JPH0249254B2 - - Google Patents
Info
- Publication number
- JPH0249254B2 JPH0249254B2 JP60216137A JP21613785A JPH0249254B2 JP H0249254 B2 JPH0249254 B2 JP H0249254B2 JP 60216137 A JP60216137 A JP 60216137A JP 21613785 A JP21613785 A JP 21613785A JP H0249254 B2 JPH0249254 B2 JP H0249254B2
- Authority
- JP
- Japan
- Prior art keywords
- chromium
- hydrochloric acid
- solution
- chromium chloride
- exchange resin
- 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.)
- Expired - Lifetime
Links
- 239000011651 chromium Substances 0.000 claims description 82
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 53
- 229910052804 chromium Inorganic materials 0.000 claims description 43
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 39
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 36
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 36
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052742 iron Inorganic materials 0.000 claims description 27
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 25
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 25
- 239000003729 cation exchange resin Substances 0.000 claims description 24
- 239000012535 impurity Substances 0.000 claims description 18
- 229910000604 Ferrochrome Inorganic materials 0.000 claims description 16
- 239000008188 pellet Substances 0.000 claims description 14
- -1 iron ions Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000000284 extract Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 6
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 28
- 239000011550 stock solution Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 19
- 238000000605 extraction Methods 0.000 description 14
- 238000011282 treatment Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910019589 Cr—Fe Inorganic materials 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Description
（産業上の利用分野）
本発明は塩化クロムの製造方法に関し、さらに
詳しくは陽イオン交換樹脂を使用して高純度の塩
化クロムを収率良く製造する方法に関するもので
ある。
（従来の技術）
従来、塩化クロムの製造方法としてはクロム鉱
石をアルカリ酸化焙焼してクロムを重クロム酸ナ
トリウムとし、これを水で抽出して六価クロムを
含むクロム酸ナトリウム溶液とし、これに硫酸を
加えたのち還元して硫酸クロム溶液とし、さらに
ソーダ灰を加えて炭酸クロムの沈澱を作り、
過、水洗したのち酸塩を加えて溶解し、これを加
熱濃縮する方法がとられていた。
また、クロム鉱石を電気炉を用いて炭素質還元
剤で還元して高炭素フエロクロムとし、高炭素フ
エロクロム中のクロムを硫酸抽出した溶液を電気
分解して金属クロムとし、金属クロムに塩酸を加
えて塩化クロムを製造する方法、あるいは高炭素
フエロクロムを塩酸で溶解し、その溶解抽出液を
アミン等の有機溶媒と接触させて抽出液中の塩化
鉄を有機溶媒側に移行させ、鉄分を分離した抽出
残液より高純度の塩化クロムを回収する方法も知
られている。（特開昭50−137895、特開昭53−
65292、特開昭54−84891参照）
（発明が解決しようとする問題点）
上記従来方法のうちクロム鉱石をアルカリ酸化
焙焼する方法は毒性の強い六価クロム塩を経由し
て処理するので作業環境面で問題が多く、また廃
