CN104973573A - Preparation method of highly pure hydrogen fluoride and preparation method of highly pure hydrofluoric acid - Google Patents
Preparation method of highly pure hydrogen fluoride and preparation method of highly pure hydrofluoric acid Download PDFInfo
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Abstract
The invention discloses a preparation method of highly pure hydrogen fluoride and a preparation method of highly pure hydrofluoric acid. The preparation method of the highly pure hydrogen fluoride comprises the following steps of: (1) under the condition of isolated air, 1-17 DEG C and 0.1-0.2MPa, adding a barium compound and/or a calcium compound to a liquid hydrogen fluoride raw material for performing a reaction so as to obtain a mixture; (2) leading the fluorine and nitrogen mixed gas into the mixture obtained in the step (1) to perform an oxidation reaction so as to obtain crude hydrogen fluoride; (3) performing negative pressure crude distillation on the crude hydrogen fluoride so as to obtain mixed gas; and (4) performing negative pressure rectification on the mixed gas obtained in the step (3) so as to obtain the highly pure hydrogen fluoride. The highly pure hydrogen fluoride is allocated so as to obtain the highly pure hydrofluoric acid. According to the preparation of the highly pure hydrogen fluoride and the preparation method of the highly pure hydrofluoric acid, disclosed by the invention, impurities in the raw materials of the hydrogen fluoride and the industrial hydrofluoric acid have different boiling points, and the transformed impurities in the raw materials of the hydrogen fluoride and the industrial hydrofluoric acid have different solubility in acid, so that various impurities can be removed, particularly anion impurities and fluosilicic acid components can be removed, the highly pure hydrogen fluoride is obtained, and further, the highly pure hydrofluoric acid is obtained.
Description
Technical field
The invention belongs to super clean, high purified hydrofluoric acid preparing technical field, be specifically related to the preparation method of a kind of high-purity hydrofluoric preparation method and 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, is fuming in atmosphere, irritant smell, severe toxicity; Can react with common metal, metal oxide and oxyhydroxide and generate various salt; Its corrodibility is comparatively strong, and energy attack glass and silicate generate the silicon tetrafluoride of gaseous state; Soluble in water, alcohol, is insoluble in other organic solvents.
High-pure hydrofluoric acid is strongly-acid cleaning, etching reagent, can prepare with nitric acid, Glacial acetic acid, hydrogen peroxide, sulfuric acid, hydrochloric acid and ammonium hydroxide etc. and use, be mainly used in cleaning and the corrosion of unicircuit (IC) and super large-scale integration (VLSI) chip, be one of key foundation chemical materials in microelectronic industry making processes, also can be used for making analytical reagent and the highly purified fluorine-containing chemical of preparation.At present, be for microelectronic industry at home substantially as etching reagent and clean-out system.
International SEMI (Semiconductor Equipment and Materials International) standardization body is according to high purity reagent practical development situation worldwide, classify by kind, each kind merger is a guiding standard, comprising multiple grade for different process technology.The external existing high-pure hydrofluoric acid produced meets SEMI-Grade5 requirement, be applicable to the making requirement being less than 0.09 μm of IC technology, but the high-pure hydrofluoric acid that domestic enterprise produces is only applicable to SEMI-C7 (Grade2) requirement at present mostly, be applicable to the making requirement of 0.8-1.2 μm of IC technology, and quality product is uneven.
Impurity in commercial fluorided hydrogen raw material is mainly derived from fluorite and sulfuric acid, the fluorite impurity component of Different sources is different, about the removal of impurity, relate generally to the cation impurities such as arsenic, magnesium, calcium, chromium, the anionic impurities such as muriate, nitrate, vitriol, phosphoric acid salt, and silicofluoric acid (H
2siF
6) composition.
