JP7469108B2 - Method for producing inorganic fluoride compound particles - Google Patents
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- 239000002245 particle Substances 0.000 title claims description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 229910001506 inorganic fluoride Inorganic materials 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 title description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 28
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 150000002484 inorganic compounds Chemical class 0.000 claims description 17
- 229910010272 inorganic material Inorganic materials 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 40
- 239000003513 alkali Substances 0.000 description 21
- 229940074371 monofluorophosphate Drugs 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 230000002776 aggregation Effects 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 238000005054 agglomeration Methods 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000007561 laser diffraction method Methods 0.000 description 3
- 125000005341 metaphosphate group Chemical group 0.000 description 3
- 238000000790 scattering method Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000004712 monophosphates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229910013804 M2HPO4 Inorganic materials 0.000 description 1
- 229910013926 M4P2O7 Inorganic materials 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000000551 dentifrice Substances 0.000 description 1
- DGTVXEHQMSJRPE-UHFFFAOYSA-N difluorophosphinic acid Chemical class OP(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-N 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-N fluorophosphoric acid Chemical compound OP(O)(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-N 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、無機化合物粒子とフッ化水素とを反応させ、フッ化無機化合物粒子を製造する方法に関する。 The present invention relates to a method for producing inorganic fluoride particles by reacting inorganic compound particles with hydrogen fluoride.
フッ化無機化合物、なかでもアルカリモノフルオロホスフェートは、近年、所謂「フッ素入り歯磨き剤」に用いられるフッ素含有成分であり、身近なヘルスケア製品の成分として、その需要が拡大している。一方で、需要拡大に伴い、安全で、しかも低コストの製造方法が求められている。 Inorganic fluoride compounds, especially alkali monofluorophosphates, are fluoride-containing components used in so-called "fluoride toothpastes" in recent years, and demand for them as ingredients in familiar health care products is growing. On the other hand, as demand expands, a safe and low-cost manufacturing method is required.
従来、アルカリモノフルオロホスフェートの工業的製造方法としては、（１）無水フッ化水素酸と五酸化リンとから生成されるモノフルオロリン酸（Ｈ２ＰＯ３Ｆ）をアルカリ金属塩で中和する方法〔非特許文献１：Ｉｎｄ．Ｅｎｇ．Ｃｈｅｍ．ｖｏｌ４３、２４６－２４８（１９５１）〕、あるいは（２）メタリン酸塩とフッ化アルカリを溶融して製造する方法、またはメタリン酸塩の代りに対応する温度でメタリン酸塩を与えるＭＨ２ＰＯ４もしくはＭ２Ｈ２Ｐ２Ｏ７を使用する方法（特許文献１：米国特許第２４８１８０７号明細書）などがある。
上記の（１）の方法は毒性が高く極めて腐食性の強い原料を使用するためその取扱いは極めて慎重を期す必要があり、更に装置がこれら原料のため急速に腐食損傷を受け易い。この為、工業的に生産するには、かなりの熟練と高度の安全装備を付した設備を必要とするので、コスト高となる傾向がある。
（２）の方法は、液状状態での反応であり、反応が均一に進行することが期待できる。一方で６５０～７００℃の加熱を要し、原料の溶融物が反応容器を侵食する性質を持つため、生成物に反応容器由来の不純物を含む可能性が有る。
Conventional industrial methods for producing alkali monofluorophosphate include (1) a method in which monofluorophosphoric acid (H 2 PO 3 F), generated from anhydrous hydrofluoric acid and phosphorus pentoxide, is neutralized with an alkali metal salt [Non-Patent Document 1: Ind. Eng. Chem. vol. 43, pp. 246-248 (1951)], or (2) a production method in which a metaphosphate is melted with an alkali fluoride, or a method in which MH 2 PO 4 or M 2 H 2 P 2 O 7 , which gives a metaphosphate at a corresponding temperature, is used instead of a metaphosphate (Patent Document 1: U.S. Pat. No. 2,481,807).
The above method (1) uses highly toxic and highly corrosive raw materials, which must be handled with extreme care, and the equipment is easily damaged by corrosion due to these raw materials. For this reason, industrial production requires considerable skill and equipment equipped with advanced safety equipment, which tends to be expensive.
Method (2) is a reaction in a liquid state, and it is expected that the reaction will proceed uniformly. However, it requires heating at 650 to 700°C, and the molten raw material has the tendency to corrode the reaction vessel, so there is a possibility that the product will contain impurities from the reaction vessel.
