JP4652948B2 - Method for producing hydrogen fluoride using recovered calcium fluoride - Google Patents
Method for producing hydrogen fluoride using recovered calcium fluoride Download PDFInfo
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 title claims description 77
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims description 65
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims description 65
- 229910001634 calcium fluoride Inorganic materials 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 238000002156 mixing Methods 0.000 claims description 41
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 22
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 2
- 239000010436 fluorite Substances 0.000 description 28
- 229940095672 calcium sulfate Drugs 0.000 description 18
- 239000000843 powder Substances 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229940095564 anhydrous calcium sulfate Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、天然のフッ化カルシウム（蛍石）を使用する従来の方法と比べて、フッ素リサイクルを目的に回収された比較的高純度のフッ化カルシウムを用いることにより、エネルギー面から、反応収率の面から、さらには設備面から、フッ化水素を効率的に製造するための方法に関する。 Compared with the conventional method using natural calcium fluoride (fluorite), the present invention uses a relatively high-purity calcium fluoride collected for the purpose of fluorine recycling. The present invention relates to a method for efficiently producing hydrogen fluoride from the aspect of efficiency and further from the aspect of equipment.
通常、フッ化水素の製造は、蛍石原石を粉砕し浮遊選鉱法などにより９７％以上の純度に高められた蛍石（アシッドグレード）と硫酸および発煙硫酸とを混合して反応させ、フッ化水素と無水硫酸カルシウムを得ている（反応式１）。 Normally, hydrogen fluoride is produced by mixing and reacting fluorite (acid grade) with sulfuric acid and fuming sulfuric acid, which is obtained by crushing the raw fluorite and increasing its purity to 97% or higher by the flotation method. Hydrogen and anhydrous calcium sulfate are obtained (Reaction Formula 1).
蛍石と硫酸および発煙硫酸との反応においてフッ化水素を製造する一般の工業的製造方法では、蛍石の反応性が悪いために、硫酸および発煙硫酸はあらかじめ加熱し、スチームにて高温に加熱した混合・反応機である程度反応させた後、外熱式の反応機（ロータリーキルン）で４００℃〜５００℃の高い温度で６時間〜１２時間保持して反応を完結させているのが現状である。 In the general industrial production method for producing hydrogen fluoride in the reaction of fluorite with sulfuric acid and fuming sulfuric acid, the reactivity of fluorite is poor, so sulfuric acid and fuming sulfuric acid are heated in advance and heated to high temperature with steam. The reaction is completed after the reaction is carried out to some extent in the mixed / reactor, and the reaction is completed by holding at a high temperature of 400 ° C. to 500 ° C. for 6 hours to 12 hours in an externally heated reactor (rotary kiln). .
この高い温度での反応のため、特に熱濃硫酸が存在する部分の装置腐食が激しく、混合・反応機の材質に耐食性の高い高ニッケル合金を使用し、反応機であるロータリーキルンの前面には内面にスチール板を張り、数年で張り替えることによりフッ化水素製造設備の寿命を延ばしており、フッ化水素製造設備の建設費が高価であるだけでなく、この設備を保持するための補修費も高額である。 Because of the reaction at this high temperature, the equipment corrosion is particularly severe in the area where hot concentrated sulfuric acid is present, and a high-nickel alloy with high corrosion resistance is used for the material of the mixing / reactor. The life of a hydrogen fluoride production facility has been extended by stretching the steel plate over and replacing it in a few years. Not only is the construction cost of the hydrogen fluoride production facility expensive, but also the repair costs for maintaining this facility. Is also expensive.
代表的なフッ化水素製造設備の概要は、次の特許文献１および非特許文献１に記載されている。 Outlines of typical hydrogen fluoride production facilities are described in the following Patent Document 1 and Non-Patent Document 1.
一方、通常の回収フッ化カルシウムは、平均粒径が小さく二次凝集していること、比表面積が非常に大きいために反応性が高い。しかしながら、嵩密度が小さいこと、塩素などの不純物が多いこと等の問題があるため、乾燥時の粉塵の問題や蛍石との混合性が悪く、硫酸との反応性が高いこと、塩素不純物が増加するなどの理由により、フッ化水素製造用原料としてはほとんど利用されていない。 On the other hand, normal recovered calcium fluoride has high reactivity because it has a small average particle size and secondary agglomeration and a very large specific surface area. However, there are problems such as low bulk density and a large amount of impurities such as chlorine, so there are problems of dust during drying and miscibility with fluorite, high reactivity with sulfuric acid, chlorine impurities It is hardly used as a raw material for hydrogen fluoride production due to the increase.
また、回収フッ化カルシウムを、フッ化水素製造原料である蛍石と混ぜて使用する試みもなされているが、蛍石の流動性が悪くなると共に製品であるフッ化水素中の不純物が増加するために、せいぜい数パーセント混合し処理しているに過ぎない。 In addition, attempts have been made to use the recovered calcium fluoride in combination with fluorite, which is a raw material for producing hydrogen fluoride, but the flowability of fluorite deteriorates and impurities in the product hydrogen fluoride increase. For this reason, only a few percent are mixed and processed.
