CN1332118A - Cryolite producing process with fluorine containing waste water - Google Patents
Cryolite producing process with fluorine containing waste water Download PDFInfo
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- CN1332118A CN1332118A CN 01123585 CN01123585A CN1332118A CN 1332118 A CN1332118 A CN 1332118A CN 01123585 CN01123585 CN 01123585 CN 01123585 A CN01123585 A CN 01123585A CN 1332118 A CN1332118 A CN 1332118A
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Abstract
The cryolite producing process with fluorine containing waste water, especially that from IC producer, comprises adding aluminum hydroxide and sodium hydroxide to the waste water. Fluorine ion and aluminium ion and sodium ion react to produce sodium hydrofluoaluminate, which is separated as precipitate, dewatered and dried to obtain high purity cryolite.
Description
Technical Field
The present invention relates to a method for producing cryolite from fluorine-containing wastewater, and more particularly to a method for producing powdered cryolite from fluorine-containing wastewater discharged from an integrated circuit manufacturing plant.
Technical Field
The waste water discharged from the Integrated Circuit (IC) manufacturing process comprises acid-base waste water and fluorine-containing waste water, wherein the acid-base waste water can be discharged after being neutralized by acid and base. The most widely used method for fluorine-containing wastewater is chemical precipitation, i.e. calcium hydroxide is added into fluorine-containing wastewater to release calcium ions, so that calcium ions and fluorine ions in the wastewater react to generate water-insoluble calcium fluoride, thereby removing fluorine ions in the wastewater. The aforesaid drawbacks of the treatment of fluorine-containing wastewater by chemical precipitation are: the solubility and the dissolution rate of calcium hydroxide are both low and the generation rate of calcium fluoride is too high, so that calcium fluoride sediments are quickly coated on the surfaces of calcium hydroxide particles to prevent the calcium hydroxide particles from being dissolved continuously, therefore, the calcium hydroxide particles can not be fully utilized, and the sludge generated by wastewater treatment contains a large amount of calcium hydroxide, but the purity of calcium fluoride is low, so that the sludge has no utilization value.
Because the chemical precipitation method has the defects, the research institute of the chemical industry of the institute of the industrial technology researches and develops a set of fluidized bed crystallization technology which can convert the fluorine-containing wastewater into fluorite, and the method is that a precise sensing instrument is used for detecting the concentration of fluorine ions in the wastewater and controlling the flow rate of the fluorine ions, and then the adding amount of the calcium hydroxide aqueous solution is determined; under the condition of specific temperature range and crystal seed (silica sand), the fluoride ion in the waste water will react with the added calcium hydroxide to gradually form calcium fluoride on the surface of the crystal seed. Thus, the fluorine ions in the wastewater can be converted into useful substances; the industrial research institute, chemical industry institute, the crystallization technology can also convert fluoride ions into cryolite by only changing additives into aluminum sulfate and sodium salt. The disadvantage of this method is that the cost of the fluidized bed crystallization equipment is high, and it requires professional operation, and the purity of the obtained product is not high due to the silica sand contained therein, which causes the trouble of recycling, and is very inconvenient.
The present invention intends to provide a method capable of overcoming the above problems.
Summary of The Invention
Because the fluidized bed crystallization technology has the defects of higher equipment cost and operation requirement of professional personnel, the method adopts aluminum hydroxide and sodium hydroxide as wastewater treatment agents, and the aluminum hydroxide and the sodium hydroxide are added into the fluorine-containing wastewater to generate cryolite precipitates. The method can reduce the fluorine content of the waste water to below 15ppm without expensive equipment or complex operation, and meets the requirement of environmental protection.
The method for producing cryolite by using fluorine-containing wastewater according to the invention comprises the following steps:
a. adding aluminum hydroxide and sodium hydroxide into the fluorine-containing wastewater to enable fluorine ions to react with aluminum ions and sodium ions to generate sodium fluoroaluminate precipitates; and
b. and dehydrating and drying the precipitated sodium fluoroaluminate precipitate.
