JPH0288421A - Production of ammonium alum - Google Patents
Production of ammonium alumInfo
- Publication number
- JPH0288421A JPH0288421A JP63240529A JP24052988A JPH0288421A JP H0288421 A JPH0288421 A JP H0288421A JP 63240529 A JP63240529 A JP 63240529A JP 24052988 A JP24052988 A JP 24052988A JP H0288421 A JPH0288421 A JP H0288421A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- oxalic acid
- ammonium
- ammonium alum
- complex
- 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
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 title claims abstract description 36
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 title claims abstract 6
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 102
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 33
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000002378 acidificating effect Effects 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000002699 waste material Substances 0.000 claims abstract description 8
- 239000007983 Tris buffer Substances 0.000 claims abstract description 5
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 12
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 7
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 4
- 239000003990 capacitor Substances 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 2
- 150000004684 trihydrates Chemical class 0.000 abstract description 2
- 150000003863 ammonium salts Chemical class 0.000 abstract 1
- WZUKKIPWIPZMAS-UHFFFAOYSA-K Ammonium alum Chemical compound [NH4+].O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WZUKKIPWIPZMAS-UHFFFAOYSA-K 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 229940037003 alum Drugs 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- -1 nitrate ions Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 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
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000004691 decahydrates Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、アンモニウムミョウバンの製造法に関し、
より詳細には、酸性アルミニウム水溶液からアルミニウ
ムのシュウ酸錯体を経て、アンモニウムミョウバンを製
造する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] This invention relates to a method for producing ammonium alum,
More specifically, the present invention relates to a method for producing ammonium alum from an acidic aluminum aqueous solution via an aluminum oxalate complex.
アンモニウムミョウバンの製造法には、従来、硫酸アル
ミニウムと硫酸アンモニウムを加熱下で水に溶解した後
、これを冷却してアンモニウムミョウバンの結晶を得る
方法、天然鉱物に含まれるアンモニウムミョウバンを抽
出して、アンモニウムミョウバンの結晶を得る方法など
がある。Conventionally, methods for producing ammonium alum include dissolving aluminum sulfate and ammonium sulfate in water under heating and then cooling the solution to obtain ammonium alum crystals; or extracting ammonium alum contained in natural minerals to obtain ammonium alum. There are many ways to obtain alum crystals.
しかしながら、従来のアンモニウムミョウバンの製造法
では、原料に不純物が多く含まれている場合、その不純
物がそのまま製造されたアンモニウムミョウバン中に入
り込み、不純物を除去する精製が困難であり、追加の精
製工程は、製造コストを高くする。However, in the conventional method for producing ammonium alum, if the raw material contains many impurities, those impurities will enter the produced ammonium alum as they are, making it difficult to purify the impurities and require an additional purification step. , increasing manufacturing costs.
この発明は、上述の背景に基づきなされたものであり、
その目的とするところは、共存する不純鞠が多い場合で
も、純度の高いアンモニウムミョウバンを経済的に製造
する方法を提供することにある。This invention was made based on the above background,
The purpose is to provide a method for economically producing ammonium alum with high purity even when there are many impurities present.
本発明者らは、上述の課題解決のために、種々の試験研
究を行なった結果、中間水としてアルミニウムのシ、１
つ酸錯体を生成してアンモニウムミョウバンを製造すれ
ば、この発明の目的達成に有効であることを見出だし、
この発明を完成するに至った。In order to solve the above-mentioned problems, the present inventors conducted various tests and research, and as a result, they found that aluminum sheets, 1
They have discovered that producing ammonium alum by producing an acid complex is effective in achieving the object of the present invention,
This invention was completed.
すなわち、この発明によるアンモニウムミョウバンの製
造方法は、下記（イ）および（ロ）の工程を含むことを
特徴とするものである。That is, the method for producing ammonium alum according to the present invention is characterized by including the following steps (a) and (b).
（イ）酸性アルミニウム水溶液からアルミニウムのシュ
ウ酸錯体を生成させる］１程。(B) Generating an aluminum oxalate complex from an acidic aluminum aqueous solution] Step 1.
（ロ）そのシュウ酸錯体に硫酸を反応させて、アンモニ
ウムミョウバンを製造し、遊離したシュウ酸を回収する
工程。(b) A step of reacting the oxalic acid complex with sulfuric acid to produce ammonium alum and recovering liberated oxalic acid.
