JPS63117902A - Method and device for removing fluorine and chlorine in spent sulfuric acid - Google Patents
Method and device for removing fluorine and chlorine in spent sulfuric acidInfo
- Publication number
- JPS63117902A JPS63117902A JP26476886A JP26476886A JPS63117902A JP S63117902 A JPS63117902 A JP S63117902A JP 26476886 A JP26476886 A JP 26476886A JP 26476886 A JP26476886 A JP 26476886A JP S63117902 A JPS63117902 A JP S63117902A
- Authority
- JP
- Japan
- Prior art keywords
- sulfuric acid
- chlorine
- waste sulfuric
- waste
- fluorine
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 260
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011737 fluorine Substances 0.000 title claims abstract description 43
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 43
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000000460 chlorine Substances 0.000 title claims abstract description 41
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 16
- 239000007921 spray Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000005201 scrubbing Methods 0.000 claims abstract description 5
- 239000002699 waste material Substances 0.000 claims description 66
- 239000000945 filler Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000010908 plant waste Substances 0.000 claims 1
- 239000011550 stock solution Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000012856 packing Methods 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract 1
- 229910052602 gypsum Inorganic materials 0.000 description 7
- 239000010440 gypsum Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000007789 gas 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
- 238000010586 diagram Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- -1 that is Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、廃硫酸からフッ素、塩素を除去する方法及び
その装置に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method and apparatus for removing fluorine and chlorine from waste sulfuric acid.
非鉄金属精練、硫＃製造プラントに於ける廃硫酸中には
、各種金属類の外にフッ素、塩素が含まれている。Waste sulfuric acid from non-ferrous metal smelting and sulfur # production plants contains fluorine and chlorine in addition to various metals.
従来、廃硫酸に含まれる金属類については、透析膜、イ
オン交換等により除去できるが、フッ素。Conventionally, metals contained in waste sulfuric acid can be removed using dialysis membranes, ion exchange, etc., but fluorine.
塩素は回収しようとする硫酸そのものと同様に陰イオン
で且つ拡散速度も硫酸よりも大きいため、除去が困難で
あった。Chlorine, like the sulfuric acid itself to be recovered, is an anion and has a higher diffusion rate than sulfuric acid, making it difficult to remove.
そこで、従来は、廃硫酸を水酸化カルシウム又は炭酸カ
ルシウムによる中和生成物、即ち石膏として回収してい
た。Therefore, conventionally, waste sulfuric acid has been recovered as a neutralization product with calcium hydroxide or calcium carbonate, that is, gypsum.
然し、回収石膏中に、フッ素、塩素が含まれると、腐食
性が高くなり、この石膏の用途は殆ど限られ、好ましく
ない。However, if the recovered gypsum contains fluorine or chlorine, it becomes highly corrosive, and the uses of this gypsum are almost limited, which is not preferable.
そこで、石膏中に如何にしてフッ素、塩素の含まれない
石膏を回収するかが問題となり、この解決策として各種
の提案が為されている（例えば、特公昭５９−３４６４
４号公報、特開昭６０−２２８６２７号公報等）。Therefore, the problem became how to recover gypsum that does not contain fluorine and chlorine, and various proposals have been made as solutions to this problem (for example, Japanese Patent Publication No. 59-3464
4, JP-A-60-228627, etc.).
然し、これらは何れも、廃硫酸を石膏として回収するも
のであるから、大量の中和剤を必要とすると共に、回収
した石膏の処理場所を確保する必要があり、不経済なも
のである。However, since all of these methods recover waste sulfuric acid as gypsum, they require a large amount of neutralizing agent and a place to process the recovered gypsum, making them uneconomical.
又、廃硫酸を濃縮して再利用することも色々検討された
が、回収硫酸中にフッ素、塩素が含まれると、非常に腐
食性が高くなり、事実上再利用が不可能となる。Various studies have also been made to concentrate and reuse waste sulfuric acid, but if the recovered sulfuric acid contains fluorine and chlorine, it becomes extremely corrosive, making reuse virtually impossible.
