased, control reflux ratio, make in tower air-liquid two-phase close contact repeatedly, entirely slightly evaporate process control top of tower
Outlet temperature is -8 DEG C, removes lower boiling impurity, such as SO2、SiF4Deng mixed gas are obtained from the top of topping still；
4) by step 3) obtained by mixed gas be passed through rectifier bottoms, in control kettle, pressure is less than 0.1MPa, at 50 DEG C
At a temperature of material is continuously increased, control reflux ratio and top of tower outlet temperature remove high boiling impurity, such as at 17 DEG C
H2SO4、H2O and metal ion etc., obtain high-purity hydrogen fluoride.
The preparation flow schematic diagram of the present embodiment high-pure hydrofluoric acid is as shown in figure 1, comprise the following steps：
Step 1)～step 4) it is identical the step of prepare high-purity hydrogen fluoride with the present embodiment；
5) by rectifying column export high-purity hydrogen fluoride from spray-absorption tower bottom be passed through with tower top spray under high purity water by
Ratio mixing preparation, is obtained 49.3% thick hydrofluoric acid solution, is filled Jing after the micro-pore-film filtration of 0.1 μm and 0.02 μm of one-level automatically
Dress makes 49.3% high-pure hydrofluoric acid finished product 579kg.
Embodiment 4
The preparation method of the high-purity hydrogen fluoride of the present embodiment, comprises the following steps：
1) Nitrogen gas purifying system is used, air in removal system maintains 22.5 DEG C of room temperature, and the temperature of operating position is 22.5
DEG C, humidity is maintained at 40%；The pretreatment reaction kettle with heat exchanger is added to carry out pre- place the liquid fluorinated hydrogen feedstock of 300kg
Reason, controls temperature for 5 DEG C, and in kettle, pressure is 0.1MPa；Calcirm-fluoride and calcium carbonate, its total addition is added (to account for liquid for 3.02kg
State hydrogen fluoride material quality 1.0%), ocratation, sulfur dioxide, sulfur trioxide, sulfate in liquid fluorinated hydrogen feedstock,
Phosphate etc. is reacted with calcium compound and generates the compounds such as calcium fluosilicate, calcium sulfate and the calcium phosphate of indissoluble, and above-mentioned reaction carries out 3
Hour, obtain mixture；
2) to step 1) obtained by be passed through the fluorine nitrogen mixed gas that fluorine gas accounts for 20wt% in mixture, intake is 0.019kg, instead
Answer 5 hours and lower boiling arsenide is converted into into high boiling arsenide, gas is entered by 5 μm of filter after terminating by reaction
Row is removed by filtration bulky grain mechanical admixture, obtains thick hydrogen fluoride about 303kg；
3) by step 2) obtained by thick hydrogen fluoride be passed through topping still bottom, in control kettle, pressure is less than 0.1MPa, at 22 DEG C
Material is continuously increased, control reflux ratio, make in tower air-liquid two-phase close contact repeatedly, entirely slightly evaporate process control top of tower
Outlet temperature is -6 DEG C, removes lower boiling impurity, such as SO2、SiF4Deng mixed gas are obtained from the top of topping still；
4) by step 3) obtained by mixed gas be passed through rectifier bottoms, in control kettle, pressure is less than 0.1MPa, at 55 DEG C
At a temperature of material is continuously increased, control reflux ratio and top of tower outlet temperature remove high boiling impurity, such as at 18 DEG C
H2SO4、H2O and metal ion etc., obtain high-purity hydrogen fluoride.
The preparation flow schematic diagram of the present embodiment high-pure hydrofluoric acid is as shown in figure 1, comprise the following steps：
Step 1)～step 4) it is identical the step of prepare high-purity hydrogen fluoride with the present embodiment；
5) by rectifying column export high-purity hydrogen fluoride from spray-absorption tower bottom be passed through with tower top spray under high purity water by
Ratio mixing preparation, is obtained 48.5% thick hydrofluoric acid solution, is filled Jing after the micro-pore-film filtration of 0.1 μm and 0.02 μm of one-level automatically
Dress makes 48.5% high-pure hydrofluoric acid finished product 586kg.
Comparative example
The concrete preparation method of comparative example high-pure hydrofluoric acid is：
1) Nitrogen gas purifying system is used, air in removal system maintains 22.5 DEG C of room temperature, and the temperature of operating position is 22.5
DEG C, humidity is maintained at 40%；The liquid fluorinated hydrogen feedstock of 300kg is added into the pretreatment reaction kettle with heat exchanger, keeping temperature
For 17 DEG C, in kettle, pressure is 0.2MPa；
2) to step 1) liquid fluorinated hydrogen feedstock in be passed through the fluorine nitrogen mixed gas of 20wt%, intake is 0.020kg, instead
After answering 5 hours, lower boiling arsenide is converted into high boiling arsenide, and gas is entered after terminating by reaction by 5 μm of filter
Row is removed by filtration bulky grain mechanical admixture, obtains thick hydrogen fluoride about 300kg.
3) by step 2) obtained by thick hydrogen fluoride be passed through topping still bottom, in control kettle, pressure is less than 0.1MPa, at 22 DEG C
Material is continuously increased, control reflux ratio, make in tower air-liquid two-phase close contact repeatedly, entirely slightly evaporate process control top of tower
Outlet temperature removes lower boiling impurity, such as SO between -5～-10 DEG C2、SiF4Deng gaseous mixture is obtained from the top of topping still
Body；
4) by step 3) obtained by mixed gas be passed through rectifier bottoms, in control kettle, pressure is less than 0.1MPa, at 40 DEG C
At a temperature of material is continuously increased, control reflux ratio and top of tower outlet temperature remove high boiling impurity, such as at 15 DEG C
H2SO4、H2O and metal ion etc.；
5) gas for exporting rectifying column is passed through from spray-absorption tower bottom and is mixed with the high purity water under tower top spray in proportion
Allotment is closed, 48.5% thick hydrofluoric acid solution is obtained, auto-filling is made Jing after the micro-pore-film filtration of 0.1 μm and 0.02 μm of one-level
48.5% high-pure hydrofluoric acid finished product 578kg.
