WO2004018369A1 - Procede de recuperation de fluor - Google Patents

Procede de recuperation de fluor Download PDF

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Publication number
WO2004018369A1
WO2004018369A1 PCT/JP2003/010450 JP0310450W WO2004018369A1 WO 2004018369 A1 WO2004018369 A1 WO 2004018369A1 JP 0310450 W JP0310450 W JP 0310450W WO 2004018369 A1 WO2004018369 A1 WO 2004018369A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorine
calcium
fluoride
wastewater
particle size
Prior art date
Application number
PCT/JP2003/010450
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English (en)
Japanese (ja)
Inventor
Norio Moriya
Original Assignee
Cabot Supermetals K.K.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cabot Supermetals K.K. filed Critical Cabot Supermetals K.K.
Priority to AU2003262247A priority Critical patent/AU2003262247A1/en
Publication of WO2004018369A1 publication Critical patent/WO2004018369A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds

Definitions

  • the present invention relates to a method for recovering fluorine dissolved in wastewater or the like.
  • Solid electrolytic capacitors with anode electrodes made of tantalum are small, have low ESR, and have high capacitance, and have rapidly become popular as components for mobile phones and personal computers.
  • niobium which is a homologous element to tantalum, is cheaper than tantalum, and the dielectric constant of niobium oxide is high.
  • tantalum powder and niobium powder used as Anodo electrode material is usually a fluoride potassium salts, such as K 2 T a F 7, K 2 N b F 6, K 2 N b F 7, melting diluted It is obtained by reacting with a reducing agent such as sodium in a salt, cooling the reaction melt after completion of the reduction reaction, and washing the obtained agglomerate to remove dilute salts and the like.
  • a fluoride potassium salts such as K 2 T a F 7, K 2 N b F 6, K 2 N b F 7, melting diluted It is obtained by reacting with a reducing agent such as sodium in a salt, cooling the reaction melt after completion of the reduction reaction, and washing the obtained agglomerate to remove dilute salts and the like.
  • a fluoride potassium salts such as K 2 T a F 7, K 2 N b F 6, K 2 N b F 7, melting diluted It is obtained by reacting with a reducing agent such as sodium in a salt, cooling the reaction melt after completion
  • a method for treating such wastewater a method is generally used in which a calcium compound is added to the wastewater to precipitate calcium fluoride, and the calcium fluoride is recovered by membrane treatment.
  • the generated calcium fluoride is very fine, and it often takes a long time for the membrane treatment or the membrane is clogged, and thus there is a problem in the filterability. Disclosure of the invention
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for recovering fluorine, which is capable of easily generating calcium fluoride having a relatively large particle diameter and good filterability in membrane treatment.
  • the first method for recovering fluorine is a method for recovering fluorine by mixing an aqueous solution in which fluorine is dissolved and calcium carbonate to generate calcium fluoride.
  • the calcium carbonate has a particle size of 5 It is characterized by using particles of ⁇ 5 ⁇ .
  • the number of moles of the fluorine and (M F), the ratio M C a / 2M F of Karushiu moles of beam and (M C a) in the calcium carbonate 1. be 2 to 2.0 range Is preferred.
  • the second method for recovering fluorine is characterized by recovering fluorine by mixing an aqueous solution in which fluorine is dissolved and calcium sulfate to generate calcium fluoride.
  • particles having a particle size of 5 to 5 ⁇ are preferably used.
  • the number of moles of the fluorine and (M F), the ratio M C a Z 2M F of Karushiu moles of beam and (M C a) in the calcium sulfate 1. be 2 to 2.0 range Is preferred.
  • Figure 1 shows the ratio of fluorine to calcium 5 is a graph in which the residual fluorine concentration is plotted with respect to FIG.
  • FIG. 2 is a graph showing a change in the residual fluorine concentration with respect to the stirring time.
  • the aqueous solution in which fluorine is dissolved is not particularly limited, and includes wastewater generated in various manufacturing industries.
  • a potassium fluoride of tantalum is reduced in a dilute salt to be used in a capacitor. Wastewater generated in the process of manufacturing tantalum powder can be mentioned.
  • K 2 T a tantalum of full Tsu of potassium ⁇ beam salts F 7, etc., 8 00-9 00 is heated to about ° C in a molten state KC 1, N a
  • a dilute salt consisting of Cl, KF and their eutectic salts, etc., together with an alkali metal such as sodium, magnesium, calcium, etc., together with a reducing agent such as an alkaline earth metal, or a hydride of these is subjected to reduction reaction I do.
  • the potassium fluoride salt of tantalum and the reducing agent may be charged all at once or alternately little by little.
  • the reduction reaction is usually performed with stirring.