本発明は斯る従来の問題点を解決するために為されたも
ので、その目的は、廃硫酸を中和して石膏として回収す
るのではなく、廃硫酸を硫酸として回収すると共に、こ
れに含まれているフッ素。The present invention was made to solve the conventional problems, and its purpose is not to neutralize waste sulfuric acid and recover it as gypsum, but to recover waste sulfuric acid as sulfuric acid, and to recover it as sulfuric acid. Contains fluorine.
塩素を除去することができる廃硫酸中のフッ素。Fluorine in waste sulfuric acid can remove chlorine.
塩素の除去方法及びその装置を提供することにある。An object of the present invention is to provide a method and device for removing chlorine.
本発明に係る廃硫酸中のフッ素、塩素の除去方法は、廃
硫酸中よりフッ素、塩素を除去するに当り、廃硫酸中の
硫酸濃度を４００ｇ／ρ以上に高め、フッ素又は塩素を
揮発除去するように構成したものである。In the method for removing fluorine and chlorine from waste sulfuric acid according to the present invention, when removing fluorine and chlorine from waste sulfuric acid, the sulfuric acid concentration in the waste sulfuric acid is increased to 400 g/ρ or more, and fluorine or chlorine is removed by volatilization. It is configured as follows.
又、本発明に係る廃硫酸中のフッ素、塩素の除去装置は
、筒内に充填材を配設し、この充填材の上方に濃硫酸を
散布するスプレーと廃硫酸を散布するスプレーとを設け
、これらスプレーの上方にデミスタを設け、このデミス
タの上方に排ガスを排出する排気口を設け、上記充填材
の下方に空気を導入する空気導入口と充填材を通過して
流下する硫酸を排出する硫酸排出口を設けた処理塔と、
経路に加熱器を備え、処理筒の廃硫酸を散布するスプレ
ーに連結する廃硫酸供給管と、処理塔の空気導入口に空
気を供給する空気供給器とから構成されたものである。Further, the device for removing fluorine and chlorine from waste sulfuric acid according to the present invention includes a filler disposed in a cylinder, and a sprayer for spraying concentrated sulfuric acid and a sprayer for spraying waste sulfuric acid above the filler. A demister is provided above these sprays, an exhaust port is provided above the demister for discharging the exhaust gas, an air inlet is introduced below the filler, and the sulfuric acid flowing down through the filler is discharged. A treatment tower equipped with a sulfuric acid outlet,
It is equipped with a heater in the path, and consists of a waste sulfuric acid supply pipe connected to a sprayer for dispersing waste sulfuric acid in the processing column, and an air supply device that supplies air to the air inlet of the processing tower.
本発明に於ては、廃硫酸中よりフッ素、塩素を除去する
に当り、廃硫酸中の硫酸濃度を４００ｇ／ｌ以上に高め
るから、沸点の低いフッ素（フッ化水素又はケイフッ酸
の状態と考えられる）、塩素が揮発し始める。即ち、フ
ッ素、塩素は、水との親和性が非常に高く、水溶液から
揮発除去することは困難であるが、硫酸濃度が高くなる
に連れて、硫酸に水分子が配位されて、自由な水分子が
少なくなり、このため、硫酸濃度が４００ ｇ／β以上
になると、沸点の低いフッ素、塩素が揮発し始める。In the present invention, when removing fluorine and chlorine from waste sulfuric acid, the sulfuric acid concentration in the waste sulfuric acid is increased to 400 g/l or more, so fluorine with a low boiling point (considered to be in the form of hydrogen fluoride or fluorosilicic acid) is removed. ), chlorine begins to volatilize. In other words, fluorine and chlorine have a very high affinity with water and are difficult to remove by evaporation from an aqueous solution, but as the concentration of sulfuric acid increases, water molecules are coordinated with sulfuric acid and free There are fewer water molecules, and therefore, when the sulfuric acid concentration reaches 400 g/β or higher, fluorine and chlorine, which have low boiling points, begin to volatilize.
以下、本発明の実施例を図面を参照しながら説明する。 Embodiments of the present invention will be described below with reference to the drawings.
