JPH0388718A - Treatment of sulfuric acid used to produce titanium oxide by sulfuric acid process - Google Patents
Treatment of sulfuric acid used to produce titanium oxide by sulfuric acid processInfo
- Publication number
- JPH0388718A JPH0388718A JP1223308A JP22330889A JPH0388718A JP H0388718 A JPH0388718 A JP H0388718A JP 1223308 A JP1223308 A JP 1223308A JP 22330889 A JP22330889 A JP 22330889A JP H0388718 A JPH0388718 A JP H0388718A
- Authority
- JP
- Japan
- Prior art keywords
- sulfuric acid
- titanium oxide
- concentration
- waste sulfuric
- waste
- 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 146
- 238000000034 method Methods 0.000 title claims abstract description 42
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 239000002699 waste material Substances 0.000 claims description 30
- 239000003495 polar organic solvent Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 150000002576 ketones Chemical class 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- -1 alkyl phosphoric acids Chemical class 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- CZSABVBCTRZESY-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].OS(O)(=O)=O Chemical compound [O-2].[O-2].[Ti+4].OS(O)(=O)=O CZSABVBCTRZESY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 210000003371 toe Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Iron (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は硫酸法酸化チタンの製造工程で副生ずる廃硫酸
から濃硫酸を回収し再利用する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for recovering and reusing concentrated sulfuric acid from waste sulfuric acid produced as a by-product in the sulfuric acid method titanium oxide production process.
〔従来の技術及び発明が解決しようとする課題〕酸化チ
タンは主に硫酸法により製造されている。[Prior art and problems to be solved by the invention] Titanium oxide is mainly produced by a sulfuric acid method.
すなわち、イルメナイトを原料とし、これを微粉砕した
後、硫酸に蒸解し冷却して硫酸鉄を析出させ分離する。That is, ilmenite is used as a raw material, which is finely pulverized, then digested in sulfuric acid and cooled to precipitate and separate iron sulfate.
次に、加熱濃縮し加水分解して、水酸化チタンを析出さ
せてろ過分離する。これを充分洗浄して不純物を除いた
後、ロータリーキルンで７００〜１０００℃で焙焼し酸
化チタンを得る。Next, the mixture is concentrated by heating and hydrolyzed to precipitate titanium hydroxide, which is separated by filtration. After thoroughly washing this to remove impurities, it is roasted in a rotary kiln at 700 to 1000°C to obtain titanium oxide.
この硫酸法酸化チタン製造工程では、主に水酸化チタン
を固液分離する際に多量の高濃度廃硫酸が発生するほか
、イルメナイトを蒸解した後セットリングした際に生じ
る希硫酸、分離された硫酸鉄及びこれに付着する希硫酸
、水酸化チタンの洗浄時に使用した希硫酸、ロータリー
キルンの廃ガス処理液など多量の廃硫酸が生じる。In this sulfuric acid method titanium oxide manufacturing process, a large amount of highly concentrated waste sulfuric acid is generated mainly during solid-liquid separation of titanium hydroxide, as well as dilute sulfuric acid generated when settling after cooking ilmenite, and separated sulfuric acid. A large amount of waste sulfuric acid is generated, such as iron and dilute sulfuric acid adhering to it, dilute sulfuric acid used when cleaning titanium hydroxide, and waste gas treatment liquid from rotary kilns.
従来、前述した硫酸法酸化チタンの製造工程で副生ずる
廃硫酸から濃硫酸を回収する方法としては、以下のよう
な方法が知られている。Conventionally, the following method is known as a method for recovering concentrated sulfuric acid from waste sulfuric acid produced as a by-product in the above-mentioned sulfuric acid method titanium oxide manufacturing process.
■廃硫酸をそのまま濃縮する方法（例えば、特公昭４Ｂ
−５５６８号公報、ＵＳＰ、 ２，８６４，４７０、ｕ
ｓｐ 。■Method of concentrating waste sulfuric acid as it is (for example,
-5568 Publication, USP, 2,864,470, u
sp.
２．９８０，３９１など）。2.980, 391, etc.).
■廃硫酸を真空結晶工程と濃縮工程とを組み合わせて処
理する方法。■A method of processing waste sulfuric acid by combining a vacuum crystallization process and a concentration process.
■液中バーナーを利用して廃硫酸を濃縮する方法。■A method of concentrating waste sulfuric acid using a submerged burner.
しかしながら、これらの方法には以下のような問題があ
る。However, these methods have the following problems.
