JPS6183143A - Preparation of solution - Google Patents

Abstract

PURPOSE:To prepare a mixed solution acidified with oxalic acid, containing various metallic ions, and useful as a raw material for the synthesis of various ceramics, stably, economically, with simple operation, at high concentration, by reacting a metal with a solution containing metallic ion and acidified with oxalic acid. CONSTITUTION:An acidic solution acidified with oxalic acid and containing at least one kind of metallic ion, preferably the ion of a metal of the 4a or 5a group of the periodic table and forming a complex ion with oxalic acid, e.g. ions of Ti, Zr, Nb, Ta, etc., is made to react with at least one kind of metal such as Li, Na, K, Be, Mg, Ca, Sr, Ba, Mn, Sn, Zr, Cd, Ni, Co, Fe, etc. by conventional method, to obtain a mixed solution acidified with oxalic acid, having easily controllable composition, and containing various metallic ions stably ions stably at high concentration, at a low cost. The met al is preferably powdery metal because of high reactivity to enable the preparation of the above mixed solution effectively in a short time.

Description

【発明の詳細な説明】 （産業上の利用分野） 本発明は、各種金属イオンを含むシュウ酸酸性混合溶液
の調製法の改良、特に、高濃度で安定なシュウ酸酸性混
合溶液の調製法に関する。Detailed Description of the Invention (Industrial Application Field) The present invention relates to an improved method for preparing an acidic mixed solution of oxalic acid containing various metal ions, and particularly to a method for preparing a highly concentrated and stable acidic mixed solution of oxalic acid. .

エレクトロセラミックスな液相から製造しようとする場
合、高濃度で安定なシュウ酸酸性混合溶叔を簡単に、し
かも安価に調製することは工業的に大変重要である。When manufacturing electroceramics from a liquid phase, it is industrially very important to easily and inexpensively prepare a highly concentrated and stable oxalic acid mixed solution.

（従来技術とその問題点） 従来、各種金属イオンを含むシュウ酸酸性混合溶液の調
製法としては、単独金属イオンを含むシュウ酸酸性溶液
を調製後、それらの金属濃度の定量分析を行ない所望の
組成となるよ５に混合する手法が一般的であった。(Prior art and its problems) Conventionally, as a method for preparing an acidic oxalic acid mixed solution containing various metal ions, after preparing an acidic oxalic acid solution containing a single metal ion, quantitative analysis of the metal concentration is performed to obtain the desired concentration. The common method was to mix the ingredients so that the composition was as follows.

また単独金属イオンを含むシュウ酸酸性溶液の調製法と
しては、（１）シュウ酸塩を水に溶解する方法、（２）
金属をシュウ酸水溶液に溶解する方法、（３）金属の水
和物沈殿なシュウ酸水溶液に溶解する方法などがある。In addition, methods for preparing oxalic acid acidic solutions containing single metal ions include (1) a method of dissolving oxalate in water; (2) a method of dissolving oxalate in water;
There are methods such as dissolving the metal in an oxalic acid aqueous solution, and (3) dissolving the metal in an oxalic acid aqueous solution to precipitate a hydrate of the metal.

これらの方法で得られるシュウ散散性溶液の金属濃度の
上限値は、その金属のシュウ酸塩の溶解度によって限定
され、溶解度以上の高濃度溶液の調製は困難であった。The upper limit of the metal concentration of the oxalate solution obtained by these methods is limited by the solubility of the oxalate of the metal, and it has been difficult to prepare a highly concentrated solution exceeding the solubility.

（一般に金属のシュウ酸塩は溶解度の低いものが多い。(In general, many metal oxalates have low solubility.

） また（２）の方法では準安定的にシュウ酸塩の溶解度よ
りも高濃度溶液が調製可能な場合があるが、調製された
溶液は非常に不安定で７ユウ段塩が析出する欠点があっ
た。) In addition, with method (2), it may be possible to prepare a metastable solution with a concentration higher than the solubility of oxalate, but the prepared solution is very unstable and has the drawback of precipitating 7-stage salt. there were.

以上説明したように安定な単独金属イオンを含むシュウ
酸酸性溶液は低濃度しかとれないため、単位金属量当り
のシュウ酸の使用量が非常に多（なり、高価な溶液とな
るため工業的に利用することは困難であった。As explained above, an acidic oxalic acid solution containing a stable single metal ion can only be prepared at a low concentration, so the amount of oxalic acid used per unit amount of metal is extremely large (and the solution is expensive, so it is not suitable for industrial use). It was difficult to use.