第１図は本発明に係る廃硫酸中のフッ素、塩素の除去装
置を示す。FIG. 1 shows an apparatus for removing fluorine and chlorine from waste sulfuric acid according to the present invention.
図に於て、■は処理塔で、筒２内に充填材３を配設し、
この充填祠３の上方に９８％濃硫酸を散布するスプレー
４と廃硫酸を散布するスプレー５とを設け、これらスプ
レー４，５の上方にデミスタ６を設け、このデミスタ６
の上方に排ガスを排出する排気ロアを設け、」配量充填
材３の下方に空気を導入する空気導入口８と充填材３を
通過して流下する硫酸を排出する硫酸排出口９を設けた
ものである。In the figure, ■ is a treatment tower, in which a packing material 3 is arranged in a cylinder 2,
A spray 4 for spraying 98% concentrated sulfuric acid and a spray 5 for spraying waste sulfuric acid are provided above the filling shrine 3, and a demister 6 is provided above these sprays 4 and 5.
An exhaust lower for discharging exhaust gas is provided above, an air inlet 8 for introducing air below the metering filler 3, and a sulfuric acid outlet 9 for discharging the sulfuric acid flowing down through the filler 3. It is something.
充＠＋Ａ３は、硫酸によって侵されない合成樹脂＋Ａが
望ましく、例えばＰＰ、テフロン（商品名）等がある。The material +A3 is preferably a synthetic resin +A that is not attacked by sulfuric acid, such as PP and Teflon (trade name).
１０ば廃硫酸供給管で、経路に加熱器１１を備え、処理
筒１の廃硫酸を散布するスプレー５に連結する。10 is a waste sulfuric acid supply pipe, which is equipped with a heater 11 in its path and is connected to a sprayer 5 that sprays waste sulfuric acid from the processing cylinder 1.
２０は空気供給器で、処理筒１の空気導入口８に空気を
供給する。An air supply device 20 supplies air to the air inlet 8 of the processing cylinder 1.
３０は回収槽で、処理塔ｌの硫酸排出口９の下部にもう
けられている。この回収槽３０には廃硫酸供給管１０に
連結する管路３１が設けられ、これにはポンプ３２が取
り付けである。30 is a recovery tank, which is provided at the bottom of the sulfuric acid outlet 9 of the treatment tower 1. This recovery tank 30 is provided with a pipe line 31 connected to the waste sulfuric acid supply pipe 10, and a pump 32 is attached to this pipe line 31.
以上のように構成された本実施例によれば、フッ素及び
塩素を含む廃硫酸が廃硫酸供給管１０を介して処理塔１
に送られる際に、加熱器１１によって６０〜１００℃程
度に加温される。従って、処理塔１では、加温された廃
硫酸がスプレー５を介して処理塔ｌに散布される。又、
９８％濃硫酸が、廃硫酸の濃度を４００ｇ／ｊ！以上に
なるように、スプレー４を介して処理塔１に常時散布さ
れる。According to this embodiment configured as described above, waste sulfuric acid containing fluorine and chlorine is supplied to the treatment tower 1 through the waste sulfuric acid supply pipe 10.
When it is sent to the storage room, it is heated to about 60 to 100°C by the heater 11. Therefore, in the treatment tower 1, heated waste sulfuric acid is sprayed into the treatment tower 1 via the spray 5. or,
98% concentrated sulfuric acid reduces the concentration of waste sulfuric acid to 400g/j! As mentioned above, the treatment tower 1 is constantly sprayed via the spray 4.
而して、処理塔１では、廃硫酸の濃度が４００ｇ／βに
なるように９８％濃硫酸によって調整されると共に、そ
の液温が６０〜１００℃に保たれているから、スクラビ
ングが効率良く行なわれ、廃硫酸に含まれているフッ素
、塩素が除去される。In the treatment tower 1, the concentration of waste sulfuric acid is adjusted to 400 g/β using 98% concentrated sulfuric acid, and the liquid temperature is maintained at 60 to 100°C, so scrubbing can be performed efficiently. This process removes fluorine and chlorine contained in waste sulfuric acid.
