JPS6212176B2 - - Google Patents
Info
- Publication number
- JPS6212176B2 JPS6212176B2 JP17004983A JP17004983A JPS6212176B2 JP S6212176 B2 JPS6212176 B2 JP S6212176B2 JP 17004983 A JP17004983 A JP 17004983A JP 17004983 A JP17004983 A JP 17004983A JP S6212176 B2 JPS6212176 B2 JP S6212176B2
- Authority
- JP
- Japan
- Prior art keywords
- chromium
- alum
- sulfate
- solution
- amount
- 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
Links
- 239000011651 chromium Substances 0.000 claims description 27
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 19
- 229910052804 chromium Inorganic materials 0.000 claims description 19
- 229940037003 alum Drugs 0.000 claims description 17
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 9
- 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 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は、クロム明ばんの製造方法に関し、更
に詳細には硫酸クロム（緑色ズルフア型）より紫
色のアクオ型クロム明ばんの結晶を製造すること
を特徴とするクロム明ばんの製造方法に関するも
のである。
通常、明ばんは各種あり、その用途も媒染剤、
皮なめし、水の清澄剤、食品加工、医薬等多岐に
亘つている。
ただ従来からある紫色のアクオ型明ばんを製造
する場合は、一般に緑色のズルフア型クロム明ん
を長時間（10日以上）静置したり、このクロム明
ばんに種子を添加し徐々にアクオ型のクロム明ば
んを結晶化させている。又最近は強力な還元剤の
添加によつて結晶化は若干促進されたがそれでも
まだ数日を要しており、液中に残留するクロム量
が多いため収率が低く非能率的であつた。
本発明は、かかる結晶化を速めるために創案し
たものであり、その要旨は予め脱鉄した硫酸塩を
含有するクロム明ばん液を陰極液とし、H2SO4を
陽極液として一定電流密度の基に隔膜を保持する
電解槽でもつて酸化電位がOmvに達するまで還
元電解した後、該還元電解溶液に亜硫酸塩若しく
はSO2ガスを通じて紫色のアクオ型クロム明ばん
を析出させることを特徴とするクロム明ばんの製
造方法であり、無害なクロム明ばんを短時間に液
中から効率よく結晶化させるようにしている。
以下、本発明方法について詳述する。
まず、フエロクロム又は水酸化クロムを硫酸
（H2SO4）で溶出しクロム（Cr）と鉄（Fe）を硫
酸塩として溶出させ、この溶液のFe量に対し略
６倍当量の硫酸アンモニア（（NH4）2SO4）を添加
し充分反応させた後冷凍機等で５℃まで急冷して
鉄イオン（Fe〓）を硫酸第一鉄アンモンとして
結晶化させ析出させて脱鉄を行う。脱鉄した硫酸
クロム液には、脱鉄の際に添加した硫酸塩が過剰
に添加されているため、クロム明ばんを形成させ
るに充分な量の場合は追加する必要は無いが、
Cr（OH）3等Fe含有量が少なく硫酸塩の添加量が
少なくてクロム明ばんの形成に不足する場合は
1.1当量以上になる量の硫酸塩を補充する。
以上のようにして脱鉄した硫酸クロム液は電解
槽の陰極室に又隔膜を保持せる陽極室には／Ｎ―
H2SO4液を入れ通電する。
電解の際の電極密度は0.1A／ｄm2以上20A／ｄ
m2までが有効であるが、特に1.0A／ｄm2〜
5.0A／ｄm2の間がより好ましい。又、電解液中
のクロム（Cr）濃度は10〜100ｇ／であり、三
価クロム（Cr3+）、六価クロム（Cr6+）又は両者
の混合液の場合も、クロム濃度は同一である。
更に、電解時間は、酸化電位がOmvになるま
でとし、所定の電位に達した場合、電解液に
NH4HSO3、又はNaHSO3等の亜硫酸塩又はSO2ガ
スを通じ、SO2量0.05〜2.0ｇ／望ましくは0.1
〜1.0ｇ／になるように添加して紫色のクロム
明ばんを短時間に晶析させる。
次に、本発明の実施例を具体的に説明する。
実施例 １
予め脱鉄した硫酸クロム液を溶量2.0の電解
槽の陰極室に1.2入れ、陽極室には1N―H2SO4
液を0.3入れて、電流密度4A／ｄm2、常温にお
いて、陽極板を１％Ag含有pb板、陰極板をステ
ン鋼板、硫酸クロム中のCrの濃度及びPHそれに
酸化電位をそれぞれ62.3ｇ／、0.5、＋850mvと
して通電し酸化電位が0mvに達するまで通電を継
続した。
（尚上記陽極室には隔膜を設けた）
酸化電位が0mvに達した後、NH4HSO3を0.1〜
2.0ml添加し16時間放置後紫色のクロム明ばん
（アンモニウムクロム明ばん）を過し固液分離
した。尚電解時間は略16時間であり、NH4HSO3
の添加量とクロム明ばん析出量との関係を、
NH4HSO3を５段階に変えて求めた結果が第１表
に示されている。
尚、上記せる脱鉄反応式及びクロム明ばんの生
成反応式を示すと、
脱鉄反応式(1)
FeSO4＋（NH4）2SO4＋6H2O
＝（NH4）2SO4・FeSO4・6H2O
クロム明ばんの生成反応式(2)
Cr2（SO4）3＋（NH4）2SO4＋24H2O
＝（NH4）2Cr2・（SO4）4・24H2O
クロム明ばん
The present invention relates to a method for producing chrome alum, and more particularly to a method for producing chrome alum, which is characterized by producing crystals of purple aquo-type chromium alum from chromium sulfate (green Zulfur type). be. Generally, there are various types of alum, and its uses are as a mordant,