これらの問題点のほかに、さらに前記したように単独金
属イオンを含むシュウ酸酸性溶液を調製した後、各種金
属イオンを含むシュウ酸酸性混合溶液を調製する場合、
所望の組成となるように混合するためには単独金属イオ
ンを含むシュウ酸酸性溶液中の金属濃度をそれぞれ混合
前に定量分析しなければならず操作かばん雑となる問題
点があった。In addition to these problems, when preparing an oxalic acid acidic solution containing a single metal ion as described above, and then preparing an oxalic acid acidic mixed solution containing various metal ions,
In order to mix to obtain a desired composition, it is necessary to quantitatively analyze the metal concentration in each oxalic acid solution containing a single metal ion before mixing, which poses a problem in that the operation bag is complicated.

（問題点を解決するための手段） 本発明者らは金属のシュ酸酸性溶液が単独溶液では不安
定で低濃度の溶液しか調製できないのに対し、金属イオ
ンを含むシュウ酸敗性溶液と金属とを反応させることに
より、高濃度でしかも安定なシュウ酸酸性混合溶液が簡
単な操作で調製可能であることを見出し本発明に到った
ものである。(Means for Solving the Problems) The present inventors found that an oxalic acidic solution of a metal is unstable when used as a single solution, and only a low concentration solution can be prepared. The inventors have discovered that a highly concentrated and stable oxalic acid acidic mixed solution can be prepared by a simple operation by reacting the oxalic acid, which led to the present invention.

すなわち、本発明は少なくとも１種、の金属イオンを含
むシュウ酸酸性溶液と少なくとも１種の金属とを反応さ
せることを特徴とする高濃度、安定、低コストのシュウ
廠酸性混合溶液の調製法である。That is, the present invention provides a method for preparing a highly concentrated, stable, and low-cost oxalic acid mixed solution, which is characterized by reacting an oxalic acid acidic solution containing at least one type of metal ion with at least one type of metal. be.

以下さらに詳しく本発明を説明する。The present invention will be explained in more detail below.

本発明で用いる少なくとも１種の金属イオンを含むシュ
ウ酸酸性溶液を構成する金属イオンとしては元素の周期
律表第４族ａ及び第５族ａのもので、シュウ酸と錯イオ
ンを形成するものが好ましく、その具体例としてはＴｉ
、　Ｚｒ　、　Ｎｂ、　Ｔａなどの金属イオンがあげら
れる。The metal ions constituting the oxalic acid acidic solution containing at least one metal ion used in the present invention are those from Group 4 a and Group 5 a of the periodic table of elements, and those that form complex ions with oxalic acid. is preferable, and a specific example is Ti
, Zr, Nb, Ta, and other metal ions.

また、少なくとも１種の金属イオンを含むシュウ酸酸性
溶液の調製法としては、特に限定されないがさきに本願
出願人が提案した特願昭５９−１５６２９３号記載の方
法は好ましい。その方法は各種金属の水和物沈殿にシュ
ウ酸粉末又は濃硝酸を添加混合した後、さらにこれらに
添加した酸と同一の酸性水溶液又は水を添加するもので
ある。The method for preparing the oxalic acid solution containing at least one kind of metal ion is not particularly limited, but the method described in Japanese Patent Application No. 156293/1987 proposed by the applicant of the present invention is preferred. The method involves adding and mixing oxalic acid powder or concentrated nitric acid to hydrate precipitates of various metals, and then adding the same acidic aqueous solution or water as the added acid.

本発明で用いる金属としてはシュウ酸と反応するもので
あれはすべて用いることができる。その具体例としては
Ｌｉ、Ｎａ、になどのアルカリ金属、Ｂｅ、　Ｍｇ、　
Ｃａ、　Ｓｒ、　Ｂａなどのアルカリ土類金属、Ｍｎ、
　Ｓｎ、　Ｚｒ、　Ｃｄ、　Ｎｉ、　Ｃｏ、　Ｆｅ、　
Ｃｒ。As the metal used in the present invention, any metal that reacts with oxalic acid can be used. Specific examples include alkali metals such as Li, Na, and Be, Mg,
Alkaline earth metals such as Ca, Sr, and Ba, Mn,
Sn, Zr, Cd, Ni, Co, Fe,
Cr.

Ｓｃ、Ｙｂ、Ｌｕ、Ｉｎ、Ｙ、Ｓｂ、Ｃｕなどがあげら
れる。Examples include Sc, Yb, Lu, In, Y, Sb, and Cu.