その中で、発明者らは一段目で冷却させながら回収フッ化カルシウムのみを硫酸および発煙硫酸と反応させることにより、まず不純物の塩素分、シリカ分、炭酸カルシウム分などを分解して、塩酸、４フッ化珪素、炭酸ガスなどの揮発分として取り除いたのち、二段目で加熱してフッ化水素のみを発生させた（特許文献２参照）。 Among them, the inventors reacted only the recovered calcium fluoride with sulfuric acid and fuming sulfuric acid while cooling in the first stage, thereby firstly decomposing impurities such as chlorine, silica, calcium carbonate, etc. After removing as volatile components such as silicon tetrafluoride and carbon dioxide gas, the second stage was heated to generate only hydrogen fluoride (see Patent Document 2).
また、発明者らは塩酸酸性雰囲気下でフッ素含有廃液と塩化カルシウムを同時に供給しながらフッ化カルシウムの結晶を成長させることにより、純度９８％以上の粒径が大きく均一なフッ化カルシウムを回収することができた（特許文献３参照）。 In addition, the inventors collect calcium fluoride crystals while simultaneously supplying fluorine-containing waste liquid and calcium chloride in an acidic atmosphere of hydrochloric acid to recover large and uniform calcium fluoride having a purity of 98% or more. (See Patent Document 3).
本発明の目的は、高純度の回収フッ化カルシウムを用いてフッ化水素を製造するための条件や装置・材料を見出すことにより、より経済的なフッ化水素製造設備を提供し、さらに、フッ素リサイクルシステムを構築することにある。また、資源的に乏しいアシッドグレードの蛍石を使用せずに、効率的にフッ化水素を製造する方法を提供することを目的とする。 The object of the present invention is to provide a more economical hydrogen fluoride production facility by finding conditions, equipment and materials for producing hydrogen fluoride using high purity recovered calcium fluoride. The goal is to build a recycling system. It is another object of the present invention to provide a method for efficiently producing hydrogen fluoride without using acid-grade fluorite that is scarce in resources.
本発明者等は、かかる目的を達成するために鋭意検討を重ねた結果、蛍石は硫酸および発煙硫酸と混合してもゆるやかに発熱・反応するのに対して、特許文献３で示した方法により得られた回収フッ化カルシウムは、硫酸および発煙硫酸と混合するだけでかなりの発熱が見られ、さらに十分に混合することにより大半を反応させることができることを見出した。また、反応による混合物中のフッ化水素含量が高くなることにより、反応熱に加えて、僅かな熱を加えることによりフッ化水素を気体として放出できることを見出した。 The inventors of the present invention have made extensive studies in order to achieve such an object. As a result, fluorite gradually generates heat and reacts even when mixed with sulfuric acid and fuming sulfuric acid, whereas the method shown in Patent Document 3 It was found that the recovered calcium fluoride obtained by the above method generates a considerable exotherm only by mixing with sulfuric acid and fuming sulfuric acid, and most of the calcium fluoride can be reacted by mixing sufficiently. It has also been found that hydrogen fluoride can be released as a gas by adding a slight amount of heat in addition to the heat of reaction due to an increase in the hydrogen fluoride content in the mixture resulting from the reaction.
また、フッ化水素を化学量論量の４０％以上放出した状態の反応混合物は、フッ化水素、硫酸、フッ化カルシウムおよび硫酸カルシウムの混合物であるが、比較的流動性の良い粉体になることも見出した。 Further, the reaction mixture in which hydrogen fluoride is released in an amount of 40% or more of the stoichiometric amount is a mixture of hydrogen fluoride, sulfuric acid, calcium fluoride and calcium sulfate, but becomes a powder having relatively good fluidity. I also found out.
この状態では、前記反応混合物を通常のスクリュー式の粉体輸送機で問題なく送ることができる。従って、反応を完結させるために設けた外熱式の反応機（ロータリーキルン）に前記反応混合物を容易に輸送できる。 In this state, the reaction mixture can be sent without any problem by an ordinary screw type powder transport machine. Therefore, the reaction mixture can be easily transported to an externally heated reactor (rotary kiln) provided to complete the reaction.
即ち、回収フッ化カルシウム（例えば、図２に示されたもの）はアシッドグレードの蛍石（例えば、図３に示されたもの）と比較すると、細かい結晶集合体であるため、硫酸および発煙硫酸との反応性や混合性が非常に高く、外熱式の反応機（ロータリーキルン）の温度が１５０℃程度でも反応が十分に完結することを見出した。このように、回収フッ化カルシウムの反応性の高さを最大限に利用することにより、本発明を完成させるに至った。 That is, since the recovered calcium fluoride (for example, shown in FIG. 2) is a fine crystal aggregate compared to acid grade fluorite (for example, shown in FIG. 3), sulfuric acid and fuming sulfuric acid It was found that the reaction was sufficiently completed even when the temperature of the externally heated reactor (rotary kiln) was about 150 ° C. As described above, the present invention has been completed by making maximum use of the high reactivity of the recovered calcium fluoride.
そして、例えば、特許文献３で代表されるような方法により回収された純度９７％以上の高純度なフッ化カルシウムをフッ化水素製造用原料に使用し、このフッ化カルシウムと硫酸および発煙硫酸とを混合することにより、フッ化水素を効率的に製造することができる。 For example, high-purity calcium fluoride having a purity of 97% or more recovered by a method represented by Patent Document 3 is used as a raw material for producing hydrogen fluoride, and the calcium fluoride, sulfuric acid, fuming sulfuric acid, By mixing these, hydrogen fluoride can be efficiently produced.
