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WO2005068356A1 - Procede pour produire du fluorure d'hydrogene - Google Patents

Procede pour produire du fluorure d'hydrogene Download PDF

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Publication number
WO2005068356A1
WO2005068356A1 PCT/JP2005/000552 JP2005000552W WO2005068356A1 WO 2005068356 A1 WO2005068356 A1 WO 2005068356A1 JP 2005000552 W JP2005000552 W JP 2005000552W WO 2005068356 A1 WO2005068356 A1 WO 2005068356A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorine
calcium
fluoride
sulfuric acid
hydrogen fluoride
Prior art date
Application number
PCT/JP2005/000552
Other languages
English (en)
Japanese (ja)
Inventor
Norio Moriya
Kuniaki Momota
Original Assignee
Cabotsupermetals K.K.
Morita Chemical Industries Co., Ltd.
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 Cabotsupermetals K.K., Morita Chemical Industries Co., Ltd. filed Critical Cabotsupermetals K.K.
Publication of WO2005068356A1 publication Critical patent/WO2005068356A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/19—Fluorine; Hydrogen fluoride
    • C01B7/191—Hydrogen fluoride
    • C01B7/192—Preparation from fluorspar
    • 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 producing hydrogen fluoride, and more particularly, to a method capable of effectively utilizing fluorine in a fluorine-containing solution to reduce the amount of solid waste.
  • the present invention relates to a method for producing hydrogen nitride.
  • the treatment of a fluorine-containing solution such as a fluorine-containing wastewater is performed by reacting with a calcium compound such as quick lime, slaked lime or calcium chloride to fix most of the fluorine as hardly soluble calcium fluoride.
  • a calcium compound such as quick lime, slaked lime or calcium chloride.
  • further treatments such as the aluminium / minium salt method, the fluoroapatite method, the activated alumina method, the basic anion exchange resin method, and the A1 chelate resin method are carried out.
  • the calcium fluoride obtained by the immobilization treatment in this way has a very fine particle size and cannot be filtered as it is, so it is flocculated using a flocculant, and then subjected to sedimentation separation and filter press filtration. I have.
  • the water content is as high as 50 to 80%, making it difficult to reuse it for industrial purposes. Therefore, a part of the generated calcium fluoride sludge is returned to its original state, and the amount of sludge to be discarded is reduced by increasing the particle size at least a little by giving a role of seed crystal (for example, Drainage, Vol. 42, No. 10, page 27-32 (2000)).
  • An object of the present invention is to fix fluorine present in a solution such as wastewater as calcium fluoride, use it as a raw material for hydrogen fluoride production, and use calcium fluoride produced as a by-product of hydrogen fluoride production as a solution. It is used to fix fluorine in water.
  • the company will produce hydrogen fluoride, a key material in the fluorine chemical industry, without using, and provide a fluorine recycling system that uses sulfuric acid as a by-product to fix fluorine in wastewater.
  • the gist of the present invention is that calcium sulfate produced as a by-product in the production of hydrogen fluoride is used for immobilizing fluorine in a fluorine-containing solution, and calcium fluoride obtained by the immobilization is reacted with sulfuric acid.
  • a method for producing hydrogen fluoride comprising producing hydrogen fluoride, and subjecting the by-produced calcium sulfate to the step of immobilizing fluorine in the fluorine-containing solution.
  • Figure 1 is a conceptual diagram of the fluorine recycling system of the present invention.
  • FIG. 2 shows a hydrogen fluoride generator used in an example (beaker test) of the present invention.
  • FIG. 3 shows a hydrogen fluoride generator used in an embodiment (pilot test) of the present invention.
  • the method for producing hydrogen fluoride of the present invention calcium sulfate by-produced in producing hydrogen fluoride is used for immobilizing fluorine in a fluorine-containing solution, and the fluoride obtained by the immobilization is used. Hydrogen fluoride is produced by reacting calcium with sulfuric acid. To a step of immobilizing fluorine in a fluorine-containing solution.
  • the fluorine-containing solution is not particularly limited, and fluorine-containing wastewater discharged from various production processes can be suitably used.
  • the calcium sulfate used for immobilizing fluorine may be anhydrous, hemihydrate or gypsum.