Domestic existing hydrofluoric acid purification techniques mainly contains malleation rectifying, negative pressure rectifying and sub-boiling distillation three kinds, and wherein sub-boiling distillation is only suitable for laboratory preparation in a small amount, not easily industrial applications.Malleation rectifying and negative pressure rectifying are most widely used hydrofluoric acid methods of purification.Most cation impurity is all removed by rectifying means, but AsF
3be more or less the same with hydrofluoric acid boiling point, only unsatisfactory by rectifying separation effect, the method adopted at present is, by oxygenant, volatility trivalent arsenic is become nonvolatile pentavalent arsenic, is then removed by washing, rectifying.The method of oxygenant arsenic removal comprises hydrogen oxide method, potassium permanganate process, fluorine gas method, PtF
6method and high-molecular chelating agent and mixed bed zwitterion system absorption method etc., these methods have only paid close attention to the removal of the cation impurities such as arsenic, anionic impurity and silicofluoric acid (H
2siF
6) removal of composition seldom mentions, because anionic impurity forms the stable component such as vitriol, phosphoric acid salt in aqueous phase, silicofluoric acid (H
2siF
6) composition stable existence in aqueous phase, anionic impurity and silicofluoric acid (H
2siF
6) composition remove difficulty very large.
Patent CN103086327A discloses a kind of preparation method of super clean, high purified hydrofluoric acid, its with technical grade dry state hydrogen fluoride for raw material, the hydrogen fluoride gas of deriving is by after molecular sieve adsorption, 0.01 μm of filter element filtering, barium fluoride and silver fluoride aqueous solution, absorb with ultrapure water, and add hydrogen peroxide reaction, prepare high-pure hydrofluoric acid after carrying out rectifying.The cation impurity levels of product is at below 0.01ppb, and anionic impurity is no more than 20ppb, but silicofluoric acid (H
2siF
6) composition at least at more than 13000ppb, single silicofluoric acid (H
2siF
6) the too high making processes that can affect microelectronic industry equally of component content.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of high-purity hydrofluoric preparation method and high-pure hydrofluoric acid, not only can effectively remove the cation impurities such as arsenic, magnesium, calcium, chromium, anionic impurity and silicofluoric acid (H can also be removed further
2siF
6) composition, thus greatly improve product purity, and to be applicable to microelectronics industry technology, especially super large-scale integration.
In order to realize above object, the technical solution adopted in the present invention is: a kind of high-purity hydrofluoric preparation method, comprises the following steps:
1) isolated air, 1 ~ 17 DEG C, under the condition of 0.1 ~ 0.2MPa, barium compound and/or calcium cpd are joined in liquid hydrogen fluoride raw material and react, obtain mixture;
2) to step 1) pass into fluorine nitrogen mixed gas in gained mixture and carry out oxidizing reaction, obtain thick hydrogen fluoride;
3) by step 2) the thick hydrogen fluoride of gained carries out negative pressure and slightly heats up in a steamer, and obtains mixed gas;
4) by step 3) gained mixed gas carries out negative pressure rectifying, obtains high-purity hydrogen fluoride.
Step 1 of the present invention) (removal of impurities) reaction and step 2) oxidation reaction process in hydrogen fluoride raw material exist in liquid form, the impurity such as barium compound and/or calcium cpd and silicon, phosphorus, sulphur, arsenic are combined difficulty soluble salts such as generating barium silicofluoride, barium sulfate, calcium silicofluoride, calcium sulfate or barium phosphate, thus utilize the difference of solubleness in hydrofluoric acid to remove.Prior art carries out removal of impurities and oxidising process mainly with gaseous form to commercial fluorided hydrogen raw material, easily introduces introduced contaminants, and very high to the purity requirement of reagent treatment, inevitably introduces other foreign ions in a lot of situation.
Lower boiling arsenide is converted into high boiling arsenide by fluorine nitrogen mixed gas by the present invention, so by slightly heating up in a steamer, rectifying, remove lower-boiling impurity and high-boiling-point impurity respectively, and remove the anionic impurity such as sulphur, silicon further.
The present invention, by liquid phase impurity conversion and oxidizing process, solves anionic impurity and the silicofluoric acid (H such as silicon, sulphur, phosphorus, arsenic
2siF
6) difficult problem that not easily removes of composition, adopt thick, rectifying, product purity is promoted further.
The fluorochemicals of byproduct in process of the present invention can directly be taken out after purification processes, slightly, the residual acid (being generally the mixture of hydrofluoric acid, silicofluoric acid) after smart gold-plating at the bottom of tower can be used for producing sodium aluminum fluoride, what this invented alleviates environmental protection pressure, reduces consumption, has saved cost.
