JPH03164433A - Production of jarosite particles - Google Patents
Production of jarosite particlesInfo
- Publication number
- JPH03164433A JPH03164433A JP30421889A JP30421889A JPH03164433A JP H03164433 A JPH03164433 A JP H03164433A JP 30421889 A JP30421889 A JP 30421889A JP 30421889 A JP30421889 A JP 30421889A JP H03164433 A JPH03164433 A JP H03164433A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- soln
- jarosite
- aqueous solution
- jarosite particles
- 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.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 64
- 229910052935 jarosite Inorganic materials 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 16
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 8
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 abstract description 12
- 238000003756 stirring Methods 0.000 abstract description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 3
- 229910052936 alkali metal sulfate Inorganic materials 0.000 abstract description 2
- 238000007664 blowing Methods 0.000 abstract description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 2
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 2
- 229910003202 NH4 Inorganic materials 0.000 abstract 1
- 239000007832 Na2SO4 Substances 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 ammonium ions Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 241001605695 Pareronia Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910006540 α-FeOOH Inorganic materials 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、硫酸第一鉄を用いてジャロサイト粒子粉末を
生成させる製造法に関し、詳しくは、ＲＦｅｓ（Ｓｏｎ
）ｘ（Ｏｆ｛）ａ （Ｒ＝Ｋ’ 、Ｎａ’ ＮＨ４
”など）で示されるジャロサイト粒子粉末を、工業的、
経済的に有利に製造することができる新規な製造法を提
供することを目的とする．
〔従来の技術〕
ジャロザイト粒子粉末の工業的な製造法としては、例え
ば、特公昭５５−４６９７５号公報に開示されているよ
うに、硫酸第二鉄を用いる方法がよく知られている。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a manufacturing method for producing jarosite particles using ferrous sulfate.
)x(Of{)a (R=K', Na'NH4
Jarosite particles shown in
The purpose is to provide a new manufacturing method that can be economically advantageous. [Prior Art] As an industrial method for manufacturing jarozite particles, a method using ferric sulfate is well known, for example, as disclosed in Japanese Patent Publication No. 55-46975.
一方、硫酸第一鉄を用いてジャロサイ１・粒子粉末を工
業的に製造する方法としては、特開昭５４−５６００６
号公報に開示された方法が挙げられる。On the other hand, as a method for industrially manufacturing Jarosi 1/particle powder using ferrous sulfate, Japanese Patent Application Laid-Open No. 54-56006
For example, the method disclosed in Japanese Patent Publication No.
（発明が解決しようとする課題］
特開昭５４−５６００６号公報に開示された方法は、硫
酸第−鉄を１・・・・該ジャロサイ１・形威化合物は酸
素と結合した硫酸第一銖溶液、即ち硫酸第二鉄でジャＤ
４３イトを形戊ずる・・・・」なる記載の通り、硫酸
第二鉄に変威して用いており、更に同公報には、「所要
の作業温度を得るため、オー１・クレープの・・・・最
終区画室内の温度を１７０乃至２３０゜Ｃ・・・・」な
る記載の通り、オー１・クレープを用いて高温でジャロ
ザイト粒子を生或させる方法である。(Problems to be Solved by the Invention) The method disclosed in Japanese Patent Application Laid-open No. 54-56006 discloses that ferrous sulfate is converted into 1... solution, i.e. ferric sulfate.
As stated in ``Form 43ite...'', ferric sulfate was modified and used, and the same publication further stated, ``In order to obtain the required working temperature,... . . The temperature in the final compartment is 170 to 230° C." As described in this method, jarozite particles are produced at a high temperature using O-1 crepe.
尚、硫酸第一鉄とアルカリ金属又はアンモニウムイオン
の硫酸塩との混合水溶液に、酸素含有ガスを通気して常
温で酸化反応を行うことによって、ジャロサイト粒子ど
ゲータイ１粒子との混合物を生成させたことが、粉体わ
｝未冶金脇会発行「昭和４３年度春季人会講演概ｇ集Ｊ
（昭和４３年）第８８〜８９頁に報告されている。In addition, by passing oxygen-containing gas into a mixed aqueous solution of ferrous sulfate and a sulfate of an alkali metal or ammonium ion to carry out an oxidation reaction at room temperature, a mixture of jarosite particles and 1 particle of jarosite is generated. This is the Powder Wanderer. Published by Miyakin Sekikai, ``1964 Spring Meeting Lecture Summary G Collection J.