  • a mixture of the diluted salt and the reaction product in a molten state, that is, the reaction melt is cooled, and the obtained agglomerate is washed to remove and purify the diluted salt and the like. Thereby, a tantalum powder can be obtained.
  • the reduction reaction is a reaction represented by the above formula (1), and KC 1 is used as a diluting salt
  • the obtained agglomerate is composed of the target product tantalum and the diluting salt.
  • KC 1 is a KF and N a F a by-product, and thus containing a small amount of K 2 T a F 7 and N a is the unreacted residue.
  • acid such as hydrofluoric acid
  • cleaning is performed, and finally, cleaning with hydrogen peroxide and nitric acid is performed.
  • wastewater generated by washing with water includes water Fluorine is contained at a concentration of about 10 to 300 ppm because by-products (KF and NaF) as well as diluted salts (KC 1) having high solubility in water are dissolved. In this case, if KF is used as the diluting salt, the fluorine concentration in the first wastewater may be higher.
  • -Waste water generated by washing with acid such as hydrofluoric acid (hereinafter referred to as “second waste water”) reacts with fluorine in hydrofluoric acid, a part of tantalum, and the reaction rim from dilute salts to produce water.
  • K 2 T a F 2 0 4 K 3 T a 0 2 F 4 which forms is dissolved, contains fluorine in a concentration of about 1 0 0 ⁇ 2 0 000 ppm.
  • the first wastewater and the second wastewater generated in the process of manufacturing tantalum powder contain relatively high concentrations of fluorine derived from raw materials, by-products, and dilute salts.
  • Wastewater generated by washing with aqueous hydrogen peroxide and nitric acid (hereinafter referred to as “third wastewater”) contains almost no fluorine.
  • p pm is based on mass.
  • the calcium carbonate and calcium sulfate used here may be added directly to the wastewater in the form of particles, or may be added in the form of a slurry previously dispersed in water.
  • the particle size of calcium carbonate and calcium sulfate is preferably in the range of 5 to 5 ⁇ .
  • the particle size of the generated calcium fluoride is 5 to 50 ⁇ , which is almost the same as that of the used calcium carbonate and calcium sulfate. Excellent filtration properties, such as less clogging of the membrane during recovery and shorter time.
  • the particle size of the finally obtained calcium fluoride is considered to be almost the same as the particle size of the calcium carbonate and calcium sulfate originally used.
  • the particle size of the calcium carbonate and calcium sulfate used is less than 5 ⁇ , the particle size of the generated calcium fluoride also becomes small, and as a result, the filterability by membrane treatment tends to decrease.
  • the particle size exceeds 5 ⁇ the formation rate of calcium fluoride becomes extremely slow, and the efficiency tends to decrease.
  • the number of moles of fluorine is dissolved with (M F), the ratio M C a / 2M F with calcium carbonate Oyo Pi moles of calcium in the calcium sulfate (M C a) is 1.2 It is preferable to mix calcium carbonate and calcium sulfate with an aqueous solution such as wastewater in which fluorine is dissolved so as to be in the range of 2.0 to 2.0.
  • the M Ca Z 2M F is 1. less than 2, the rate of formation of calcium fluoride tends to be slower.
  • the use of excess calcium and calcium sulfate carbonate exceeding M C a / 2M F force S 2. 0, the recovery effect of the fluorine does not change much.
  • Ratio M Ca Z 2M F is 1.
  • the dissolution rate is high C a S 0 4 preferable.
  • the mixing of the aqueous solution in which fluorine is dissolved with calcium carbonate and calcium sulfate may be performed continuously or in a batch system, but the batch system is more effective in reducing the fluorine concentration. it can.
  • the generated calcium fluoride may be recovered by a method such as coagulation separation, centrifugation, sedimentation, or the like, but is preferably performed by a membrane treatment using a hollow fiber membrane, a filter press, or the like. .
  • calcium carbonate and calcium sulfate having extremely low solubility in water are used as the calcium compound. Therefore, the formation reaction of calcium fluoride is performed using calcium carbonate and calcium sulfate. On the surface of the particles. Therefore, the particle size of the obtained calcium fluoride is controlled to be substantially the same as the particle size of the calcium carbonate and sulfated calcium used, and by appropriately selecting the particle size of the calcium carbonate and calcium sulfate used, the desired particle size is obtained. A diameter of calcium fluoride can be produced. According to such a method, calcium fluoride having a relatively large particle size and excellent filterability can be easily generated, so that the recovery by membrane treatment is performed in a short time to effectively reduce the fluorine concentration in the wastewater. Can be reduced.
  • the tantalum raw material compound was charged together with a reducing agent into a diluted salt that was heated to about 870 ° C and was in a molten state, and a reduction reaction was performed.
  • K 2 Ta F 7 was used as a tantalum raw material compound