この発明の好ましい態様において、酸性アルミニウム水
溶液が酸性アルミニウム含有廃液である。In a preferred embodiment of this invention, the acidic aluminum aqueous solution is an acidic aluminum-containing waste liquid.
この発明の好ましい態様において、上述のシュウ酸錯体
とし゛Ｃ，トリス（オキサラト）アルミニウム（Ｉ［Ｉ
）酸アンモニウムを用いることができる。In a preferred embodiment of the present invention, the above-mentioned oxalate complex and C, tris(oxalato) aluminum (I[I
) acid can be used.
以下、この発明をより詳細に説明する。This invention will be explained in more detail below.
この発明において用いることができる酸性アルミニウム
水溶液は、塩化物イオン、硫酸イオン、リン酸イオン、
硝酸イオン、またはこｉｌらの混合イオンを含む酸性ア
ルミニウム水溶液である。このような酸性アルミニウム
水溶液として、例えば、アルミニウム電解コンデンサ製
造に際して排出されるエツチング廃液を用いることがで
きる。この廃液は、塩化物イオン、硫酸イオン、リン酸
イオン、硝酸イオンなどを含む強酸性アルミニウム水溶
液である。The acidic aluminum aqueous solution that can be used in this invention includes chloride ions, sulfate ions, phosphate ions,
This is an acidic aluminum aqueous solution containing nitrate ions or a mixture of these ions. As such an acidic aluminum aqueous solution, for example, etching waste liquid discharged during the manufacture of aluminum electrolytic capacitors can be used. This waste liquid is a strongly acidic aluminum aqueous solution containing chloride ions, sulfate ions, phosphate ions, nitrate ions, etc.
この発明によるアンモニウムミョウバンの製造方法の（
イ）工程において、酸性アルミニウム水溶液からアルミ
ニウムのシュウ酸錯体を生成させる。この工程は、通常
の方法により実施することができる。例えば、酸性アル
ミニウム水溶液を塩基性物質で中和して水酸化アルミニ
ウムを生成させ、ついで得られた水酸化アルミニウムを
シュウ酸とシュウ酸アンモニウムとの混液に溶解させ、
これを′１ａ縮してアルミニウムのシュウ酸錯体を生成
させることができる。The method for producing ammonium alum according to the present invention (
In the step b), an aluminum oxalate complex is produced from an acidic aluminum aqueous solution. This step can be carried out by a conventional method. For example, an acidic aluminum aqueous solution is neutralized with a basic substance to generate aluminum hydroxide, and then the obtained aluminum hydroxide is dissolved in a mixed solution of oxalic acid and ammonium oxalate.
This can be reduced by '1a to produce an aluminum oxalate complex.
この態様で用いられる塩基性物質としては、水酸化ナト
リウム、水酸化カリウム、炭酸ナトリウム、アンモニア
などがあり、好ましくはアンモニアである。塩基性：肉
質の添加星は、酸性アルミニウム溶液の濃度、酸性度な
どにより適宜変更することができる。Basic substances used in this embodiment include sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and the like, with ammonia being preferred. Basicity: The addition star of flesh quality can be changed as appropriate depending on the concentration of acidic aluminum solution, acidity, etc.
中和して沈澱した水酸化アルミニウムは、好ま１、＜は
沢別して水洗する。得られた水酸化アルミニウムをシュ
ウ酸とシュウ酸アンモニウムの混液に溶解させる。未溶
解の水酸化アルミニウムがある場合、沢別しておくこと
が好ましい。水酸化アルミニウムのシュウ酸とシュウ酸
アンモニウムとの混液への溶解は、例えば、８０°Ｃの
湯浴上で加熱して行なわれる。次いで、水酸化アルミニ
ウムを溶解させた混液を濃縮してアルミニウムのシュウ
酸錯体を生成させる。この濃縮は、例えば、加熱して溶
媒の水を蒸発除去して行なうことができる。濃縮度は、
元の混液の濃度により異なるが、例えば、体積で約１
／’ Ｌ Ｏ程度である。アルミニウムのシュウ酸錯体
の晶析は、濃縮のほか、冷却により促進させることがで
きる。The aluminum hydroxide precipitated by neutralization is preferably separated and washed with water. The obtained aluminum hydroxide is dissolved in a mixed solution of oxalic acid and ammonium oxalate. If there is undissolved aluminum hydroxide, it is preferable to separate it. Dissolution of aluminum hydroxide in a mixed solution of oxalic acid and ammonium oxalate is carried out by heating on a water bath at 80° C., for example. Next, the mixed solution in which aluminum hydroxide is dissolved is concentrated to produce an aluminum oxalate complex. This concentration can be performed, for example, by heating to evaporate and remove water as a solvent. The concentration is
Although it varies depending on the concentration of the original mixed liquid, for example, approximately 1 in volume
/' It is about LO. Crystallization of the aluminum oxalate complex can be accelerated by cooling as well as concentration.