  • Fluorine immobilization reaction (C a SO 4 + 2 F- ⁇ C a F 2 + SO 4 2 one: Equation (2)) is solid one-pack reaction salt exchange, yet retaining the shape of the calcium sulfate Since the reaction proceeds as it is, the average particle size of calcium sulfate is preferably 200 ⁇ m or less. In consideration of increasing the purity of the calcium fluoride after the reaction and filterability, 10 to 200 / zm is preferable, and 30 to 150 ⁇ is more preferable. However, exceeding 200 ⁇ only decreases the content of fluorinated calcium, and does not hinder use in the next hydrogen fluoride production process.
  • the calcium fluoride obtained in the present invention has excellent sedimentation properties, and can be easily dehydrated by ordinary filtration means. For example, when dehydration is performed using a normal suction filtration device in a laboratory, calcium fluoride having a water content of about 25 to 35% can be obtained. Furthermore, the use of a centrifugal dehydrator or a filter press can easily reduce the water content to about 15 to 20%. Compared to 50-60%, it can be less than half. In producing hydrogen fluoride by reacting the resulting fluoridated solution with sulfuric acid, it is preferable to use calcium fluoride having a water content of 40% or less, and more preferably to a water content of 25%. It is as follows.
  • the calcium fluoride obtained in the present invention has a loss on ignition (500 ° C, 1 hour) after drying (120 ° C, 2 hours) of 5% or less, preferably 3% or less, usually It is around 2%, which is different from that obtained by ordinary fluorine immobilization treatment at 7 to 10%.
  • the calcium fluoride obtained in the present invention can be dried with a small amount of energy due to a small amount of water and a small loss on ignition, and is suitable as a raw material for producing hydrogen fluoride.
  • the bulk specific gravity is about 1/2 to 1/3 smaller than that of fluorite. This is because fluorite is almost crystalline but porous.
  • Fluorite used as a raw material for the production of hydrogen fluoride is generally a powder having an average particle size of about 50 to 100 ⁇ m and containing about 10% water to prevent scattering. The whole amount is imported from overseas.
  • the reaction between fluorite and sulfuric acid with good crystallinity gradually progresses from the surface of the fluorite, and is covered with the generated sulfuric acid. Therefore, the mixture is sufficiently mixed and then mixed with a rotary kiln. It is usually carried out at a temperature of up to 500 ° C. for 6 to 8 hours. However, the large particles do not react completely, leaving calcium fluoride in the core.
  • the calcium fluoride obtained in the present invention is a porous and polycrystalline substance, and the reaction of the above formula (3) occurs smoothly. Therefore, the reaction is usually completed in about 200 ° C. for about 1 hour. It is possible even below 150 ° C. As described above, the relatively mild reaction conditions cause the equipment materials and reactor The range of choices will be expanded, and it will be possible to design inexpensive and compact equipment.
  • the reaction when the calcium fluoride obtained by the immobilization is reacted with sulfuric acid to produce hydrogen fluoride, the reaction is usually carried out at a temperature of 250 ° C. or lower, preferably 100 ° C. or less. It can be performed at 200 ° C. It is preferable that the content of calcium fluoride used is higher, but there is no problem even if the content is about 60%, as described later, since most of the impurities are calcium sulfate.
  • the calcium fluoride obtained by the reaction of the formula (2) hardly contains silica, which is a major impurity of fluorite, and therefore has the advantage of not producing the problematic by-product ky hydrofluoric acid. Have.
  • the sulfuric acid to be used is fuming sulfuric acid or a mixture of fuming sulfuric acid and sulfuric acid.
  • the amount of sulfuric acid is proportional to the content of calcium fluoride, but it is preferable to use sulfuric acid having an equivalent amount or less with respect to the amount of calcium fluoride. is there. An excessive amount of sulfuric acid remains in the generated calcium sulfate and is not preferable because it is wasted. On the other hand, if the amount is less than the equivalent, unreacted calcium fluoride remains, but it is used for the next immobilization of fluorine. In order to increase the recovery rate of hydrogen fluoride and the corrosion resistance of the apparatus, it is preferable to minimize the amount of water present in the reaction system.
  • fuming sulfuric acid that matches the amount of water in the sulfuric acid and the water loss corresponding to the ignition loss of calcium fluoride, or prepare a fuming sulfuric acid of about 10% by mixing fuming sulfuric acid and sulfuric acid in advance. It is preferable to keep it. As described above, in the present invention, it is most preferable to use sulfuric acid in an amount equivalent to 0.8 times the amount of calcium fluoride.
  • the solid content mainly composed of calcium sulfate by-produced in this reaction is preferably pulverized to an average particle diameter of 200 ⁇ m or less in order to use the solid content of fluorine in a fluorine-containing solution.