これらに対してピロリン酸アルカリ金属塩またはリン酸２アルカリ金属塩とフッ化水素を直接反応させる方法が開示されている（特許文献２：特開昭５６－７３６１０号公報）。
このときの反応は次の式の通りである。
Ｍ４Ｐ２Ｏ７＋２ＨＦ→２Ｍ２ＰＯ３Ｆ＋Ｈ２Ｏ・・・（１）
Ｍ２ＨＰＯ４＋ＨＦ→Ｍ２ＰＯ３Ｆ＋Ｈ２Ｏ・・・（２）
（上記のＭはアルカリ金属を表す。）
In response to these, a method has been disclosed in which an alkali metal pyrophosphate or a dialkali metal phosphate is reacted directly with hydrogen fluoride (Patent Document 2: Japanese Patent Laid-Open Publication No. 56-73610).
The reaction at this time is as follows:
M4P2O7 + 2HF → 2M2PO3F + H2O ... ( 1)
M2HPO4 + HF → M2PO3F + H2O ... (2)
(The above M represents an alkali metal.)
この方法では、反応器にアルカリ金属リン酸塩を装入し２５０～４００℃の反応温度に昇温した後、フッ化水素ガスを導入する。この方法を常温のフッ化水素ガスを用いて行うと、上記（１），（２）式の他に、下記の（３）、（４）式の反応が進行し、フッ化アルカリ金属塩（ＭＦ）を含む場合があることが知られている。
Ｍ４Ｐ２Ｏ７＋２ＨＦ→Ｍ２Ｈ２Ｐ２Ｏ７＋２ＭＦ・・・（３）
２Ｍ２ＨＰＯ４＋２ＨＦ→Ｍ２Ｈ２Ｐ２Ｏ７＋２ＭＦ＋Ｈ２Ｏ・・（４）
In this method, an alkali metal phosphate is charged into a reactor, and hydrogen fluoride gas is introduced after the temperature is raised to a reaction temperature of 250 to 400° C. It is known that when this method is carried out using hydrogen fluoride gas at room temperature, in addition to the reactions of the above formulas (1) and (2), the following reactions of the formulas (3) and (4) proceed, and alkali metal fluoride (MF) may be contained.
M 4 P 2 O 7 + 2HF → M 2 H 2 P 2 O 7 + 2MF ... (3)
2M2HPO4 + 2HF → M2H2P2O7 + 2MF + H2O ... (4)
一方、前記のフッ化水素を用いる製造方法で、フッ化水素を１００℃以上に予熱することで、上記（３），（４）式のような副反応を抑制できることが報告されている。（特許文献３：特開昭５７－８８０１４号公報）
特許文献３では、原料として用いるアルカリ金属リン酸塩の好ましい粒径が、「５０～１００μｍ以下」と開示されている。
On the other hand, it has been reported that in the above-mentioned production method using hydrogen fluoride, by preheating the hydrogen fluoride to 100° C. or higher, the side reactions such as those represented by the above formulas (3) and (4) can be suppressed (Patent Document 3: JP-A-57-88014).
Patent Document 3 discloses that the preferred particle size of the alkali metal phosphate used as a raw material is "50 to 100 μm or less."
上記特許文献２，３の方法は、比較的低温で製造出来る優れた製法である一方で、不均一系の固気反応であり、水（水蒸気）の副生を伴う。
本発明者らの検討によれば、原料として用いるアルカリ金属リン酸塩の状態によっては、生成するアルカリモノフルオロホスフェートが塊状となる場合がある。塊のサイズによるが、大きな塊が発生した場合、反応器からノズルなどを介しての抜出が困難となり、工業的な製造方法とするには問題がある。
The methods of Patent Documents 2 and 3 are excellent methods that can produce the product at a relatively low temperature, but they involve a heterogeneous solid-gas reaction and involve the by-production of water (water vapor).
According to the study by the present inventors, depending on the state of the alkali metal phosphate used as a raw material, the alkali monofluorophosphate produced may be in the form of a lump. Depending on the size of the lump, if a large lump is produced, it becomes difficult to extract it from the reactor through a nozzle or the like, which is problematic for industrial production.