即ち、本発明では、フッ素リサイクル技術において、塩酸酸性雰囲気下でフッ素含有廃液と塩化カルシウムを同時に供給することにより回収された純度９７％以上のフッ化カルシウムをフッ化水素製造用の原料として使用し、この回収フッ化カルシウムと硫酸および発煙硫酸とを８０〜１５０℃に加温または加温無しに混合・反応機で充分混合することにより、化学量論量の４０％以上のフッ化水素を発生させ、それを系外へ放出する。 That is, in the present invention, in fluorine recycling technology , calcium fluoride having a purity of 97% or more recovered by simultaneously supplying fluorine-containing waste liquid and calcium chloride in hydrochloric acid acidic atmosphere is used as a raw material for hydrogen fluoride production. , The recovered calcium fluoride, sulfuric acid and fuming sulfuric acid are heated to 80-150 ° C or mixed thoroughly in a reactor with or without heating to generate 40% or more of stoichiometric hydrogen fluoride. And release it out of the system.
この場合において、前記混合・反応機として、反応で生成した硫酸カルシウムなどからなる混合物の付着および固化を防止するために二軸または三軸のセルフクリーニング機能を有するものを使用することが好ましい。 In this case, it is preferable to use an apparatus having a biaxial or triaxial self-cleaning function as the mixing / reactor in order to prevent adhesion and solidification of a mixture composed of calcium sulfate or the like produced by the reaction.
また、前記混合・反応機での工程において、反応で生成したフッ化水素が容易に系外に抜けるように、混合・反応機の上面にポケットと排ガスラインを設けることが好ましい。 Further, in the step of the mixing / reactor, it is preferable to provide a pocket and an exhaust gas line on the upper surface of the mixing / reactor so that hydrogen fluoride generated by the reaction can easily escape from the system.
前記混合・反応機の材質としては、汎用性のスチールまたはステンレススチールを使用することが好ましい。 As the material of the mixing / reactor, it is preferable to use general-purpose steel or stainless steel.
回収フッ化カルシウムと硫酸および発煙硫酸とを混合・反応機で混合するに当っては、反応により生成した混合物を内部雰囲気が硫酸の分解が起こらない２００℃以下に加熱された外熱式の反応機（ロータリーキルン）に導入することにより反応を完結させることができる。 Is hitting the mixing recovered calcium fluoride and sulfuric acid and oleum in a mixing-reactor, reaction of externally heated to an internal atmosphere mixture produced was heated to 200 ° C. or less does not occur decomposition of sulfuric acid by The reaction can be completed by introducing it into a reactor (rotary kiln).
請求項１記載の発明によれば、資源的に乏しいアシッドグレードの蛍石を使用すること無く、低い温度で高効率にフッ化水素を製造することができ、エネルギー面からも十分配慮された製造設備の提供が可能となる。 According to the first aspect of the present invention, hydrogen fluoride can be produced with high efficiency at a low temperature without using acid-grade fluorite, which is scarce in resources, and production with sufficient consideration in terms of energy Equipment can be provided.
請求項２記載の発明によれば、固化および付着など機械的負荷に影響を与える問題を抑制する効果がある。 According to invention of Claim 2, there exists an effect which suppresses the problem which influences mechanical load, such as solidification and adhesion.
請求項３記載の発明によれば、反応により生成した混合物の性質を制御できる効果がある。 According to invention of Claim 3, there exists an effect which can control the property of the mixture produced | generated by reaction.
請求項４記載の発明によれば、装置材質を低コストに抑えることができ、また、加工性が容易なため、修繕費および維持費を抑える効果がある。 According to the fourth aspect of the present invention, the material of the apparatus can be suppressed at a low cost, and the workability is easy.
請求項５記載の発明によれば、低温かつ短時間で反応を完結させる効果がある。 According to the invention of claim 5, there is an effect of completing the reaction at a low temperature and in a short time.
以下、本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
フッ素含有廃液処理で得られた回収フッ化カルシウムは、原石を砕き、浮遊選鉱により純化された蛍石と比較して、その一例として示す図２と図３から明らかなように、形状が大きく異なる。 The recovered calcium fluoride obtained in the treatment of the fluorine-containing waste liquid is greatly different in shape as shown in FIG. 2 and FIG. 3 as an example, compared with fluorite crushed and purified by flotation. .
蛍石は粒径１〜２００μｍの粒子が万遍なく存在し、平均粒径が５０〜１００μｍであるのに対し、回収フッ化カルシウムは比較的粒径が均一であり、平均粒径２０〜５０μｍである。また、結晶成長を行わない場合には、大きくても１〜５μｍと細かいものが得られる。 Fluorite has a uniform particle size of 1 to 200 μm and an average particle size of 50 to 100 μm, whereas recovered calcium fluoride has a relatively uniform particle size and an average particle size of 20 to 50 μm. It is. Further, when crystal growth is not performed, a fine one of 1 to 5 μm can be obtained.