棄物として利用されない成分が多いので経済的に
も得策でない。
また、高炭素フエロクロムを経由する方法のう
ち硫酸抽出する方法は、分離する際に鉄含有物の
処理量が多くなり、無害化処理などに多大の費用
を要する欠点があり、最近では塩酸抽出法が主流
となつている。
しかしながら塩酸抽出法ではフエロクロムの塩
酸溶解液中の不純物の大部分が有機溶媒で鉄分を
抽出分離した後のクロム分を含んだ抽出残液に残
るため、得られた塩化クロムの純度が低い欠点が
有つた。
本発明はこの欠点を解消し、Mg、Al、Ni、
Ｖ、Mn、Ca、Si、Co、Ti、Zu、Mo、Fe等の
不純物含有量の少ない極めて高純度な塩化クロム
を得ることを目的とするものである。
第一の発明は塩化クロム溶液中の不純物を陽イ
オン交換樹脂を使用して除去して塩化クロムを製
造する方法において、塩化クロムを加熱濃縮した
後、該濃縮物を希塩酸で溶解した溶液を陽イオン
交換樹脂で処理して高純度の塩化クロムを製造す
る方法にかかわるものである。
第二の発明は高炭素フエロクロムまたはクロム
鉱石還元焼結ペレツトを出発原料とし、これらの
出発原料を塩酸溶解し、該溶液中に含まれる鉄イ
オンを３価の鉄イオンに酸化した溶液をMIBKと
接触させてFe分を除去した後、第１の発明にか
かわる処理、すなわち加熱濃縮した後、該濃縮物
を希塩酸で溶解した溶液を陽イオン交換樹脂で処
理して、高純度の塩化クロムを製造することを要
旨とするものである。
（問題点を解決するための手段）
一般に溶媒を用いて固体または液体物質の中か
ら、成分物質の１種または２種以上を溶解させて
分離する方法は、溶媒抽出法として広く用いられ
ている。
CrおよびFeを主成分として含有する塩酸溶液
を有機溶媒と接触させ、塩化鉄と塩化クロムとに
分離回収することも当然可能である。この場合に
使用する有機溶媒としてはベンゼン、酢酸エチ
ル、クロロホルム、第１、２、３級アミン、メチ
ルイソブチルケトン（MIBK）等が利用可能であ
る。これらの有機溶媒のうち、FeとCrの分離に
は６〜8N HCl液でのFe抽出率がきわめて高いこ
とから、MIBKが最も有効である。
しかしながら、MIBKでFe分を除去したあと
のCr含有溶液中にはなおMg、Al、Ni、Ｖ、
Mn、Ca、Si、Co、Ti、Zn、Mo等の不純物イオ
ンが含まれており、これから得られた塩化クロム
は純度が低く商品価値も低いものとなる。
一方、液体中の不純物イオンを分離する方法と
してイオン交換樹脂法が知られている。
しかしながら塩化クロム溶液を通常の陽イオン
交換樹脂法で処理したのではクロム収率（ηCr）
が50％以下と低く実用的でない。これは塩化クロ
ムには
塩化六アクオ第二クロム
〔Cr（OH2）6〕Cl3 （Cr）
塩化クロロ五アクオ第二クロム
〔Cr（OH2）5Cl〕Cl2・H2O （Cr）
塩化二クロロ四アクオ第二クロム
〔Cr（OH2）4Cl2〕Cl・2H2O （Cr）
の三種の錯塩がある平衡状態で存在し、その平衡
状態によりηCrが変化するためと推定される。な
ぜならば、一般にイオン交換樹脂への吸着性はイ
オン価が高いほど大きいので、Cr、Crが多
い場合はこれらCr、CrがMg等の不純物と共
に陽イオン交換樹脂に吸着されるためηCrが低
く、反対にCrが多い場合は陽イオン交換樹脂
に吸着されるCr分が少なくなり、ηCrが高くなる
ものと推定される。
そこでCrの塩酸溶液に種々の処理を施こした
後、陽イオン交換処理をするテストを行つた結
果、次に示す処理をした後陽イオン交換樹脂を通
すと、ηCrを高く維持し、しかも効果的に不純物
の除去が可能であることを見出し本発明に至つた
ものである。
即ち第一の方法は塩化クロム溶液を加熱濃縮し
た後、10℃以下の冷希塩酸で溶解した塩酸溶液を
陽イオン交換樹脂で処理するものであり、第二の
方法は先づ塩化クロム溶液を加熱濃縮した後冷却
して結晶させる。次にこの結晶はCrの錯塩の
粗製品であるかさらに精製する。精製方法は粗製
品結晶容量の二分の一量の水を加えて溶解して
過したのち、寒剤で冷却しながら塩化水素を飽和
させる。次に数時間そのまま放置したのち、手早
く吸引過する。得られた結晶を10℃以下の冷水
で溶解し0.3N以下の塩酸濃度にした後、陽イオ
ン交換樹脂を通す方法である。
以下に第一の発明について詳説する。
クロム鉱石を出発原料とした硫酸クロム溶液に
ソーダ灰を加えて炭酸カルシウムとしこれを塩酸
溶解した溶液中には、クロムや鉄の他に各種の金
属不純物が陽イオンとして溶解している。これら
の不純物は陽イオン交換樹脂を使用して分離除去
することが可能である。
また、一般の塩化クロムについても陽イオン交
換樹脂を使用して不純物を除去し、高純度品を得
ることが可能である。
陽イオン交換樹脂としては、強酸性陽イオン交
換樹脂（ポリスチレン系、交換基＝−SO3H）ま
たは弱酸性陽イオン交換樹脂（メタクリル系、交
換基＝−COOH）のいずれでも使用可能である。
陽イオン交換樹脂を使用してCrイオンと他の
金属イオンとを分離するには、Crイオンは１価
にしておくことが重要である。このため本発明で
は不純物を含むクロム原液を濃縮乾固させた後、
再び希塩酸で溶解する手段を採用した。
クロム原液の加熱濃縮にあたつては、加熱溶液
が高すぎたり、完全に固体状態まで乾固させると
塩化クロムが一部酸化クロムとなるので、温度は
250℃以下、好ましくは100℃前後に抑え、シロツ
プ状で結晶水が残る程度にとどめるのが良い。こ
の濃縮物を希塩酸溶解するにあたり、前述のろ過
操作を加えれば、不純物除去に一層有効である。
イオン交換処理に際してはCr原液の液温は低
温であるほどCr錯塩が安定するので、15℃以