よって、本発明は、無機化合物粒子とフッ化水素とからフッ化無機化合物粒子を製造する方法において、生成物の粒子を好適な形状と出来る方法を提供することを課題としてなされたものである。最も好ましい態様として、アルカリ金属リン酸塩とフッ化水素とからアルカリモノフルオロホスフェートの好適な粒子形状で得ることが出来る方法を提供することを課題とするものである。 The present invention has been made with the objective of providing a method for producing inorganic fluoride compound particles from inorganic compound particles and hydrogen fluoride, which can give the product particles a suitable shape. In the most preferred embodiment, the objective of the present invention is to provide a method for obtaining alkali monofluorophosphate in a suitable particle shape from an alkali metal phosphate and hydrogen fluoride.
本発明者らは、仮説として、前記の副生する水分が、原料のアルカリ金属リン酸塩やアルカリモノフルオロホスフェートの表面を溶解させて、粒子同士を凝集させて塊の発生を引き起こすと予想した。 The inventors hypothesized that the water by-product dissolves the surface of the raw material alkali metal phosphate or alkali monofluorophosphate, causing the particles to aggregate and form lumps.
前記した通り、前記のアルカリモノフルオロホスフェートを得る反応は、固気反応であり、通常、原料のアルカリ金属リン酸塩の粒径は小さい方が、比表面積は広くなるので、好適と考えられる。一方、比表面積が広いと、前記の粒子同士の凝集は多発すると予想できる。
本発明者らは上記の視点に立って検討したところ、特定の粒度分布条件を有するアルカリ金属リン酸塩を用いることで、塊状化を抑制し、高い反応効率でアルカリモノフルオロホスフェートを製造出来ることを見出した。
As described above, the reaction for obtaining the alkali monofluorophosphate is a solid-gas reaction, and it is generally considered preferable that the particle size of the raw material alkali metal phosphate is small because the specific surface area is large. On the other hand, if the specific surface area is large, it is expected that the aggregation of the particles occurs frequently.
The present inventors have conducted research based on the above viewpoints and have found that by using an alkali metal phosphate having specific particle size distribution conditions, it is possible to suppress agglomeration and produce an alkali monofluorophosphate with high reaction efficiency.
即ち本発明は以下の要件によって特定できる。
（１）平均粒径が１１０～８００μｍであり、１０５μｍ以下の粒子含有率が５０質量％以下であり、アルカリ金属、アルカリ土類金属、チタン、鉄、コバルト、ニッケル、および銅からなる群より選ばれる金属の、硫酸塩、硝酸塩、リン酸塩、またはスルホン酸塩である無機化合物粒子とフッ化水素ガスとを２００～４５０℃、撹拌環境下で反応させるフッ化無機化合物粒子の製造方法。
（２）前記の無機化合物粒子がアルカリ金属、アルカリ土類金属、チタン、鉄、コバルト、ニッケル、および銅からなる群より選ばれる金属の、硫酸塩、硝酸塩、またはリン酸塩である（１）の製造方法。
（３）前記の無機化合物粒子がアルカリ金属リン酸塩である（１）の製造方法。
（４）前記１０５μｍ以下の粒子含有率が２０質量％以下である（１）の製造方法。
（５）前記１０５μｍ以下の粒子含有率が１０質量％以下である（１）の製造方法。
（６）前記無機化合物粒子の９９６μｍ以上の粒子含有率が８質量％以下である（１）の製造方法。
（７）前記アルカリ金属リン酸塩が、リン酸ナトリウム塩である（３）の製造方法。
That is, the present invention can be specified by the following requirements.
(1) A method for producing fluorinated inorganic compound particles, comprising reacting inorganic compound particles, which have an average particle size of 110 to 800 μm, a particle content of 105 μm or less, and are a sulfate, nitrate, phosphate, or sulfonate of a metal selected from the group consisting of alkali metals, alkaline earth metals, titanium, iron, cobalt, nickel, and copper, with hydrogen fluoride gas at 200 to 450° C. in a stirred environment.
(2) The method according to (1), wherein the inorganic compound particles are sulfates, nitrates, or phosphates of a metal selected from the group consisting of alkali metals, alkaline earth metals, titanium, iron, cobalt, nickel, and copper.
( 3 ) The method according to (1), wherein the inorganic compound particles are alkali metal phosphate particles.
( 4 ) The manufacturing method according to (1), wherein the content of particles having a size of 105 μm or less is 20 mass % or less.