Step 1) in, isolated air, 1 ~ 17 DEG C, the envrionment conditions of 0.1 ~ 0.2MPa, can ensure that liquid hydrogen fluoride raw material is stablized, for the impurity conversion of next stage and oxidizing reaction ready.
Step 1) mechanism of action of described barium compound utilizes a large amount of silicon tetrafluoride of containing in barium compound and industrial liquid hydrogen fluoride raw material or silicofluoride, sulfurous gas, sulphur trioxide, vitriol, phosphate reaction to generate the material being insoluble in hydrofluoric acid, thus be easy to remove.Barium compound can meet above-mentioned requirements, and preferably, barium compound is at least one in barium fluoride, bariumchloride, barium carbonate.
Step 1) described calcium cpd is identical with the mechanism of action of barium compound, and preferably, calcium cpd is at least one in Calcium Fluoride (Fluorspan), calcium carbonate.
Step 1) to react the preferred reaction time be 1 ~ 3h to the removal of impurities that occurs of barium compound and/or calcium cpd and silicon, sulphur, phosphorus, arsenic etc.The add-on of barium compound and/or calcium cpd is determined according to commercial fluorided hydrogen raw material impurity content, ensure barium compound and/or calcium cpd excessive a little, preferably, in commercial fluorided hydrogen raw materials quality, the add-on of barium compound and/or calcium cpd is 0.5 ~ 2%.
Step 2) use fluorine nitrogen mixed gas, react too fierce after can avoiding passing into pure fluorine gas, easily cause the disadvantage of security incident, preferably, fluorine gas accounts for 5% ~ 20% of fluorine nitrogen mixed gas quality, and the consumption of fluorine nitrogen mixed gas is 0.005 ~ 0.03% of liquid hydrogen fluoride raw materials quality.Sulfurous gas in industrial liquid hydrogen fluoride raw material and arsenous fluoride are oxidized to sulphur trioxide and arsenic pentafluoride by the strong oxidizing property of fluorine gas, thus are easy to remove.For ensureing fully carrying out of oxidizing reaction, the reaction times is preferably 1 ~ 5h.
According to the content of impurities of commercial fluorided hydrogen raw material, step 2) after oxidizing reaction terminates, filtering and impurity removing can be carried out according to practical situation.Various filter plant can be adopted to carry out removal of impurities, preferably utilize the strainer of 5 μm to carry out removal of impurities.
Step 3) slightly heat up in a steamer process, by step 2 for negative pressure) the thick hydrogen fluoride of gained passes into bottom topping still, makes raw material acid increase continuously at the temperature of 10 ~ 22 DEG C, control reflux ratio, make gas in tower, liquid two-phase close contact repeatedly, remove lower boiling impurity, as SO
2, SiF
4deng, for ensureing slightly to heat up in a steamer efficiency and quality product, control the bottom temperature 10 ~ 22 DEG C slightly heated up in a steamer, temperature out is-5 ~-10 DEG C, and pressure is less than 0.1Mpa.
Step 4) be negative pressure rectifying, step 3) gained mixed gas passes into rectifier bottoms, makes raw material acid increase continuously at the temperature of 40 ~ 65 DEG C, and control reflux ratio, remove high boiling impurity, as H
2sO
4, H
2o and metal ion etc., for ensureing rectification efficiency and quality product, the bottom temperature controlling rectifying is 40 ~ 65 DEG C, and temperature out is 15 ~ 20 DEG C, and pressure is less than 0.1Mpa.
The preparation method of high-pure hydrofluoric acid provided by the invention, comprises the following steps:
1) isolated air, 1 ~ 17 DEG C, under the condition of 0.1 ~ 0.2MPa, barium compound and/or calcium cpd are joined in liquid hydrogen fluoride raw material and react, obtain mixture;
2) to step 1) pass into fluorine nitrogen mixed gas in gained mixture and carry out oxidizing reaction, obtain thick hydrogen fluoride;
3) by step 2) the thick hydrogen fluoride of gained carries out negative pressure and slightly heats up in a steamer, and obtains mixed gas;
4) by step 3) gained mixed gas carries out negative pressure rectifying, obtains high-purity hydrogen fluoride;
5) by step 4) the high-purity hydrogen fluoride of gained adds water and allocates, and obtains high-pure hydrofluoric acid.