下、好ましくは10℃以下が望ましい。イオン交換
カラムも冷却機能を備えたものが好ましい。
塩酸濃度については高いほどCr錯塩は安定
するが、イオン交換樹脂のクロムと他のイオンと
の分離能力は低濃度ほど良好となる。従つて塩酸
濃度は1N以下、好ましくは0.3N程度とするのが
良い。
陽イオン交換処理で所望の品質が得られない場
合は、Cr原液の塩酸濃度を1.5Nないし9Nとし、
強塩基性陰イオン交換樹脂にて処理すれば、さら
に高品質の製品を得ることも可能である。
次に第二の発明について説明する。
クロム鉱石はクロムおよび鉄が酸化物として存
在し、酸に不溶である。クロム鉱石を還元したフ
エロクロムや還元焼結ペレツトは、クロムおよび
鉄がメタリツクあるいは炭化物として存在し、酸
に可溶となる。フエロクロムは商業ベースで多量
に使用されており、中間原料である還元焼結ペレ
ツトも多量に生産されている。これらは一般に製
鋼用原料として使用されるが、冶金用としては好
ましくない小サイズ品も多量に発生しているのが
現状である。これらを塩化クロム用原料として利
用できれば資源利用の面からも極めて有効な手段
となる。本発明はこれらフエロクロムやクロム鉱
石還元焼結ペレツトを出発原料とし、高純度の塩
化クロムを製造する方法を提供するものである。
本発明で使用するフエロクロムは、クロム鉱石
またはクロム鉱石還元焼結ペレツトを、コークス
および珪石と共に電気炉で還元して得られる主と
して高炭素のフエロクロムである。
また、本発明においては出発原料としてクロム
鉱石還元焼結ペレツトを利用することもできる。
クロム鉱石還元焼結ペレツトはクロム鉱石粉末と
炭素質還元剤粉末とを混合造粒し、ロータリーキ
ルンやシヤフトキルンを使用して固相還元して得
られるものである。クロム鉱石還元焼結ペレツト
ではクロムおよび鉄は還元されてクロム・鉄カー
バイドになつており還元率は通常40〜90％であ
る。カーバイドの他にはMgO、Al2O3、SiO2等
の脈石成分と未還元のクロム・鉄酸化物、および
未反応の炭素質還元剤を含んでいる。
これらの原料からクロム分を抽出する方法を第
１図に従つて説明する。
先ずフエロクロムまたはクロム鉱石還元焼結ペ
レツトを１mm以下程度にまで粉砕し塩酸で溶解す
る。塩酸濃度は1N以上、好ましくは８〜12Nが
良い。温度は60〜130℃、好ましくは100〜120℃
で溶解する。
溶解は反応容器中で塩酸に浸漬させても良い
し、塩酸を循環接触させても良い。この工程で金
属状のクロム及び鉄の90％以上が溶出する。
冷却後スラグ成分である未溶解残渣分を過し
て除去してCr−Fe原液を得る。
次にCr−Fe原液中のFe分を溶媒抽出するため、
Cr−Fe原液中に塩素ガスを吹込むか、無水クロ
ム酸のような酸化剤を添加し、Cr−Fe原液中の
鉄イオンを３価の鉄イオン（Fe+3）とする。
Fe+3を含むCr−Fe原液の塩酸濃度を３〜8Nに
調整した後、有機溶媒抽出する。使用する有機溶
媒としては第１〜第３級アミン、酢酸エチル、ク
ロロホルム、ベンゼン、ケトン類が利用可能であ
る。このうちFeの抽出率が良く、Feの他にCo、
Ｖ、Ti、Ca等が同時に抽出できるものとして、
メチルイソブチルケトン（MIBK）が最適であ
る。
溶媒としてMIBKを使用してFeを分離抽出す
るには、Cr−Fe原液とMIBKとを混合接触させ
れば良い。この際Cr−Fe原液中のFe濃度は20〜
100ｇ／MIBKとするのが好ましい。また抽出
温度は０〜80℃、好ましくは15〜40℃とするのが
良い。MIBK抽出処理後のCr−Fe原液はCr分に
富んだCr原液とFe分に富んだFe原液とに分かれ
る。
このCr原液を第１の発明で示した方法に従つ
て処理すれば高純度の塩化クロムが得られる。
一方、Fe原液からは塩化鉄が得られ、これは
汚水処理沈降剤、金属腐食液、ベンガラやフエラ
イトまたは鉄粉の原料として利用できる。
次に実施例をあげて本発明を説明する。
実施例 １
表１に示す組成のクロム鉱石還元焼結ペレツト
を粒径１mm程度まで粉砕し、粉砕物中のクロム及
び鉄分を塩素化するのに必要な理論当量の1.5倍
の塩酸（濃度10N）を加え、110℃の温度で60分
間溶解し、CrおよびFe分を抽出した。
(Industrial Application Field) The present invention relates to a method for producing chromium chloride, and more particularly to a method for producing high-purity chromium chloride in good yield using a cation exchange resin. (Prior art) Conventionally, the method for producing chromium chloride is to roast chromium ore with alkali oxidation to convert chromium into sodium dichromate, extract this with water to make a sodium chromate solution containing hexavalent chromium, and After adding sulfuric acid to the solution, it is reduced to a chromium sulfate solution, and then soda ash is added to form a chromium carbonate precipitate.