■の方法では濃縮管に硫酸鉄（ＩＩ）などの塩類が析出
するため、連続的に濃縮することができず、最高でも濃
度７０％台の硫酸が回収されるにすぎない。In method (2), since salts such as iron (II) sulfate are deposited in the concentration tube, continuous concentration is not possible, and sulfuric acid with a concentration of 70% at most is recovered.
■の方法では、経済性がない。Method (2) is not economical.
■の方法でも、硫酸鉄（ＩＩ）などの固形分の処理が困
難であり、連続的な濃縮が不可能であることから、やは
り高濃度の硫酸を回収することはできない。Even with method (2), it is difficult to treat solids such as iron (II) sulfate, and continuous concentration is impossible, so it is still not possible to recover high-concentration sulfuric acid.
現状では、■の方法で回収された低濃度の硫酸を再利用
しているものの、濃度の点から用途が限定されている。Currently, low-concentration sulfuric acid recovered by method (2) is reused, but its use is limited due to its concentration.
また、余剰の廃硫酸については、公害処理対策として炭
酸カルシウムによる中和処理（例えば、特公昭４３−３
０１７２号公報、特公昭４７−２３３８８号公報）、ア
ンモニアによる中和処理（例えば、特公昭４５−３２６
１６号公報、ＵＳＰ、 ２，５２９．８７４など）、チ
タン濃縮処理すなわちイルメナイト溶解による中和処理
（例えば特公昭４９−１８３３０号公報、特公昭４９−
２５８０３号公報、特公昭４９−３７１７１号公報）を
行い、系外へ排出している。したがって、本来のプロセ
ス内での再利用は極めて限られていた。In addition, surplus waste sulfuric acid is neutralized with calcium carbonate as a pollution treatment measure (for example,
No. 0172, Japanese Patent Publication No. 47-23388), neutralization treatment with ammonia (for example, Japanese Patent Publication No. 45-326
No. 16, USP, 2,529.874, etc.), titanium concentration treatment, i.e., neutralization treatment by dissolving ilmenite (e.g., Japanese Patent Publication No. 18330, No. 18330, Japanese Patent Publication No. 1983-1983), titanium concentration treatment, i.e., neutralization treatment by dissolving ilmenite
25803, Japanese Patent Publication No. 49-37171) and discharged to the outside of the system. Therefore, reuse within the original process was extremely limited.
このように、従来の硫酸法酸化チタンの製造工程では、
廃硫酸の処理が経済的に行われず、製造工程全体が経済
的でないという問題があった。In this way, in the conventional sulfuric acid method titanium oxide manufacturing process,
There was a problem in that waste sulfuric acid was not processed economically, and the entire manufacturing process was not economical.
本発明は前記問題点を解決するためになされたものであ
り、硫酸法酸化チタンの製造工程で副生する廃硫酸から
高濃度の硫酸を経済的に回収することができる方法を提
供することを目的とする。The present invention has been made to solve the above-mentioned problems, and aims to provide a method that can economically recover high-concentration sulfuric acid from waste sulfuric acid that is a by-product in the sulfuric acid method titanium oxide production process. purpose.
本発明の硫酸法酸化チタン廃硫酸の処理方法は、Ｔｉ”
Ｔｉ” Ｆｅ” Ｆｅ’＋を含有する硫酸法酸
化チタン廃硫酸（硫酸水溶液）中のＴｉ’＋及びＦｅ２
＋を酸化する工程と、廃硫酸から極性有機溶媒によりＴ
ｉ４＋及びＦｅ’＋を選択的に抽出する工程と、残存し
た遊離硫酸を濃縮して濃硫酸を回収する工程とを具備し
たことを特徴とするものである。The method for treating titanium oxide waste sulfuric acid using the sulfuric acid method of the present invention is
Sulfuric acid method titanium oxide containing Ti'+ and Fe2 in waste sulfuric acid (sulfuric acid aqueous solution)
The process of oxidizing + and T from waste sulfuric acid using a polar organic solvent.
This method is characterized by comprising a step of selectively extracting i4+ and Fe'+, and a step of concentrating the remaining free sulfuric acid to recover concentrated sulfuric acid.
