JPS6112849B2 - - Google Patents
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- Publication number
- JPS6112849B2 JPS6112849B2 JP5238881A JP5238881A JPS6112849B2 JP S6112849 B2 JPS6112849 B2 JP S6112849B2 JP 5238881 A JP5238881 A JP 5238881A JP 5238881 A JP5238881 A JP 5238881A JP S6112849 B2 JPS6112849 B2 JP S6112849B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- aqueous solution
- hydrochloric acid
- cuprous chloride
- cuprous
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は、塩化第一銅食塩錯体水溶液の製造方
法に関するものである。
塩化第一銅は、船底塗料の原料やガラスの着色
剤として有用な亜酸化銅の製造原料、顔料、染料
の製造原料、殺虫剤、触媒などとして広く利用さ
れている。
従来、塩化第一銅の製造方法としては、(1)硫酸
銅の食塩溶液に亜硫酸ガスを通し沈殿させる方
法、(2)塩化第二銅溶液に塩酸を加えて金属銅と接
触させ沈殿させる方法等が知られているが、これ
らの方法は、原料の銅源が限定されていること、
又、不安定な塩化第一銅を沈殿分離するために工
程が煩雑になるなどの欠点がある。
本発明は、このような点を鑑みてなされたもの
で、原料として広範囲の銅源を利用でき、又、塩
化第一銅を沈殿として分離することなく食塩の錯
体溶液として特に亜酸化銅の製造に使用すること
のできる塩化第一銅食塩錯体水溶液の製造方法を
提供することを目的とする。
即ち、炭酸銅、塩基性塩化銅、塩基性炭酸銅、
酸化銅、水酸化銅及び表面の一部が化学的に腐食
されている金属銅粉末から選ばれる水不溶性の銅
化合物の１種又は２種以上に食塩及び塩酸を添加
して、塩化第二銅食塩水溶液又はそのスラリーと
し、次いで金属銅と接触させることを特徴とする
塩化第一銅食塩錯体水溶液の製造方法である。
次に本発明を詳細に説明する。
本発明は、１種又は２種以上の炭酸銅、、塩基
性塩化銅、塩基性炭酸銅、酸化銅、水酸化銅及び
表面の一部が化学的に腐食されている金属粉末等
の水不溶性の銅化合物を食塩水溶液に添加し、次
いで原料を塩化第二銅にするに要する所定量の塩
酸を加え、塩化第二銅食塩水溶液又はそのスラリ
ー状の化合物とする。次いで、不活性ガス中でそ
の液又はスラリーを金属銅と、加熱下接触させ、
金属銅以外のすべての銅分が均一に溶解した塩化
第一銅の食塩錯体を製造する。
本発明に使用する水不溶性の銅化合物として
は、CuC２・2CuO・4H2O、CuC２・Cu
（OH）2、CuC２・3Cu（OH）2、CuC２・4Cu
（OH）2等の塩基性塩化銅、炭酸銅、CuCO3・Cu
（OH）2、2CuCO3・Cu（OH）2等の塩基性炭酸
銅、CuO、Cu2O、Cu（OH）2等の酸化銅、水酸
化銅又はその混合物、一部表面が酸素、炭酸ガ
ス、塩素で化学的に腐食されている金属銅粉末等
があげられる。
本発明において、銅化合物に食塩及び塩酸を加
え塩化第二銅食塩水溶液又はそのスラリー状物と
し、次いで不活性ガス中で金属銅と接触させ塩化
第一銅の食塩錯体とするが、この溶液中の過剰に
加えられた遊離塩酸（以下ｆ・HCと記す）の
濃度は、溶液１に対して２〜10ｇ（以下ｇ／
と記す）になる様にする。この場合、ｆ・HC
＜２ｇ／では液中にオキシ塩化銅を生成し好ま
しくなく、ｆ・HC＞10ｇ／では必要以上に
塩酸を使用する事になり、経済的でない。
本発明の塩化第一銅食塩錯体水溶液中の銅濃
度、食塩濃度は特に制限はなく、本錯体溶液の用
途により、適宜選択すればよい。例えば、亜酸化
銅製造に用いる場合は、
Cu 50〜75ｇ／
NaC 230〜280ｇ／
ｆ・HC ２〜10ｇ／
が好ましい。
不活性ガスは窒素ガス、炭酸ガス、ネオン、ア
ルゴン、クリプトン等の一種又は二種以上を用い
ることができる。
金属銅は故銅（回収銅）、電気銅、電線クス等
のいずれも使用でき、又、塩酸は35％工業用塩酸
が好ましいが、合成塩酸、副生塩酸等いずれを用
いてもよい。
塩化第二銅食塩水溶液を金属銅により接触還元
して塩化第一銅にする反応は、不活性ガス雰囲気
中で(1)金属銅を水溶液中に沈殿させ、溶液を撹拌
して反応を行なうバツチ式、(2)金属銅を充填した
充填塔に溶液を循環接触せしめる循環式で行な
う。金属銅と接触させる反応温度は常温以上、
110℃以下で行なうが、この時加熱温度は、装置
等の耐熱性にもよるが、液の沸点範囲内で、可能
な限り高い方が反応時間を短縮でき有利である。
例えば25℃で約10時間、110℃で約30分で反応は
終る。
従来、塩化第一銅製造原料としての銅源は、硫
酸銅、ないしは塩化第二銅の様に、極めて限定さ
れたものでしかなかつたが、本発明によれば、
種々の銅化合物を使用する事ができ、製造原料と
しての銅源を拡大する事ができた。しかも本発明
により製造された塩化第一銅食塩錯体は、必らず
しも、塩化第一銅を沈殿させ、分離する必要はな
く、例えば、亜酸化銅製造の際には、そのままカ
セイアルカリで中和し、沈殿を生成させ、その沈
殿を高温で熟成し、亜酸化銅を製造する事が可能
である。又、冷却等により塩化第一銅を沈殿さ
せ、分離し、顔料、染料の製造原料、殺虫剤、触
媒等の用途に供することができる。
次に、本発明の実施例及び参考例を示す。
実施例 １
The present invention relates to a method for producing a cuprous chloride salt complex aqueous solution. Cuprous chloride is widely used as a raw material for ship bottom paint, a raw material for producing cuprous oxide, which is useful as a coloring agent for glass, a raw material for producing pigments and dyes, an insecticide, a catalyst, etc. Conventionally, methods for producing cuprous chloride include (1) passing sulfur dioxide gas through a saline solution of copper sulfate to precipitate it, and (2) adding hydrochloric acid to a cupric chloride solution and bringing it into contact with metallic copper to precipitate it. etc., but these methods have the disadvantage that the raw material copper source is limited,
In addition, there is a drawback that the process becomes complicated because unstable cuprous chloride is separated by precipitation. The present invention has been made in view of these points, and allows the use of a wide range of copper sources as a raw material, and also enables the production of cuprous oxide in particular as a complex solution of common salt without separating cuprous chloride as a precipitate. The purpose of the present invention is to provide a method for producing a cuprous chloride salt complex aqueous solution that can be used for. That is, copper carbonate, basic copper chloride, basic copper carbonate,