また、蛍石が緻密なフッ化カルシウムの固まりであるのに対し、回収フッ化カルシウムは５〜１０μｍの結晶が二次凝集した形状を示し、比表面積が大きい。このため、回収フッ化カルシウムの嵩比重は蛍石の０．５〜０．７倍と小さく、嵩高いものになる。 Further, while fluorite is a dense mass of calcium fluoride, recovered calcium fluoride has a shape in which crystals of 5 to 10 μm are secondary aggregated and has a large specific surface area. Therefore, the bulk specific gravity of the recovered calcium fluoride is as small as 0.5 to 0.7 times that of fluorite and becomes bulky.
このことにより、硫酸および発煙硫酸と混合するだけでかなりの発熱が見られ、その混合物はゲル状として存在する。この混合物を、さらに十分に混合することにより大半を反応することが可能であり、反応による混合物中のフッ化水素含有量が高くなることにより、反応熱に加え僅かな熱を加えることによりフッ化水素を気体として放出できる。 Due to this, a considerable exotherm is seen just by mixing with sulfuric acid and fuming sulfuric acid, and the mixture exists as a gel. It is possible to react most of this mixture by further thorough mixing. By increasing the hydrogen fluoride content in the mixture resulting from the reaction, fluorination can be achieved by adding a little heat to the reaction heat. Hydrogen can be released as a gas.
一方、蛍石を硫酸および発煙硫酸と混合すると低い反応性のために、蛍石および反応固形物に吸着できない硫酸および発煙硫酸が液体で流出し、設備を著しく腐食する。 On the other hand, when fluorite is mixed with sulfuric acid and fuming sulfuric acid, due to the low reactivity, sulfuric acid and fuming sulfuric acid that cannot be adsorbed on the fluorite and the reaction solids will flow out in liquid, and the equipment will be significantly corroded.
このために、従来のフッ化水素製造設備の混合・反応機では、ハステロイＣ（商品名）などの高価な耐食性高ニッケル合金を使用すると共に、反応性を高めるために供給する硫酸および発煙硫酸を加熱し、混合・反応機も加熱して、さらに構造を複雑化することで、できるだけ硫酸カルシウムを生成させて、硫酸および発煙硫酸が液体で存在することを防止している。 For this reason, in conventional mixing / reactors of hydrogen fluoride production facilities, expensive corrosion-resistant high nickel alloys such as Hastelloy C (trade name) are used, and sulfuric acid and fuming sulfuric acid supplied to increase the reactivity are used. By heating, the mixing / reactor is also heated to further complicate the structure, so that calcium sulfate is generated as much as possible to prevent sulfuric acid and fuming sulfuric acid from being present in liquid form.
前記反応式１で生成したフッ化水素は、未反応の硫酸および発煙硫酸への溶解度が高く、また、それは温度が低いほど大きい。そのため、回収フッ化カルシウムを原料に用いた場合において、大気圧下で内温が８０℃以上になると、フッ化水素が気体として放出され始めると共に反応がさらに進行する。 The hydrogen fluoride produced in the reaction formula 1 has higher solubility in unreacted sulfuric acid and fuming sulfuric acid, and it is larger as the temperature is lower. Therefore, when the recovered calcium fluoride is used as a raw material, when the internal temperature becomes 80 ° C. or higher under atmospheric pressure, hydrogen fluoride begins to be released as a gas and the reaction further proceeds.
このことから、反応により硫酸カルシウムが生成すると固形物分の増加により、混合物の状態はゲルから粉体に移行する。特に、化学量論量の４０％以上のフッ化水素を放出した状態での反応混合物は、主成分が硫酸カルシウムで、未反応の硫酸、回収フッ化カルシウムおよび反応生成物のフッ化水素を含み、比較的良好な流動性を示す粉体になる。 From this, when calcium sulfate is generated by the reaction, the state of the mixture shifts from a gel to a powder due to an increase in the solid content. In particular, the reaction mixture in a state where 40% or more of the stoichiometric amount of hydrogen fluoride has been released contains calcium sulfate as a main component, and includes unreacted sulfuric acid, recovered calcium fluoride, and hydrogen fluoride as a reaction product. It becomes a powder showing relatively good fluidity.
また、この状態は、回収フッ化カルシウムを原料にした場合、混合・反応機を揮発させるフッ化水素の蒸発潜熱分の熱量を加えることにより容易に達成できる。混合・反応機からフッ化水素を円満に系外に排出できるよう、例えば図１に示すような混合・反応機１の上面にポケット１ｂとそれに連続させて排ガスライン４を設けるのが良い。 In addition, this state can be easily achieved by adding the amount of heat of the latent heat of evaporation of hydrogen fluoride that volatilizes the mixing / reactor when the recovered calcium fluoride is used as a raw material. For example, an exhaust gas line 4 may be provided on the upper surface of the mixing / reactor 1 as shown in FIG. 1 so as to be continuous with the pocket 1b so that hydrogen fluoride can be discharged out of the system from the mixing / reaction device.
これらのことから、反応を完結させるために設けた外熱式の反応機（ロータリーキルン）への反応混合物の輸送は、通常のスクリュー式の粉体輸送機で問題なく送ることができる。 From these facts, the reaction mixture can be transported to an externally heated reactor (rotary kiln) provided to complete the reaction with a normal screw-type powder transporter without any problem.