本発明において、廃硫酸中のＴ１３＋及びＦ ｅ ”を
酸化する方法としては、通常の空気酸化又は電解酸化を
用いることができる。なお、次の抽出工程が可能となる
ように、通常、廃硫酸は予め適当な濃度にまで希釈され
る。希釈の程度は、全Ｈ２ＳＯ４濃度が１５０〜２５０
ｇ／ＩＩ）、フリーＨ２Ｓｏ、濃度が１００〜１５０
ｇ／ｌ 、全Ｆｅ濃度が２０〜３５ｇ／ｊ）となる範囲
が好ましい。この酸化工程は、例えば電解酸化の場合に
は電極としてチタン系電極を用い、印加電圧４〜５Ｖ／
ｃｅｌｌ、電流密度１〜２ Ａ ／ （ｆＯｃｍ）”と
いう条件で実施される。また、この酸化処理はバッチ処
理で又は連続的に行われる。この酸化工程により、Ｔｉ
３＋はＴ ｉ ”へ、Ｆｅ’＋はＦｅ３＋へと変化する
。この酸化工程により生成したＴｉ０の一部は加水分解
してケーキとしてろ過分酸することができる。In the present invention, ordinary air oxidation or electrolytic oxidation can be used to oxidize T13+ and Fe'' in waste sulfuric acid. is diluted in advance to an appropriate concentration.The degree of dilution is such that the total H2SO4 concentration is 150 to 250.
g/II), free H2So, concentration 100-150
g/l, the total Fe concentration is preferably 20 to 35 g/j). In this oxidation process, for example, in the case of electrolytic oxidation, a titanium-based electrode is used as an electrode, and an applied voltage of 4 to 5 V/
cell, current density 1 to 2 A/(fOcm)''.This oxidation treatment is carried out in a batch process or continuously.This oxidation process allows Ti
3+ changes to T i '', and Fe'+ changes to Fe3+. A part of Ti0 generated by this oxidation step can be hydrolyzed and separated by filtration as a cake.
本発明において、廃硫酸からＴ ｉ ”″及びＦｅ３′
″を選択的に抽出する際に用いられる極性有機溶媒とし
ては、ケトン、リン酸系有機溶媒、ヒドロキシオキシム
などが挙げられる。In the present invention, T i "" and Fe3' are extracted from waste sulfuric acid.
Examples of polar organic solvents used for selectively extracting "" include ketones, phosphoric acid-based organic solvents, and hydroxyoximes.
ケトンのうちでは、特にメチルイソブチルケトンが望ま
しい。Among ketones, methyl isobutyl ketone is particularly desirable.
リン酸系有機溶媒としては、アルキルリン酸、アルキル
もしくはアリールジチオリン酸などが挙げられる。Examples of phosphoric acid-based organic solvents include alkyl phosphoric acids, alkyl or aryldithiophosphoric acids, and the like.
アルキルリン酸は、次式（Ａ）〜（Ｆ）（Ａ）
（Ｂ） （ｃ）（式中、Ｒは４〜
１４の炭素原子を含むアルキル基である。）
で表わされる化合物である。アルキルリン酸の具体例と
しては、例えば前記式（Ａ）のＲが２−エチルヘキシル
基であるジー２−エチルへキシルリン酸などがある。Alkyl phosphoric acid is represented by the following formulas (A) to (F) (A)
(B) (c) (wherein R is 4-
It is an alkyl group containing 14 carbon atoms. ) is a compound represented by Specific examples of alkyl phosphoric acids include di-2-ethylhexyl phosphoric acid in which R in the formula (A) is a 2-ethylhexyl group.
アルキル又はアリールジチオリン酸は、次式（式中、Ｒ
は４〜１８個の炭素原子を含むアルキル基又はアリール
基である。）で表わされる化合物である。The alkyl or aryldithiophosphoric acid has the following formula (wherein R
is an alkyl or aryl group containing 4 to 18 carbon atoms. ) is a compound represented by
ヒドロキシオキシムは、例えば次式
（式中、Ｒは水素原子、メチル基、フェニル基又はベン
ジル基、Ｘは塩素原子又は水素原子である。）
で表わされる化合物である。Hydroxyoxime is, for example, a compound represented by the following formula (wherein R is a hydrogen atom, a methyl group, a phenyl group, or a benzyl group, and X is a chlorine atom or a hydrogen atom).
この抽出工程での極性有機溶媒の使用量は、廃硫酸の０
．５〜２倍の量であることが望ましい。この抽出工程は
０〜８０℃、極性有機溶媒の粘度を調整するために好ま
しくは１０〜６０℃の温度で行われる。また、極性有機
溶媒の粘度を調整するためには、希釈剤として芳香族炭
化水素、脂肪族炭化水素、又はこれらの混合物を用いて
もよい。また、ケロシンのように雑多な炭化水素の混合
物を使用することもできる。The amount of polar organic solvent used in this extraction process is 0% of the waste sulfuric acid.