When being allocated by high-purity hydrogen fluoride, high purity water is selected to be deployed into a certain proportion of hydrofluoric acid solution.Allocation process is prior art, can according to needs allotment to proper ratio.Preferably, the gas that rectifying tower exports is passed into from spray-absorption tower bottom, is mixed in proportion allotment with the high purity water under tower top sprays, the high-pure hydrofluoric acid finished product of obtained 48% ~ 49%.
According to foreign matter content and each enterprise practical condition of production of commercial fluorided hydrogen raw material, microporous membrane filter techniques can be selected to control granule foreign content according to needs.The associated viscera that microporous membrane filter techniques can adopt patent CN101570318B to record, in step 4) after the high-purity hydrogen fluoride allotment of deriving, first obtain thick hydrofluoric acid solution, after micro-pore-film filtration, obtain high-pure hydrofluoric acid finished product.Preferably, thick hydrofluoric acid solution, after one-level 0.1 μm with the micro-pore-film filtration of secondary 0.02 μm, auto-filling makes the high-pure hydrofluoric acid finished product of 48% ~ 49%.Filtered by two-stage mocromembrane, granule foreign content can be reduced further, the problem that some domestic high-pure hydrofluoric acid producer particle is not up to standard can be solved.
The high-pure hydrofluoric acid of gained of the present invention reaches semi-conductor SEMI-Grade5 standard, meets the demand of semicon industry, especially the needs of super large-scale integration.Finished product index: positively charged ion≤0.01ppb, silicofluoric acid (H
2siF
6), vitriol is (with SO
4meter), phosphoric acid salt is (with PO
4meter) anion-content is all not more than 10ppb.
Accompanying drawing explanation
Fig. 1 is preparation method's schematic flow sheet of the high-pure hydrofluoric acid of the embodiment of the present invention 2 ~ 4.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
The high-purity hydrofluoric preparation method of the present embodiment, comprises the following steps:
1) with Nitrogen gas purifying system, air in removal system, maintain room temperature 22.5 DEG C, the temperature of operating station is 22.5 DEG C, and humidity remains on 40%; The liquid hydrogen fluoride raw material of 300kg is added the pretreatment reaction still of band interchanger, control temperature is 17 DEG C, and still internal pressure is 0.1MPa; Add barium fluoride and calcium chloride, its total add-on is 4.50kg (accounting for 1.5% of liquid hydrogen fluoride raw materials quality), calcium silicofluoride, barium sulfate and the barium phosphate etc. that generate indissoluble are reacted with the silicon tetrafluoride in liquid hydrogen fluoride raw material, sulfurous gas, sulphur trioxide, vitriol, phosphoric acid salt etc., the above-mentioned reaction times is 1 hour, obtains mixture;
2) to step 1) pass into the fluorine nitrogen mixed gas that fluorine gas accounts for 15wt% in gained mixture, intake is 0.025kg, reacts and lower boiling arsenide is converted into high boiling arsenide in 3 hours, obtain thick hydrogen fluoride and be about 304kg;
3) by step 2) the thick hydrogen fluoride of gained passes into bottom topping still, control still internal pressure and be less than 0.1MPa, at 22 DEG C, make material increase continuously, control reflux ratio, make gas in tower, liquid two-phase close contact repeatedly, whole process control top of tower temperature out of slightly heating up in a steamer is-5 DEG C, removes lower boiling impurity, as SO
2, SiF
4deng, mixed gas is obtained from topping still top;
4) by step 3) gained mixed gas passes into rectifier bottoms, controls still internal pressure and is less than 0.1MPa, make material increase continuously at the temperature of 40 DEG C, and control reflux ratio and top of tower temperature out at 15 DEG C, remove high boiling impurity, as H
2sO
4, H