( 5 ) The manufacturing method according to (1), wherein the content of particles having a size of 105 μm or less is 10 mass % or less.
( 6 ) The manufacturing method according to (1), wherein the inorganic compound particles have a particle content of 996 μm or more of 8 mass % or less.
( 7 ) The method according to ( 3 ), wherein the alkali metal phosphate is a sodium phosphate.
本発明は特定の粒子形状を有する無機化合物粒子を用いているので、生成物であるフッ化無機化合物粒子、特にアルカリモノフルオロホスフェートが塊状化することなく、所望とする粒子性状で得ることが出来る。この為、比較的マイルドな条件での工業レベルでの生産が期待できる。 The present invention uses inorganic compound particles having a specific particle shape, so the product, inorganic fluoride compound particles, especially alkali monofluorophosphate, can be obtained with the desired particle properties without agglomeration. For this reason, industrial-level production under relatively mild conditions is expected.
前記の通り、アルカリ金属リン酸塩とフッ化水素ガスとの反応でアルカリモノフルオロホスフェートが得られるような、無機化合物粒子とフッ化水素ガスの固体と気体の反応でフッ化無機化合物粒子を得ること自体は公知である。本発明は、その反応過程で生じるフッ化無機化合物やその原料、例えば、アルカリモノフルオロホスフェートあるいは原料のアルカリ金属リン酸塩などが塊状化することを抑制して、好適な形状のフッ化無機化合物（好ましくはアルカリモノフルオロホスフェート）を製造する方法である。 As described above, it is known that inorganic fluoride particles are obtained by a solid-gas reaction between inorganic compound particles and hydrogen fluoride gas, such as the reaction between an alkali metal phosphate and hydrogen fluoride gas to obtain an alkali monofluorophosphate. The present invention is a method for producing an inorganic fluoride compound (preferably an alkali monofluorophosphate) in a suitable shape by suppressing the agglomeration of the inorganic fluoride compound or its raw material, such as the alkali monofluorophosphate or the raw alkali metal phosphate, generated during the reaction.
本発明の前記無機化合物は特に制限はないが、その好ましい態様は、金属と周期表の15族、16族元素から選ばれる元素とを含む化合物であり、より好ましくは金属と周期表の15族、16族元素から選ばれる元素とを含む無機塩であり、さらに好ましくは、アルカリ金属リン酸塩である。この様な無機化合物としては、例えば前記の金属と周期表の15族、16族元素から選ばれる元素とを含む化合物としては、金属酸化物や金属窒化物を好ましい例として挙げることが出来る。また金属と周期表の15族、16族元素から選ばれる元素とを含む無機塩としては、例えば、アルカリ金属やアルカリ土類金属や、チタン、鉄、コバルト、ニッケル、銅などの遷移金属の、硫酸塩、硝酸塩、リン酸塩、スルホン酸塩などの、酸金属塩を挙げることが出来る。特に好ましい態様は、アルカリ金属リン酸塩である。
以下、本発明は、無機化合物として、アルカリ金属リン酸塩を例として説明するが、基本的な考え方は、どの無機化合物に対しても同じであり、この内容に制限されない。
本発明は、前記のアルカリ金属リン酸塩粒子形状が特定の条件を満たすことを特徴とする。即ち、その平均粒径が１１０～８００μｍであり、１０５μｍ以下の粒子含有率が５０質量％以下であることを特徴とする。
The inorganic compound of the present invention is not particularly limited, but a preferred embodiment thereof is a compound containing a metal and an element selected from Groups 15 and 16 of the periodic table, more preferably an inorganic salt containing a metal and an element selected from Groups 15 and 16 of the periodic table, and even more preferably an alkali metal phosphate. As such an inorganic compound, for example, a metal oxide or metal nitride can be mentioned as a preferred example of a compound containing a metal and an element selected from Groups 15 and 16 of the periodic table. In addition, as an inorganic salt containing a metal and an element selected from Groups 15 and 16 of the periodic table, for example, an acid metal salt such as sulfate, nitrate, phosphate, or sulfonate of an alkali metal, an alkaline earth metal, or a transition metal such as titanium, iron, cobalt, nickel, or copper can be mentioned. A particularly preferred embodiment is an alkali metal phosphate.
Hereinafter, the present invention will be described using an alkali metal phosphate as an example of an inorganic compound, but the basic concept is the same for any inorganic compound and is not limited to this content.