．． It is desirable that the amount be 5 to 2 times as much. This extraction step is carried out at a temperature of 0 to 80°C, preferably 10 to 60°C in order to adjust the viscosity of the polar organic solvent. Further, in order to adjust the viscosity of the polar organic solvent, an aromatic hydrocarbon, an aliphatic hydrocarbon, or a mixture thereof may be used as a diluent. It is also possible to use mixtures of miscellaneous hydrocarbons, such as kerosene.
廃硫酸と前記の極性有機溶媒とを混合すると、両者は乳
化層を形成せずにシャープに２層に分離し、廃硫酸中の
Ｔ Ｉ ”及びＦｅ”はほぼ完全に極性有機溶媒層へ抽
出される。When waste sulfuric acid and the above polar organic solvent are mixed, they sharply separate into two layers without forming an emulsified layer, and T I " and Fe" in the waste sulfuric acid are almost completely extracted into the polar organic solvent layer. be done.
本発明において、残存した遊離硫酸はバッチ処理で又は
連続的に濃縮される。本発明方法では、従来の方法で問
題となった硫酸鉄（ｎ）などの塩類の析出を招くことな
く連続的な濃縮が可能となり、濃度９７％以上の濃硫酸
を回収することができる。なお、濃縮前の硫酸水溶液に
は、Ｔ１％Ｆｅ以外の金属塩が蓄積されているが、これ
らの金属塩は量的には極めて少なく、かつ濃縮工程で若
干は除去される。そして、回収された濃硫酸中に若干Ｔ
ｉ、Ｆｅ以外の金属塩が含まれていたとしても、これを
原料の蒸解工程で再利用することにあたっては差支えな
い。In the present invention, the remaining free sulfuric acid is concentrated either batchwise or continuously. In the method of the present invention, continuous concentration is possible without causing the precipitation of salts such as iron (n) sulfate, which was a problem with conventional methods, and concentrated sulfuric acid with a concentration of 97% or more can be recovered. Note that metal salts other than T1%Fe are accumulated in the sulfuric acid aqueous solution before concentration, but these metal salts are extremely small in quantity, and some are removed in the concentration step. There was some T in the recovered concentrated sulfuric acid.
i. Even if metal salts other than Fe are contained, there is no problem in reusing them in the raw material cooking process.
一方、抽出工程で分離された極性有機溶媒中のＴｉ４＋
及びＦｅ”は、水又はアルカリ水溶液による逆抽出でほ
ぼ完全に回収することができるので、極性有機溶媒を再
利用することができる。この逆抽出工程は０〜８０℃、
好ましくは１０〜６０℃の温度で行われ′る。On the other hand, Ti4+ in the polar organic solvent separated in the extraction process
and Fe'' can be almost completely recovered by back extraction with water or an alkaline aqueous solution, so the polar organic solvent can be reused.
It is preferably carried out at a temperature of 10 to 60°C.
以下、本発明の詳細な説明する。 The present invention will be explained in detail below.
硫酸法談化チタンの製造工程で多量に副生する廃硫酸を
採取した。これらの廃硫酸の平均的な組成は以下の通り
である。We collected waste sulfuric acid, which is a large amount of by-product during the manufacturing process of titanium. The average composition of these waste sulfuric acids is as follows.
Ｈ２Ｓ Ｏａ （ｔｏｔａｌ）
Ｈ２Ｓ Ｏａ （ｔｒｅｅ）
Ｆ ｅ （ｔｏｔａｌ）
Ｔｉ
ｎ
Ｉ
ｎ
ｇ
Ｃ「
ｂ
３００〜４００ｇ／１
２００〜３００ｇ／２
３０〜５０ｇ／１
５ ｇ／Ｄ
１０ ｇ／１
１ ｇ／Ｎ
１〜 Ｌａｇ／１
０．２ ｇ／ＩＩ
Ｏ，２ｇ７９
０．１ ｇ／Ｄ
Ｏ，０２ｇ／ｌ
これらの廃硫酸のうち１種を選択し、これを約２倍に希
釈して主要成分の濃度が
Ｈ２Ｓ Ｏａ （ｔｏｔａｌ） １９
２ ｇ ／ＤＨ２Ｓ Ｏ４（ｆ’ｒｅｅ）
１４０ ｇ／Ｊ？Ｆ ｅ （ｉｏｔａり
２４ ｇ ／ＩＴｉ
１．２５ｇ／Ｎとなったものを原
液こして使用した。H2S Oa (total) H2S Oa (tree) Fe (total) Tin Ing C'b 300~400g/1 200~300g/2 30~50g/1 5 g/D 10 g/1 1 g/N 1 to Lag/1 0.2 g/II O, 2g79 0.1 g/D O, 02g/l Select one type of waste sulfuric acid and dilute it approximately twice to determine the concentration of the main components. is H2S Oa (total) 19
2 g/DH2S O4 (f'ree)
140 g/J? F e (iota ri 24 g /ITi
The stock solution with a concentration of 1.25 g/N was filtered and used.