Impurity component in the high-pure hydrofluoric acid of embodiment 1～4 and comparative example preparation is detected, 1 is the results are shown in Table.Table
1 result shows that the high-pure hydrofluoric acid that the present invention is provided effectively eliminates nitrate, phosphorus on the basis of cation impurity is removed
The anionic impurities such as hydrochlorate, sulfate and fluosilicic acid composition, index of correlation is far beyond the UP-SS that HG/T4509-2013 specifies
Level, product meet the making requirement of super large-scale integration.
1 high-pure hydrofluoric acid quality measurements of table
Claims (8)
1. a kind of preparation method of high-purity hydrogen fluoride, it is characterised in that comprise the following steps：
1) under conditions of isolation air, 1～17 DEG C, 0.1～0.2MPa, barium compound and/or calcium compound are added into liquid
Reacted in fluorination hydrogen feedstock, obtained mixture；
2) to step 1) obtained by be passed through fluorine nitrogen mixed gas in mixture and carry out oxidation reaction, obtain thick hydrogen fluoride；
3) by step 2) obtained by thick hydrogen fluoride carry out negative pressure and slightly evaporate, obtain mixed gas；
4) by step 3) obtained by mixed gas carry out negative pressure rectifying, obtain final product high-purity hydrogen fluoride；
Step 3) 10～22 DEG C of bottom temperature slightly evaporating of negative pressure, outlet temperature is -5～-10 DEG C；
Step 4) negative pressure rectifying bottom temperature be 40～65 DEG C, outlet temperature be 15～20 DEG C.
2. the preparation method of high-purity hydrogen fluoride according to claim 1, it is characterised in that：Step 1) barium compound is
At least one of barium fluoride, barium chloride, brium carbonate；Calcium compound is at least one of calcirm-fluoride, calcium carbonate.
3. the preparation method of high-purity hydrogen fluoride according to claim 1, it is characterised in that：Step 1) reaction reaction
Time is 1～3h.
4. the preparation method of high-purity hydrogen fluoride according to claim 1, it is characterised in that：Step 1) barium compound and/or
The consumption of calcium compound for liquid hydrogen fluoride material quality 0.5～2%.
5. the preparation method of high-purity hydrogen fluoride according to claim 1, it is characterised in that：Step 2) in fluorine nitrogen mixed gas,
Fluorine gas accounts for the 5%～20% of fluorine nitrogen mixed gas quality, the consumption of fluorine nitrogen mixed gas for liquid hydrogen fluoride material quality 0.005～
0.03%.
6. the preparation method of high-purity hydrogen fluoride according to claim 1, it is characterised in that：Step 2) oxidation reaction reaction
Time is 1～5h.
7. a kind of preparation method of high-pure hydrofluoric acid, it is characterised in that comprise the following steps：
1) under conditions of isolation air, 1～17 DEG C, 0.1～0.2MPa, barium compound and/or calcium compound are added into liquid
Reacted in fluorination hydrogen feedstock, obtained mixture；
2) to step 1) obtained by be passed through fluorine nitrogen mixed gas in mixture and carry out oxidation reaction, obtain thick hydrogen fluoride；
3) by step 2) obtained by thick hydrogen fluoride carry out negative pressure and slightly evaporate, obtain mixed gas；
4) by step 3) obtained by mixed gas carry out negative pressure rectifying, obtain final product high-purity hydrogen fluoride；
5) by step 4) obtained by high-purity hydrogen fluoride add water and allocated, obtain high-pure hydrofluoric acid；
Step 3) 10～22 DEG C of bottom temperature slightly evaporating of negative pressure, outlet temperature is -5～-10 DEG C；
Step 4) negative pressure rectifying bottom temperature be 40～65 DEG C, outlet temperature be 15～20 DEG C.
8. the preparation method of high-pure hydrofluoric acid as claimed in claim 7, it is characterised in that step 5) high-purity hydrogen fluoride adjusted
After matching somebody with somebody, the micro-pore-film filtration that 0.1 μm and two grades 0.02 μm of Jing one-levels obtains 48%～49% high-pure hydrofluoric acid.
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| CN110844885A (en) * | 2019-09-06 | 2020-02-28 | 浙江东氟塑料科技有限公司 | Method for recovering and regenerating hydrofluoric acid from waste liquid |
| CN113880058B (en) * | 2021-10-28 | 2023-10-20 | 河南省氟基新材料科技有限公司 | Purification method of industrial grade nitric acid |
| CN113998725A (en) * | 2021-11-30 | 2022-02-01 | 贵州红星发展股份有限公司 | Barium fluoride and preparation method thereof |
| CN115072665B (en) * | 2022-06-14 | 2023-10-03 | 多氟多新材料股份有限公司 | Impurity removal method for anhydrous hydrogen fluoride, and preparation method and device for electronic grade hydrofluoric acid |
| CN115010091B (en) * | 2022-06-17 | 2023-10-31 | 多氟多新材料股份有限公司 | Impurity removal method for hydrogen fluoride, purification method for hydrogen fluoride and purification device for hydrogen fluoride |
| CN116354349A (en) * | 2023-03-12 | 2023-06-30 | 李林 | Dechlorination method and system for producing hydrogen fluoride by fluosilicic acid |
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