その結果、回収槽３０に流下した硫酸に含まれるフッ素
、塩素の濃度は、極めて微量となる。As a result, the concentrations of fluorine and chlorine contained in the sulfuric acid flowing down into the recovery tank 30 are extremely small.
例えば、上記装置を用いて、硫酸濃度１４０ｇ／ρ、フ
ッ素３ ｇ ／ （１、塩素６ ｇ ／ ｌの廃硫酸を
、加熱器１１にて８０℃にして処理塔ｌ内にスプレー５
にて散布し、これに９８％濃硫酸をスプレー４にて加え
て、硫酸濃度５００ ｇ／βに保ってスクラビングした
処、フッ素１００■／Ｉｌ、塩素２００■／ｌまで除去
できた。For example, using the above apparatus, waste sulfuric acid with a sulfuric acid concentration of 140 g/ρ and 3 g of fluorine/(1, 6 g/l of chlorine) is heated to 80°C with a heater 11 and sprayed into the treatment tower l.
98% concentrated sulfuric acid was added to this using Spray 4, and scrubbing was carried out while maintaining the sulfuric acid concentration at 500 g/β. Fluorine was removed to 100 μ/Il and chlorine to 200 μ/L.
又、上記操作を繰り返す間に、回収槽３０の硫酸をポン
プ３１を介して廃硫酸に添加して、硫酸の濃度を高める
ことができるため、廃硫酸濃度を５００ｇ／ｊ！以」二
とすることができる。Also, while repeating the above operations, the sulfuric acid in the recovery tank 30 can be added to the waste sulfuric acid via the pump 31 to increase the concentration of sulfuric acid, so the concentration of waste sulfuric acid can be reduced to 500 g/j! 2.
而も、スクラビングによって水の蒸発も同時に生じるた
め、回収硫酸の硫酸濃度を５００ ｇ／ｌよりも高くす
ることができる。この場合には、廃硫酸の供給量を少な
くすることによって、濃硫酸を添加しなくても、系内を
４００ ｇ／ｌ以上に保ことも可能である。However, since water evaporation occurs simultaneously with scrubbing, the sulfuric acid concentration of the recovered sulfuric acid can be made higher than 500 g/l. In this case, by reducing the amount of waste sulfuric acid supplied, it is possible to maintain the concentration in the system at 400 g/l or more without adding concentrated sulfuric acid.
第２図は本発明に係る廃硫酸中のフッ素、塩素の除去装
置の別の例を示す。FIG. 2 shows another example of the apparatus for removing fluorine and chlorine from waste sulfuric acid according to the present invention.
図に於て、４０は処理塔で、複数の孔空き棚４１が設け
てあり、上部には９８％濃硫酸と廃硫酸を散布するスプ
レー４２が設けられ、更にその上部にはデミスタ４３が
設けである。そして、デミスタ４３の上方には、蒸気を
排出する排気口４４が設けである。この排気口４４には
、冷却器４５を設けた排出管４６が設けられている。又
、処理塔４０の下部には加熱蒸気を取り込むスプレー４
７が設けられると共に、この部位に硫酸が回収される。In the figure, 40 is a treatment tower, which is equipped with a plurality of perforated shelves 41, a sprayer 42 for spraying 98% concentrated sulfuric acid and waste sulfuric acid is installed at the top, and a demister 43 is installed at the top. It is. An exhaust port 44 for discharging steam is provided above the demister 43. This exhaust port 44 is provided with an exhaust pipe 46 provided with a cooler 45 . Further, at the bottom of the treatment tower 40, there is a spray 4 that takes in heated steam.
7 is provided, and sulfuric acid is recovered at this site.
この装置では、処理塔４０の底部から加熱蒸気が吹き込
まれる中を、上部からフッ素、塩素を含む廃硫酸と９８
％濃硫酸とをスプレー４２によって散布するから、各欄
４１の孔から蒸気が上昇する時に霧状になっている硫酸
中のフッ素、塩素を伴って上昇して、排気口４４から吐
出する。そして、冷却器４５によって冷却されて、フッ
素、塩素及び水が排出管４６から排出される。In this device, heated steam is blown from the bottom of the treatment tower 40, and waste sulfuric acid containing fluorine and chlorine is passed through the top of the treatment tower 40.