Other objects, advantages and novel features of the invention will become apparent from the following detailed description.
Description of the preferred embodiments
The principle, treatment procedure and advantages of the method for producing cryolite from fluorine-containing wastewater of the present invention are described as follows:
1. the principle is as follows:
a. the aluminum hydroxide converts hydrofluoric acid (hydrogen fluoride) in the wastewater into aluminum fluoride
Hydrogen fluoride + aluminium hydroxide → aluminium fluoride + water
b. Sodium hydroxide converts aluminum fluoride to sodium fluoroaluminate (i.e., cryolite)
Aluminium fluoride + sodium hydroxide → sodium fluoroaluminate + aluminium hydroxide
c. Part of fluoride in the waste water exists in the form of sodium fluoride, and can be converted into aluminum fluoride after reacting with aluminum hydroxide, and the aluminum fluoride can also generate cryolite after reacting with the sodium hydroxide.
According to the above reaction formula, the amount of aluminum hydroxide and sodium hydroxide required by the fluorine-containing wastewater to be treated can be calculated according to the content of hydrogen fluoride and sodium fluoride in the fluorine-containing wastewater, wherein 78 kg of aluminum hydroxide and 60 kg of sodium hydroxide are required to be added to every 60 kg of hydrofluoric acid in the fluorine-containing wastewater for complete reaction, so that the hydrofluoric acid is completely converted into cryolite crystals (sodium fluoroaluminate); for every 126 kg of sodium fluoride in the fluorine-containing wastewater, 78 kg of aluminum hydroxide (no sodium hydroxide needs to be added) needs to be added, so that the sodium fluoride can be completely converted into cryolite crystals (sodium fluoroaluminate).
Wherein the temperature of the reaction is not particularly limited as long as the reaction can take place, for example, at a temperature of 0 to 85 ℃, preferably at ambient temperature.
The reaction time is such that the hydrogen fluoride and sodium fluoride are completely converted into cryolite, and the cryolite crystals can be generated when the average retention time of the waste water in the reaction tank is higher than 20 minutes.
The above reaction can recover more than 80% of fluorine ions in the fluorine-containing wastewater.
Then, drying is carried out, and the manner and temperature of drying are not particularly limited as long as dried cryolite can be obtained smoothly, for example, by operating at around 100 ℃.
2. The processing procedure or steps are as follows:
a. adding aluminum hydroxide and sodium hydroxide into the fluorine-containing wastewater to enable fluorine ions to react with aluminum ions and sodium ions to generate sodium fluoroaluminate precipitates; and
b. after the precipitation of sodium fluoroaluminate, dewatering and drying to obtain high-purity powdered cryolite.
3. The advantages are that:
a. the aluminum hydroxide is soluble in the wastewater, so the obtained final product (cryolite) has high purity and has recycling value. The traditional precipitation method has low calcium hydroxide content and no recycling value because calcium hydroxide is not easy to dissolve.
b. The method can properly treat the fluorine-containing wastewater without using expensive fluidized bed crystallization equipment.
c. The method can produce cryolite with recycling value without changing the waste water treatment equipment.
Although the above examples are described with respect to wastewater containing fluorine from an integrated circuit manufacturing plant, it should be understood that the method of the present invention can be used to treat wastewater containing fluorine from other manufacturing plants or sources.
Although the present invention has been described in terms of preferred embodiments, many other modifications and variations are possible without departing from the spirit and scope of the invention, which should be limited only by the claims appended hereto.
Claims (5)
1. A method for producing cryolite by using fluorine-containing wastewater comprises the following steps:
a. adding aluminum hydroxide and sodium hydroxide into the fluorine-containing wastewater to enable fluorine ions to react with aluminum ions and sodium ions to generate sodium fluoroaluminate precipitates; and
b. and dehydrating and drying the precipitated sodium fluoroaluminate precipitate.
2. The method according to claim 1, wherein the fluorine-containing waste water contains hydrogen fluoride and sodium fluoride.
3. The method according to claim 1, wherein the fluorine-containing waste water is discharged from an integrated circuit manufacturing plant.