After filtering and washing with water, an acid salt was added and dissolved, followed by heating and concentrating. In addition, chromium ore is reduced with a carbonaceous reducing agent in an electric furnace to produce high carbon ferrochrome, and a solution in which chromium in the high carbon ferrochrome is extracted with sulfuric acid is electrolyzed to produce metallic chromium, and hydrochloric acid is added to the metallic chromium. A method for producing chromium chloride, or an extraction method in which high-carbon ferrochrome is dissolved in hydrochloric acid, the dissolved extract is brought into contact with an organic solvent such as an amine, and the iron chloride in the extract is transferred to the organic solvent to separate the iron content. A method of recovering highly purified chromium chloride from the residual liquid is also known. (Unexamined Japanese Patent Publication No. 137895, No. 53-
65292, see JP-A-54-84891) (Problems to be solved by the invention) Of the conventional methods mentioned above, the method of roasting chromium ore with alkali oxidation requires a lot of work because it is processed through highly toxic hexavalent chromium salt. There are many environmental problems, and since many components are not used as waste, it is not economically advantageous. In addition, among the methods that go through high-carbon ferrochrome, the sulfuric acid extraction method has the disadvantage that a large amount of iron-containing substances must be treated during separation, requiring a large amount of cost for detoxification treatment. has become the mainstream. However, in the hydrochloric acid extraction method, most of the impurities in the hydrochloric acid solution of ferrochrome remain in the extraction residue containing chromium after extracting and separating iron with an organic solvent, so the purity of the obtained chromium chloride is low. There was. The present invention eliminates this drawback and allows Mg, Al, Ni,
The purpose is to obtain extremely high purity chromium chloride with a low content of impurities such as V, Mn, Ca, Si, Co, Ti, Zu, Mo, and Fe. The first invention is a method for producing chromium chloride by removing impurities in a chromium chloride solution using a cation exchange resin. This relates to a method for producing high-purity chromium chloride by treatment with an ion exchange resin. The second invention uses high carbon ferrochrome or chromium ore reduced sintered pellets as starting materials, dissolves these starting materials in hydrochloric acid, oxidizes the iron ions contained in the solution to trivalent iron ions, and converts the solution into MIBK. After contacting to remove Fe content, the process according to the first invention is performed, that is, heating and concentrating, and then a solution of the concentrate dissolved in dilute hydrochloric acid is treated with a cation exchange resin to produce high purity chromium chloride. The gist of this is to (Means for solving the problem) Generally, a method of dissolving and separating one or more component substances from a solid or liquid substance using a solvent is widely used as a solvent extraction method. . Of course, it is also possible to separate and recover iron chloride and chromium chloride by contacting a hydrochloric acid solution containing Cr and Fe as main components with an organic solvent. Examples of organic solvents that can be used in this case include benzene, ethyl acetate, chloroform, primary, secondary, and tertiary amines, and methyl isobutyl ketone (MIBK). Among these organic solvents, MIBK is the most effective for separating Fe and Cr because it has an extremely high Fe extraction rate with a 6-8N HCl solution. However, after removing the Fe content with MIBK, the Cr-containing solution still contains Mg, Al, Ni, V,
It contains impurity ions such as Mn, Ca, Si, Co, Ti, Zn, and Mo, and the chromium chloride obtained from it has low purity and low commercial value. On the other hand, an ion exchange resin method is known as a method for separating impurity ions in a liquid. However, when chromium chloride solution is treated with the usual cation exchange resin method, the chromium yield (ηCr)
is less than 50%, which is impractical. This is chromium chloride, which is chromic hexachloride [Cr(OH 2 ) 6 ] Cl 3 (Cr) chromic pentachloride chromic chloride [Cr(OH 2 ) 5 Cl] Cl 2・H 2 O (Cr) It is presumed that this is because the three complex salts of dichlorotetraaquoconic dichromium chloride [Cr(OH 2 ) 4 Cl 2 ]Cl・2H 2 O (Cr) exist in a certain equilibrium state, and ηCr changes depending on the equilibrium state. Ru. This is because, in general, the higher the ionic valence, the greater the adsorption to ion exchange resins, so if there is a large amount of Cr, Cr will be adsorbed to the cation exchange resin along with impurities such as Mg, resulting in a low ηCr. On the other hand, if there is a large amount of Cr, it is estimated that the amount of Cr adsorbed to the cation exchange resin decreases and ηCr