It is used in a wide variety of fields, including leather tanning, water clarifiers, food processing, and pharmaceuticals. However, when manufacturing conventional purple Aquo-type alum, it is generally necessary to leave the green Zulfur-type chrome alum for a long time (10 days or more), or add seeds to this chrome alum and gradually produce the Aquo-type alum. chrome alum is crystallized. Recently, crystallization has been slightly accelerated by the addition of strong reducing agents, but it still takes several days, and the yield is low and inefficient due to the large amount of chromium remaining in the solution. . The present invention was devised to speed up such crystallization, and its gist is to use a chromium alum solution containing sulfate that has been deironated in advance as the catholyte and H 2 SO 4 as the anolyte at a constant current density. Chromium is characterized in that after reduction electrolysis is carried out in an electrolytic cell holding a diaphragm at the base until the oxidation potential reaches Omv, purple aquo-type chromium alum is deposited by passing sulfite or SO 2 gas into the reduced electrolytic solution. This is a method for producing alum that efficiently crystallizes harmless chromium alum from liquid in a short time. The method of the present invention will be described in detail below. First, ferrochrome or chromium hydroxide is eluted with sulfuric acid (H 2 SO 4 ), chromium (Cr) and iron (Fe) are eluted as sulfates, and ammonia sulfate ((( After adding NH 4 ) 2 SO 4 ) and causing a sufficient reaction, the mixture is rapidly cooled to 5° C. using a refrigerator or the like to crystallize and precipitate iron ions (Fe〓) as ferrous ammonium sulfate to remove iron. Since the deironated chromium sulfate solution contains an excess of sulfate added during deironation, there is no need to add it if the amount is sufficient to form chromium alum.
Cr(OH) 3 If the Fe content is low and the amount of sulfate added is insufficient to form chromium alum,
Replenish the amount of sulfate to 1.1 equivalents or more. The chromium sulfate solution deironated as described above is stored in the cathode chamber of the electrolytic cell and in the anode chamber that holds the diaphragm.
Add H 2 SO 4 solution and turn on electricity. Electrode density during electrolysis is 0.1A/ dm2 or more 20A/d
It is effective up to 1.0A/ dm2 , but especially up to 1.0A/ dm2 .
More preferably between 5.0 A/dm 2 . In addition, the chromium (Cr) concentration in the electrolyte is 10 to 100 g/, and the chromium concentration is the same in the case of trivalent chromium (Cr 3+ ), hexavalent chromium (Cr 6+ ), or a mixture of both. be. Furthermore, the electrolysis time is set until the oxidation potential reaches Omv, and when the specified potential is reached, the electrolyte is
Through sulfite such as NH 4 HSO 3 or NaHSO 3 or SO 2 gas, the amount of SO 2 is 0.05 to 2.0 g/preferably 0.1
It is added in an amount of ~1.0 g/ml to crystallize purple chrome alum in a short time. Next, examples of the present invention will be specifically described. Example 1 1.2 chromium sulfate solution, which had been deironated in advance, was put into the cathode chamber of an electrolytic cell with a solution volume of 2.0, and 1N-H 2 SO 4 was placed in the anode chamber.