以上のことから、回収フッ化カルシウムをフッ化水素製造用の原料にした場合において、混合・反応機は、蛍石を原料にした場合に比較して、腐食が起こりにくい条件下で運転ができるため、その材質として安価な汎用性の高いスチールまたはステンレススチールが使用できるが、本発明ではこの二種類のもののみに限定されるものではない。 From the above, when the recovered calcium fluoride is used as a raw material for hydrogen fluoride production, the mixing / reactor can be operated under conditions where corrosion is less likely to occur than when fluorite is used as a raw material. Therefore, inexpensive and highly versatile steel or stainless steel can be used as the material, but the present invention is not limited to these two types.
従って、例えば、ハステロイＣ（商品名）などの耐食性高ニッケル合金などを用いてもよく、また、装置設備の加熱温度が低いことからも、耐食性を有する樹脂を使用しても良い。ここで、耐食性を有する樹脂としては、ポリテトラフルオロエチレン樹脂等のフッ素系樹脂や、テトラフルオロエチレン／パーフロロアルキルビニールエーテル共重合などを挙げることができる。 Therefore, for example, a corrosion-resistant high nickel alloy such as Hastelloy C (trade name) may be used, and a resin having corrosion resistance may be used because the heating temperature of the equipment is low. Here, examples of the resin having corrosion resistance include fluorine resins such as polytetrafluoroethylene resin, and tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer.
また、回収フッ化カルシウムを原料にした場合、反応性が著しく高いために、混合・反応機に硫酸カルシウムからなる混合物が付着し易いため、セルフクリーニング機能を有する混合・反応機を使用するのが良い。ここで、二軸もしくは三軸を有するセルフクリーニング機能を有するものが適応できる。 In addition, when recovered calcium fluoride is used as a raw material, since the reactivity is extremely high, a mixture of calcium sulfate is likely to adhere to the mixing / reactor, so it is necessary to use a mixing / reactor having a self-cleaning function. good. Here, a device having a self-cleaning function having two or three axes is applicable.
この混合・反応機の加熱手段としては、例えば、保温ジャケットを備え、スチームを流すことにより、または外面から電熱によって加熱する形式のものを利用することもできる。混合・反応機内の混合物の温度は、８０〜１５０℃、より好ましくは８０〜１１０℃の範囲で運転すると良い。反応温度が過度に高いと装置に負担を生じ、逆に、反応温度が過度に低いと生成したフッ化水素が系外へ放出されにくくなり、流動性の良い粉体を得ることができない。 As the heating means of this mixing / reactor, for example, a type equipped with a heat insulation jacket and heated by flowing steam or by electric heat from the outer surface can be used. The temperature of the mixture in the mixing / reactor is preferably 80 to 150 ° C, more preferably 80 to 110 ° C. If the reaction temperature is excessively high, the apparatus is burdened. Conversely, if the reaction temperature is excessively low, the generated hydrogen fluoride is difficult to be released out of the system, and powder with good fluidity cannot be obtained.
また、混合・反応機より排出された混合物は、外熱式の反応機（ロータリーキルン）へ移送される。この間の輸送距離は、通常わずかな距離以上、特に０．５ｍ以上であり、通常５ｍ以下、特に３ｍ以下である。これにより、装置メンテナンス性が向上する効果が期待できる。 The mixture discharged from the mixing / reactor is transferred to an externally heated reactor (rotary kiln). The transport distance during this period is usually a slight distance or more, particularly 0.5 m or more, and is usually 5 m or less, particularly 3 m or less. Thereby, the effect that apparatus maintainability improves can be expected.
外熱式の反応機（ロータリーキルン）の温度は高いほど前記反応式１の反応を速く完結させることができる。特に、蛍石を原料に使用した場合は、５０μｍ以上の粒径の大きな蛍石の中心部まで硫酸カルシウムに転換させるために、高い温度と長い滞留時間を保持している。 The higher the temperature of the externally heated reactor (rotary kiln), the faster the reaction of reaction formula 1 can be completed. In particular, when fluorite is used as a raw material, a high temperature and a long residence time are maintained in order to convert calcium sulfate to the center of a large fluorite having a particle size of 50 μm or more.
即ち、通常のフッ化水素製造設備の外熱式の反応機（ロータリーキルン）は、４００〜５００℃の高い温度で、平均滞留時間を６〜１２時間保持して反応を完結させている。このため、大きな設備を必要とし、腐食が激しい反応機（ロータリーキルン）の前面は３０〜５０ｍｍのスチール板を内面に張り、数年で張り替えることにより装置の寿命を延ばしており、この設備を保持するための補修費も高額である。 That is, an externally heated reactor (rotary kiln) of a normal hydrogen fluoride production facility maintains an average residence time of 6 to 12 hours at a high temperature of 400 to 500 ° C. to complete the reaction. For this reason, a large facility is required, and the front of the reactor (rotary kiln), which is severely corroded, has a 30-50mm steel plate on the inner surface. The cost of repairs is also high.
一方、回収フッ化カルシウムは５〜１０μｍの結晶が２次凝集した形状を示し、かつ比表面積が大きく空洞部分が多く存在するため、硫酸カルシウムに転化させるために、高い温度と長い滞留時間を必要としない。例えば、内温１５０℃、滞留時間１時間でも反応は完結する。 On the other hand, recovered calcium fluoride has a shape in which crystals of 5 to 10 μm are secondary-aggregated, and has a large specific surface area and a large number of cavities, so a high temperature and a long residence time are required to convert it into calcium sulfate. And not. For example, the reaction is completed even at an internal temperature of 150 ° C. and a residence time of 1 hour.