晶析するアルミニウムのシュウ酸錯体は、生成条件によ
り種々の組成のものが得られるが、例えば、
（ＮＨ４） ３ ［Ａ ｌ （Ｃ２０４Ｌ３ ］・３Ｈ
２０で表されるトリス（オキサラト）アルミニウム（Ｉ
［Ｉ）酸アンモニウムの３水塩である。The aluminum oxalate complex that crystallizes can have various compositions depending on the formation conditions, but for example, (NH4) 3 [A l (C204L3 ] ・3H
Tris(oxalato)aluminum (I
[I) Ammonium acid trihydrate.
この発明の（ロ）工程において、得られたシュウ酸錯体
に硫酸を反応させてアンモニウムミョウバンを製造する
。反応液は、撹拌しながら、例えば、７℃に冷却する。In step (b) of this invention, ammonium alum is produced by reacting the obtained oxalic acid complex with sulfuric acid. The reaction solution is cooled to, for example, 7° C. while being stirred.
冷却に伴ないシュウ酸が遊離するので、これを枦刑する
。シュウ酸のン戸別後に、炉液を放置するとアンモニウ
ムミョウバンが析出する。アンモニウムミョウバン中に
混入したシュウ酸は、エタノールで還流すると、エタノ
ールにシュウ酸が全て溶解する。エタノールを蒸留して
回収し、また後述のようにシュウ酸も再利用することが
できる。添加する硫酸量は、例えば、ミョウバン生成に
必要な理論量と等量では、ミョウバン７０％とシュウ酸
８７％が析出し、理論量の０．８０倍では、ミョウバン
４０％とシュウ酸７６％が析出し、理論量の１．２倍で
は、ミョウバン７３％とシュウ酸９０％が析出する。こ
の発明において、この工程で得られたシュウ酸は、再び
シュウ酸錯体合成の（イ）工程で再利用される。As oxalic acid is liberated as it cools, this is removed. If the furnace solution is left to stand after the oxalic acid is poured into each house, ammonium alum will precipitate out. When the oxalic acid mixed in ammonium alum is refluxed with ethanol, all of the oxalic acid is dissolved in the ethanol. The ethanol can be recovered by distillation, and the oxalic acid can also be recycled as described below. For example, if the amount of sulfuric acid to be added is equal to the theoretical amount required for alum production, 70% of alum and 87% of oxalic acid will precipitate, and if the amount is 0.80 times the theoretical amount, 40% of alum and 76% of oxalic acid will precipitate. At 1.2 times the theoretical amount, 73% of alum and 90% of oxalic acid are precipitated. In this invention, the oxalic acid obtained in this step is reused in step (a) of oxalic acid complex synthesis.
この発明のアンモニウムミョウバンの製造方法は、次の
ような反応・作用メカニズムによって進行すると考えら
れる。The method for producing ammonium alum of the present invention is thought to proceed through the following reaction/action mechanism.
酸性アルミニウム水溶液をアンモニアで中和すると、水
酸化アルミニウムが生成する（１式）。When an acidic aluminum aqueous solution is neutralized with ammonia, aluminum hydroxide is produced (formula 1).