The present invention is characterized in that the particle shape of the alkali metal phosphate satisfies certain specific conditions, that is, the average particle size is 110 to 800 μm, and the content of particles having a size of 105 μm or less is 50 mass % or less.
前記のアルカリ金属リン酸塩の平均粒径の好ましい下限値は１５０μｍ、より好ましくは２００μｍ、さらに好ましくは２５０μｍ、特に好ましくは３００μｍである。一方、好ましい上限値は７００μｍ、より好ましくは６００μｍ、さらに好ましくは５５０μｍである。上記の範囲内であれば、粒子同士の凝集によると考えられる塊状化を抑制できると共に、フッ化水素ガスとの反応が進行し易い。アルカリ金属リン酸塩の平均粒径が８００μｍを超えると、前記の反応性が低下し、反応収率が低下する場合がある。 The preferred lower limit of the average particle size of the alkali metal phosphate is 150 μm, more preferably 200 μm, even more preferably 250 μm, and particularly preferably 300 μm. On the other hand, the preferred upper limit is 700 μm, more preferably 600 μm, and even more preferably 550 μm. Within the above range, agglomeration, which is believed to be due to the aggregation of particles, can be suppressed, and the reaction with hydrogen fluoride gas can easily proceed. If the average particle size of the alkali metal phosphate exceeds 800 μm, the reactivity described above may decrease, and the reaction yield may decrease.
本発明のアルカリ金属リン酸塩の１０５μｍ以下の粒子含有率の好ましい上限値は４０質量％、より好ましくは３０質量％、さらに好ましくは２０質量％、特に好ましくは１０質量％、殊に好ましくは５質量％である。好ましい下限値は、勿論０質量％である。 The preferred upper limit of the content of particles of 105 μm or less in the alkali metal phosphate of the present invention is 40% by mass, more preferably 30% by mass, even more preferably 20% by mass, particularly preferably 10% by mass, and especially preferably 5% by mass. The preferred lower limit is, of course, 0% by mass.
アルカリ金属リン酸塩とフッ化水素ガスとの反応の過程で生じる塊状化現象は、前記の通り、副生する水によって、アルカリ金属リン酸塩粒子やアルカリモノフルオロホスフェート粒子の表面に水が接触し、その表面を溶解させ、粒子同士の凝集が起こり易くなるためと本発明者らは推測している。これに対し、本発明においては、その比表面積が相対的に高くなる傾向を示す比較的小粒径である１０５μｍ以下の粒子の含有率が５０質量％以下であるので、前記の様な粒子同士の凝集や起こり難いのであろう。また瞬間的にそのような凝集が起こったとしても、より大きな粒子との衝突によって凝集状態が破壊されるため、塊状化が抑制されることも考えられる。 The inventors speculate that the agglomeration phenomenon that occurs during the reaction between the alkali metal phosphate and hydrogen fluoride gas is due to the fact that the by-product water comes into contact with the surfaces of the alkali metal phosphate particles and the alkali monofluorophosphate particles, dissolving the surfaces and making it easier for the particles to aggregate together, as described above. In contrast, in the present invention, the content of particles of 105 μm or less, which are relatively small diameters that tend to have a relatively high specific surface area, is 50 mass% or less, so the above-mentioned aggregation of particles is unlikely to occur. Furthermore, even if such aggregation occurs momentarily, it is thought that agglomeration is suppressed because the aggregated state is destroyed by collision with larger particles.
この様な複数の要因によって、本発明のアルカリモノフォスフェートの製造方法では、塊状化が起こり難いのだと考えられる。
本発明に用いるアルカリ金属リン酸塩は、大径の粒子を含まないことが好ましい。具体的には粒径が９９６μｍ以上の粒子含有率が８質量％以下であることが好ましい。より好ましくは５質量％以下、さらに好ましくは３質量％以下、特に好ましくは２質量％以下である。粒径が９９６μｍ以上のような大径の粒子は、その比表面積が比較的狭い為、フッ化水素との反応が進行し難く、反応収率が低下する場合がある。
It is believed that due to these multiple factors, agglomeration is less likely to occur in the method for producing alkali monophosphate of the present invention.