2o 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) with Nitrogen gas purifying system, air in removal system, maintain room temperature 22.5 DEG C, the temperature of operating station is 22.5 DEG C, and humidity remains on 40%; The liquid hydrogen fluoride raw material of 300kg is added the pretreatment reaction still of band interchanger, control temperature is 17 DEG C, and still internal pressure is 0.2MPa; Add barium fluoride and calcium chloride, its total add-on is 4.50kg (accounting for 1.5% of liquid hydrogen fluoride raw materials quality), calcium silicofluoride, barium sulfate and the barium phosphate etc. that generate indissoluble are reacted with the silicon tetrafluoride in liquid hydrogen fluoride raw material, sulfurous gas, sulphur trioxide, vitriol, phosphoric acid salt etc., the above-mentioned reaction times is 1 hour, obtains mixture;
2) to step 1) pass into the fluorine nitrogen mixed gas that fluorine gas accounts for 15wt% in gained mixture, intake is 0.025kg, reacts and lower boiling arsenide is converted into high boiling arsenide in 3 hours, obtain thick hydrogen fluoride and be about 304kg;
3) by step 2) the thick hydrogen fluoride of gained passes into bottom topping still, control still internal pressure and be less than 0.1MPa, at 22 DEG C, make material increase continuously, control reflux ratio, make gas in tower, liquid two-phase close contact repeatedly, whole process control top of tower temperature out of slightly heating up in a steamer is-5 DEG C, removes lower boiling impurity, as SO
2, SiF
4deng, mixed gas is obtained from topping still top;
4) by step 3) gained mixed gas passes into rectifier bottoms, controls still internal pressure and is less than 0.1MPa, make material increase continuously at the temperature of 40 DEG C, and control reflux ratio and top of tower temperature out at 15 DEG C, remove high boiling impurity, as H
2sO
4, H
2o and metal ion etc., obtain high-purity hydrogen fluoride;
5) high-purity hydrogen fluoride that rectifying tower exports is passed into the high purity water spraying with tower top from spray-absorption tower bottom and be mixed in proportion allotment, the high-pure hydrofluoric acid finished product 585kg of obtained 48.7%.
Embodiment 2
The high-purity hydrofluoric preparation method of the present embodiment, comprises the following steps:
1) with Nitrogen gas purifying system, air in removal system, maintain room temperature 22.5 DEG C, the temperature of operating station is 22.5 DEG C, and humidity remains on 40%; The liquid hydrogen fluoride raw material of 300kg is added the pretreatment reaction still of band interchanger, control temperature is 1 DEG C, and still internal pressure is 0.1MPa; Add barium carbonate, its add-on is 5.05kg (accounting for 1.7% of liquid hydrogen fluoride raw materials quality), silicon tetrafluoride in liquid hydrogen fluoride raw material, sulfurous gas, sulphur trioxide, vitriol, phosphoric acid salt etc. and barium compound react barium silicofluoride, barium sulfate and the barium phosphate etc. that generate indissoluble, the above-mentioned reaction times is 2 hours, obtains mixture;
2) to step 1) pass into the fluorine nitrogen mixed gas that fluorine gas accounts for 15wt% in gained mixture; intake is 0.025kg; react and lower boiling arsenide was converted into high boiling arsenide in 2 hours; after reaction terminates, gas is carried out removed by filtration macrobead mechanical impurity by the strainer of 5 μm, obtain thick hydrogen fluoride and be about 305kg.
3) by step 2) the thick hydrogen fluoride of gained passes into bottom topping still, control still internal pressure and be less than 0.1MPa, at 10 DEG C, make material increase continuously, control reflux ratio, make gas in tower, liquid two-phase close contact repeatedly, whole process control top of tower temperature out of slightly heating up in a steamer is-10 DEG C, removes lower boiling impurity, as SO
2, SiF
4deng, mixed gas is obtained from topping still top;
4) by step 3) gained mixed gas passes into rectifier bottoms, controls still internal pressure and is less than 0.1MPa, make material increase continuously at the temperature of 65 DEG C, and control reflux ratio and top of tower temperature out at 20 DEG C, remove high boiling impurity, as H
2sO
4, H
2o and metal ion etc., obtain high-purity hydrogen fluoride.