% concentrated sulfuric acid is sprayed by the spray 42, when the steam rises from the holes in each column 41, it rises with the fluorine and chlorine in the sulfuric acid in the form of mist, and is discharged from the exhaust port 44. The fluorine, chlorine and water are then cooled by the cooler 45 and discharged from the discharge pipe 46.
一方、硫酸は、順次棚４１を流下し乍ら、蒸気によって
加熱され、硫酸濃度を高めて行く。そして、処理塔４０
の底部に溜まった時には、硫酸濃度を４００ ｇ／ｌ！
以上とすることができる。On the other hand, while the sulfuric acid sequentially flows down the shelf 41, it is heated by the steam, increasing the sulfuric acid concentration. And the processing tower 40
When it accumulates at the bottom of the tank, the sulfuric acid concentration is 400 g/l!
It can be more than that.
又、第２図に於ける蒸気吹き込みに代えて、熱交換によ
る加熱とすれば、回収硫酸濃度が５００ｇ／ｊ！以」二
となり、この回収硫酸を９８％濃硫酸の代わりに循環さ
−１４，濃硫酸の添加を減少又は不要とすることも可能
となる。Also, if heating by heat exchange is used instead of steam blowing in Figure 2, the concentration of recovered sulfuric acid will be 500 g/j! Therefore, this recovered sulfuric acid can be recycled in place of 98% concentrated sulfuric acid, making it possible to reduce or eliminate the need to add concentrated sulfuric acid.
尚、本発明は、上記実施例に限定するものではなく、例
えば、硫酸濃度１４０ｇ／ρ、フッ素３ｇ／ｐ、塩素６
ｇ ／ ７！の廃硫酸に９８％濃硫酸を加えたものを
、加熱蒸発させた処、フッ素６０■／ｌ、塩素１２０ｎ
ｗ／＃まで除去することができた。It should be noted that the present invention is not limited to the above-mentioned examples; for example, the concentration of sulfuric acid is 140 g/ρ, fluorine is 3 g/p,
g/7! When 98% concentrated sulfuric acid was added to the waste sulfuric acid of
It was possible to remove up to w/#.
又、真空蒸発させることによっても同様の処理を為すこ
とが可能である。Similar treatment can also be achieved by vacuum evaporation.
更に、本発明では、如何なる廃硫酸でも処理することは
可能であるが、経済的な処理を考慮すると、廃硫酸の硫
酸濃度は１００ ｇ／ｌ以上することが望ましい。従っ
て、若し硫酸濃度が１００ｇ／β以下の場合には、予備
濃縮してその値以上とすることが好ましい。Further, in the present invention, it is possible to treat any kind of waste sulfuric acid, but in consideration of economical treatment, it is desirable that the sulfuric acid concentration of the waste sulfuric acid be 100 g/l or more. Therefore, if the sulfuric acid concentration is less than 100 g/β, it is preferable to preconcentrate it to a value higher than that value.
以上のように本発明によれば、廃硫酸が硫酸として回収
して利用できるようになる。そのため、処理工程中で回
収した硫酸を濃硫酸に代えて使用することができるよう
になり、経済的な処理が可能となる。又、中和処理を行
なわないため、廃硫酸の中和処理、及び中和処理残渣の
処分問題が減少する。更に、フッ素、塩素が分離される
ため、これらを利用することもできる。特に、分離した
フッ素は、フッ化カルシウム、ケイフッ化ナトリウム等
として回収することができる。As described above, according to the present invention, waste sulfuric acid can be recovered and used as sulfuric acid. Therefore, the sulfuric acid recovered during the treatment process can be used in place of concentrated sulfuric acid, making economical treatment possible. Further, since no neutralization treatment is performed, the problems of neutralization treatment of waste sulfuric acid and disposal of neutralization treatment residues are reduced. Furthermore, since fluorine and chlorine are separated, they can also be used. In particular, the separated fluorine can be recovered as calcium fluoride, sodium silicofluoride, and the like.