Cupric chloride is produced by adding common salt and hydrochloric acid to one or more water-insoluble copper compounds selected from copper oxide, copper hydroxide, and metallic copper powder whose surface is partially chemically corroded. This is a method for producing a cuprous chloride salt complex aqueous solution, which is characterized in that it is made into a salt aqueous solution or a slurry thereof, and then brought into contact with metallic copper. Next, the present invention will be explained in detail. The present invention provides water-insoluble materials such as one or more types of copper carbonate, basic copper chloride, basic copper carbonate, copper oxide, copper hydroxide, and metal powder whose surface is partially chemically corroded. is added to a saline solution, and then a predetermined amount of hydrochloric acid required to convert the raw material into cupric chloride is added to form a cupric chloride salt aqueous solution or a slurry-like compound thereof. Then, the liquid or slurry is brought into contact with metallic copper under heating in an inert gas,
To produce a cuprous chloride salt complex in which all copper content except metallic copper is uniformly dissolved. The water-insoluble copper compounds used in the present invention include CuC 2.2CuO.4H 2 O, CuC 2.Cu
(OH) 2 , CuC 2・3Cu(OH) 2 , CuC 2・4Cu
Basic copper chloride such as (OH) 2 , copper carbonate, CuCO 3・Cu
(OH) 2 , 2CuCO 3・Basic copper carbonates such as Cu(OH) 2 , copper oxides such as CuO, Cu 2 O, Cu(OH) 2 , copper hydroxide, or mixtures thereof, partially containing oxygen or carbonic acid on the surface. Examples include metallic copper powder that has been chemically corroded by gas or chlorine. In the present invention, a copper compound is added with common salt and hydrochloric acid to form a cupric chloride salt aqueous solution or a slurry thereof, and then brought into contact with metallic copper in an inert gas to form a cuprous chloride salt complex. The concentration of free hydrochloric acid (hereinafter referred to as f・HC) added in excess of
). In this case, f・HC
If it is less than 2g/, copper oxychloride will be produced in the liquid, which is undesirable, and if f.HC>10g/, more hydrochloric acid will be used than necessary, which is not economical. The copper concentration and the salt concentration in the cuprous chloride salt complex aqueous solution of the present invention are not particularly limited, and may be appropriately selected depending on the use of the complex solution. For example, when used for producing cuprous oxide, it is preferably Cu 50 to 75 g/NaC 230 to 280 g/f·HC 2 to 10 g/. As the inert gas, one or more of nitrogen gas, carbon dioxide gas, neon, argon, krypton, etc. can be used. As the metal copper, any of deceased copper (recovered copper), electrolytic copper, electric wire scraps, etc. can be used, and as the hydrochloric acid, 35% industrial hydrochloric acid is preferable, but synthetic hydrochloric acid, by-product hydrochloric acid, etc. may be used. The reaction of catalytic reduction of aqueous cupric chloride salt solution with metallic copper to produce cuprous chloride is a batch process in which (1) metallic copper is precipitated in an aqueous solution and the solution is stirred in an inert gas atmosphere. (2) A circulating method is used in which the solution is circulated and brought into contact with a packed column filled with metallic copper. The reaction temperature in contact with metallic copper is above room temperature,
Although the heating temperature is 110° C. or lower, it depends on the heat resistance of the equipment, etc., but it is advantageous to set the heating temperature as high as possible within the boiling point range of the liquid because it can shorten the reaction time.