The preparation flow schematic diagram of the present embodiment high-pure hydrofluoric acid as shown in Figure 1, comprises the following steps:
Step 1) ~ step 4) to prepare high-purity hydrofluoric step identical with the present embodiment;
5) high-purity hydrogen fluoride that rectifying tower exports is passed into the high purity water spraying with tower top from spray-absorption tower bottom and be mixed in proportion allotment, the thick hydrofluoric acid solution of obtained 49.5%, after the micro-pore-film filtration of one-level 0.1 μm and 0.02 μm, auto-filling makes the high-pure hydrofluoric acid finished product 573kg of 49.5%.
Embodiment 3
The high-purity hydrofluoric preparation method of the present embodiment, comprises the following steps:
1) with Nitrogen gas purifying system, air in removal system, maintain room temperature 22.5 DEG C, the temperature of operating station is 22.5 DEG C, and humidity remains on 40%; The liquid hydrogen fluoride raw material of 300kg is added the pretreatment reaction still of band interchanger, control temperature is 10 DEG C, and still internal pressure is 0.15MPa; Add Calcium Fluoride (Fluorspan), its add-on is 2.12kg (accounting for 0.7% of liquid hydrogen fluoride raw materials quality), silicon tetrafluoride in liquid hydrogen fluoride raw material, sulfurous gas, sulphur trioxide, vitriol, phosphoric acid salt etc. and Calcium Fluoride (Fluorspan) react the compounds such as calcium silicofluoride, calcium sulfate and the calcium phosphate generating indissoluble, the above-mentioned reaction times is 2.5 hours, obtains mixture;
2) to step 1) pass into the fluorine nitrogen mixed gas that fluorine gas accounts for 5wt% in gained mixture, intake is 0.075kg, react and lower boiling arsenide was converted into high boiling arsenide in 4 hours, after reaction terminates, gas is carried out removed by filtration macrobead mechanical impurity by the strainer of 5 μm, obtain thick hydrogen fluoride and be about 302kg;
3) by step 2) the thick hydrogen fluoride of gained passes into bottom topping still, control still internal pressure and be less than 0.1MPa, at 22 DEG C, make material increase continuously, control reflux ratio, make gas in tower, liquid two-phase close contact repeatedly, whole process control top of tower temperature out of slightly heating up in a steamer is-8 DEG C, removes lower boiling impurity, as SO
2, SiF
4deng, mixed gas is obtained from topping still top;
4) by step 3) gained mixed gas passes into rectifier bottoms, controls still internal pressure and is less than 0.1MPa, make material increase continuously at the temperature of 50 DEG C, and control reflux ratio and top of tower temperature out at 17 DEG C, remove high boiling impurity, as H
2sO
4, H
2o and metal ion etc., obtain high-purity hydrogen fluoride.
The preparation flow schematic diagram of the present embodiment high-pure hydrofluoric acid as shown in Figure 1, comprises the following steps:
Step 1) ~ step 4) to prepare high-purity hydrofluoric step identical with the present embodiment;
5) high-purity hydrogen fluoride that rectifying tower exports is passed into the high purity water spraying with tower top from spray-absorption tower bottom and be mixed in proportion allotment, the thick hydrofluoric acid solution of obtained 49.3%, after the micro-pore-film filtration of one-level 0.1 μm and 0.02 μm, auto-filling makes the high-pure hydrofluoric acid finished product 579kg of 49.3%.