第１図は本発明の装置の一例を示す説明図、第２図は本
発明を実施するための装置の一例を示す説明図である。
■・・・処理塔、２・・・筒、３・・・充填材、４．５
・・・スプレー、６・・・デミスタ、７・・・排ガスを
排出する排気口、８・・・空気導入口、９・・・硫酸排
出口、１０・・・廃硫酸供給管、１１・・・加熱器、２
０・・・空気供給器、３０・・・回収槽、３１・・・管
路、３２・・・ポンプ。
第 １ Ａ
挿ガス
７ スクラバへ
９８り膚Ｅ地 ４
′ ２
１１ −一１
卑石紀絞
°° 第・・・・４４
９８３班渣 ４５
廊緒帥 〆４０
力１ｐべ φ
一； 口奴箭駁
７７０閃１ｙ銭FIG. 1 is an explanatory diagram showing an example of the apparatus of the present invention, and FIG. 2 is an explanatory diagram showing an example of the apparatus for implementing the present invention. ■...Treatment tower, 2...Cylinder, 3...Filling material, 4.5
... Spray, 6... Demister, 7... Exhaust port for discharging exhaust gas, 8... Air inlet, 9... Sulfuric acid discharge port, 10... Waste sulfuric acid supply pipe, 11...・Heating device, 2
0...Air supply device, 30...Recovery tank, 31...Pipe line, 32...Pump. 1st A Insertion 7 98 skin E place to scrubber 4' 2 11 -11 Heiseki Shibori °° No. 44 983 group residue 45 Roushu Shuai 〆40
Power 1 pbe φ 1; Mouth slave refutation 770 sen 1y sen
Claims (10)
硫酸中の硫酸濃度を４００ｇ／ｌ以上に高め、フッ素又
は塩素を揮発除去することを特徴とする廃硫酸中のフッ
素、塩素の除去方法。(1) When removing fluorine and chlorine from waste sulfuric acid, the sulfuric acid concentration in the waste sulfuric acid is increased to 400 g/l or more, and the fluorine or chlorine is removed by volatilization. Removal method.
４００ｇ／ｌ以上に高めることを特徴とする特許請求の
範囲第１項記載の廃硫酸中のフッ素、塩素の除去方法。(2) The method for removing fluorine and chlorine from waste sulfuric acid according to claim 1, which comprises adding concentrated sulfuric acid to the waste sulfuric acid to increase the sulfuric acid concentration in the waste sulfuric acid to 400 g/l or more.
硫酸濃度を４００ｇ／ｌ以上に高めることを特徴とする
特許請求の範囲第１項記載の廃硫酸中のフッ素、塩素の
除去方法。(3) The method for removing fluorine and chlorine from waste sulfuric acid according to claim 1, which comprises increasing the sulfuric acid concentration in the waste sulfuric acid to 400 g/l or more by evaporating and concentrating the waste sulfuric acid.
を特徴とする特許請求の範囲第３項記載の廃硫酸中のフ
ッ素、塩素の除去方法。(4) A method for removing fluorine and chlorine from waste sulfuric acid according to claim 3, which comprises scrubbing the waste sulfuric acid at 60 to 100°C.
特許請求の範囲第３項記載の廃硫酸中のフッ素、塩素の
除去方法。(5) A method for removing fluorine and chlorine from waste sulfuric acid according to claim 3, which comprises evaporating the waste sulfuric acid at its boiling point.
求の範囲第３項記載の廃硫酸中のフッ素、塩素の除去方
法。(6) The method for removing fluorine and chlorine from waste sulfuric acid according to claim 3, which comprises evaporating the waste sulfuric acid in a vacuum.
あることを特徴とする特許請求の範囲第１項乃至第６項
の何れかに記載の廃硫酸中のフッ素、塩素の除去方法。(7) The method for removing fluorine and chlorine from waste sulfuric acid according to any one of claims 1 to 6, wherein the sulfuric acid concentration in the waste sulfuric acid stock solution is 100 g/l or more. .