また、これらの金属の形態としては、粉末状のものの方
が反応性があり、短時間で効率的に溶液調製が可能であ
るため好ましい。Further, as for the form of these metals, powdered ones are preferable because they are more reactive and can efficiently prepare solutions in a short time.

また、少なくとも１種の金属イオンを含むシュウ酸酸性
溶液と少なくとも１種の金属を反応させる方法としては
、攪拌しながら混合する一般的な手法でよ（、反応温度
についても特に限定されないが、常温で行うことができ
る。反応の際に気体を発生する場合があるので注意を要
する。In addition, as a method for reacting an oxalic acid solution containing at least one type of metal ion with at least one type of metal, a general method of mixing while stirring is used (the reaction temperature is also not particularly limited, but at room temperature Caution is required as gas may be generated during the reaction.

本発明で調製された溶液は単独あるいは他の溶液と混合
して各種セラミックス合成用原液などに用いることがで
きる。The solution prepared according to the present invention can be used alone or mixed with other solutions as a stock solution for synthesizing various ceramics.

（実　施　例） 以下実施例をあげて、さらに具体的に説明する。(Example) The present invention will be described in more detail below with reference to Examples.

実施例に ニオブの７ツ酸溶液にアンモニア水を加えて生成した水
酸化ニオブ沈殿を充分洗浄してフッ素濃度をｓ　ｏ　ｏ
　ｐｐｍ以下とした。この水酸化ニオブ沈殿を用いてニ
オブのシュ゛つ酸酸性溶液を調製した。In the example, the niobium hydroxide precipitate generated by adding ammonia water to the niobium heptazate solution was thoroughly washed to reduce the fluorine concentration.
ppm or less. Using this niobium hydroxide precipitate, a niobium oxalic acid solution was prepared.

この溶液を分析した結果、ニオブ金属濃度０．４６５ｍ
ｏｌ／ｌ、シュウ酸濃度１．２２８　ｍｏ’／ａ　テア
ツタ。As a result of analyzing this solution, the niobium metal concentration was 0.465 m
ol/l, oxalic acid concentration 1.228 mo'/a Tea ivy.

その分析法はそれぞれ誘起結合プラズマ分析法及び酸化
還元滴定法で行なった。このニオブのシュウ酸酸性溶液
６２．６５ｍ／を水で稀釈し、ニオブ金属濃度０．３３
９　ｒｎｏｌ／ｌ、　シュウ酸濃度［］、８８９５ｍ／
７とした。この溶液８５．９５ｍ１に金属マグネシウム
粉末０．３５４０　ｇを攪拌しながら加え濃茶褐色の溶
液を得た。この溶液は２８後観察したところ透明溶液と
なっており、１ケ月後も全く変化は見られなかった。The analytical methods were inductively coupled plasma analysis and redox titration, respectively. This niobium acidic solution of oxalic acid (62.65 m) was diluted with water, and the niobium metal concentration was 0.33.
9 rnol/l, oxalic acid concentration [], 8895 m/l
It was set at 7. 0.3540 g of metallic magnesium powder was added to 85.95 ml of this solution while stirring to obtain a dark brown solution. When this solution was observed after 28 days, it was found to be a transparent solution, and no change was observed even after one month.

比較例１ 実施例１と同−濃°度、すなわちニオブを含まない０．
８９５　ｍｏｌ／ｌのシュウ酸溶液を調製し、この溶液
８５．９５尻ｅに実施例１と同様に０．３５４０　ｇの
金属マグネシウム粉末を攪拌しながら加えたところ白濁
した液を得た。この液は１８後観察したところ多量の白
色沈殿が生成沈降しており均一で安定した溶液でないこ
とがわかった。Comparative Example 1 The same concentration as Example 1, i.e. 0.00% without niobium.
An 895 mol/l oxalic acid solution was prepared, and 0.3540 g of metallic magnesium powder was added to this solution with stirring in the same manner as in Example 1 to obtain a cloudy white liquid. When this solution was observed after 18 days, it was found that a large amount of white precipitate had formed and settled, indicating that it was not a homogeneous and stable solution.