Embodiment 4
The high-purity hydrofluoric preparation method of the present embodiment, comprises the following steps:
1) with Nitrogen gas purifying system, air in removal system, maintain room temperature 22.5 DEG C, the temperature of operating station is 22.5 DEG C, and humidity remains on 40%; The pretreatment reaction still liquid hydrogen fluoride raw material of 300kg being added band interchanger carries out pre-treatment, and control temperature is 5 DEG C, and still internal pressure is 0.1MPa; Add Calcium Fluoride (Fluorspan) and calcium carbonate, its total add-on is 3.02kg (accounting for 1.0% of liquid hydrogen fluoride raw materials quality), silicon tetrafluoride in liquid hydrogen fluoride raw material, sulfurous gas, sulphur trioxide, vitriol, phosphoric acid salt etc. and calcium cpd react the compounds such as calcium silicofluoride, calcium sulfate and the calcium phosphate generating indissoluble, above-mentioned reaction carries out 3 hours, obtains mixture;
2) to step 1) pass into the fluorine nitrogen mixed gas that fluorine gas accounts for 20wt% in gained mixture, intake is 0.019kg, react and lower boiling arsenide was converted into high boiling arsenide in 5 hours, after reaction terminates, gas is carried out removed by filtration macrobead mechanical impurity by the strainer of 5 μm, obtain thick hydrogen fluoride and be about 303kg;
3) by step 2) the thick hydrogen fluoride of gained passes into bottom topping still, control still internal pressure and be less than 0.1MPa, at 22 DEG C, make material increase continuously, control reflux ratio, make gas in tower, liquid two-phase close contact repeatedly, whole process control top of tower temperature out of slightly heating up in a steamer is-6 DEG C, removes lower boiling impurity, as SO
2, SiF
4deng, mixed gas is obtained from topping still top;
4) by step 3) gained mixed gas passes into rectifier bottoms, controls still internal pressure and is less than 0.1MPa, make material increase continuously at the temperature of 55 DEG C, and control reflux ratio and top of tower temperature out at 18 DEG C, remove high boiling impurity, as H
2sO
4, H
2o and metal ion etc., obtain high-purity hydrogen fluoride.
The preparation flow schematic diagram of the present embodiment high-pure hydrofluoric acid as shown in Figure 1, comprises the following steps:
Step 1) ~ step 4) to prepare high-purity hydrofluoric step identical with the present embodiment;
5) high-purity hydrogen fluoride that rectifying tower exports is passed into the high purity water spraying with tower top from spray-absorption tower bottom and be mixed in proportion allotment, the thick hydrofluoric acid solution of obtained 48.5%, after the micro-pore-film filtration of one-level 0.1 μm and 0.02 μm, auto-filling makes the high-pure hydrofluoric acid finished product 586kg of 48.5%.
Comparative example
The concrete preparation method of comparative example high-pure hydrofluoric acid is:
1) with Nitrogen gas purifying system, air in removal system, maintain room temperature 22.5 DEG C, the temperature of operating station is 22.5 DEG C, and humidity remains on 40%; The liquid hydrogen fluoride raw material of 300kg is added the pretreatment reaction still of band interchanger, keep temperature to be 17 DEG C, still internal pressure is 0.2MPa;
2) to step 1) liquid hydrogen fluoride raw material in pass into the fluorine nitrogen mixed gas of 20wt%; intake is 0.020kg; react lower boiling arsenide after 5 hours and be converted into high boiling arsenide; after reaction terminates, gas is carried out removed by filtration macrobead mechanical impurity by the strainer of 5 μm, obtain thick hydrogen fluoride and be about 300kg.
3) by step 2) the thick hydrogen fluoride of gained passes into bottom topping still, control still internal pressure and be less than 0.1MPa, at 22 DEG C, make material increase continuously, control reflux ratio, make gas in tower, liquid two-phase close contact repeatedly, whole process control top of tower temperature out of slightly heating up in a steamer, between-5 ~-10 DEG C, removes lower boiling impurity, as SO
2, SiF
4deng, mixed gas is obtained from topping still top;
4) by step 3) gained mixed gas passes into rectifier bottoms, controls still internal pressure and is less than 0.1MPa, make material increase continuously at the temperature of 40 DEG C, and control reflux ratio and top of tower temperature out at 15 DEG C, remove high boiling impurity, as H
2sO
4, H
2o and metal ion etc.;
5) gas that rectifying tower exports is passed into the high purity water spraying with tower top from spray-absorption tower bottom and be mixed in proportion allotment, the thick hydrofluoric acid solution of obtained 48.5%, after the micro-pore-film filtration of one-level 0.1 μm and 0.02 μm, auto-filling makes the high-pure hydrofluoric acid finished product 578kg of 48.5%.
Impurity component in the high-pure hydrofluoric acid prepare embodiment 1 ~ 4 and comparative example detects, and the results are shown in Table 1.Table 1 result shows, high-pure hydrofluoric acid provided by the invention is on the basis of removing cation impurity, effectively eliminate anionic impurity and the silicofluoric acid compositions such as nitrate, phosphoric acid salt, vitriol, the UP-SS level that index of correlation specifies far beyond HG/T4509-2013, product meets the making requirement of super large-scale integration.