従って、硫酸の熱分解が起こらない、２５０℃以下の温度で外熱式の反応機（ロータリーキルン）を運転できれば、装置の腐食を画期的に押さえることができる。よって、装置内の粉体温度を２００℃以下に、より好ましくは１５０〜２００℃に保持して反応を完結させるのが良い。 Therefore, if the externally heated reactor (rotary kiln) can be operated at a temperature of 250 ° C. or less at which the thermal decomposition of sulfuric acid does not occur, the corrosion of the apparatus can be significantly reduced. Therefore, it is preferable to complete the reaction by maintaining the powder temperature in the apparatus at 200 ° C. or lower, more preferably 150 to 200 ° C.
反応により得られた硫酸カルシウムは、未反応のフッ化カルシウムや硫酸および発煙硫酸を含むことが考えられるが、反応条件を調整することにより、高純度な硫酸カルシウムを得ることができる。この反応条件の調整は、硫酸が熱分解しないことから容易に達成できる。 Although calcium sulfate obtained by the reaction may contain unreacted calcium fluoride, sulfuric acid, and fuming sulfuric acid, high-purity calcium sulfate can be obtained by adjusting the reaction conditions. Adjustment of this reaction condition can be easily achieved because sulfuric acid is not thermally decomposed.
以上、本発明により資源的に乏しいアシッドグレードの蛍石を使用すること無く、低い温度で高効率にフッ化水素を製造することが可能であり、また、高価な耐食性材料を用いることなく、エネルギー問題からも十分配慮したコンパクトな設備でフッ化水素を製造することができる。 As described above, according to the present invention, it is possible to produce hydrogen fluoride with high efficiency at a low temperature without using acid-grade fluorite, which is scarce in resources, and without using an expensive corrosion-resistant material. It is possible to produce hydrogen fluoride with compact equipment that gives due consideration to problems.
また、これら反応により得られたフッ化水素および硫酸カルシウムは、蛍石を原料とした場合に比べて高純度のものが得られ、特に含フッ素無機化合物、含フッ素有機化合物などの原料、半導体などの洗浄液など各種方面に対して有用である。 In addition, hydrogen fluoride and calcium sulfate obtained by these reactions can be obtained with a higher purity than when fluorite is used as a raw material, particularly raw materials such as fluorine-containing inorganic compounds and fluorine-containing organic compounds, semiconductors, etc. It is useful for various fields such as cleaning liquid.
以下、実施例および比較例を挙げて本発明をより具体的に説明するが、本発明はその要旨を逸脱しない限り、これらの実施例のみに限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited only to these Examples, unless it deviates from the summary.
図１は、本実施形態の一例を示すフッ化水素製造設備の模式図である。図１において、１は二軸セルフクリーニングスクリュー１ａと上面にポケット１ｂを備えた混合・反応機である。２は混合・反応機１で排出された粉体を輸送するためのスクリューフィーダー、３は熱風などの加熱手段を備えた外熱式の反応機（ロータリーキルン）、４は混合・反応機１のフッ化水素の排ガスラインである。また、５は外熱式の反応機（ロータリーキルン）３により発生したフッ化水素の排ガスラインである。 FIG. 1 is a schematic diagram of a hydrogen fluoride production facility showing an example of the present embodiment. In FIG. 1, 1 is a mixing / reacting machine having a biaxial self-cleaning screw 1a and a pocket 1b on the upper surface. 2 is a screw feeder for transporting the powder discharged from the mixing / reactor 1, 3 is an externally heated reactor (rotary kiln) equipped with heating means such as hot air, and 4 is a foot of the mixing / reactor 1. This is a hydrogen fluoride exhaust gas line. Reference numeral 5 denotes an exhaust gas line of hydrogen fluoride generated by an externally heated reactor (rotary kiln) 3.
（実施例１）
混合・反応機１に原料である回収フッ化カルシウムを１１．５ｋｇ／ｈｒ（１４７．４ｍｏｌ／ｈｒ）、５％のＳＯ３を含む発煙硫酸を７．９Ｌ／ｈｒ（１４７．４ｍｏｌ／ｈｒ）で定量的に同時導入した。その際、混合・反応機内の紛体温度を８０℃になるように外部温度を設定し、排出された混合物の転化率を分析した。
Example 1
In the mixing / reactor 1, the recovered calcium fluoride as a raw material is 11.5 kg / hr (147.4 mol / hr), and fuming sulfuric acid containing 5% SO 3 is 7.9 L / hr (147.4 mol / hr). Simultaneously introduced quantitatively. At that time, the external temperature was set so that the powder temperature in the mixing / reactor was 80 ° C., and the conversion rate of the discharged mixture was analyzed.