(1968), reported on pages 88-89.
従って、硫酸第一鉄を用いて、沸点以下の条件でジャロ
ザイ１・拉子のみを生成させることができ、しかも、工
業的、経済的にジャロ４ノイト粒子粉末が製造できる方
法は、いまだ確立されておらず、その方法の確立が強く
要求されており、本発明はこの要求に応えることを技術
的課題とするものである．
〔課題を解決する為の手段〕
本発明者は、前記技術的５題を解決すべく種々検討を重
ねた結果、本発明に到達したのである。Therefore, a method that can produce only Jarozai-1 and Lazi under conditions below the boiling point using ferrous sulfate, and also that can industrially and economically produce Jaro-4-noite powder, has not yet been established. However, there is a strong demand for the establishment of a method for doing so, and the technical objective of the present invention is to meet this demand. [Means for Solving the Problems] The present inventor has arrived at the present invention as a result of repeated studies to solve the five technical problems mentioned above.
即ち、本発明は、硫酸第一銖水溶液とアルカリ金属又は
アンモニウムイオンの硫酸塩水溶液と硫酸水溶液との混
合７容液に、酸素含有ガスを通気して４５℃〜沸点の温
度範囲で酸化反応を行うことにより、ジャロザイト粒子
を生成さセ“、生成したジャロザイト粒子をｐ別、洗浄
、乾燥してジャロザイト粒子粉末を得ることからなるジ
ャロザイト粒子粉末の製造法並びに、
硫酸第一鉄水溶液とアルカリ金属又はアンモニウムイオ
ンの硫酸塩水溶液と硫酸水溶液との混合溶液に、酸素含
有ガスを通気して４５゛Ｃ〜沸点の温度範囲で酸化反応
を行・）ことにより、ジャロづイ１・粒子を生成させ、
生成したジャロザイト粒子を枦別して濾液を回収する第
１の工程と、次いで、第１の工程で回収した濾液に新た
に硫酸第一鉄と水酸化アルカリ又はアンモニアとを加え
た新たな混合溶液に、酸素含有ガスを通気して４５゛Ｃ
〜沸点の温度範囲で酸化反応を行うことにより、ジャロ
サイト粒子を生成さセる第２の工程と、続いて、第２の
工程で生成したジャロサイト粒子をが別して回収した濾
液を用いて第２の工程の反応を繰り返すことによって、
ジャロザイト粒子を生成させ、生成したジャロサイト粒
子を：濾別する第３の工程と、
前記第１−・３の各工程で得られたジャロザイト粒子を
洗浄、乾燥してジャロザイＩ・粒？−粉末を得る工程と
からなるジャロサイト粒子粉末の製造法である．
（作 用〕
本発明においては、硫酸第一銖水溶液とアルカリ金属又
はアンモニウムイオンの硫酸塩水溶液と硫酸水溶液との
混合溶液に、酸素含有ガスを通気して４５℃〜沸点の温
度範囲で酸化反応を行うことにより、板状、六面体状、
八面体状等の粒子が凝集した平均粒子径３〜３０μｍの
球形を呈したジャロサイト粒子のみを生成させることが
出来る。That is, in the present invention, an oxygen-containing gas is passed through a 7-volume mixed solution of a sulfuric acid solution, an alkali metal or ammonium ion sulfate aqueous solution, and a sulfuric acid aqueous solution to carry out an oxidation reaction in a temperature range of 45° C. to the boiling point. A method for producing jarozite particles, which comprises: producing jarozite particles by carrying out the process, separating the produced jarozite particles, washing and drying them to obtain jarozite particles; By passing an oxygen-containing gas through a mixed solution of an aqueous sulfate solution of ammonium ions and an aqueous sulfuric acid solution and carrying out an oxidation reaction at a temperature range of 45°C to the boiling point, Jarozui 1 particles are generated.