increases. Therefore, we conducted a test in which a Cr hydrochloric acid solution was subjected to various treatments and then subjected to cation exchange treatment.The results showed that when passed through a cation exchange resin after the following treatment, ηCr remained high and was effective. The inventors discovered that it is possible to remove impurities in a similar manner, leading to the present invention. That is, the first method is to heat and concentrate the chromium chloride solution, and then treat the hydrochloric acid solution dissolved in cold dilute hydrochloric acid at 10°C or less with a cation exchange resin, and the second method is to first heat the chromium chloride solution. After concentrating, it is cooled and crystallized. This crystal is then further purified to determine whether it is a crude product of a complex salt of Cr. The purification method involves adding half the volume of water to the crystal volume of the crude product, dissolving it, and then saturating it with hydrogen chloride while cooling with a cryogen. Next, leave it as it is for several hours, then quickly aspirate it. This is a method in which the obtained crystals are dissolved in cold water of 10°C or less to a hydrochloric acid concentration of 0.3N or less, and then passed through a cation exchange resin. The first invention will be explained in detail below. In addition to chromium and iron, various metal impurities are dissolved as cations in a solution prepared by adding soda ash to a chromium sulfate solution starting from chromium ore to form calcium carbonate, which is then dissolved in hydrochloric acid. These impurities can be separated and removed using a cation exchange resin. It is also possible to remove impurities from general chromium chloride using a cation exchange resin to obtain a highly pure product. As the cation exchange resin, either a strongly acidic cation exchange resin (polystyrene type, exchange group = -SO3H ) or a weakly acidic cation exchange resin (methacrylic type, exchange group = -COOH) can be used. In order to separate Cr ions from other metal ions using a cation exchange resin, it is important that the Cr ions be monovalent. Therefore, in the present invention, after concentrating and drying the chromium stock solution containing impurities,
Again, a method of dissolving with dilute hydrochloric acid was adopted. When heating and concentrating a chromium stock solution, the temperature should be adjusted carefully, as if the temperature of the heated solution is too high or if it is completely dried to a solid state, some of the chromium chloride will turn into chromium oxide.
It is best to keep the temperature below 250°C, preferably around 100°C, to the extent that it remains syrupy with water of crystallization. When dissolving this concentrate in diluted hydrochloric acid, it is more effective to remove impurities if the above-mentioned filtration operation is added. During the ion exchange treatment, the temperature of the Cr stock solution is desirably 15°C or lower, preferably 10°C or lower, because the lower the temperature, the more stable the Cr complex salt is. Preferably, the ion exchange column also has a cooling function. The higher the concentration of hydrochloric acid, the more stable the Cr complex salt becomes, but the lower the concentration, the better the ability of the ion exchange resin to separate chromium from other ions. Therefore, the hydrochloric acid concentration is preferably 1N or less, preferably about 0.3N. If the desired quality cannot be obtained by cation exchange treatment, adjust the hydrochloric acid concentration of the Cr stock solution to 1.5N to 9N,
It is also possible to obtain a product of even higher quality by treating it with a strongly basic anion exchange resin. Next, the second invention will be explained. Chromium ore contains chromium and iron as oxides and is insoluble in acids. In ferrochrome obtained by reducing chromium ore and reduced sintered pellets, chromium and iron exist as metallic or carbide and are soluble in acids. Ferrochrome is used in large quantities on a commercial basis, and reduced sintered pellets, which are intermediate raw materials, are also produced in large quantities. Although these materials are generally used as raw materials for steelmaking, there are currently a large number of small-sized products that are not suitable for metallurgy. If these can be used as raw materials for chromium chloride, it will be an extremely effective means in terms of resource utilization. The present invention provides a method for producing high-purity chromium chloride using these ferrochromes and chromium ore reduced sintered pellets as starting materials. The ferrochrome used in the present invention is mainly high carbon ferrochrome obtained by reducing chromium ore or chromium ore reduced sintered pellets together with coke and silica stone in an electric furnace. Further, in the present invention, chromium ore reduced sintered pellets can also be used as a starting material.
