CN1955115A - Synthetic method of special ammonium fluoride for electronic industry - Google Patents
Synthetic method of special ammonium fluoride for electronic industry Download PDFInfo
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- CN1955115A CN1955115A CN 200510030782 CN200510030782A CN1955115A CN 1955115 A CN1955115 A CN 1955115A CN 200510030782 CN200510030782 CN 200510030782 CN 200510030782 A CN200510030782 A CN 200510030782A CN 1955115 A CN1955115 A CN 1955115A
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- ammonium fluoride
- electronic industry
- fluoride
- step synthesis
- hydrogen fluoride
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Abstract
A press for synthesizing the ammonium fluoride dedicated for electronic industry includes such steps as purifying gas-state hydrogen fluoride and gas-state ammonia, filling tem in a reactor containing solvent while controlling flow speed, regulating pH value, and reaction.
Description
Technical field
The present invention relates to a kind of synthetic method of inorganic acid salt, specifically, relate to a kind of synthetic method of special inorganic hydrochlorate, i.e. a kind of synthetic method of special ammonium fluoride for electronic industry.
Background technology
Neutral ammonium fluoride is a kind of colourless lobate or needle crystal, is a kind of important electron chemical materials.The production technique of traditional special ammonium fluoride for electronic industry is: drop into the hydrofluoric acid of specified amount in plastic containers, under water cooling, slowly feed ammonia, reach about 7 to the pH value of reaction solution.After the question response liquid cooling but, under agitation use the hydrofluoric acid acidity correction, then, obtain fluoridizing by finished product by the Crystallization Separation dehydration.With this explained hereafter electronics special ammonium fluoride, the production cycle is long, takes 14 days approximately, and it is more to enter airborne ammonia and hydrogen fluoride gas during production, and environmental pollution is serious, and mother liquor processing energy consumption is big.Outstanding debatablely be, the acidity of Productivity product is inhomogeneous in the technical indicator, add in recent years, along with developing rapidly of electronic industry, the application surface of Neutral ammonium fluoride is more and more wider, and its quality index is had higher requirement, particularly, proposed to require less than 0.00005% harsh like this quality index for cupric ion impurity.By the Neutral ammonium fluoride that above-mentioned traditional technology is produced, the content 0.003% of cupric ion impurity about, obviously can not meet consumers' demand.
Chinese patent CN1346331A discloses a kind of method of using gaseous hydrogen fluoride to prepare high-purity solutions, this is a kind of hydrogen fluoride gas to be fed the method that anhydrous solvent prepares the high-purity solutions of fluorinated hydrogen or its salt, this method is very high to the requirement of reactor and solvent, must accomplish anhydrous condition.
Chinese patent CN1385369A discloses a kind of direct synthetic method of fluorine ammonium salt, it is earlier to insert reactor in liquid state hydrogen fluoride, feed liquefied ammonia to reactor again, make liquefied ammonia in reactor, generate the fluorine ammonium salt with hydrogen fluoride liquid direct reaction, because what use is liquid hydrogen fluoride, heat-exchanger rig in the interlayer of reactor and the still must be efficiently, so that hydrogen fluoride keeps liquid, and the heat that produces will guarantee reaction the time is taken away.Can not contain moisture in the raw material, otherwise the meeting etching apparatus, quality product influenced.Main is the content of copper impurity in all not mentioned products obtained therefrom of above-mentioned two patented methods.
Summary of the invention
The present invention is intended to overcome the defective of the above-mentioned processing method that adopts in the Neutral ammonium fluoride production, provide a kind of product can satisfy the brand-new specification of quality that present electronic industry proposes, but both save energy, can shorten the production cycle again, also can be at the producing and manufacturing technique of the special ammonium fluoride for electronic industry of compliance with environmental protection requirements aspect the three waste discharge.This gas-liquid that to be a kind of gas phase synthesis method combine with liquid phase synthesizing method is the one-step synthesis processing method mutually.