A first step of separating the generated jarozite particles and collecting a filtrate, and then adding ferrous sulfate and alkali hydroxide or ammonia to the filtrate collected in the first step to create a new mixed solution. 45°C by venting oxygen-containing gas
A second step in which jarosite particles are produced by performing an oxidation reaction in a temperature range of ~ boiling point, followed by a second step in which the jarosite particles produced in the second step are separated and the collected filtrate is used. By repeating the reaction in step 2,
A third step of generating jarozite particles and separating the generated jarosite particles by filtration, and washing and drying the jarozite particles obtained in each of the steps 1-3 above to obtain jarozite I particles. - This is a method for producing jarosite particle powder, which consists of the steps of obtaining powder. (Function) In the present invention, an oxygen-containing gas is bubbled through a mixed solution of an aqueous sulfuric acid solution, an aqueous sulfate solution of an alkali metal or ammonium ion, and an aqueous sulfuric acid solution to carry out the oxidation reaction in a temperature range from 45°C to the boiling point. By doing this, plate-like, hexahedral-like,
Only spherical jarosite particles with an average particle diameter of 3 to 30 μm, which are agglomerated octahedral particles, can be produced.
本発明の第１の工程においては、硫酸第一鉄水溶液とア
ルカリ金属又はアンモニウｌ１イオンの硫酸塩水溶液と
硫酸水溶液との混合溶液に、酸素含有ガスを通気して４
５゛Ｃ〜沸点の温度範囲で酸化反応を行うことにより、
板状、六面体状、八面体状等の粒子が凝集した平均粒子
径３〜３０μｍの球形を呈したジャロザイト粒子のみを
生成さ丑ることか出来る．
次いで、第２の工程においては、第Ｉの工程でジ十口サ
イト粒子を濾別して回収した〆液に、反応溶液の総容量
が増加しないように、下記反応式（１）に基づいて、第
１の工程で生成したジャロサイト粒子の収量に相当する
量の硫酸第一鉄の結晶と水酸化アルカリの結晶又はアン
モニアガスを補給して新たな混合溶液とする。得られた
新たな混合溶液を用いて、第１の工程と同条件による酸
化反応を行うことにより、第１の工程と同等のジャロサ
イト粒子のみを生成させることが出来る．本発明者は、
第２の工程の反応式は、
３ＦｅＳＯ．＋３Ｒ０１１−＋ＲＦｅｉ（ＳＯａ）ｉ（
Ｏｆ−１）ｉ ＋ＲｔＳＯ４”（１）（但し、Ｒ一κ”
、Ｎａ” ＮＨ．’などである．）と考えている
．
尚、本発明の第１の工程で回収した濾液及び第２の工程
で回収した濾液の組成は、ほぼ同等であり以下の通りで
ある．
Ｆｅ”゜− ５ 〜４０ｇ／ Ｉ
Ｆｅ’゜−５〜１５ｇ／ｌ
Ｒ−０．５〜３０ｇ／Ｉ
ＳＯａ”−− ７０ −１５０ｇ／ １（但し、Ｒ＝κ
゜、Ｎａ” ＮＨ４”などである．）従って、第２
の工程で回収した濾液を用いて、第２の工程と同様の反
応を繰り返すことによってジャロサイト粒子のみを生成
させることが出来るのである．
次に、本発明方法実施にあたっての諸条件について述べ
る．
本発明における反応溶液の濃度はＦｅとして０．１〜２
．０ｓｏｌ／ｊ！である。より好ましくは０．２ 〜１
．０ｍｏｌ／ｌである， ０．１ｍｏｌ／ｊ！未満の
場合には、生産性が悪くなり経済的ではなく、２． ０
ｍｏｌ／ ｌを超える場合には、反応槽内等においてジ
ャロサイト粒子以外の芒硝等の結晶が析出したりするの
でハンドリングが困難となる．
本発明において使用されるアルカリ金属又はアンモニウ
ムイオンの硫酸塩水溶液としては、硫酸ナトリウム、硫
酸カリウム、硫酸アンモニウムなどの水溶液を使用する
ことができる．
本発明における上記硫酸塩水溶液は、硫酸第一鉄水溶液