Ａ１３”十３ＮＨＯＨ→ Ａｔ（ＯＨ）３ ↓＋
３ＮＨ４＋
・・・■水酸化アルミニウムにシュウ酸とシュウ酸
アンモニウムを反応させると、１〜リス（オキサラト）
アルミニウム（Ｉｎ ＞ ′ｆｉｔｉアンモニウムが生
成する（■式）。A13” 13NHOH→ At(OH)3 ↓+
3NH4+
... ■ When aluminum hydroxide is reacted with oxalic acid and ammonium oxalate, 1 to lith (oxalato)
Aluminum (In >'fiti) Ammonium is produced (Formula ■).
２Ａ Ｉ （ＯＨ） ３ ＋ ３ （Ｎ）（４） ２
Ｃ２０４十 ３Ｈ２Ｃ２０４
−２（ＮＨ４）３ ［Ａ ｌ （Ｃ２０４）
３ ］ ・ ３■］２０
・・・■トリス（オキサラト）アルミニウム（Ｉ［Ｉ）
酸アンモニウムに硫酸を作用させると、アンモニウムミ
ョウバンが生成する（■式）。2A I (OH) 3 + 3 (N) (4) 2
C204 10 3H2C204 -2(NH4)3 [A l (C204)
3] ・3■]20
...■ Tris(oxalato)aluminum (I [I)
When ammonium acid is reacted with sulfuric acid, ammonium alum is produced (Formula ■).
（ＮＨ，ｓ ＞ ３ ［Ａ Ｉ （Ｃ２０４） ３ ］
・３Ｈ２０＋ ３ Ｈ２ＳＯ４＋ ９Ｈ２０→
（ＮＨ４） Ａ Ｉ （Ｓｏ、１ ） ２・１２Ｈ２
゜十 ３Ｈ２Ｃ２０，＋ （Ｎｌ−１４）２ＳＯ
４・・・■
溶解変の差を利用して、まずシーＬつ酸を遊離させて、
回収する。次いで、アンモニウムミョウバンを析出させ
る。副生成物であるｇＬ酸アンモニウムは、別の酸性ア
ルミニウム溶液と反応させてなどして、アンモニウムミ
ョウバンの合成に用いることができる。(NH,s > 3 [A I (C204) 3 ]
・3H20+ 3 H2SO4+ 9H20→
(NH4) A I (So, 1) 2・12H2
゜10 3H2C20, + (Nl-14)2SO
4...■ Utilizing the difference in solubility, first liberate the citric acid,
to recover. Next, ammonium alum is precipitated. The by-product ammonium gLate can be used in the synthesis of ammonium alum, such as by reacting with another acidic aluminum solution.
上述の反応は、定量的に進行する。したがって、回収率
が高い。The reaction described above proceeds quantitatively. Therefore, the recovery rate is high.
また、中間体としてアルミニウムのシュウ酸錯体が生成
され、この大きな負の電荷を持つために、再結晶過程で
他のアニオン性の不純物から容易に分離精製することが
できる。通常の分離で除去できないリン酸イオンをもこ
の発明の方法では、後述する実施例で実証されるように
、１回の操作で検出限界以下に下げることができる。Furthermore, an oxalate complex of aluminum is produced as an intermediate, and because it has a large negative charge, it can be easily separated and purified from other anionic impurities during the recrystallization process. According to the method of the present invention, even phosphate ions that cannot be removed by conventional separation can be reduced to below the detection limit in a single operation, as will be demonstrated in the Examples described below.
以下、この発明を実施例によって説明する。 This invention will be explained below with reference to Examples.
アルミニウム電解コンデンサ製造に際して排出されるア
ルミニウムイオン濃度７８ｇ／ｌのエツチング廃液３４
５ｍ１（アルミニウムイオン１モル相当）に水１リット
ルを加えて希釈した。この溶液に、２８％アンモニア水
２４６ｍ１を水２リットルに希釈した溶液を加えて、水
酸化アルミニウムの沈澱を生成さぜな。この沈澱を濾過
して水洗した。Etching waste liquid with an aluminum ion concentration of 78 g/l discharged during the manufacture of aluminum electrolytic capacitors 34
1 liter of water was added to 5 ml (equivalent to 1 mole of aluminum ion) to dilute it. A solution prepared by diluting 246 ml of 28% aqueous ammonia in 2 liters of water is added to this solution to form a precipitate of aluminum hydroxide. This precipitate was filtered and washed with water.