まず、この原液を空気酸化するか、又はこの原液にチタ
ン系電極を浸し、印加電圧４〜５Ｖ／ｃｅｌｌ、電流密
度１〜２ Ａ ／ （ｔｏｅｓ）２の条件で酸化を行い
、Ｔｉ３＋をＴｉ’＋へ、Ｆｅ”をＦｅ３＋へε変化さ
せた。これらの手段による酸化工程により生成したＴｉ
４＋のうち加水分解してケーキさなって沈殿したものを
ろ過して分離した。酸化後の廃硫酸にメチルイソブチル
ケトンを混合し、廃硫酸中のＴｉ”及びＦｅ”をほぼ完
全にメチルイソブチルケトン層へ抽出した。First, this stock solution is oxidized in the air, or a titanium-based electrode is immersed in this stock solution, and oxidation is performed under the conditions of an applied voltage of 4 to 5 V/cell and a current density of 1 to 2 A/(toes)2, converting Ti3+ into Ti' +, and Fe” was changed to Fe3+.The Ti produced by the oxidation process by these means
Of the 4+, a precipitated cake formed by hydrolysis was separated by filtration. Methyl isobutyl ketone was mixed with the waste sulfuric acid after oxidation, and Ti" and Fe" in the waste sulfuric acid were almost completely extracted into the methyl isobutyl ketone layer.
そして、残存した遊離硫酸を連続的に濃縮することによ
り、濃度９７％以上の濃硫酸を回収することができた。By continuously concentrating the remaining free sulfuric acid, concentrated sulfuric acid with a concentration of 97% or more could be recovered.
この濃硫酸は原料の蒸解工程で再利用することができる
。This concentrated sulfuric acid can be reused in the raw material cooking process.
一方、抽出工程で分離されたメチルイソブチルケトン中
のＴｉ４＋及びＦｅ’＋は、アルカリ水溶液による逆抽
出でほぼ完全に回収することができ、メチルイソブチル
ケトンを再利用することができた。On the other hand, Ti4+ and Fe'+ in the methyl isobutyl ketone separated in the extraction step could be almost completely recovered by back extraction with an aqueous alkaline solution, and the methyl isobutyl ketone could be reused.
むお、メチルイソブチルケトンの代わりに、ジー２−エ
チルへキシルリン酸を用いた場合にも、前記実施例と同
様の効果を得ることができた。Furthermore, even when di-2-ethylhexyl phosphoric acid was used instead of methyl isobutyl ketone, the same effect as in the above example could be obtained.
また、抽出工程では、前記実施例の用いた溶媒に限らず
、硫酸濃度、Ｆｅ濃度、酸化還元度、・ｒオン濃度に応
じて適当な溶媒を用いることができる。In addition, in the extraction step, an appropriate solvent can be used in addition to the solvent used in the above embodiments depending on the sulfuric acid concentration, Fe concentration, redox degree, and .r-on concentration.
以上詳述したように本発明方法を用いれば、硫酸性酸化
チタンの製造工程で副生する廃硫酸から高濃度の硫酸を
経済的に回収することができ、硫酸コストを低減できる
だけでなく、公害防止にも有効であるなど、その工業的
価値は極めて大きい。As detailed above, if the method of the present invention is used, it is possible to economically recover high-concentration sulfuric acid from waste sulfuric acid, which is a by-product in the manufacturing process of sulfuric acid titanium oxide, which not only reduces sulfuric acid costs but also reduces pollution. Its industrial value is extremely large, as it is also effective for prevention.