比較例２ 比較例１と同一濃度、すなわちニオブを含まない０．８
９５　ｍｏｚｙｇのシュウ酸溶液８５．９５　ｄに０．
２００　ｇの金属マグネシウム粉末を攪拌しながら加え
た。この液も比較例１同様１日後に観察したところ多量
の白色沈殿を生成していた。この液中のマグネシウム濃
度は実施例１００．５６倍でありながら不安定であった
。Comparative Example 2 Same concentration as Comparative Example 1, i.e. 0.8 without niobium
95 mozyg of oxalic acid solution 0.95 d to 85.95 d.
200 g of magnesium metal powder was added with stirring. Similar to Comparative Example 1, this solution was also observed after one day to find that a large amount of white precipitate had formed. Although the magnesium concentration in this liquid was 0.56 times higher than that of Example, it was unstable.

実施例２ 実施例１で用いたニオブのシュウ酸酸性溶液にオ・ブ金
属濃度肌３３９　ｍｏｌ／ｌ　、シュウ酸濃度０．８９
５　ｍｏｌ／ｌ　）　８５．９５　ｄに金属マンガン粉
末０．８００２　ｇを攪拌しながら加え濃茶褐色の溶液
を得た。この溶液は２日後に透明溶液となり１ケ月後観
察したが全く変化は見られなかった。Example 2 The acidic solution of niobium in oxalic acid used in Example 1 had a metal concentration of 339 mol/l and an oxalic acid concentration of 0.89.
5 mol/l) 85.95 d was added with 0.8002 g of metallic manganese powder while stirring to obtain a dark brown solution. This solution became a transparent solution after 2 days and was observed after 1 month, but no change was observed.

この溶液中のＭｎ濃度は約肌１６９　ｍｏｌ／ｌである
。The Mn concentration in this solution is approximately 169 mol/l.

比較例３ 実施例２と同一濃度、すなわちニオブを含まなイ０．８
９５　ｍｏ’／ｌＩ）’／ユウｅ溶液８５．９．５　ｍ
ｌ　Ｋ　以下実施例２と同様に金属マンガン粉末０．８
　［１Ｄ　２Ｉを攪拌しながら加えた。Comparative Example 3 Same concentration as Example 2, i.e. niobium-free i0.8
95 mo'/lI)'/Yue solution 85.9.5 m
l K Hereinafter, metal manganese powder 0.8 as in Example 2
[1D 2I was added with stirring.

この液は１日後観察したところ多量の白色沈殿及び未反
応の金属Ｍｎ粉末が沈降していた。この液を濾過して濾
液中のＭｎ濃度を分析したところ０．０５３…Ｏｌ／／
ｌであった。When this liquid was observed after one day, a large amount of white precipitate and unreacted metal Mn powder were found to have precipitated. This liquid was filtered and the Mn concentration in the filtrate was analyzed and was found to be 0.053...Ol//
It was l.

実施例６ 実施例１で用いたニオブのシュウ酸酸性溶液（二オシ金
属濃度Ｃ１，３３９ｍｏｌ／ｌ　、シュウ酸濃度０．８
９５　ｍｏ’／ｌ　）　８５．９５　ｍｌ　Ｋ、金属マ
グネシウム粉末０．３５４０．９及び金属マンガン粉末
０．２６６７１を攪拌しながら加えたところ実施例１と
同様に濃茶褐色の溶液となり、２日後に透明溶液となっ
ており、１ケ月後も全（変化は見られなρ・った。Example 6 Oxalic acid acid solution of niobium used in Example 1 (niobium concentration C1,339 mol/l, oxalic acid concentration 0.8
95 mo'/l) 85.95 ml K, 0.3540.9 of metallic magnesium powder, and 0.26671 of metallic manganese powder were added with stirring, resulting in a dark brown solution as in Example 1, which became transparent after 2 days. It became a solution, and no change was observed even after one month.

実施例４ 実施例１で用いたニオブのシュウ酸酸性＃液にオプ金属
濃度０．３３９　［ｎｏ”／６　、シュウ酸濃度０．８
９５　ｍＯ’／ｌ　）　８５．９５　ｒｒｔｌ　Ｉｃ金
属亜鉛粉末０、口４１２．９を攪拌しながら塀え濃茶褐
色溶層を得た。この溶液は１日後に透明溶液となり、１
ケ月後観察したところ全く変化は見られなかった。Example 4 The niobium oxalic acid acid # solution used in Example 1 had an op metal concentration of 0.339 [no''/6 and an oxalic acid concentration of 0.8.
95 mO'/l) 85.95 rrtl Ic Metal zinc powder 0, mouth 412.9 was stirred to obtain a dark brown molten layer. This solution became a clear solution after 1 day and 1
When observed after several months, no changes were observed.