次いで、シュウ酸アンモニウム２１３ｇ（１，５モル）
とシュウ酸１８９ｇを水４ワットルに溶解させ、この溶
液に上記水酸（ヒアルミニラムを全量加えた。Then 213 g (1.5 mol) of ammonium oxalate
and 189 g of oxalic acid were dissolved in 4 watts of water, and the entire amount of the above hydric acid (hyaluminum) was added to this solution.
８０°Ｃの湯洛北で溶解させ、約３０分後に未反応水酸
化アルミニウム沈澱を枦別した。得られた涙液３．９リ
ットルを約１リツトルに濃縮し、冷却後に９５９６エタ
ノール１．５リツトルを加えて沈澱７５ｇを析出させた
。沈澱の枦別最に、更にン農１？ｉを続（す、；農看市
＾が約４００ｍ１となったところで、９５９６工タノー
ル６００ｍ１を加えて、冷却した。その結果、シュウ酸
錯体の結晶２２０ｇが析出した。この結晶は、トリス（
オキサラｌ−）アルミニウム（ＩＩＩ）酸アンモニウム
の３水塩であった。The mixture was dissolved in a hot water bath at 80°C, and unreacted aluminum hydroxide precipitate was separated after about 30 minutes. The obtained 3.9 liters of tear fluid was concentrated to about 1 liter, and after cooling, 1.5 liters of 9596 ethanol was added to precipitate 75 g. At the end of the precipitation, is it even more? Continuing with step i, when the volume of agricultural chemicals became approximately 400 ml, 600 ml of 9596 ethanol was added and cooled. As a result, 220 g of oxalic acid complex crystals were precipitated.
It was the trihydrate salt of ammonium oxal-1-)aluminum(III) acid.
ここで得られたシュウ酸錯体中のリン酸イオンの分析を
モリブデンブルー法で実施した。その結果、その濃度は
検出限界以下であった。Phosphate ions in the oxalic acid complex obtained here were analyzed using the molybdenum blue method. As a result, the concentration was below the detection limit.
次いで、得られたｌへリス（オキサラト）アルミニウム
（Ｉｌｌ）酸アンモニウムの３水塙２００ ｇを水５０
０ｍ１に溶かしこの溶液を７°Ｃに冷却し撹拌しながら
硫酸を添力１山た。アンモニウムミョウバン生成のため
の理論量の２倍までの硫酸を加えると、初めにシュウ酸
が析出し、炉別後に放置するとアンモニウムミョウバン
が析出した。アンモニウムミョウバンに混じって析出し
なシュウ酸は、エタノールで還流することにより全てエ
タノール中に溶解した。エタノールは蒸留により回収し
た。Then, 200 g of the obtained ammonium heli(oxalato)aluminum(Ill)ate was added to 50 g of water.
The solution was cooled to 7°C, and one mound of sulfuric acid was added while stirring. When sulfuric acid was added in an amount up to twice the theoretical amount for producing ammonium alum, oxalic acid precipitated first, and when left after furnace separation, ammonium alum precipitated. All of the oxalic acid that was mixed with ammonium alum and precipitated was dissolved in ethanol by refluxing with ethanol. Ethanol was recovered by distillation.
アンモニウムミョウバン生成のための理論量との比とし
て表した硫酸添加量と、シュウ酸およびアンモニウムミ
ョウバンの回収率との関係を、第１図に示す。The relationship between the amount of sulfuric acid added, expressed as a ratio to the theoretical amount for producing ammonium alum, and the recovery of oxalic acid and ammonium alum is shown in FIG.
る。Ru.
この発明の製造方法により、次の効果を得ることができ
る。By the manufacturing method of the present invention, the following effects can be obtained.
請求項第１項記載の製造方法により、廃液のような共存
不純物が多い場合でも、純度の高いアンモニウムミョウ
バンを経済的に製造することができる。According to the production method described in claim 1, ammonium alum with high purity can be produced economically even when there are many coexisting impurities such as waste liquid.
請求項第１項記載の製造方法により、シュウ酸錯体の合
成に用いたシュウ酸を、容易に回収でき、しかも溶媒と
して用いたエタノールも回収が可能であるなめ、経済的
である。The production method according to claim 1 is economical because the oxalic acid used in the synthesis of the oxalic acid complex can be easily recovered, and the ethanol used as a solvent can also be recovered.