4. The method according to claim 1, wherein 78 kg of aluminum hydroxide and 60 kg of sodium hydroxide are added per 60 kg of hydrofluoric acid in the fluorine-containing wastewater.
5. The method according to claim 1, wherein 78 kg of aluminum hydroxide is added to 126 kg of sodium fluoride in the fluorine-containing waste water.
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| CN 01123585 CN1332118A (en) | 2001-08-03 | 2001-08-03 | Cryolite producing process with fluorine containing waste water |
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| CN 01123585 CN1332118A (en) | 2001-08-03 | 2001-08-03 | Cryolite producing process with fluorine containing waste water |
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| CN 01123585 Pending CN1332118A (en) | 2001-08-03 | 2001-08-03 | Cryolite producing process with fluorine containing waste water |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG99953A1 (en) * | 2001-08-15 | 2003-11-27 | Liou Ding Chung | Method for producing cryolite form fluorine-containing wastewater |
| CN1294082C (en) * | 2003-03-19 | 2007-01-10 | 多氟多化工股份有限公司 | Method for producing granular cryolite |
| CN1329302C (en) * | 2003-02-21 | 2007-08-01 | 姜战 | Method for manufacturing sodium aluminium fluoride by pickling aluminium slag |
| CN1865173B (en) * | 2005-05-20 | 2010-10-20 | 廖明辉 | Fluorine-containing waste water treatment method and its treating agent |
| CN104071820A (en) * | 2014-07-21 | 2014-10-01 | 扬州百德光电有限公司 | Method for producing calcium fluoride by waste LCD panel glass etching liquid |
| CN104176755A (en) * | 2014-08-10 | 2014-12-03 | 安徽锦洋氟化学有限公司 | Preparation method of cryolite |
| CN104591462A (en) * | 2015-01-15 | 2015-05-06 | 桂林电子科技大学 | Fluoride coprecipitation method for treating strong-acidity high-fluorine wastewater |
| CN104743560A (en) * | 2013-12-25 | 2015-07-01 | 贵州大学 | Method for preparing silicon/aluminium series product by taking gangue as raw material |
| CN105621733A (en) * | 2014-11-21 | 2016-06-01 | 大桂环境科技股份有限公司 | Method for treating fluorine-containing wastewater |
| CN106348328A (en) * | 2016-10-25 | 2017-01-25 | 嘉善蓝欣涂料有限公司 | Method for recycling acid liquor by utilizing aluminum-containing electric cast liquid and fluorine-containing wastewater |
| CN106396202A (en) * | 2016-12-07 | 2017-02-15 | 武汉工程大学 | Method for resource utilization of waste acid with arsenic and fluorine import |
| CN106477610A (en) * | 2016-09-21 | 2017-03-08 | 广西大学 | A kind of preparation method of technical grade cryolite with high molecular ratio |
| CN107399750A (en) * | 2016-05-21 | 2017-11-28 | 上海问鼎环保科技有限公司 | A kind of method and device that liquid and fluoride waste recycling recovery acid solution are thrown using the electricity containing aluminium |
| CN108128790A (en) * | 2017-12-29 | 2018-06-08 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | A kind of system and technique for stewing mould liquid production ice crystal |
| CN108314166A (en) * | 2018-03-22 | 2018-07-24 | 昆山明宽环保节能科技有限公司 | A kind of neutralization alkaline agent and neutralisation treatment technique for Removal of Phosphorus in Wastewater and fluoride waste |
| CN108975468A (en) * | 2017-05-31 | 2018-12-11 | 广铭化工股份有限公司 | The processing method and system and its product liquid and solid product of fluorine-containing liquid |
| TWI733438B (en) * | 2019-12-20 | 2021-07-11 | 財團法人工業技術研究院 | Composite material and method of removing fluorine in waste liquid |
| CN116081690A (en) * | 2023-01-13 | 2023-05-09 | 中铝郑州有色金属研究院有限公司 | Method for producing ammonium polyvanadate from high-sodium high-oxalate vanadium slag |