  • the pulverization may be either dry or wet.
  • slaked lime, hydroxylated It is preferable to adjust the pH of the fluorine-containing solution to 5 to 9 by adding an alkaline substance such as sodium.
  • the calcium sulfate in the method of mixing calcium sulfate with a fluorine-containing solution and fixing and recovering fluorine in the solution as calcium fluoride, has a particle diameter of 10 to 200.
  • ⁇ is Paiiota, and the molar ratio of calcium in the calcium sulfate to fluorine (M ca / 2 M F) (wherein, M ca / the number of moles of calcium; M F is the number of moles of fluorine).
  • force SO 8 or more Less than 1.2.
  • the molar ratio is preferably at least 0.8 and less than 1.1.
  • fluorine can be recovered from various fluorine-containing solutions by immobilizing it as calcium fluoride having a relatively large particle size and good filterability. This method is particularly useful when the obtained calcium fluoride is not used for the production of hydrogen fluoride but is recovered using a membrane such as a hollow fiber membrane or a filter press.
  • Anhydrous gypsum produced as a by-product in a hydrofluoric acid production brand was pulverized (average particle size: 65 ⁇ ) (100 g) and inorganic fluoride synthetic wastewater (fluorine concentration: 8,800 ppm) (40 kg). , Placed in a 50 L polyethylene reaction vessel equipped with a stirrer, stirred for 1 hour, and settled solids for a while Then, the supernatant was removed, and the mixture was dehydrated using a suction filter to collect 820 g of a solid.
  • the collected solids are ground to 200 ⁇ m or less, of which 353.2 g and inorganic fluoride synthetic wastewater (fluorine concentration of 12,200 ppm)
  • the solid matter recovered in the same manner as in Example 2 was similarly immobilized with fluorine without being ground.
  • the calcium fluoride content in the obtained solid was 56%.
  • Example 2 252.3 g of the solid obtained in Example 1 (lost loss of 1.7%, calcium fluoride content of 87.8%, calcium sulfate content of 10.5%) was prepared from a fluororesin PFA.
  • 5% fuming sulfuric acid prepared by mixing sulfuric acid and 25% fuming sulfuric acid
  • 27.8.3 g of sulfuric acid made of fluoroplastic PFA It was weighed on a dropping funnel and set as shown in Fig.2. Slowly add 5% fuming sulfuric acid, and after confirming that sulfuric acid has become sufficiently compatible with calcium fluoride, gradually raise the temperature of the oil path and raise the temperature to 180 ° C over 3 hours. I let it.
  • Example 6 7,003 g of solid matter obtained by treating calcium sulfate and inorganic fluorine compound synthetic wastewater (loss on ignition 1.8%, calcium fluoride content 91.2%, calcium sulfate content 7.0%) Put into a Hastelloy C22 10 L reaction vessel (11) equipped with a stirrer, steam jacket, thermometer, etc., and add 5% fuming sulfuric acid equivalent to the theoretical amount of calcium fluoride put in the reaction vessel (11%). (Prepared by mixing sulfuric acid and 25% fuming sulfuric acid) 8,034 g was weighed into a sulfuric acid dropping funnel (12) made of fluororesin PFA, and set as shown in Fig. 3 (A is Calcium fluoride, B is sulfuric acid).
  • the collected solid is ground to 200 ⁇ or less, and the entire amount is made up of inorganic fluoride synthetic wastewater (fluorine concentration: 12,100 ppm). And stirred. To make the pH of the slurry solution neutral, 670 g of a 20% aqueous calcium hydroxide solution was added. One hour later, the stirring was stopped to allow a solid to settle for a while, and then the supernatant was removed, followed by dehydration using a suction filter to recover 8,498 g of the solid.
  • Example 6 The solid obtained in Example 6 (ignition loss 2.3 ° /., Calcium fluoride) (91.5%, calcium sulfate content 7.2%) 6, 998 g was placed in a 10 L reaction vessel made of Hastelloy C22 equipped with a stirrer, steam jacket, thermometer, etc., and reacted. 5% fuming sulfuric acid (prepared by mixing sulfuric acid and 25% fuming sulfuric acid) corresponding to the theoretical amount of calcium fluoride in a container 8,045 g was weighed into a sulfuric acid dropping funnel made of fluoroplastic PFA. And set as shown in Figure 3. After slowly dropping 5% fuming sulfuric acid with stirring, steam was flowed through the jacket to gradually raise the temperature. The internal temperature was raised to 150 ° C.