At room temperature, the anode plate was a PB plate containing 1% Ag, the cathode plate was a stainless steel plate, and the concentration of Cr in chromium sulfate, pH, and oxidation potential were 62.3 g/, respectively. The current was applied at 0.5, +850mv, and the current was continued until the oxidation potential reached 0mV. (A diaphragm was provided in the anode chamber above.) After the oxidation potential reached 0 mv, NH 4 HSO 3 was added to the
After adding 2.0 ml and leaving it for 16 hours, the purple chrome alum (ammonium chrome alum) was filtered to separate solid and liquid. The electrolysis time was approximately 16 hours, and NH 4 HSO 3
The relationship between the amount of addition and the amount of chromium alum precipitation is
Table 1 shows the results obtained by changing NH 4 HSO 3 in five stages. The iron removal reaction equation and chromium alum production reaction equation shown above are as follows: Iron removal reaction equation (1) FeSO 4 + (NH 4 ) 2 SO 4 +6H 2 O = (NH 4 ) 2 SO 4・FeSO 4・6H 2 O Chromium alum production reaction equation (2) Cr 2 (SO 4 ) 3 + (NH 4 ) 2 SO 4 +24H 2 O = (NH 4 ) 2 Cr 2・(SO 4 ) 4・24H 2 O Chrome Alum
【表】
実施例 ２（従来法との比較例）
同一の硫酸クロム液を使つて従来法と本発明方
法についてクロム明ばん析出量の比較を行つた。
従来法
１ 原液をそのまま自然放置して結晶析出させ
る。
２ NH4HSO3を添加し放置して結晶析出させ
る。
３ 還元電解のみによる場合。
４ NH4HSO3を添加した後還元電解した。
本発明方法と上記４方法でもつて実験した結果
を第２表に示す。[Table] Example 2 (Comparative Example with Conventional Method) Using the same chromium sulfate solution, the amount of chromium alum precipitated was compared between the conventional method and the method of the present invention. Conventional method 1: Leave the stock solution as it is to allow crystals to precipitate. 2 Add NH 4 HSO 3 and leave to stand to precipitate crystals. 3 When using only reduction electrolysis. After adding 4 NH 4 HSO 3 , reduction electrolysis was performed. Table 2 shows the results of experiments conducted using the method of the present invention and the four methods described above.
【表】
即ち、第２表に示した如く、本発明方法によれ
ば、従来方法に比較して短時間の内に多量のクロ
ム明ばんを結晶化させて析出することができるも
のであり、設備もコンパクトになつて結晶化効率
を著しく向上させることができる等の優れた効果
を奏するものである。[Table] That is, as shown in Table 2, according to the method of the present invention, a large amount of chromium alum can be crystallized and precipitated in a shorter time compared to the conventional method. The equipment can also be made more compact and the crystallization efficiency can be significantly improved.
Claims (1)
液を陰極液とし、H2SO4を陽極液として一定電流
密度の基に隔膜を保持する電解槽でもつて酸化電
位がOmvに達するまで還元電解した後、該還元
電解溶液に亜硫酸塩若しくはSO2ガスを通じて紫
色のアクオ型クロム明ばんを析出させることを特
徴とするクロム明ばんの製造方法。1 Reduction electrolysis is carried out in an electrolytic cell in which a diaphragm is maintained at a constant current density with a chromium alum solution containing sulfate that has been previously deironated as the catholyte and H 2 SO 4 as the anolyte until the oxidation potential reaches Omv. and then passing sulfite or SO 2 gas into the reduced electrolytic solution to precipitate purple aquo-type chromium alum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17004983A JPS6060928A (en) | 1983-09-14 | 1983-09-14 | Manufacture of chrome alum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17004983A JPS6060928A (en) | 1983-09-14 | 1983-09-14 | Manufacture of chrome alum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6060928A JPS6060928A (en) | 1985-04-08 |
| JPS6212176B2 true JPS6212176B2 (en) | 1987-03-17 |
Family
ID=15897666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17004983A Granted JPS6060928A (en) | 1983-09-14 | 1983-09-14 | Manufacture of chrome alum |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6060928A (en) |
-
1983
- 1983-09-14 JP JP17004983A patent/JPS6060928A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6060928A (en) | 1985-04-08 |
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