The chromium ore reduced sintered pellets are obtained by granulating a mixture of chromium ore powder and carbonaceous reducing agent powder and subjecting the mixture to solid phase reduction using a rotary kiln or shaft kiln. In chromium ore reduced sintered pellets, chromium and iron are reduced to chromium-iron carbide, and the reduction rate is usually 40 to 90%. In addition to carbide, it contains gangue components such as MgO, Al 2 O 3 , and SiO 2 , unreduced chromium and iron oxides, and unreacted carbonaceous reducing agents. A method for extracting chromium from these raw materials will be explained with reference to FIG. First, ferrochrome or chromium ore reduced sintered pellets are ground to about 1 mm or less and dissolved in hydrochloric acid. The concentration of hydrochloric acid is 1N or more, preferably 8 to 12N. Temperature is 60-130℃, preferably 100-120℃
Dissolve with. Dissolution may be carried out by immersing the reaction vessel in hydrochloric acid or by circulating hydrochloric acid. More than 90% of metallic chromium and iron are eluted in this process. After cooling, the undissolved residue, which is a slag component, is removed by filtration to obtain a Cr-Fe stock solution. Next, in order to solvent extract the Fe content in the Cr-Fe stock solution,
By blowing chlorine gas into the Cr-Fe stock solution or adding an oxidizing agent such as chromic anhydride, the iron ions in the Cr-Fe stock solution are converted to trivalent iron ions (Fe +3 ). After adjusting the hydrochloric acid concentration of the Cr-Fe stock solution containing Fe +3 to 3 to 8N, it is extracted with an organic solvent. As the organic solvent used, primary to tertiary amines, ethyl acetate, chloroform, benzene, and ketones can be used. Among these, the extraction rate of Fe is good, and in addition to Fe, Co,
Assuming that V, Ti, Ca, etc. can be extracted at the same time,
Methyl isobutyl ketone (MIBK) is the best choice. In order to separate and extract Fe using MIBK as a solvent, it is sufficient to mix and contact the Cr-Fe stock solution and MIBK. At this time, the Fe concentration in the Cr-Fe stock solution is 20~
It is preferable to set it as 100g/MIBK. Further, the extraction temperature is preferably 0 to 80°C, preferably 15 to 40°C. The Cr-Fe stock solution after the MIBK extraction process is divided into a Cr stock solution rich in Cr content and an Fe stock solution rich in Fe content. If this Cr stock solution is treated according to the method shown in the first invention, highly pure chromium chloride can be obtained. On the other hand, iron chloride is obtained from the Fe stock solution, which can be used as a raw material for sewage treatment sedimentation agents, metal corrosive solutions, red iron oxide, ferrite, and iron powder. Next, the present invention will be explained with reference to Examples. Example 1 Reduced chromium ore sintered pellets having the composition shown in Table 1 were crushed to a particle size of approximately 1 mm, and hydrochloric acid (concentration 10N) was added in an amount 1.5 times the theoretical equivalent required to chlorinate the chromium and iron in the crushed product. was added and dissolved at a temperature of 110°C for 60 minutes to extract Cr and Fe components.
【表】
この抽出でペレツト中のクロム・鉄カーバイド
の95％以上が抽出される。
冷却後、未溶解残渣分を過し、液中に塩素
ガスを通じて鉄イオンを酸化させ３価の鉄イオン
にした。塩素ガスを吹込んだ際の過剰残留塩素は
エアレーシヨンにより除去した。
この溶液の塩酸濃度を4Nに調整した後、
MIBKを抽出剤として処理してFe分を抽出除去
した。MIBK使用量は20ｇFe／MIBKとし、
室温で撹拌し混合静置して、Fe原液とCr原液に
分離した。Cr原液のCr濃度は6.34％であつた。
MIBK抽出処理後のCr原液の不純物の割合を
表２に示す。表２ではCr100ｇ当りの量で表示し
た。[Table] This extraction extracts more than 95% of the chromium and iron carbide in the pellets. After cooling, undissolved residue was filtered out, and chlorine gas was passed into the solution to oxidize iron ions to trivalent iron ions. Excess residual chlorine when chlorine gas was blown was removed by aeration. After adjusting the hydrochloric acid concentration of this solution to 4N,
MIBK was used as an extractant to extract and remove Fe content. The amount of MIBK used is 20gFe/MIBK,
The mixture was stirred and left to stand at room temperature to separate into Fe stock solution and Cr stock solution. The Cr concentration of the Cr stock solution was 6.34%. Table 2 shows the impurity ratio of the Cr stock solution after the MIBK extraction process. In Table 2, the amount is expressed per 100g of Cr.
【表】
MIBK抽出処理後のCr原液を100℃に加熱し、
溶解残存しているMIBKを除去した。
次にこのCr原液を100℃で加熱し、結晶水のみ
が残る程度まで蒸発乾固させ濃縮した。
この濃縮物を冷却後、10℃、0.3Nの希塩酸で
溶解し、溶液の塩酸濃度を0.3Nに調整した。
次いでこの希塩酸Cr溶液を陽イオン交換樹脂
を使用して精製した。陽イオン交換樹脂としては
強酸性カチオン交換樹脂を使用した。カラムは直
径２cm、高さ19cmであり溶液の流速は4.8c.c.／
min、液温は10℃に保持して処理した。
処理後の精製塩化クロム溶液の不純物の割合を
表３に示す。不純物濃度はCr100ｇ当りで表示し
た。[Table] Heat the Cr stock solution after MIBK extraction to 100℃,
The remaining MIBK was removed. Next, this Cr stock solution was heated at 100°C and concentrated by evaporation to dryness until only crystal water remained. After cooling this concentrate, it was dissolved in 0.3N diluted hydrochloric acid at 10°C, and the hydrochloric acid concentration of the solution was adjusted to 0.3N. This dilute Cr hydrochloric acid solution was then purified using a cation exchange resin. A strongly acidic cation exchange resin was used as the cation exchange resin. The column has a diameter of 2 cm and a height of 19 cm, and the flow rate of the solution is 4.8 cc/
min, and the liquid temperature was maintained at 10°C. Table 3 shows the percentage of impurities in the purified chromium chloride solution after treatment. The impurity concentration was expressed per 100g of Cr.