のＦｅに対して５ 〜２００ｍｏｌ％である， ５ｍｏ
ｌ％未溝の場合には、ジャロサイト粒子が生成し難＜
、２００１１０１％を超える場合には、反応速度が遅く
なり経済的ではない．
本発明において使用される硫酸水溶液は、０．０２〜０
．１ｍｏｌ／ｊ！である． ０．０２ｍｏｌ／ １未満
の場合には、α−ＦｅＯＯＨが混入するため好ましくな
く、ｏ．ｉ指ｏｆ／ｉを超える場合には、反応速度が遅
くなり好ましくない．
本発明における第２の工程において使用される水酸化ア
ルカリとしては、水酸化ナトリウム、水酸化カリウムな
どの結晶か、又はアンモニアガスを用いることができる
．水酸化アルカリ又はアンモニアは、第２の工程におい
て使用する硫酸第一鉄に対して等モルである．
尚、本発明における第２の工程で使用する水酸化アルカ
リ又はアンモニアは、第１の工程で用いたアルカリ金属
又はアンモニウムイオンの硫酸塩水溶液と同一のものを
使用する．同一のものを使用しない場合にもジャロサイ
ト粒子は生成するが、アルカリによって組戒が異なるた
め、異なった組成のジャロサイト粒子が混ざってしまう
．本発明における反応温度は４５℃〜沸点の温度範囲で
ある．より好ましくは６０〜８０℃である。４５゜Ｃ未
満の場合には、反応速度が非常に遅くなり、沸点を超え
る場合には、特別の設備を要するなど好ましくない．
本発明における酸化手段は、酸素含有ガス（例えば、空
気）を溶液中に通気することにより行い、また、当該通
気ガスや機械的操作により撹拌しながら行う．
本発明は、実施例に示した回分弐を繰り返す方法に限ら
ず、反応液を連続的に抜き出し、ジャロサイト粒子と濾
液を濾別し、ｐ液を反応槽に戻すと共に硫酸第一鉄とア
ルカリとを連続的に反応槽に供給する方法で行うことも
できる．
本発明においては、ジャロサイト粒子粉末の使用目的に
より、ジャロサイト粒子の生成に際し、Ａ１、ＳＬ Ｐ
−， ＰＩｎＳＣｏＳＮ１％ ＣｕＳＺｎ１ＰＩｇ，
Ｃａｓ ｈｓＣｒ， Ｓｎ， Ｐｂ等の異種元素を添
加することもできる．〔実 施 例〕
次に、実施例並びに比較例により本発明を説明する。In the first step of the present invention, an oxygen-containing gas is bubbled through a mixed solution of a ferrous sulfate aqueous solution, an alkali metal or ammonium l1 ion sulfate aqueous solution, and a sulfuric acid aqueous solution.
By carrying out the oxidation reaction at a temperature range of 5°C to the boiling point,
It is possible to produce only spherical jarozite particles with an average particle diameter of 3 to 30 μm, which are agglomerated particles of plate, hexahedral, and octahedral shapes. Next, in the second step, based on the following reaction formula (1), a third solution is added to the final solution collected by filtering out the di-decasite particles in the first step so as not to increase the total volume of the reaction solution. A new mixed solution is prepared by replenishing ferrous sulfate crystals and alkali hydroxide crystals or ammonia gas in an amount corresponding to the yield of jarosite particles produced in step 1. By performing an oxidation reaction using the obtained new mixed solution under the same conditions as in the first step, it is possible to generate only jarosite particles equivalent to those in the first step. The inventor is
The reaction formula for the second step is 3FeSO. +3R011-+RFei(SOa)i(
Of-1)i +RtSO4"(1) (However, R-κ"
, Na"NH.', etc.). The compositions of the filtrate collected in the first step of the present invention and the filtrate collected in the second step are almost the same, and are as follows. There is.