Table 1 high-pure hydrofluoric acid quality measurements
Claims (10)
1. a high-purity hydrofluoric preparation method, is characterized in that, comprise the following steps:
1) isolated air, 1 ~ 17 DEG C, under the condition of 0.1 ~ 0.2MPa, barium compound and/or calcium cpd are added in liquid hydrogen fluoride raw material and react, obtain mixture;
2) to step 1) pass into fluorine nitrogen mixed gas in gained mixture and carry out oxidizing reaction, obtain thick hydrogen fluoride;
3) by step 2) the thick hydrogen fluoride of gained carries out negative pressure and slightly heats up in a steamer, and obtains mixed gas;
4) by step 3) gained mixed gas carries out negative pressure rectifying, obtains high-purity hydrogen fluoride.
2. high-purity hydrofluoric preparation method according to claim 1, is characterized in that: step 1) described barium compound is at least one in barium fluoride, bariumchloride, barium carbonate; Calcium cpd is at least one in Calcium Fluoride (Fluorspan), calcium carbonate.
3. high-purity hydrofluoric preparation method according to claim 1, is characterized in that: step 1) reaction times of described reaction is 1 ~ 3h.
4. high-purity hydrofluoric preparation method according to claim 1, is characterized in that: step 1) consumption of barium compound and/or calcium cpd is 0.5 ~ 2% of liquid hydrogen fluoride raw materials quality.
5. high-purity hydrofluoric preparation method according to claim 1, it is characterized in that: step 2) in fluorine nitrogen mixed gas, fluorine gas accounts for 5% ~ 20% of fluorine nitrogen mixed gas quality, and the consumption of fluorine nitrogen mixed gas is 0.005 ~ 0.03% of liquid hydrogen fluoride raw materials quality.
6. high-purity hydrofluoric preparation method according to claim 1, is characterized in that: step 2) reaction times of oxidizing reaction is 1 ~ 5h.
7. high-purity hydrofluoric preparation method according to claim 1, is characterized in that: step 3) bottom temperature 10 ~ 22 DEG C that negative pressure is slightly heated up in a steamer, temperature out is-5 ~-10 DEG C.
8. high-purity hydrofluoric preparation method according to claim 1, is characterized in that: step 4) bottom temperature of negative pressure rectifying is 40 ~ 65 DEG C, temperature out is 15 ~ 20 DEG C.
9. a preparation method for high-pure hydrofluoric acid, is characterized in that, comprises the following steps:
1) isolated air, 1 ~ 17 DEG C, under the condition of 0.1 ~ 0.2MPa, barium compound and/or calcium cpd are added in liquid hydrogen fluoride raw material and react, obtain mixture;
2) to step 1) pass into fluorine nitrogen mixed gas in gained mixture and carry out oxidizing reaction, obtain thick hydrogen fluoride;
3) by step 2) the thick hydrogen fluoride of gained carries out negative pressure and slightly heats up in a steamer, and obtains mixed gas;
4) by step 3) gained mixed gas carries out negative pressure rectifying, obtains high-purity hydrogen fluoride;
5) by step 4) the high-purity hydrogen fluoride of gained adds water and allocates, and obtains high-pure hydrofluoric acid.
10. the preparation method of high-pure hydrofluoric acid as claimed in claim 9, is characterized in that, step 5) after high-purity hydrogen fluoride allocates, the micro-pore-film filtration through one-level 0.1 μm and secondary 0.02 μm obtains the high-pure hydrofluoric acid of 48% ~ 49%.
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| CN112441604A (en) * | 2019-08-28 | 2021-03-05 | 多氟多化工股份有限公司 | Method for preparing high-purity fluoride |
| CN113880058A (en) * | 2021-10-28 | 2022-01-04 | 河南省氟基新材料科技有限公司 | Purification method of industrial-grade nitric acid |
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Address after: 454191 Henan Province, Jiaozuo City Station area coke Rd Patentee after: Duofudo New Material Co.,Ltd. Address before: 454191, Feng County, Henan Province, Jiaozuo Feng Feng Chemical Industry Zone Patentee before: DO-FLUORIDE CHEMICALS Co.,Ltd. |