【表】
また、Cr収率：ηCr（Cr原液中のCr量に対する
精製塩化クロム液中のCr量の割合）は83.5％であ
り、MIBK抽出液を何ら予備的処理することなく
陽イオン交換樹脂処理した場合の53.3％に比し
て、著しく高収率が達成された。
実施例 ２
表４に示す組成の高炭素フエロクロムを１mm以
下に粉砕し、粉砕フエロクロム中のクロム及び鉄
を塩素化するのに必要な理論当量の1.5倍の塩酸
（濃度10N）を加え、110℃の温度で60分間溶解抽
出した。[Table] In addition, the Cr yield: ηCr (ratio of the amount of Cr in the purified chromium chloride solution to the amount of Cr in the Cr stock solution) was 83.5%. A significantly higher yield was achieved compared to 53.3% when treated. Example 2 High-carbon ferrochrome having the composition shown in Table 4 was ground to 1 mm or less, and 1.5 times the theoretical equivalent of hydrochloric acid (concentration 10N) required to chlorinate the chromium and iron in the ground ferrochrome was added, and the mixture was heated at 110°C. The mixture was dissolved and extracted for 60 minutes at a temperature of .
【表】
冷却後、未溶解残渣を過し液中に塩素ガス
を吹込んで鉄イオンを酸化し、３価の鉄イオンと
した。過剰溶解酸素をエアレーシヨンにより除去
した後、MIBKを抽出液として処理し鉄分を除去
した。MIBK抽出条件は実施例１と同一条件で行
つた。
MIBK抽出処理後のCr原液の不純物の割合を
表５に示す。[Table] After cooling, the undissolved residue was filtered and chlorine gas was blown into the liquid to oxidize iron ions to trivalent iron ions. After removing excess dissolved oxygen by aeration, MIBK was treated as an extract to remove iron. The MIBK extraction conditions were the same as in Example 1. Table 5 shows the proportion of impurities in the Cr stock solution after the MIBK extraction process.
【表】
MIBK抽出後のCr原液を100℃に加熱し、溶解
残存しているMIBKを除去した。
次にこのCr原液を120℃に加熱し、結晶水のみ
が残る程度まで蒸発乾固させ濃縮した。原液がシ
ロツプ状になつたら冷却し結晶させた。
次にこの結晶の２分の１容量の冷水を加えて溶
解して過した後、寒剤で冷却しながら塩化水素
を吹込み飽和させた。３時間そのまま放置したの
ち手早く吸引過した。得られた液を10℃以下
の冷水を使用して0.2Nの塩酸濃度に調整した。
以上のごとく精製処理した0.2Nの希塩酸Cr溶
液を陽イオン交換樹脂を使用して精製した。陽イ
オン交換樹脂処理は実施例１の場合と同様な条件
でおこなつた。
処理後の精製塩化クロム溶液の不純物の割合を
表６に示す。[Table] The Cr stock solution after MIBK extraction was heated to 100°C to remove the remaining dissolved MIBK. Next, this Cr stock solution was heated to 120°C and concentrated by evaporation to dryness to the extent that only water of crystallization remained. When the stock solution became syrupy, it was cooled and crystallized. Next, 1/2 volume of cold water was added to the crystals to dissolve and filter them, and hydrogen chloride was blown into the crystals while cooling with a cryogen to saturate the crystals. After leaving it as it was for 3 hours, it was quickly aspirated. The resulting liquid was adjusted to a hydrochloric acid concentration of 0.2N using cold water at 10°C or lower. The 0.2N diluted hydrochloric acid Cr solution purified as described above was purified using a cation exchange resin. The cation exchange resin treatment was carried out under the same conditions as in Example 1. Table 6 shows the percentage of impurities in the purified chromium chloride solution after treatment.