The alkali metal phosphate used in the present invention preferably does not contain large particles. Specifically, the content of particles having a particle size of 996 μm or more is preferably 8 mass% or less. More preferably, it is 5 mass% or less, further preferably, it is 3 mass% or less, and particularly preferably, it is 2 mass% or less. Since large particles having a particle size of 996 μm or more have a relatively narrow specific surface area, it is difficult to react with hydrogen fluoride, and the reaction yield may decrease.
本発明の平均粒径は、粒度分布曲線における５０体積％での粒径、すなわちｄ５０で特定されるメディアン径である。前記、粒度分布曲線は、例えば、多段の篩による振動篩法や超音波振動法、レーザー回折・散乱法、コールターカウンター等、公知のあらゆる方法を用いることが出来る。好ましくはレーザー回折・散乱法である。本発明の実施例、比較例での粒径の値は、レーザー回折・散乱法の市販の装置で測定した値である。 The average particle size in the present invention is the particle size at 50% by volume in the particle size distribution curve, i.e., the median diameter specified by d50. The particle size distribution curve can be obtained by any known method, such as a vibrating sieve method using multiple sieves, an ultrasonic vibration method, a laser diffraction/scattering method, or a Coulter counter. The laser diffraction/scattering method is preferred. The particle size values in the examples and comparative examples of the present invention are values measured using a commercially available device for the laser diffraction/scattering method.
前記のアルカリ金属リン酸塩は、本発明の目的に反しない限り、市販品を制限なく用いることが出来る。市販のアルカリ金属リン酸塩は、その粒度分布などが本発明の規定から外れるものもあるであろう。その様な製品は、公知の方法で粉砕や篩による微粒部、粗粒部の除去などによって本発明の要件を満たす粒度分布に調整することも出来る。
フッ化水素ガスは市販の製品を制限なく用いることが出来る。好ましくは純度の高いフッ化水素ガスであるが、価格と反応効率とを考慮して適宜決定できる。
The alkali metal phosphate may be any commercially available product without limitation, provided that it does not violate the object of the present invention. Some commercially available alkali metal phosphates may have particle size distributions that do not meet the requirements of the present invention. Such products may be adjusted to a particle size distribution that satisfies the requirements of the present invention by known methods such as pulverization or removal of fine and coarse particles through a sieve.
The hydrogen fluoride gas may be any commercially available product without any restrictions. High purity hydrogen fluoride gas is preferable, but the type may be appropriately determined taking into consideration the cost and reaction efficiency.
以下、本発明をアルカリ金属塩としてナトリウム塩を用いた場合を例にとって具体的に説明するが、リチウム塩やカリウム塩もまた使用できることはいうまでもない。
本発明の反応に用いる反応容器は耐無水フッ酸材料であれば制限なく用いることが出来る。具体的にはニッケル、ニッケルを含む合金（商品名：インコネル、モネル、ハステロイ等）を用いることが出来る。また、アルミニウム製の装置が使用できると言う報告もある。
また本発明の反応に用いる装置には撹拌装置を付して撹拌させることが好ましい。一方、回転式ドラム型反応器の様な反応装置の回転によって撹拌する方法を用いることも出来る。また、流動層装置を用いたガス流通による撹拌も適用できる。即ち、アルカリ金属リン酸塩や生成するアルカリモノフルオロホスフェートなどが撹拌される環境が保持される限り、反応装置の形態は制限されない。
The present invention will be specifically described below taking as an example the case where a sodium salt is used as the alkali metal salt, but it goes without saying that lithium salts and potassium salts can also be used.
The reaction vessel used in the reaction of the present invention can be made of any material that is resistant to anhydrous hydrofluoric acid. Specifically, nickel and alloys containing nickel (product names: Inconel, Monel, Hastelloy, etc.) can be used. There are also reports that equipment made of aluminum can be used.
It is also preferable to provide an agitator for the apparatus used in the reaction of the present invention for agitation. On the other hand, a method of agitation by rotation of a reaction apparatus such as a rotary drum type reactor can also be used. Agitation by gas flow using a fluidized bed apparatus can also be applied. In other words, the form of the reaction apparatus is not limited as long as an environment in which the alkali metal phosphate and the generated alkali monofluorophosphate are agitated is maintained.