゜, Na"NH4", etc. ) Therefore, the second
By repeating the same reaction as in the second step using the filtrate collected in step 1, it is possible to generate only jarosite particles. Next, various conditions for implementing the method of the present invention will be described. The concentration of the reaction solution in the present invention is 0.1 to 2 as Fe.
．． 0sol/j! It is. More preferably 0.2 to 1
．． 0mol/l, 0.1mol/j! If it is less than 2, productivity will be poor and it will not be economical. 0
If it exceeds mol/l, crystals such as mirabilite other than jarosite particles may precipitate in the reaction tank, making handling difficult. As the aqueous sulfate solution of alkali metal or ammonium ions used in the present invention, aqueous solutions of sodium sulfate, potassium sulfate, ammonium sulfate, etc. can be used. The sulfate aqueous solution in the present invention contains 5 to 200 mol% of Fe in the ferrous sulfate aqueous solution.
If 1% is not grooved, it is difficult to generate jarosite particles.
, 2001101%, the reaction rate slows down and is not economical. The sulfuric acid aqueous solution used in the present invention is 0.02 to 0.
．． 1mol/j! It is. If it is less than 0.02 mol/1, it is not preferable because α-FeOOH will be mixed in, and o. If it exceeds i fingers of/i, the reaction speed becomes slow, which is undesirable. As the alkali hydroxide used in the second step of the present invention, crystals of sodium hydroxide, potassium hydroxide, etc., or ammonia gas can be used. The alkali hydroxide or ammonia is equimolar to the ferrous sulfate used in the second step. The alkali hydroxide or ammonia used in the second step of the present invention is the same as the aqueous alkali metal or ammonium ion sulfate solution used in the first step. Jarosite particles are produced even if the same alkali is not used, but since the composition differs depending on the alkali, jarosite particles with different compositions will be mixed together. The reaction temperature in the present invention is in the temperature range of 45°C to the boiling point. More preferably it is 60 to 80°C. If the temperature is less than 45°C, the reaction rate becomes very slow, and if it exceeds the boiling point, special equipment is required, which is undesirable. The oxidation means in the present invention is carried out by aerating an oxygen-containing gas (for example, air) into the solution, and is also carried out while stirring with the aerated gas or mechanical operation. The present invention is not limited to the method of repeating batch 2 as shown in the example, but the present invention is not limited to the method of repeating batch 2 as shown in the example. This can also be carried out by continuously supplying both to the reaction tank. In the present invention, A1, SL P
−, PINSCoSN1% CuSZn1PIg,
It is also possible to add different elements such as Cr, Sn, and Pb. [Examples] Next, the present invention will be explained with reference to Examples and Comparative Examples.
尚、以下の実施例並びに比較例にお（ノる粒子の平均粒
子梯ば、電子顕微鏡写真から測定した数値の平均値で示
した、
実施例１
１．８ｌＩｏｌ／ ＥのＦｅＳＯ４水溶液２．５１と、
０． ４５ｖａｏ Ｉ ／ｉのＮａｚＳＯ．水｝容液１
．Ｏｆｆｉ （ＦｃＳｏ，水溶液中のＦｅに対し１０
ｍｏｌ％に該当する．）及び０．２３ｍｏｌ／ｌのＨ
８ｓｏ４ｔ．ＯＲ （全反応溶液中で０．０５ｍｏｌ／
（！に該当する。）を反応容器に投入して混合？８液
とし、空気＋５ １！／ｓｉｎの割合で吹き込んで撹拌
し，ながら、温度７０゛Ｃにおいて２４時間酸化反応を
行って、沈澱物を生成させた。In addition, in the following Examples and Comparative Examples (the average particle ladder of the particles is shown as the average value of the numerical values measured from the electron micrograph), Example 1 1.8 lIol/E FeSO4 aqueous solution 2.51 and ,
0. 45vao I/i NazSO. Water} Volume 1
．． Offi (FcSo, 10 for Fe in aqueous solution
Corresponds to mol%. ) and 0.23 mol/l H
8so4t. OR (0.05 mol/in total reaction solution
(corresponds to !) into the reaction vessel and mix? 8 liquids, air + 5 1! The oxidation reaction was carried out at a temperature of 70° C. for 24 hours while stirring at a rate of 70° C. to form a precipitate.