比較例４ 実施例４と同一濃度すなわちニオブを含まない０．８９
５　ｍＯ１／ｌの７ユウ酸溶液８５．９５ｒｒｔｌとし
た以外は実施例４と同様に行った結果白濁液を得た。Comparative Example 4 Same concentration as Example 4, i.e. 0.89 without niobium
A cloudy white liquid was obtained as a result of carrying out the same procedure as in Example 4 except that 85.95 rrtl of the 5 mO1/l 7-euric acid solution was used.

この液は１日後観察したところ多量の白色沈殿が沈降し
て（・た。When this liquid was observed after one day, a large amount of white precipitate had settled out.

実施例５ 実施例１で用いたニオブの７ユウ酸酸性溶液（ニオブ金
属濃度０．３３９　ｍｏｌ／１％シュウ酸濃度０．８９
５　””／１１　）　８５．９５　ｔｒｔｌＫ金属コバ
ルト［３，０４１２Ｐを攪拌しながら加え桃色溶液を得
た。Example 5 A 7-oxalic acid acidic solution of niobium used in Example 1 (niobium metal concentration 0.339 mol/1% oxalic acid concentration 0.89)
5""/11) 85.95 trtlK metallic cobalt [3,0412P] was added with stirring to obtain a pink solution.

この溶液は１ケ月後も全く変化は見られず安定であった
。This solution remained stable with no change observed even after one month.

比較例５ 実施例５と同一濃度、すなわちニオブを含まなイ０．８
９５　ｍｏｌ／６　ｃｒ）　シュウ酸溶液８５．９５ｍ
／！とした以外は実施例５と同様に行った結果、桃白濁
液を得た。この液は１日後観察したところ多量の桃白色
沈殿が沈降していた。Comparative Example 5 Same concentration as Example 5, i.e. niobium-free i0.8
95 mol/6 cr) Oxalic acid solution 85.95 m
/! The procedure was carried out in the same manner as in Example 5 except that a milky white liquid was obtained. When this liquid was observed after one day, a large amount of pink-white precipitate had settled out.

実施例６ 実施例１で用いたニオブのシュウ酸酸性溶液にオブ金属
濃度０．３３９１　ｍｏｉｙ６　、シュウ酸濃度０．８
９５　””／ｌ）　８５−９５　ｒｕｇに金属鉄０．０
４３１１を攪拌しながら加えたところ深緑溶液を得た。Example 6 The niobium oxalic acid acid solution used in Example 1 had a metal concentration of 0.3391 moiy6 and an oxalic acid concentration of 0.8.
95 ””/l) 85-95 rug with metal iron 0.0
4311 was added with stirring to obtain a deep green solution.

この溶液は１ケ月後も全く変化は見られず安定であった
。This solution remained stable with no change observed even after one month.

比較例６ 実施例６と同一濃度、すなわちニオブを含まな１、−０
．８９５　ｍ”／ｌのシュウ酸溶液８５．９５ｍｅとり
。Comparative Example 6 Same concentration as Example 6, i.e. 1, -0 without niobium
．． Take 85.95 me of 895 m”/l oxalic acid solution.

た以外は実施例６と同様に行った結果、深緑白濁液を得
た。この液は１日後観察したところ多量の深緑白色沈殿
が沈降していた。As a result of carrying out the same procedure as in Example 6 except for the above, a deep green cloudy liquid was obtained. When this liquid was observed one day later, a large amount of dark green-white precipitate had settled out.

実施例７ ２、Ｏｍｏｌ／ｌの四塩化チタン水溶液にアンモニア水
を加え水酸チタン沈殿を生成し蒸留水を用いて硝酸銀に
よる塩素イオンの反応がなくなるまで充分洗浄した後、
この沈殿を用いてチタンのシュウ酸酸性溶液を調製した
。この溶液を分析したところチタン金属濃度０．４１５
　ｍＯ’／ｌ　、シュウ酸濃度０．７１２ｍｏｌ／ｌで
あった。分析方法は実施例１と同様の手法によった。こ
のチタンのシュウ酸酸性溶液５０１ｄに金属マグネシウ
ム粉末０．３２８６　ｇを攪拌しながら加えたところ赤
褐色溶液を得た。Example 7 2. Aqueous ammonia was added to an aqueous solution of titanium tetrachloride at Omol/l to form a titanium hydroxide precipitate, and the precipitate was thoroughly washed with distilled water until the reaction of chlorine ions with silver nitrate disappeared.
Using this precipitate, an acidic solution of titanium in oxalic acid was prepared. Analysis of this solution revealed that the titanium metal concentration was 0.415.
mO'/l, and the oxalic acid concentration was 0.712 mol/l. The analysis method was the same as in Example 1. When 0.3286 g of metallic magnesium powder was added to this oxalic acid acidic titanium solution 501d with stirring, a reddish brown solution was obtained.