  • KF was used as a diluting salt
  • Na was used as a reducing agent.
  • the reaction melt in a molten state was cooled, and the obtained agglomerates were first washed with water.
  • the wastewater obtained here is designated as the first wastewater.
  • it was washed with 3% hydrofluoric acid.
  • the wastewater obtained here is designated as the second wastewater. Further, it was washed with 1.5% hydrogen peroxide and 9% nitric acid.
  • the wastewater obtained here is the third wastewater.
  • the concentration of fluorine dissolved in the first wastewater and the second wastewater is JISK-0102 According to the analysis, they were 100 ppm and 2000 ppm, respectively.
  • the concentration of fluorine dissolved in the third wastewater was 50 ppm.
  • the mixed wastewater 2 L (fluorine concentration 100000 Op pm) obtained by mixing the first wastewater and the second wastewater and the average particle diameter (particle diameter of the cumulative mass 50%) 38.7 7.1 ⁇ C a S_ ⁇ 4 is mixed with slurries 0. 7 L dispersed in water, calcium fluoride rollers and stirred for 10 minutes at room temperature to precipitate.
  • the average particle size of the obtained calcium fluoride (cumulative mass 50% of the particle diameter) is 4 2.
  • ⁇ ⁇ an average particle diameter of the same order of C a S ⁇ 4 used.
  • the concentration of dissolved fluorine was 20 ppm, and fluorine could be recovered at a recovery rate of 99.8%.
  • Example 2 The average particle size of C a S_ ⁇ 4 using (cumulative mass 50% particle size), in Example 2 1 1 8. 9 5 ⁇ , except for using 5. 74 ⁇ Example 2 2
  • Example 1 Calcium fluoride was precipitated in the same manner as described above, and the mixed wastewater was subjected to membrane treatment, but was smoothly performed without clogging. T / JP2003 / 010450
  • the average particle size (particle size at a cumulative mass of 50%) of the obtained calcium fluoride was 20.2 ⁇ in Example 21 and 8.1 ⁇ in Example 22. a The average particle size of SO 4 was almost the same.
  • Example 1 Except that the average particle size in place of the C a S_ ⁇ 4 (cumulative mass 50% particle size) was used nitrate Cal Shiumu of 5 0Myupaiiota in the same manner as in Example 1, to precipitate calcium fluoride, then the mixture The wastewater was subjected to membrane treatment, and the obtained filtrate was analyzed in the same manner as in Example 1.
  • the average particle size of the obtained calcium fluoride (particle size at a cumulative mass of 50%) was as fine as 0.2 ⁇ , and the film treatment required a long time. Further, when the filtration specific resistance ⁇ at the time of filtration was calculated, a [m / kg] was in the order of 10 13 .
  • the average particle size of the obtained calcium fluoride (particle size at a cumulative mass of 50%) was as fine as 0.7 ⁇ , and the film treatment required a long time. Further, when the filtration specific resistance ⁇ at the time of filtration was calculated, a [m / kg] was in the order of 10 13 .
  • R cake filtration resistance
  • c cake mass per unit
  • V filtration flow rate
  • A filtration area, indicating the ease of filtration of the slurry.
  • Ki de be generated substantially calcium fluoride having an average particle diameter substantially equal to that of sulfuric acid calcium used, also be carried out smoothly filtered was completed. Further, M C a / 2M F is 1.1 to 2.0, more in the range of 1.2 to 2.0, it became clear that it is the this to particular reduced effectively residual fluorine concentration.
  • calcium carbonate and / or calcium sulfate having extremely low solubility in water is used as the calcium compound.
  • calcium fluoride having a desired particle size can be generated.
  • calcium fluoride having a relatively large particle size and excellent filterability can be easily produced.
  • the concentration of fluorine dissolved in the metal can be effectively reduced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne un procédé de récupération de fluor, permettant de produire du fluorure de calcium dont les grains ont un diamètre relativement important. Ledit procédé assure des performances de filtration élevées en traitement de membrane. On récupère le fluor comme suit: mélange de solution aqueuse à fluor dissous avec du carbonate de calcium et/ou du sulfate de calcium, pour la formation de fluorure de calcium. On constitue ce fluorure de calcium, selon le diamètre de grain voulu, en sélectionnant de façon appropriée le diamètre de grain du carbonate de calcium et du sulfate de calcium à mélanger, de manière à produire un fluorure de calcium à diamètre de grain relativement important qui assure des performances de filtration élevées et donc un traitement de membrane efficace, ce qui permet de réduire la concentration de fluor dans les eaux usées, etc.
PCT/JP2003/010450 2002-08-20 2003-08-19 Procede de recuperation de fluor WO2004018369A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003262247A AU2003262247A1 (en) 2002-08-20 2003-08-19 Method of recovering fluorine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002239217A JP2004074041A (ja) 2002-08-20 2002-08-20 フッ素の回収方法
JP2002-239217 2002-08-20