Claims (3)
ｅ＾３＾＋を含有する硫酸法酸化チタン廃硫酸を処理す
るにあたり、廃硫酸中のＴｉ＾３＾＋及びＦｅ＾２＾＋
を酸化する工程と、廃硫酸から極性有機溶媒によりＴｉ
＾４＾＋及びＦｅ＾３＾＋を選択的に抽出する工程と、
残存した遊離硫酸を濃縮して濃硫酸を回収する工程とを
具備したことを特徴とする硫酸法酸化チタン廃硫酸の処
理方法。(1) Ti^3^+, Ti^4^+, Fe^2^+, F
When treating titanium oxide waste sulfuric acid using the sulfuric acid method containing e^3^+, Ti^3^+ and Fe^2^+ in the waste sulfuric acid are
Ti is oxidized using a polar organic solvent from waste sulfuric acid.
a step of selectively extracting ^4^+ and Fe^3^+;
A method for treating titanium oxide waste sulfuric acid using the sulfuric acid method, comprising a step of concentrating remaining free sulfuric acid and recovering concentrated sulfuric acid.
を加水分解してケーキとしてろ過分離することを特徴と
する請求項（１）記載の硫酸法酸化チタン廃硫酸の処理
方法。(2) The treatment of waste sulfuric acid produced by the sulfuric acid method according to claim (1), characterized in that a part of Ti^4^+ oxidized from Ti^3^+ is hydrolyzed and separated by filtration as a cake. Method.
＾３＾＋を、水又はアルカリ水溶液により逆抽出し、回
収した極性有機溶媒を再利用することを特徴とする請求
項（１）記載の硫酸法酸化チタン廃硫酸の処理方法。(3) Ti^4^+ and Fe extracted into polar organic solvent
The method for treating waste sulfuric acid produced by the sulfuric acid method according to claim 1, characterized in that ^3^+ is back-extracted with water or an alkaline aqueous solution and the recovered polar organic solvent is reused.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1223308A JPH0388718A (en) | 1989-08-31 | 1989-08-31 | Treatment of sulfuric acid used to produce titanium oxide by sulfuric acid process |
| KR1019900010067A KR920004183B1 (en) | 1989-08-31 | 1990-07-04 | Treatment of sulfuric acid used to produce titanium oxide by sulfuric acid process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1223308A JPH0388718A (en) | 1989-08-31 | 1989-08-31 | Treatment of sulfuric acid used to produce titanium oxide by sulfuric acid process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0388718A true JPH0388718A (en) | 1991-04-15 |
Family
ID=16796114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1223308A Pending JPH0388718A (en) | 1989-08-31 | 1989-08-31 | Treatment of sulfuric acid used to produce titanium oxide by sulfuric acid process |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0388718A (en) |
| KR (1) | KR920004183B1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5489423A (en) * | 1991-11-08 | 1996-02-06 | Nittetsu Mining Co., Ltd. | Process for recovering sulfuric acid from metallic sulfate-containing exhaust sulfuric acid |
| US6337061B1 (en) | 1993-07-30 | 2002-01-08 | Nittetsu Mining Co., Ltd. | Method for reclaiming metal sulfate-containing waste sulfuric acid |
| JP2007282565A (en) * | 2006-04-17 | 2007-11-01 | Suzumo Machinery Co Ltd | Cooked rice supplying mechanism in food molding device |
| JP2012196459A (en) * | 2002-12-20 | 2012-10-18 | Ishihara Sangyo Kaisha Ltd | Method of producing organic compound decomposing material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220034472A (en) | 2020-09-11 | 2022-03-18 | 최욱 | Cap with holders for glasses |
-
1989
- 1989-08-31 JP JP1223308A patent/JPH0388718A/en active Pending
-
1990
- 1990-07-04 KR KR1019900010067A patent/KR920004183B1/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5489423A (en) * | 1991-11-08 | 1996-02-06 | Nittetsu Mining Co., Ltd. | Process for recovering sulfuric acid from metallic sulfate-containing exhaust sulfuric acid |
| US6337061B1 (en) | 1993-07-30 | 2002-01-08 | Nittetsu Mining Co., Ltd. | Method for reclaiming metal sulfate-containing waste sulfuric acid |
| JP2012196459A (en) * | 2002-12-20 | 2012-10-18 | Ishihara Sangyo Kaisha Ltd | Method of producing organic compound decomposing material |
| JP2007282565A (en) * | 2006-04-17 | 2007-11-01 | Suzumo Machinery Co Ltd | Cooked rice supplying mechanism in food molding device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR910004469A (en) | 1991-03-28 |
| KR920004183B1 (en) | 1992-05-30 |
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