生成した沈Ｒ物を常法により、枦別、洗浄、乾燥して２
０９ｇの粒子粉末を得た。The generated precipitate is separated, washed and dried using a conventional method.
09g of particle powder was obtained.
得られた粒子粉末は、Ｘ線回折の結果、ジャロザイ｝・
であり、２２μｍの六面体状の凝集した球形を呈した粒
子であった。As a result of X-ray diffraction, the obtained particle powder was found to be
The particles had a hexahedral agglomerated spherical shape of 22 μm.
実施例２
第１の工程の反応として，、１，８ａｉｏｌ／ｊ２のＦ
ｅＳＯａ水溶液２．５Ｅと、０．４５ｍｏｌ／ ｌのＮ
ａ．ＳＯ４水溶液ｉ．ｏｅ （ＦｅＳＯ．水溶液中の
Ｆｅに対し１０ ｍｏｌ％に該当する６）及び０．２３
ｍｏｌ／尼のＨｚＳＯａ ｉ．ｏｚ （全反応溶液中
で０．０５ｍｏＩ／ １２に該当する．）を反応容器に
投入して混合溶液とし、空気１５ ｊ！ ／＠ｉｎの割
合で吹き込んで撹拌しながら、温度７０゜Ｃにおいて２
４時間酸化反応を行って、第１の工程の沈Ｂ物を生成さ
せ、これを炉別して枦液を回収した。Example 2 As the reaction of the first step, 1,8 aiol/j2 of F
eSOa aqueous solution 2.5E and 0.45 mol/l N
a. SO4 aqueous solution i. oe (FeSO.6 corresponding to 10 mol% of Fe in aqueous solution) and 0.23
mol/ni HzSOa i. oz (corresponding to 0.05 moI/12 in the total reaction solution) into the reaction vessel to make a mixed solution, and add 15 j! of air! /@in at a temperature of 70°C while stirring.
The oxidation reaction was carried out for 4 hours to produce the precipitate B of the first step, which was separated in a furnace to recover the liquid.
次に、第２の工程の反応として、第１の工程の沈Ｂ物を
炉別して回収した濾液４、３ｌに、ＦｅＳＯ，−７１１
．０結晶３５９ｇとＮａＯＩ！結晶５２ｇ （ ＦｅＳ
Ｏ４・ＩＨｔＯに対して等モルに該当する．）を熔解し
て混合溶液とし、反応容器に投入した．ｆ！．合溶液に
空気１５ｅ ／ｗｉｎの割合で吹き込んで撹拌しながら
、温度７０℃において２４時間酸化反応を行って、第２
の工程の沈′Ｒ物を生戊させた。Next, as a reaction in the second step, FeSO, -711
．． 359g of 0 crystals and NaOI! 52g crystal (FeS
It corresponds to equimolar amount to O4・IHtO. ) was melted to make a mixed solution, and the mixture was poured into a reaction vessel. f! ．． An oxidation reaction was carried out at a temperature of 70°C for 24 hours while stirring by blowing air into the combined solution at a rate of 15e/win.
The precipitate from the step of step 1 was extracted.
続いて、第２の工程の沈澱物をが別、回収したＰｉｌｉ
ｉ．４．３１を用いて、第２の工程の反心と同一条件で
酸化反応を行って、第３の王程の沈澱物を生成させ、こ
れを枦刑した。Subsequently, the precipitate from the second step was separated and recovered.
i. Using 4.31, an oxidation reaction was carried out under the same conditions as in the second step to form a third Wang Chen precipitate, which was then processed.