本発明の反応は、２００～４５０℃で行われる工程を有する。勿論、反応工程の前半や停止の工程では、これらの温度範囲を外れることがあるのは当然である。上記の温度範囲外では、目的とするアルカリモノフルオロホスフェート以外の成分、例えば、フッ化アルカリ金属塩、アルカリジフルオロフォスフェートなどが副生し易い場合がある。 The reaction of the present invention has a process carried out at 200 to 450°C. Of course, the temperature may be outside this range in the first half of the reaction process or in the process of stopping the reaction. Outside the above temperature range, components other than the desired alkali monofluorophosphate, such as alkali metal fluoride salts and alkali difluorophosphates, may be easily produced as by-products.
本発明で用いるフッ化水素は１００℃以上の状態で、上記反応装置に供給することが好ましい。より好ましくは１５０℃以上、さらに好ましくは１８０℃以上である。一方、上限値は、４００℃であることが好ましい。
また、前記フッ化水素は、理論量の１．０～１．５倍当量反応装置に供給することが好ましい。
The hydrogen fluoride used in the present invention is preferably supplied to the above-mentioned reaction apparatus at a temperature of 100° C. or higher, more preferably 150° C. or higher, and further preferably 180° C. or higher. On the other hand, the upper limit is preferably 400° C.
The hydrogen fluoride is preferably supplied to the reaction vessel in an amount 1.0 to 1.5 times the theoretical amount.
本発明のアルカリモノフォスフェートの製造方法における反応時間に特に制限は無い。好ましくは、１０分以上、１５０時間以下である。より好ましい下限値は２０分、さらに好ましくは３０分、特に好ましくは１時間、殊に好ましくは１．５時間である。一方、より好ましい上限値は、１２０時間、さらに好ましくは１００時間、特に好ましくは８０時間である。反応時に生ずる水蒸気は、前記の粒子の凝集を抑制する観点などから、連続的にあるいは間欠式に減圧ポンプなどを用いて排気、除去することが好ましい。 There is no particular limit to the reaction time in the method for producing alkali monophosphate of the present invention. It is preferably 10 minutes or more and 150 hours or less. A more preferred lower limit is 20 minutes, even more preferably 30 minutes, particularly preferably 1 hour, and especially preferably 1.5 hours. On the other hand, a more preferred upper limit is 120 hours, even more preferably 100 hours, and especially preferably 80 hours. From the viewpoint of suppressing the aggregation of the particles, it is preferable to evacuate and remove the water vapor generated during the reaction using a vacuum pump or the like continuously or intermittently.
反応終了後は容器内の残留フッ化水素ガスをパージして、乾燥窒素などの不活性ガスや乾燥空気反応装置に導入、置換した後、反応物を回収することが出来る。
本発明の気固反応は従来の高温溶融反応に比べはるかに温和な反応で、高純度で高品質のアルカリモノフルオロホスフェートを効率よく得ることが出来る。また、生成品の塊状化を抑制できるので、取り扱い容易な性状のアルカリモノフルオロホスフェートを得ることも出来る。
After the reaction is completed, the hydrogen fluoride gas remaining in the vessel is purged and replaced with an inert gas such as dry nitrogen or dry air in the reaction apparatus, and the reaction product can then be recovered.
The gas-solid reaction of the present invention is a much milder reaction than the conventional high-temperature melting reaction, and can efficiently produce high-purity and high-quality alkali monofluorophosphate. In addition, since the formation of agglomerates in the product can be suppressed, it is also possible to obtain alkali monofluorophosphate that is easy to handle.
本発明の製造方法で得られるアルカリモノフルオロホスフェートは、製品純度が高く、公知の用途に制限なく用いることが出来る。例えば歯磨剤の成分などのヘルスケア用途向けに適している。 The alkali monofluorophosphate obtained by the manufacturing method of the present invention has a high product purity and can be used without restrictions for known applications. For example, it is suitable for healthcare applications such as an ingredient in dentifrice.
以下、実施例を挙げて本発明を説明するが、本発明は実施例によって限定されるものではない。 The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
（アルカリ金属リン酸塩の粒径、粒度分布測定）
Ｍｉｃｒｏｔｒａｃ社製粒度分布測定装置、ＭＴ３３００型装置を用い、常法で測定した。
（原料、生成物の組成分析）
Ｔｈｅｒｍｏ Ｆｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ社製－イオンクロマト分析装置を用い、常法で測定した。
（塊状生成物含有率）
生成物を目開き１．７ｍｍのふるいにかけて分別し、前記篩上に残った成分の質量分率とした。
転化率や収率は、上記組成分析値を用い、アルカリ金属リン酸塩ベースで算出する。
(Measurement of particle size and particle size distribution of alkali metal phosphates)
The particle size distribution was measured by a conventional method using a particle size distribution measuring device, MT3300, manufactured by Microtrac.