This method is achieved in that and it is characterized in that the gaseous hydrogen fluoride of process purifying treatment and gaseous ammonia feed simultaneously and fill in the reaction vessel of solvent, make it finally to generate Neutral ammonium fluoride by the control to reactant pH value under the control flow velocity.That is to say that the technical process of special ammonium fluoride for electronic industry synthetic method of the present invention is: at first technical grade hydrogen fluoride and ammonia as raw material are made refining purifying treatment, make finished product through synthetic, cooling, crystallization and dehydration then.
The present invention combines the mentioned disclosed gas phase synthesis method of two China's patent in front to become gas-liquid one-step synthesis technology mutually with liquid phase synthesizing method, promptly the hydrogen fluoride of gas phase and ammonia are fed in the solvent of liquid phase simultaneously, and reaction obtains Neutral ammonium fluoride.Used solvent is the deionized water (Neutral ammonium fluoride mother liquor) of deionized water (pure water) or fluorinated ammonium.
Hydrogen fluoride is soluble in water, obtains hydrofluoric acid after it is water-soluble, and at this moment the HF molecule becomes (HF) x with hydrogen bond association each other, influenced the ionization of hydrofluoric acid, 0.1mol/L the degree of ionization of hydrofluoric acid is about 8%, so hydrofluoric acid is a kind of weak acid, part disassociation in dilute solution:
At ammonia (NH
3) in the molecule, the electronegativity of nitrogen is bigger than hydrogen, the electron pair deflection nitrogen-atoms of N-H covalent linkage.The solubleness of ammonia in water is very big, and there is following equilibrium relationship in it in the aqueous solution:
Add acid and help balance and move right, form ammonium salt, add alkali and then help being moved to the left, discharge ammonia.In amino molecule, nitrogen-atoms except with three N-H covalent linkage of hydrogen evolution, also have a pair of lone-pair electron.Ammonia as Lewis base can with some material generation adductions, form the σ key, undertaken by these a pair of lone-pair electron.NH
4 +Ion can be regarded H as
+And NH
3The adduction product.H
+Be subjected to the attraction and the NH of lone-pair electron on the nitrogen-atoms
3Add and lump together the formation coordinate bond.Therefore, ammonia forms NH in water
4 +, OH simultaneously dissociates
-, make the aqueous solution of ammonia be alkalescence.A tree name this, in same rare aqueous solution, the H that HF dissociates out
+And F
-Can same NH
3H
2The NH that O dissociates out
4 +And OH
-Reaction generates H
2O and NH
4F:
One step of employing gas liquid phase method that the present invention that Here it is proposes is the ultimate principle of synthetic Neutral ammonium fluoride directly.
Certainly, the high purity that synthesize the electronic industry special use is fluoridized ammonium, at first must do the purifying processing to technical grade hydrogen fluoride and ammonia as raw material.Method commonly used is, allows industrial utmost point hydrogen fluoride gas by containing the sulfuric acid scrubbing liquid of potassium permanganate, Potassium monofluoride, makes the oxidizing sulfur dioxide in the gas become sulphur trioxide, sulphur trioxide to be reacted into not volatile vitriol again; Metal ion in the gas and sulfuric acid reaction generate not volatile vitriol; Silicon fluoride in the gas and Potassium monofluoride are reacted into not volatile silicofluoride.Then can allow it by containing the pure water washing bottle of potassium permanganate, EDTA for the technical grade ammonia, remove reducing impurity and metal ion.