分析の結果、回収フッ化カルシウムの転化率は７１．０％、反応混合物における硫酸カルシウムの含有量は７１．１％であった。また、その混合物内に含まれるフッ化水素は６．０％であり、化学量論量の約４５％のフッ化水素が排ガスライン４から揮発したことになり、排出物は流動性の良い粉体であった。 As a result of analysis, the conversion of recovered calcium fluoride was 71.0%, and the content of calcium sulfate in the reaction mixture was 71.1%. In addition, hydrogen fluoride contained in the mixture was 6.0%, and about 45% of the stoichiometric amount of hydrogen fluoride was volatilized from the exhaust gas line 4, and the effluent was a powder with good fluidity. It was a body.
混合・反応機１からの排出物はスクリューフィーダー２にて移送されて外熱式の反応機（ロータリーキルン）３に導入され、雰囲気温度を１５０℃、滞留時間を１時間に調整した外熱式の反応機（ロータリーキルン）３内でさらに反応を進行させた。外熱式の反応機（ロータリーキルン）３から排出された混合物を分析した結果、反応生成物は９７．８％の硫酸カルシウムであった。その他に未反応のフッ化カルシウムは０．７５％、硫酸は１．３２％、また残留フッ化水素は０．０２％であることが確認された。 Exhaust from the mixing / reactor 1 is transferred by a screw feeder 2 and introduced into an externally heated reactor (rotary kiln) 3, and the externally heated type is adjusted to an atmospheric temperature of 150 ° C. and a residence time of 1 hour. The reaction was further allowed to proceed in the reactor (rotary kiln) 3. As a result of analyzing the mixture discharged from the externally heated reactor (rotary kiln) 3, the reaction product was 97.8% calcium sulfate. In addition, it was confirmed that unreacted calcium fluoride was 0.75%, sulfuric acid was 1.32%, and residual hydrogen fluoride was 0.02%.
（実施例２）
混合・反応機１に原料である回収フッ化カルシウムを１１．５ｋｇ／ｈｒ（１４７．４ｍｏｌ／ｈｒ）、５％のＳＯ３を含む発煙硫酸を７．９Ｌ／ｈｒ（１４７．４ｍｏｌ／ｈｒ）で定量的に同時導入した。その際、混合・反応機内の紛体温度を１００℃になるように外部温度を設定し、排出された混合物の転化率を分析した。
(Example 2)
In the mixing / reactor 1, the recovered calcium fluoride as a raw material is 11.5 kg / hr (147.4 mol / hr), and fuming sulfuric acid containing 5% SO 3 is 7.9 L / hr (147.4 mol / hr). Simultaneously introduced quantitatively. At that time, the external temperature was set so that the powder temperature in the mixing / reactor was 100 ° C., and the conversion rate of the discharged mixture was analyzed.
分析の結果、回収フッ化カルシウムの転化率は８２．０％、反応混合物における硫酸カルシウムの含有量は７５．６％であった。また、その混合物内に含まれるフッ化水素は３．２％であり、化学量論量の約７０％のフッ化水素が排ガスライン４から揮発したことになり、排出物は流動性が非常に良い粉体であった。 As a result of analysis, the conversion of recovered calcium fluoride was 82.0%, and the content of calcium sulfate in the reaction mixture was 75.6%. In addition, hydrogen fluoride contained in the mixture was 3.2%, and about 70% of the stoichiometric amount of hydrogen fluoride was volatilized from the exhaust gas line 4, and the discharge was very fluid. It was a good powder.
混合・反応機１からの排出物はスクリューフィーダー２にて移送されて外熱式の反応機（ロータリーキルン）３に導入され、雰囲気温度を１８０℃、滞留時間を１時間に調整した外熱式の反応機（ロータリーキルン）３内でさらに反応を進行させた。外熱式の反応機（ロータリーキルン）３から排出された混合物を分析した結果、反応生成物は９８．７％の硫酸カルシウムであった。その他に未反応のフッ化カルシウムは０．４８％、硫酸は０．８２％、また残留フッ化水素は０．０１％であることが確認された。 The discharge from the mixing / reactor 1 is transferred by a screw feeder 2 and introduced into an externally heated reactor (rotary kiln) 3, and the externally heated type is adjusted to an atmospheric temperature of 180 ° C. and a residence time of 1 hour. The reaction was further allowed to proceed in the reactor (rotary kiln) 3. As a result of analyzing the mixture discharged from the externally heated reactor (rotary kiln) 3, the reaction product was 98.7% calcium sulfate. In addition, it was confirmed that unreacted calcium fluoride was 0.48%, sulfuric acid was 0.82%, and residual hydrogen fluoride was 0.01%.
（実施例３）
混合・反応機１に原料であるフッ化カルシウムを１１．５ｋｇ／ｈｒ（１４７．４ｍｏｌ／ｈｒ）、５％のＳＯ３を含む発煙硫酸を７．９Ｌ／ｈｒ（１４７．４ｍｏｌ／ｈｒ）で定量的に同時導入した。その際、混合・反応機を加熱することなく、排出された混合物の転化率を分析した。
(Example 3)
Mixing / reactor 1 quantifies calcium fluoride as raw material at 11.5 kg / hr (147.4 mol / hr) and fuming sulfuric acid containing 5% SO 3 at 7.9 L / hr (147.4 mol / hr). Introduced simultaneously. At that time, the conversion rate of the discharged mixture was analyzed without heating the mixing / reactor.