(Composition analysis of raw materials and products)
Measurement was performed by a conventional method using an ion chromatography analyzer manufactured by Thermo Fisher Scientific.
(Lumped product content)
The product was fractionated by passing it through a sieve with 1.7 mm mesh, and the mass fraction of the components remaining on the sieve was recorded.
The conversion rate and yield are calculated on an alkali metal phosphate basis using the above composition analysis values.
（実施例１、２、比較例１）
（基本反応操作）
アンカー翼を付した内容積１０リットルのニッケル合金（インコネル６００）製反応器を備える撹拌槽型反応装置にピロリン酸ナトリウム１．０ｋｇを窒素雰囲気下で投入口より供給し、攪拌しながら、原料温度３００℃になるよう電気炉で反応器を加熱した。
次いで、２００℃のフッ化水素を１．６ｇ／ｍｉｎの速度で１．９時間（理論量の１．２倍）流通し、反応器内は３００℃に保持した。反応器内の圧力は常圧とした。
反応で生成した水蒸気０．６０ｇ／ｍｉｎおよび未反応フッ化水素 ０．２６ｇ／ｍｉｎは反応器上部のガス排出口より経時的に排出して反応器内の圧力を常圧に保持した。
所定の時間後、フッ化水素の供給を停止し、次いで窒素を反応器内に導入し、わずかに残ったフッ化水素を置換した。更に撹拌を続けながら反応器底部に設置したバルブを開放し、反応生成物を抜き出した。この結果、得られた生成物は表の分析値を示した。
表１に各条件と反応結果とを示す。
(Examples 1 and 2, Comparative Example 1)
(Basic reaction operations)
To a stirred tank type reactor equipped with a 10 L nickel alloy (Inconel 600) reactor equipped with anchor blades, 1.0 kg of sodium pyrophosphate was fed from an inlet under a nitrogen atmosphere, and the reactor was heated in an electric furnace while stirring so that the raw material temperature reached 300°C.
Next, hydrogen fluoride at 200° C. was passed through the reactor at a rate of 1.6 g/min for 1.9 hours (1.2 times the theoretical amount), and the reactor was maintained at 300° C. The pressure inside the reactor was normal pressure.
The water vapor generated by the reaction at 0.60 g/min and the unreacted hydrogen fluoride at 0.26 g/min were discharged over time from a gas outlet at the top of the reactor to maintain the pressure inside the reactor at normal pressure.
After a predetermined time, the supply of hydrogen fluoride was stopped, and then nitrogen was introduced into the reactor to replace the small amount of hydrogen fluoride remaining. The valve installed at the bottom of the reactor was opened while continuing to stir, and the reaction product was extracted. As a result, the product obtained showed the analytical values shown in the table.
Table 1 shows the conditions and the reaction results.
Claims (7)
フッ化水素ガスとを
２００～４５０℃、撹拌環境下で反応させるフッ化無機化合物粒子の製造方法。 Inorganic compound particles having an average particle size of 110 to 800 μm, with a particle content of 105 μm or less being 50 mass % or less, which are sulfates, nitrates, phosphates, or sulfonates of a metal selected from the group consisting of alkali metals, alkaline earth metals, titanium, iron, cobalt, nickel, and copper;
The method for producing inorganic fluoride particles comprises reacting the mixture with hydrogen fluoride gas at 200 to 450°C in an agitated environment.
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| US3473887A (en) * | 1968-02-21 | 1969-10-21 | Allied Chem | Aluminum fluoride production |
| JPS594370B2 (en) * | 1979-11-22 | 1984-01-30 | セントラル硝子株式会社 | Method for producing alkali monofluorophosphate |
| JPS596806B2 (en) * | 1980-11-14 | 1984-02-14 | セントラル硝子株式会社 | Alkali monofluorophosphate manufacturing method and manufacturing equipment |
| JPS58181710A (en) * | 1982-04-13 | 1983-10-24 | Central Glass Co Ltd | Manufacture of alkali monofluorophosphate |
| JPS58199715A (en) * | 1982-05-12 | 1983-11-21 | Central Glass Co Ltd | Manufacture of potassium fluoride |
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