The hydrogen fluoride gas and direct importing of ammonia of handling through above-mentioned washing, purifying fill in deionized water or Neutral ammonium fluoride mother liquor and the built-in plastic containers with water-cooled silver coil pipe, two gases are reacted in liquid phase, reaction end is controlled at pH4～6.5, crystallisation by cooling, dehydration obtains Neutral ammonium fluoride.The result of sampling analysis, the acidity uniformity of finished product Neutral ammonium fluoride, iron, the requirement of heavy metal conformance with standard, the be near the mark upper limit of index of vitriol, silicofluoride index, copper content drops to 0.0002%, greater than desired 0.00005% index of the special-purpose grade of electronic industry.At this situation, the present inventor has done deep analysis and research, has proposed two measures, and the one, the flow velocity of reduction hydrogen fluoride gas and ammonia, allow impurity stay in the washings as much as possible the duration of contact of impurity and washings in the prolongation gas; The 2nd, utilize the distillation principle, earlier with low-temperature heat hydrogen fluoride steel cylinder, remove low-boiling-point substance sulfurous gas and silicon fluoride gas, in addition, the hydrogen fluoride steel cylinder is heated at last, and elevated temperature does not utilize high temperature to drive remaining hydrogen fluoride out of by force, sneaks into reaction mass in case contain the high boiling material of metal ion.That is to say, at first between 18～24 ℃, heating hydrogen fluoride steel cylinder, gasification is fallen more than the hydrogen fluoride 15kg, allow hydrogen fluoride gas feed the reactor that pure water or Neutral ammonium fluoride mother liquor are housed through washing bottle then, the flow velocity of control hydrogen fluoride gas is 12～16kg/h, simultaneously ammonia is fed reactor through washing bottle, press the feeding speed of hydrogen fluoride gas, the flow velocity of corresponding control ammonia.Silver coil pipe and logical tap water cooling are set in the reactor, continuously stirring, remain 15～18kg hydrogen fluoride gas in the last hydrogen fluoride steel cylinder and no longer feed reactor, control reaction solution pH4～6.5, crystallisation by cooling, dehydration obtains Neutral ammonium fluoride, and this product meets the electronic industry application standard fully through sampling analysis.
By as seen above-mentioned, use the synthetic Neutral ammonium fluoride that obtains of the inventive method, not only quality index meets the electronic industry application requiring, and owing to adopted gas-liquid phase one-step synthesis process, process cycle shortened to 8 days by original 14 days, added that the concentration of hydrofluoric acid and ammonia is lower in the reaction solution, and the hydrogen fluoride gas and the ammonia of overflowing from reaction solution reduce significantly, environmental protection condition has clear improvement, so effect of the present invention is conspicuous.
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, but the present invention is in no way limited to these embodiment.
Embodiment 1
Preparation work: in hydrofluoric sulfuric acid scrubbing bottle, add an amount of potassium permanganate, Potassium monofluoride; In the pure water washing bottle of ammonia, add an amount of potassium permanganate, EDTA; The silver coil pipe and the whipping appts of tap water connected in configuration in the 800L plastic containers, adds 300kg left and right sides pure water (deionized water).
Operation steps: at first at 18～24 ℃, hydrogen fluoride gas in the hydrogen fluoride steel cylinder is fed in the absorbing pure water device, the above hydrogen fluoride of 15kg is fallen in gasification, then, the flow of control hydrogen fluoride gas is 12～16kg/h, allows it through above-mentioned ready sulfuric acid scrubbing bottle, import in the 800L plastic containers, meanwhile, press the flow of the corresponding control steel cylinder of the flow ammonia of hydrogen fluoride gas, make it to import the 800L plastic containers through the ammonia washing bottle.When feeding gas, open whipping appts, reaction end, conditioned reaction liquid pH to 4～6.5.After stopping to feed gas, continue to stir cooling about 1 hour, then naturally cool to room temperature, dehydration obtains the Neutral ammonium fluoride crystallization.The whole production cycle is about 9 days.
Embodiment 2
Except that add 300kg left and right sides Neutral ammonium fluoride mother liquor in the 800L plastic containers, all the other are all identical with embodiment 1, make the Neutral ammonium fluoride finished product.