請求項第１項記載の製造方法において、得られたアンモ
ニウムミョウバンが再結晶により容易に純度を高めるこ
とができ、高純度アルミナ製造に有利である。In the production method according to claim 1, the purity of the obtained ammonium alum can be easily increased by recrystallization, which is advantageous for producing high-purity alumina.
請求項第２項記載の製造方法において、出発原料として
酸性アルミニウム廃液を用いるので、安価に製造するこ
とができると共に、資源保護の観点から回収再利用に資
することができる。In the manufacturing method according to claim 2, since acidic aluminum waste liquid is used as the starting material, it can be manufactured at low cost and can be recovered and reused from the viewpoint of resource conservation.
第１図は、実施例における、アンモニウムミョウバン生
成の理論量との比として表したｆｉｆ、ｌｕｊ、’Ｅ、
加量と、シュウ酸および°アンモニウムミョウバンの回
収率との関係を示す図である。
図中の記号、ＯＸは、シュウ酸２水塩、Ａｌｕｍは、ア
ンモニウムミョウバン（１２水塩）を表す。FIG. 1 shows fif, luj, 'E, expressed as a ratio to the theoretical amount of ammonium alum production in Examples.
FIG. 3 is a diagram showing the relationship between the amount added and the recovery rate of oxalic acid and ammonium alum. The symbol OX in the figure represents oxalic acid dihydrate, and Alum represents ammonium alum (decahydrate).
Claims (3)
ムミョウバンの製造方法。 （イ）酸性アルミニウム水溶液からアルミニウムのシュ
ウ酸錯体を生成させる工程。 （ロ）前記シュウ酸錯体に硫酸を反応させて、アンモニ
ウムミョウバンを製造し、遊離したシュウ酸を回収する
工程。(1) A method for producing ammonium alum including the following steps (a) and (b). (a) A step of producing an aluminum oxalate complex from an acidic aluminum aqueous solution. (b) A step of reacting the oxalic acid complex with sulfuric acid to produce ammonium alum and recovering liberated oxalic acid.
廃液である請求項（１）記載の製造方法。(2) The manufacturing method according to claim (1), wherein the acidic aluminum aqueous solution is an acidic aluminum-containing waste liquid.
ミニウム（III）酸アンモニウムである請求項（１）ま
たは（２）記載の製造方法。(3) The manufacturing method according to claim 1 or 2, wherein the oxalate complex is ammonium tris(oxalato)aluminum(III) acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63240529A JPH0288421A (en) | 1988-09-26 | 1988-09-26 | Production of ammonium alum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63240529A JPH0288421A (en) | 1988-09-26 | 1988-09-26 | Production of ammonium alum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0288421A true JPH0288421A (en) | 1990-03-28 |
| JPH0455977B2 JPH0455977B2 (en) | 1992-09-07 |
Family
ID=17060884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63240529A Granted JPH0288421A (en) | 1988-09-26 | 1988-09-26 | Production of ammonium alum |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0288421A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126735A (en) * | 2011-01-21 | 2011-07-20 | 万载县金洲化工厂 | Method for extracting tschermigite from coal gangue or stone coal |
| CN102815737A (en) * | 2012-08-14 | 2012-12-12 | 衡阳市建衡实业有限公司 | New method for producing potassium alum |
| CN106495193A (en) * | 2016-10-31 | 2017-03-15 | 航天推进技术研究院 | Based on the method that ethanol auxiliary agent extracts aluminum oxide in flyash using ammonium sulfate method |
-
1988
- 1988-09-26 JP JP63240529A patent/JPH0288421A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126735A (en) * | 2011-01-21 | 2011-07-20 | 万载县金洲化工厂 | Method for extracting tschermigite from coal gangue or stone coal |
| CN102815737A (en) * | 2012-08-14 | 2012-12-12 | 衡阳市建衡实业有限公司 | New method for producing potassium alum |
| CN106495193A (en) * | 2016-10-31 | 2017-03-15 | 航天推进技术研究院 | Based on the method that ethanol auxiliary agent extracts aluminum oxide in flyash using ammonium sulfate method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0455977B2 (en) | 1992-09-07 |
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