得られた、第１〜３の工程のそれぞれの沈澱物を常法に
より、洗浄、乾燥して２０９ｇ、２０５ｇ、２１２ｇの
粒子粉末を得た。The obtained precipitates from each of the first to third steps were washed and dried by a conventional method to obtain 209 g, 205 g, and 212 g of particle powder.
得られた、それぞれの粒子粉末は、Ｘ１９回折の結果、
ジャロサイ１・であり、図１〜図３に示す走査型電子顕
微鏡写真（ ｘ ２， ０００＞の通り、それぞれ２２
μｍ、２２μｍ、２１μｍの六面体状の凝集した球形を
呈した粒子であった。As a result of X19 diffraction, each of the obtained particle powders has the following properties:
As shown in the scanning electron micrographs (x 2,000) shown in Figs.
The particles were hexahedral, aggregated, spherical particles with dimensions of μm, 22 μm, and 21 μm.
実施例３〜７、比較例１〜２
実施例２の第１の工程における硫酸第一鉄水溶液の濃度
及び使用量、アルカリ金属の硫酸塩水溶液の種類、濃度
、使用量及びＦｅに対する割合、硫酸水溶液の濃度、使
用景及び全反応溶液に対する濃度並びに反応温度、
第２、第３の工程においては、それぞれ直前の工程にお
けるジャロサイＥ・粒子粉末の収量に相当する硫酸第一
鉄７水塩の使用董及び同一の水酸化アルカリとその使用
量並びに同一の反応温度を種々変化させた以外は、実施
例２と同様にしてジャロサイト粒子粉末を得た。Examples 3 to 7, Comparative Examples 1 to 2 Concentration and usage amount of ferrous sulfate aqueous solution in the first step of Example 2, type, concentration, usage amount and ratio to Fe of alkali metal sulfate aqueous solution, sulfuric acid Concentration of aqueous solution, use situation, concentration with respect to the total reaction solution, and reaction temperature; In the second and third steps, use of ferrous sulfate heptahydrate corresponding to the yield of Jarosi E. particles in the previous step, respectively. Jarosite particles were obtained in the same manner as in Example 2, except that the same alkali hydroxide, the amount used, and the same reaction temperature were varied.
尚、比較例１ １１．：おいてはゲータイト粒子が混入
し、比較例２においてはジャロザイト粒子が生成しなか
った。In addition, Comparative Example 1 11. : Goethite particles were mixed in, and in Comparative Example 2, jarozite particles were not produced.
この時の主要製造条件及び諸特性を表１及び表２に示す
。The main manufacturing conditions and characteristics at this time are shown in Tables 1 and 2.
表２
〔発明の効果〕
本発明によれば、安価な硫酸第一鉄を用いて、しかも、
大気圧下・沸点以下の条件でジャロサイト粒子粉末が製
造でき、しかも、ジャロサイト粒子を生成して残ったｐ
液を廃棄することなく、繰り返し循環して用いることが
できるので、工業的、経済的に非常に有利である．Table 2 [Effects of the invention] According to the present invention, inexpensive ferrous sulfate is used, and moreover,
Jarosite particles can be produced under atmospheric pressure and below the boiling point, and the remaining p
Since the liquid can be recycled and used repeatedly without being disposed of, it is very advantageous industrially and economically.
図１乃至図３は、それぞれ実施例２の第１乃至第３の工
程で得られたジャロサイト粒子粉末の粒子構造を示す走
査型電子顕微鏡写真（ｘ２．ｏｏＯ）である．1 to 3 are scanning electron micrographs (x2.ooO) showing the particle structures of jarosite particles obtained in the first to third steps of Example 2, respectively.