Publications (1)

Publication Number Publication Date
WO2004018369A1 true WO2004018369A1 (fr) 2004-03-04

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PCT/JP2003/010450 WO2004018369A1 (fr) 2002-08-20 2003-08-19 Procede de recuperation de fluor

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JP (1) JP2004074041A (fr)
AU (1) AU2003262247A1 (fr)
WO (1) WO2004018369A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1328191C (zh) * 2004-06-01 2007-07-25 三洋电机株式会社 处理装置及使用它的被处理水的处理方法
WO2013153846A1 (fr) * 2012-04-13 2013-10-17 セントラル硝子株式会社 Procédé et dispositif pour la fabrication de fluorure de calcium
WO2013153847A1 (fr) * 2012-04-13 2013-10-17 セントラル硝子株式会社 Procédé et dispositif pour la fabrication de fluorure de calcium
US10136709B2 (en) 2013-09-06 2018-11-27 Oliver Joen-An Ma Cantilever umbrella

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4747587B2 (ja) * 2005-01-27 2011-08-17 株式会社ニコン フッ化カルシウム焼結体の製造方法
JP4953586B2 (ja) * 2005-04-14 2012-06-13 キャボットスーパーメタル株式会社 フッ素の回収方法
JP4591452B2 (ja) * 2007-01-16 2010-12-01 パナソニック株式会社 フッ素含有水の処理方法および処理装置
JP5440095B2 (ja) * 2009-10-22 2014-03-12 栗田工業株式会社 フッ素含有水の処理方法および処理装置
JP2013188673A (ja) * 2012-03-13 2013-09-26 Toshiba Corp フッ素回収装置、フッ素回収システム及びフッ素回収方法
JP5502924B2 (ja) * 2012-03-30 2014-05-28 株式会社東芝 水処理方法
JP2014133188A (ja) * 2013-01-08 2014-07-24 Toshiba Corp 水処理方法及び水処理装置
DK2958916T3 (en) * 2013-02-21 2018-11-12 Pfizer Solid forms of a selective CDK4 / 6 inhibitor
JP5649749B2 (ja) * 2014-01-31 2015-01-07 株式会社東芝 水処理方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49122880A (fr) * 1973-03-28 1974-11-25
US5362461A (en) * 1991-10-03 1994-11-08 Kurita Water Industries, Ltd. Method for recovering calcium fluoride from fluoroetchant
JP2001137864A (ja) * 1999-11-10 2001-05-22 Daikin Ind Ltd フッ酸を含有する廃水の処理方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49122880A (fr) * 1973-03-28 1974-11-25
US5362461A (en) * 1991-10-03 1994-11-08 Kurita Water Industries, Ltd. Method for recovering calcium fluoride from fluoroetchant
JP2001137864A (ja) * 1999-11-10 2001-05-22 Daikin Ind Ltd フッ酸を含有する廃水の処理方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1328191C (zh) * 2004-06-01 2007-07-25 三洋电机株式会社 处理装置及使用它的被处理水的处理方法
US7452463B2 (en) 2004-06-01 2008-11-18 Sanyo Electric Co., Ltd. Apparatus for treating water
WO2013153846A1 (fr) * 2012-04-13 2013-10-17 セントラル硝子株式会社 Procédé et dispositif pour la fabrication de fluorure de calcium
WO2013153847A1 (fr) * 2012-04-13 2013-10-17 セントラル硝子株式会社 Procédé et dispositif pour la fabrication de fluorure de calcium
US10136709B2 (en) 2013-09-06 2018-11-27 Oliver Joen-An Ma Cantilever umbrella

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Publication number Publication date
AU2003262247A1 (en) 2004-03-11
JP2004074041A (ja) 2004-03-11

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