この溶液は１ケ月後も安定であった。This solution remained stable after one month.

比較例７ 実施例７と同一濃度すなわちチタンを含まない０．７１
２　ｍＯｌ／ｌ　ノシー＋−ウ酸溶液５０１１Ｌｌトシ
タ以外は実施例７と同様に行った結果、赤褐色液を得た
。Comparative Example 7 Same concentration as Example 7, i.e. 0.71 without titanium
A reddish brown liquid was obtained as a result of carrying out the same procedure as in Example 7 except for using 2 mOl/l Nocy+-Uric acid solution 5011Ll Toshita.

この液は１口径観察したところ多量の黄色沈殿が生成沈
降して８つ不安定であった。When this liquid was observed with one caliber, a large amount of yellow precipitate was formed and settled, and 8 were found to be unstable.

実施例８ 実施例７のチタンのシュウ酸酸性溶液を用いて実施例２
〜６で用いた金属について実施例２〜６と同様に実験を
行なった結果、ニオブのシュウ酸酸性溶液同様単独シュ
ウ酸酸性溶液よりも高濃度で安定な溶液が得られた。Example 8 Example 2 using the oxalic acid acidic titanium solution of Example 7
As a result of conducting experiments on the metals used in Examples 2 to 6 in the same manner as in Examples 2 to 6, a solution with higher concentration and stability than the single oxalic acid acid solution was obtained, as was the case with the niobium oxalic acid acid solution.

実施例９ 実施例１〜８で調製した溶液をそれぞれ任意の組合せで
任意の割合に混合した溶液もそれぞれ安定な溶液であっ
た。Example 9 Solutions prepared by mixing the solutions prepared in Examples 1 to 8 in arbitrary combinations and in arbitrary proportions were also stable solutions.

実施例１０ 実施例１のニオブのシュウ酸酸性溶液及び実施例７のチ
タンのシュウ酸酸性溶液を任意の割合で混合した溶液に
ついても実施例１〜６で用いた金属について実施例１〜
６と同様行なった結果、単独シュウ酸酸性溶液よりも高
濃度で安定な溶液が得られた。Example 10 A solution obtained by mixing the niobium acidic oxalic acid solution of Example 1 and the titanium oxalic acid acidic solution of Example 7 in an arbitrary ratio was also used for the metals used in Examples 1 to 6.
As a result of carrying out the same procedure as in 6, a solution with higher concentration and stability than the single acidic oxalic acid solution was obtained.

〔発明の効果〕〔Effect of the invention〕

本発明によれば、組成制御が容易にでき、高濃度で、し
かも安定なニオブを含むシュウ酸酸性溶液が安価に得ら
れる。According to the present invention, an oxalic acid solution containing niobium that is highly concentrated and stable and whose composition can be easily controlled can be obtained at low cost.

特許出願人　電気化学工業株式会社 手続補正書 昭和５９年１Ｑ月２６日 特許庁長官　　志　賀　　　学　殿 ２、発明の名称 溶液の調整法 ３、補正をする者 事件との関係　　特許出願人 住所　東京都千代田区有楽町１丁目４番１号明細書の発
明の詳細な説明の欄 ５、補正の内容 明細書第６頁第１１行「シュ酸」を「シュウ酸」と訂正
する。Patent applicant: Denki Kagaku Kogyo Co., Ltd. Procedural amendment dated 26th January 1980, Director General of the Patent Office, Mr. Manabu Shiga 2, Title of the invention: Method for preparing a solution 3, Relationship with the person making the amendment Case Patent applicant address: Tokyo In Column 5 of the Detailed Description of the Invention in the Specification No. 1-4-1, Yurakucho, Chiyoda-ku, on page 6, line 11 of the amended specification, "oxalic acid" is corrected to "oxalic acid."

Claims (1)

【特許請求の範囲】[Claims] 少なくとも１種の金属イオンを含むシユウ酸酸性溶液と
少なくとも１種の金属とを反応させることを特徴とする
シユウ酸酸性混合溶液の調製法。A method for preparing an oxalic acid mixed solution, which comprises reacting an oxalic acid acidic solution containing at least one metal ion with at least one metal.