With the several batches of Neutral ammonium fluoride products that embodiment 1 and 2 described technologies make, through sample testing, its technical feature all meets following as the desired standard index of electronics special ammonium fluoride:
| Index | Specification |
| Content, % 〉= | 96.0 |
| Clarity test | Qualified |
| Ignition residue is (with SO 4Count), %≤ | 0.02 |
| Muriate, %≤ | 0.005 |
| Vitriol, %≤ | 0.01 |
| Iron, %≤ | 0.002 |
| Heavy metal (in Pb), %≤ | 0.001 |
| Free acid is (with NH 4HF 2Count), %≤ | 0.2～0.5 |
| Silicofluoride (SiF 6Count), %≤ | 0.3 |
| Copper, %≤ | 0.00005 |
Claims (8)
1, a kind of is raw material with hydrogen fluoride and ammonia, the method of one-step synthesis special ammonium fluoride for electronic industry, it is characterized in that, gaseous hydrogen fluoride and gaseous ammonia feeding simultaneously under the control flow velocity through purifying treatment fill in the reaction vessel of solvent, make it finally to generate Neutral ammonium fluoride by the control to reactant pH value.
2, the method for one-step synthesis special ammonium fluoride for electronic industry according to claim 1 is characterized in that, described solvent is a deionized water.
3, the method for one-step synthesis special ammonium fluoride for electronic industry according to claim 1 is characterized in that, described solvent is the deionized water that contains Neutral ammonium fluoride.
4, the method for one-step synthesis special ammonium fluoride for electronic industry according to claim 1, it is characterized in that, hydrofluoric purification is adopted earlier and is removed low-boiling-point substance with the low-temperature heat distillation, and in the end the stage keep a certain amount of hydrogen fluoride in steel cylinder, do not allow the method that enters reactant.
5, the method for one-step synthesis special ammonium fluoride for electronic industry according to claim 4 is characterized in that, described low-temperature heat distillation temperature is 18～24 ℃.
6, the method for one-step synthesis special ammonium fluoride for electronic industry according to claim 4 is characterized in that, in the end the stage remaines in and do not allow the hydrogen fluoride amount that enters reactant be 15～18kg in the steel cylinder.
7, the method for one-step synthesis special ammonium fluoride for electronic industry according to claim 1 is characterized in that, is 12～16kg/h in the feeding speed control of building-up reactions stage hydrogen fluoride gas.
8, the method for one-step synthesis special ammonium fluoride for electronic industry according to claim 1 is characterized in that, the span of control of described reactant pH value is 4～6.5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510030782 CN1955115A (en) | 2005-10-27 | 2005-10-27 | Synthetic method of special ammonium fluoride for electronic industry |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510030782 CN1955115A (en) | 2005-10-27 | 2005-10-27 | Synthetic method of special ammonium fluoride for electronic industry |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303941A (en) * | 2013-05-30 | 2013-09-18 | 福建省邵武市永飞化工有限公司 | Preparation method of ammonium fluoride |
| CN107954456A (en) * | 2017-12-14 | 2018-04-24 | 江西省东沿药业有限公司 | A kind of preparation method of magnesium fluoride |
| CN116859830A (en) * | 2023-03-27 | 2023-10-10 | 福建天甫电子材料有限公司 | Production management control system for electronic grade ammonium fluoride production |
| WO2024026993A1 (en) * | 2022-08-05 | 2024-02-08 | 福建省龙氟新材料有限公司 | Automatic batching control system for ammonium fluoride preparation and control method thereof |
-
2005
- 2005-10-27 CN CN 200510030782 patent/CN1955115A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303941A (en) * | 2013-05-30 | 2013-09-18 | 福建省邵武市永飞化工有限公司 | Preparation method of ammonium fluoride |
| CN107954456A (en) * | 2017-12-14 | 2018-04-24 | 江西省东沿药业有限公司 | A kind of preparation method of magnesium fluoride |
| WO2024026993A1 (en) * | 2022-08-05 | 2024-02-08 | 福建省龙氟新材料有限公司 | Automatic batching control system for ammonium fluoride preparation and control method thereof |
| CN116859830A (en) * | 2023-03-27 | 2023-10-10 | 福建天甫电子材料有限公司 | Production management control system for electronic grade ammonium fluoride production |
| CN116859830B (en) * | 2023-03-27 | 2024-01-26 | 福建天甫电子材料有限公司 | Production management control system for electronic grade ammonium fluoride production |
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Open date: 20070502 |