-
2001
- 2001-08-03 CN CN 01123585 patent/CN1332118A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG99953A1 (en) * | 2001-08-15 | 2003-11-27 | Liou Ding Chung | Method for producing cryolite form fluorine-containing wastewater |
| CN1329302C (en) * | 2003-02-21 | 2007-08-01 | 姜战 | Method for manufacturing sodium aluminium fluoride by pickling aluminium slag |
| CN1294082C (en) * | 2003-03-19 | 2007-01-10 | 多氟多化工股份有限公司 | Method for producing granular cryolite |
| CN1865173B (en) * | 2005-05-20 | 2010-10-20 | 廖明辉 | Fluorine-containing waste water treatment method and its treating agent |
| CN104743560A (en) * | 2013-12-25 | 2015-07-01 | 贵州大学 | Method for preparing silicon/aluminium series product by taking gangue as raw material |
| CN104071820A (en) * | 2014-07-21 | 2014-10-01 | 扬州百德光电有限公司 | Method for producing calcium fluoride by waste LCD panel glass etching liquid |
| CN104176755A (en) * | 2014-08-10 | 2014-12-03 | 安徽锦洋氟化学有限公司 | Preparation method of cryolite |
| CN105621733A (en) * | 2014-11-21 | 2016-06-01 | 大桂环境科技股份有限公司 | Method for treating fluorine-containing wastewater |
| CN104591462A (en) * | 2015-01-15 | 2015-05-06 | 桂林电子科技大学 | Fluoride coprecipitation method for treating strong-acidity high-fluorine wastewater |
| CN104591462B (en) * | 2015-01-15 | 2016-08-24 | 桂林电子科技大学 | A kind of fluoride coprecipitation processing highly acid height fluorine waste water |
| CN107399750B (en) * | 2016-05-21 | 2019-09-20 | 上海问鼎环保科技有限公司 | A kind of method and device for throwing liquid and fluoride waste resource utilization acid solution using electricity containing aluminium |
| CN107399750A (en) * | 2016-05-21 | 2017-11-28 | 上海问鼎环保科技有限公司 | A kind of method and device that liquid and fluoride waste recycling recovery acid solution are thrown using the electricity containing aluminium |
| CN106477610B (en) * | 2016-09-21 | 2018-05-01 | 广西大学 | A kind of preparation method of technical grade cryolite with high molecular ratio |
| CN106477610A (en) * | 2016-09-21 | 2017-03-08 | 广西大学 | A kind of preparation method of technical grade cryolite with high molecular ratio |
| CN106348328A (en) * | 2016-10-25 | 2017-01-25 | 嘉善蓝欣涂料有限公司 | Method for recycling acid liquor by utilizing aluminum-containing electric cast liquid and fluorine-containing wastewater |
| CN106396202A (en) * | 2016-12-07 | 2017-02-15 | 武汉工程大学 | Method for resource utilization of waste acid with arsenic and fluorine import |
| CN108975468A (en) * | 2017-05-31 | 2018-12-11 | 广铭化工股份有限公司 | The processing method and system and its product liquid and solid product of fluorine-containing liquid |
| CN108128790A (en) * | 2017-12-29 | 2018-06-08 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | A kind of system and technique for stewing mould liquid production ice crystal |
| CN108128790B (en) * | 2017-12-29 | 2020-01-14 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | System and process for producing cryolite by using mold stewing liquid |
| CN108314166A (en) * | 2018-03-22 | 2018-07-24 | 昆山明宽环保节能科技有限公司 | A kind of neutralization alkaline agent and neutralisation treatment technique for Removal of Phosphorus in Wastewater and fluoride waste |
| TWI733438B (en) * | 2019-12-20 | 2021-07-11 | 財團法人工業技術研究院 | Composite material and method of removing fluorine in waste liquid |
| CN116081690A (en) * | 2023-01-13 | 2023-05-09 | 中铝郑州有色金属研究院有限公司 | Method for producing ammonium polyvanadate from high-sodium high-oxalate vanadium slag |
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