分析の結果、フッ化カルシウムの転化率は４８．２％、反応混合物における硫酸カルシウムの含有量は３７．１％であった。また、その混合物内に含まれるフッ化水素は９．８％であり、わずか化学量論量の約５％のフッ化水素が排ガスライン４から揮発したことになり、排出された反応混合物は粘着性のある粉体であり、スクリューフィーダー２による移送は困難であった。 As a result of the analysis, the conversion rate of calcium fluoride was 48.2%, and the content of calcium sulfate in the reaction mixture was 37.1%. In addition, hydrogen fluoride contained in the mixture was 9.8%, and only 5% of the stoichiometric amount of hydrogen fluoride was volatilized from the exhaust gas line 4, and the discharged reaction mixture was sticky. It was difficult to transfer with the screw feeder 2.
（比較例１）
蛍石を用いて、実施例３と同一条件で反応を行った。分析の結果、蛍石はほとんど未反応であり、その状態は高い粘性を有するゲル状であった。
(Comparative Example 1)
The reaction was performed under the same conditions as in Example 3 using fluorite. As a result of analysis, the fluorite was almost unreacted, and the state thereof was a gel having a high viscosity.
（比較例２）
図示していないが、従来のフッ化水素製造設備のスクリューのみから構成される混合フィーダーを用い、原料である回収フッ化カルシウムを１１．５ｋｇ／ｈｒ（１４７．４ｍｏｌ／ｈｒ）、５％のＳＯ３を含む発煙硫酸を７．９Ｌ／ｈｒ（１４７．４ｍｏｌ／ｈｒ）で同時に投入した。
(Comparative Example 2)
Although not shown, using a mixing feeder composed only of a screw of a conventional hydrogen fluoride production facility, the recovered calcium fluoride as a raw material is 11.5 kg / hr (147.4 mol / hr), 5% SO. The fuming sulfuric acid containing 3 was simultaneously injected at 7.9 L / hr (147.4 mol / hr).
その結果、混合フィーダーのスクリューで排出が不能となり、負荷停止した。排出が不能となった原因を解析したところ、硫酸カルシウムを７５．４％含む固形物から構成される付着によるものであった。 As a result, it became impossible to discharge with the screw of the mixing feeder, and the load was stopped. When the cause of the inability to discharge was analyzed, it was due to adhesion composed of a solid substance containing 75.4% calcium sulfate.
また、上記実施により図１に示しているフッ化水素製造設備を３ケ月間運転し観察したところ、外熱式の反応機（ロータリーキルン）は熱濃硫酸の分解による装置腐食はほとんど無く、極めて良好であることがわかった。 In addition, when the hydrogen fluoride production facility shown in FIG. 1 was operated for 3 months and observed by the above implementation, the externally heated reactor (rotary kiln) was very good with almost no equipment corrosion due to decomposition of hot concentrated sulfuric acid. I found out that
以上に詳述した通り、本発明によれば、フッ素リサイクル技術により得られた回収フッ化カルシウムは蛍石よりも反応性が非常に高く、反応により得られた硫酸カルシウムも高純度であることから、省エネルギーに十分配慮されたフッ化水素製造設備の提供が可能となる。 As described above in detail, according to the present invention, the recovered calcium fluoride obtained by the fluorine recycling technique is much more reactive than fluorite, and the calcium sulfate obtained by the reaction is also highly pure. Therefore, it is possible to provide hydrogen fluoride production facilities with sufficient consideration for energy saving.
本発明によれば、従来の天然に存在する蛍石からフッ化水素を製造する大型設備を使用することなく、コンパクトな、且つ汎用性の高い材料を用いた省エネルギー設計のフッ化水素製造が可能となり、その工業的有用性は極めて大きい。 According to the present invention, it is possible to produce hydrogen fluoride with an energy-saving design using a compact and highly versatile material without using a large-sized facility for producing hydrogen fluoride from a naturally occurring fluorite. Therefore, its industrial usefulness is extremely large.
１…混合・反応機、１ａ…二軸セルフクリーニングスクリュー、１ｂ…ポケット、２…スクリューフィーダー、３…外熱式の反応機（ロータリーキルン）、４，５…フッ化水素の排ガスライン。 DESCRIPTION OF SYMBOLS 1 ... Mixing and reaction machine, 1a ... Biaxial self-cleaning screw, 1b ... Pocket, 2 ... Screw feeder, 3 ... External-heated reaction machine (rotary kiln), 4, 5 ... Hydrogen fluoride exhaust gas line.
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| CN102612491A (en) | 2009-11-02 | 2012-07-25 | 信越化学工业株式会社 | Spherical silicon carbide powder, process for production of same, and process for production of silicon carbide ceramic molded article utilizing same |
| JP5630333B2 (en) | 2011-03-08 | 2014-11-26 | 信越化学工業株式会社 | Sinterable silicon carbide powder and sintered silicon carbide ceramics |
| WO2016006527A1 (en) * | 2014-07-11 | 2016-01-14 | ダイキン工業株式会社 | Method for producing hydrogen fluoride |
| CN105152134B (en) * | 2015-09-22 | 2017-10-13 | 中国船舶重工集团公司第七一八研究所 | A kind of method and device for preparing hydrogen fluoride |
| CN108609586B (en) * | 2018-08-08 | 2021-11-02 | 宣城亨泰电子化学材料有限公司 | Reagent-grade hydrofluoric acid manufacturing device |
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