Claims (1)
イオンの硫酸塩水溶液と硫酸水溶液との混合溶液に、酸
素含有ガスを通気して４５℃〜沸点の温度範囲で酸化反
応を行うことにより、ジャロサイト粒子を生成させ、生
成したジャロサイト粒子を濾別、洗浄、乾燥してジャロ
サイト粒子粉末を得ることを特徴とするジャロサイト粒
子粉末の製造法。 ２、硫酸第一鉄水溶液とアルカリ金属又はアンモニウム
イオンの硫酸塩水溶液と硫酸水溶液との混合溶液に、酸
素含有ガスを通気して４５℃〜沸点の温度範囲で酸化反
応を行うことにより、ジャロサイト粒子を生成させ、生
成したジャロサイト粒子を濾別して濾液を回収する第１
の工程と、 次いで、第１の工程で回収した濾液に新たに硫酸第一鉄
と水酸化アルカリ又はアンモニアとを加えた新たな混合
溶液に、酸素含有ガスを通気して４５℃〜沸点の温度範
囲で酸化反応を行うことにより、ジャロサイト粒子を生
成させる第２の工程と、続いて、第２の工程で生成した
ジャロサイト粒子を濾別して回収した濾液を用いて第２
の工程の反応を繰り返すことによって、ジャロサイト粒
子を生成させ、生成したジャロサイト粒子を濾別する第
３の工程と、 前記第１〜３の各工程で得られたジャロサイト粒子を洗
浄、乾燥してジャロサイト粒子粉末を得る工程とからな
ることを特徴とするジャロサイト粒子粉末の製造法。[Claims] 1. Oxygen-containing gas is passed through a mixed solution of a ferrous sulfate aqueous solution, an alkali metal or ammonium ion sulfate aqueous solution, and a sulfuric acid aqueous solution to carry out an oxidation reaction at a temperature ranging from 45°C to the boiling point. A method for producing jarosite particles, the method comprising: producing jarosite particles by performing the above steps, and obtaining jarosite particles by filtering, washing, and drying the produced jarosite particles. 2. By carrying out an oxidation reaction in the temperature range from 45°C to the boiling point by passing an oxygen-containing gas through a mixed solution of a ferrous sulfate aqueous solution, an alkali metal or ammonium ion sulfate aqueous solution, and a sulfuric acid aqueous solution, jarosite is produced. The first step is to generate particles, filter out the generated jarosite particles, and collect the filtrate.
Next, a new mixed solution in which ferrous sulfate and alkali hydroxide or ammonia are added to the filtrate collected in the first step is heated to a temperature of 45°C to the boiling point by passing oxygen-containing gas through it. A second step of generating jarosite particles by performing an oxidation reaction within a range of
A third step of producing jarosite particles by repeating the reaction in step 1 and filtering out the produced jarosite particles, and washing and drying the jarosite particles obtained in each of the steps 1 to 3 above. A method for producing jarosite particles, comprising the steps of: obtaining jarosite particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1304218A JP2736693B2 (en) | 1989-11-22 | 1989-11-22 | Method for producing jarosite particle powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1304218A JP2736693B2 (en) | 1989-11-22 | 1989-11-22 | Method for producing jarosite particle powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03164433A true JPH03164433A (en) | 1991-07-16 |
| JP2736693B2 JP2736693B2 (en) | 1998-04-02 |
Family
ID=17930430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1304218A Expired - Fee Related JP2736693B2 (en) | 1989-11-22 | 1989-11-22 | Method for producing jarosite particle powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2736693B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100401987B1 (en) * | 1998-12-16 | 2003-12-18 | 주식회사 포스코 | A method for preparing chromic acid from electroplating was tewater including hexavalent chrome |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5456006A (en) * | 1977-08-19 | 1979-05-04 | Sherritt Gordon Mines Ltd | Precipitating of iron as jarosite |
| JPS6123250A (en) * | 1984-07-11 | 1986-01-31 | Nec Corp | Test system |
-
1989
- 1989-11-22 JP JP1304218A patent/JP2736693B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5456006A (en) * | 1977-08-19 | 1979-05-04 | Sherritt Gordon Mines Ltd | Precipitating of iron as jarosite |
| JPS6123250A (en) * | 1984-07-11 | 1986-01-31 | Nec Corp | Test system |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100401987B1 (en) * | 1998-12-16 | 2003-12-18 | 주식회사 포스코 | A method for preparing chromic acid from electroplating was tewater including hexavalent chrome |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2736693B2 (en) | 1998-04-02 |
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