  • the collected solid is ground to 200 ⁇ or less, and the entire amount is made up of inorganic fluoride synthetic wastewater (fluorine concentration: 12,100 ppm). And stirred. To make the pH of the slurry liquid neutral, 712 g of a 20% aqueous calcium hydroxide solution was added. After 1 hour, stirring was stopped to allow a solid to settle for a while, then the supernatant was removed, and dehydration was performed using a suction filter to recover 8,416 g of the solid.
  • hydrogen fluoride which is a key material of the fluorine chemical industry, is capable of efficiently immobilizing fluorine in a solution and not using natural calcium fluoride (fluorite) which is scarce in resources.
  • fluorine recycling system that uses the calcium sulfate by-produced here to fix fluorine in wastewater will be provided.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne un procédé pour produire un fluorure d'hydrogène comprenant l'utilisation de sulfate de calcium produit en tant que sous produit dans la production de fluorure d'hydrogène de manière à fixer le fluorure d'hydrogène dans une solution contenant du fluor, la mise en réaction du fluorure de calcium formé par la fixation avec de l'acide sulfurique, de manière à produire du fluorure d'hydrogène, et alimentation en sulfate de calcium, utilisé en tant que sous-produit dans l'étape précédente et qui permet de fixer le fluor dans la solution contenant du fluor susmentionnée. Le procédé de l'invention comprend un système de recyclage de fluor, qui peut éliminer la production de déchets industriels associés aux traitements de la fixation du fluor présent dans la solution, tels que des eaux usées par le sulfate de calcium, et peut, simultanément, produire du fluorure d'hydrogène, qui est un matériau clé dans l'industrie chimique du fluor, sans utiliser de fluorure de potassium naturel (fluorite) qui est une ressource rare. Le procédé de l'invention permet d'utiliser le sulfate de calcium comme sous-produit dans la production de fluorure d'hydrogène pour la fixation de fluorure dans les eaux usées.
PCT/JP2005/000552 2004-01-13 2005-01-12 Procede pour produire du fluorure d'hydrogene WO2005068356A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004005493A JP2005200233A (ja) 2004-01-13 2004-01-13 フッ化水素の製造方法
JP2004-005493 2004-01-13

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108910825A (zh) * 2018-07-27 2018-11-30 烟台中瑞化工有限公司 一种制备氟化氢的投料反应设备及投料反应方法
CN115338238A (zh) * 2022-08-16 2022-11-15 甘肃润源环境资源科技有限公司 一种铝电解槽固氟剂及固氟方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4652948B2 (ja) * 2005-10-21 2011-03-16 森田化学工業株式会社 回収フッ化カルシウムを用いたフッ化水素の製造方法
CN101600649A (zh) * 2007-02-02 2009-12-09 苏威氟有限公司 由氟化钙和硫酸制备氟化氢
EP2268573A1 (fr) * 2008-04-22 2011-01-05 Solvay Fluor GmbH Fabrication de fluorure d'hydrogène à partir d'un déchet contenant de la fluorine ou du fluorure de calcium
CN105217576B (zh) * 2015-10-28 2017-12-01 浙江东瓯过滤机制造有限公司 氟化氢制备工艺中过滤洗涤控制方法
CN109225060B (zh) * 2018-10-17 2020-10-02 苏州知瑞光电材料科技有限公司 一种制备氟化氢移动床过滤器专用滤料造粒装置的使用方法

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JPS49122880A (fr) * 1973-03-28 1974-11-25
JPH06262170A (ja) * 1993-03-11 1994-09-20 Nec Corp フッ素含有廃水の処理方法
JP2004000846A (ja) * 2002-05-31 2004-01-08 Sadaaki Murakami フッ素含有水の処理方法

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
JPH06262170A (ja) * 1993-03-11 1994-09-20 Nec Corp フッ素含有廃水の処理方法
JP2004000846A (ja) * 2002-05-31 2004-01-08 Sadaaki Murakami フッ素含有水の処理方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108910825A (zh) * 2018-07-27 2018-11-30 烟台中瑞化工有限公司 一种制备氟化氢的投料反应设备及投料反应方法
CN108910825B (zh) * 2018-07-27 2022-10-18 烟台中瑞化工有限公司 一种制备氟化氢的投料反应设备及投料反应方法
CN115338238A (zh) * 2022-08-16 2022-11-15 甘肃润源环境资源科技有限公司 一种铝电解槽固氟剂及固氟方法

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