ト廃酸であることを特徴とする特許請求の範囲第１項乃
至第７項の何れかに記載の廃硫酸中のフッ素、塩素の除
去方法。(8) The waste sulfuric acid is non-ferrous metal smelting waste acid or sulfuric acid manufacturing plant waste acid. Removal method.
酸を散布するスプレーと廃硫酸を散布するスプレーとを
設け、これらスプレーの上方にデミスタを設け、このデ
ミスタの上方に排ガスを排出する排気口を設け、上記充
填材の下方に空気を導入する空気導入口と充填材を通過
して流下する硫酸を排出する硫酸排出口を設けた処理塔
と、経路に加熱器を備え、処理塔の廃硫酸を散布するス
プレーに連結する廃硫酸供給管と、処理塔の空気導入口
に空気を供給する空気供給器とから構成されたことを特
徴とする廃硫酸中のフッ素、塩素の除去装置。(9) A filler is placed in the cylinder, a spray for spraying concentrated sulfuric acid and a spray for spraying waste sulfuric acid are provided above the filler, a demister is provided above these sprays, and a demister is provided above the demister. A treatment tower is provided with an exhaust port for discharging exhaust gas, an air inlet for introducing air below the filling material, and a sulfuric acid discharge port for discharging the sulfuric acid flowing down through the filling material, and a heater is installed in the path. Fluorine in waste sulfuric acid, comprising a waste sulfuric acid supply pipe connected to a sprayer for dispersing waste sulfuric acid in a treatment tower, and an air supply device for supplying air to an air inlet of the treatment tower. Chlorine removal equipment.
、この槽に滴下した硫酸をポンプによって、廃硫酸供給
管と連結していることを特徴とする特許請求の範囲第９
項記載の廃硫酸中のフッ素、塩素の除去装置。(10) A tank is provided below the sulfuric acid outlet of the treatment tower, and the sulfuric acid dropped into the tank is connected to the waste sulfuric acid supply pipe by a pump.
Equipment for removing fluorine and chlorine from waste sulfuric acid as described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26476886A JPS63117902A (en) | 1986-11-06 | 1986-11-06 | Method and device for removing fluorine and chlorine in spent sulfuric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26476886A JPS63117902A (en) | 1986-11-06 | 1986-11-06 | Method and device for removing fluorine and chlorine in spent sulfuric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63117902A true JPS63117902A (en) | 1988-05-21 |
Family
ID=17407918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26476886A Pending JPS63117902A (en) | 1986-11-06 | 1986-11-06 | Method and device for removing fluorine and chlorine in spent sulfuric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63117902A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006169106A (en) * | 2006-02-20 | 2006-06-29 | Sumitomo Chemical Co Ltd | Manufacture method of high-purity sulfuric acid |
| JP2006169109A (en) * | 2006-03-07 | 2006-06-29 | Sumitomo Chemical Co Ltd | Removal method for chlorine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5518649A (en) * | 1978-07-27 | 1980-02-08 | Fujitsu Ltd | Focus adjusting system of infrared ray video apparatus |
| JPS5519883A (en) * | 1978-07-28 | 1980-02-12 | Nitto Electric Ind Co | Method of coating cover of printed circuit board |
-
1986
- 1986-11-06 JP JP26476886A patent/JPS63117902A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5518649A (en) * | 1978-07-27 | 1980-02-08 | Fujitsu Ltd | Focus adjusting system of infrared ray video apparatus |
| JPS5519883A (en) * | 1978-07-28 | 1980-02-12 | Nitto Electric Ind Co | Method of coating cover of printed circuit board |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006169106A (en) * | 2006-02-20 | 2006-06-29 | Sumitomo Chemical Co Ltd | Manufacture method of high-purity sulfuric acid |
| JP2006169109A (en) * | 2006-03-07 | 2006-06-29 | Sumitomo Chemical Co Ltd | Removal method for chlorine |
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