【表】
また、Cr収率：ηCrは85.3％であり、MIBK抽
出液を何ら予備的処理をしないで陽イオン交換樹
脂処理した場合の55.3％に比して著しく高収率と
なり、一段と高品質のものが得られた。
（発明の効果）
本発明によればきわめて純度の高い塩化クロム
の製造が可能であり、本発明により得られた高純
度塩化クロムは、高級緑色顔料、釉薬、あるいは
印刷用インキの着色剤原料として使用される酸化
クロムの原料として使用可能である。また高純度
金属クロムの原料として使用する酸化クロムとし
ても有用である。さらにレドツクス電池の電解液
としての利用価値も広がつてくる。
一方、本発明の第二の発明であるフエロクロム
またはクロム鉱石還元焼結ペレツトを使用する方
法は原料が安価で豊富に存在するため、高純度塩
化クロムを安価に得られる利点がある。[Table] In addition, Cr yield: ηCr is 85.3%, which is significantly higher than 55.3% when MIBK extract is treated with cation exchange resin without any preliminary treatment, resulting in even higher quality. I got something like this. (Effects of the Invention) According to the present invention, it is possible to produce extremely pure chromium chloride, and the high-purity chromium chloride obtained by the present invention can be used as a colorant raw material for high-grade green pigments, glazes, or printing inks. It can be used as a raw material for the chromium oxide used. It is also useful as chromium oxide, which is used as a raw material for high-purity metallic chromium. Furthermore, the value of its use as an electrolyte in redox batteries will expand. On the other hand, the method of using ferrochrome or chromium ore reduced sintered pellets, which is the second invention of the present invention, has the advantage that high purity chromium chloride can be obtained at low cost because the raw materials are inexpensive and abundant.
第１図はフエロクロムまたはクロム鉱石還元焼
結ペレツトを出発原料とした場合の本発明による
塩化クロムの製造方法を説明する工程図である。
FIG. 1 is a process diagram illustrating the method for producing chromium chloride according to the present invention when ferrochrome or chromium ore reduced sintered pellets are used as the starting material.
Claims (1)
脂を使用して除去して塩化クロムを製造する方法
において、塩化クロム溶液を250℃以下で結晶が
晶出する程度に加熱濃縮した後、該濃縮物を１規
定以下の希塩酸で溶解した溶液を、15℃以下の温
度で陽イオン交換樹脂で処理することを特徴とす
る塩化クロムの製造方法。 ２ フエロクロム又はクロム鉱石還元焼結ペレツ
トの粉末を塩酸で溶解抽出し、該抽出液中に含ま
れる鉄イオンを３価の鉄イオンに酸化した後、メ
チルイソブチルケトン（MIBK）と接触させて塩
化鉄を抽出分離し、次いで該鉄分を除去した塩化
クロム溶液を、250℃以下で結晶が晶出する程度
に加熱濃縮した後、該濃縮物を１規定以下の希塩
酸で溶解した溶液を、15℃以下の温度で陽イオン
交換樹脂で処理することを特徴とする塩化クロム
の製造方法。[Claims] 1. A method for producing chromium chloride by removing impurities in a chromium chloride solution using a cation exchange resin, in which the chromium chloride solution is heated and concentrated at 250°C or below to the extent that crystals form. A method for producing chromium chloride, which comprises treating a solution obtained by dissolving the concentrate in dilute hydrochloric acid of 1N or less with a cation exchange resin at a temperature of 15°C or less. 2. Dissolve and extract the powder of ferrochrome or chromium ore reduced sintered pellets with hydrochloric acid, oxidize the iron ions contained in the extract to trivalent iron ions, and then contact with methyl isobutyl ketone (MIBK) to form iron chloride. After extracting and separating the chromium chloride solution from which the iron content has been removed, the chromium chloride solution is heated and concentrated at a temperature below 250°C to the extent that crystals form.Then, a solution obtained by dissolving the concentrate in dilute hydrochloric acid below 1N is heated at a temperature below 15°C. A method for producing chromium chloride, comprising treating it with a cation exchange resin at a temperature of .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60216137A JPS6278117A (en) | 1985-10-01 | 1985-10-01 | Production of chromium chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60216137A JPS6278117A (en) | 1985-10-01 | 1985-10-01 | Production of chromium chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6278117A JPS6278117A (en) | 1987-04-10 |
| JPH0249254B2 true JPH0249254B2 (en) | 1990-10-29 |
Family
ID=16683844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60216137A Granted JPS6278117A (en) | 1985-10-01 | 1985-10-01 | Production of chromium chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6278117A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130280A (en) * | 2013-03-25 | 2013-06-05 | 国药集团化学试剂有限公司 | Method for improving quality of industrial chromic chloride |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5009493B2 (en) * | 2003-12-10 | 2012-08-22 | 日本化学工業株式会社 | Chromium chloride aqueous solution and method for producing the same |
| US7641721B2 (en) | 2003-12-10 | 2010-01-05 | Nippon Chemical Industrial Co., Ltd. | Aqueous solution of chromium salt and method for producing same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5111093A (en) * | 1974-07-19 | 1976-01-28 | Tetsukosha Kk | Kuromumetsuki suratsujikara jukaseibuno kaishusuru hoho |
-
1985
- 1985-10-01 JP JP60216137A patent/JPS6278117A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5111093A (en) * | 1974-07-19 | 1976-01-28 | Tetsukosha Kk | Kuromumetsuki suratsujikara jukaseibuno kaishusuru hoho |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130280A (en) * | 2013-03-25 | 2013-06-05 | 国药集团化学试剂有限公司 | Method for improving quality of industrial chromic chloride |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6278117A (en) | 1987-04-10 |
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