For example, the reaction is completed at 25°C for about 10 hours and at 110°C for about 30 minutes. Conventionally, copper sources as raw materials for producing cuprous chloride have been extremely limited, such as copper sulfate or cupric chloride, but according to the present invention,
It was possible to use various copper compounds, and it was possible to expand the copper sources as a manufacturing raw material. Moreover, the cuprous chloride salt complex produced according to the present invention does not necessarily need to precipitate and separate cuprous chloride; for example, when producing cuprous oxide, it can be directly treated with caustic alkali. It is possible to produce cuprous oxide by neutralizing, forming a precipitate, and aging the precipitate at high temperatures. Further, cuprous chloride can be precipitated and separated by cooling or the like, and can be used as a raw material for producing pigments and dyes, insecticides, catalysts, and the like. Next, examples and reference examples of the present invention will be shown. Example 1
【表】
に水を加えて15とした。次いでこの液を60℃
に加温し、窒素気流中で金属銅とバツチ式で金属
Cuを沈殿させた状態で、５時間接触せしめ、溶
液中の銅をすべて塩化第一銅食塩錯体として溶解
させた。この塩化第一銅食塩錯体水溶液の組成
は、次の通りである。
Cuイオン 63ｇ／
食塩 250ｇ／
遊離塩酸 ５ｇ／
実施例 ２
塩基性炭酸銅 738 ｇ
食塩 3.9 Kg
35％塩酸 1.730Kg
に水を加え15とした。この液を50℃に加熱
し、第一銅イオンを酸化し、すべて塩化第二銅と
し溶解させた。この塩化第二食塩水溶液の組成
は、
Cuイオン 28.25ｇ／
食塩 260 ｇ／
遊離塩酸 ８ ｇ／
である。次いでこの液を60℃に加温し、炭酸ガ
ス気流中で金属銅と実施例１と同様に接触せしめ
溶液中の塩化第二銅をすべて塩化第一銅とした。
その塩化第一銅食塩水溶液の組成は次の通りであ
る。
Cuイオン 56.5ｇ／
食塩 260 ｇ／
35％塩酸 ８ ｇ／
実施例 ３
酸化銅 638.4 ｇ
食塩 3.6 Kg
35％塩酸 1.843Kg
及び水を加えて、15とする。この液の組成
は、
Cuイオン 34ｇ／
食塩 240ｇ／
遊離塩酸 ４ｇ／
である。次にこの液を55℃に加熱し、アルゴン
ガス気流中で、充填塔につめた金属銅と接触せし
め、溶液中の銅を塩化第一銅の食塩錯体溶液とし
た。この塩化第一銅食塩錯体水溶液の組成は次の
通りである。
Cuイオン 68ｇ／
食塩 240ｇ／
遊離塩酸 ４ｇ／
実施例 ４
塩基性塩化銅 273.3ｇ
酸化銅 376 ｇ
食塩 4.05Kg
35％塩酸 1.53Kg
に水を加え、15とする。この液の組成は、
Cuイオン 30ｇ／
食塩 270ｇ／
遊離塩酸 ７ｇ／
である。次にこの液を60℃に加熱し、窒素気流
下で金属銅と接触せしめ、溶液中の銅をすべて塩
化第一銅食塩水溶液とした。この塩化第一銅食塩
錯体水溶液の組成は次の通りである。
Cuイオン 60ｇ／
食塩 270ｇ／
遊離塩酸 ７ｇ／
参考例 １
実施例１により調整した塩化第一銅食塩錯体水
溶液15を内容積20のオートクレーブにとり、
遊離塩酸を中和し、更にNaOH565ｇを含む30重
量％の苛性ソーダで液温を90〜100℃にして銅分
の95重量％を中和したところ水酸化第一銅を主体
とする微粉末スラリーを得ることができた。この
水酸化第一銅を主体とするスラリーはPHが9.0で
これを138℃で1.8Kg／cm2の加熱加圧状態で20時間
熟成することにより、平均粒子径2.5μの粒度の
揃つた亜酸化銅の製品を得ることができた。得ら
れた亜酸化銅の収量は1004ｇで収率は99.3％であ
つた。又、得られた亜酸化銅は、粒子が均一で揃
つており、色も深赤色を示し、又、JISK5630で
示す配合で船底塗料を塗布した鉄板に塗布したが
その性能も極めて優秀なものである。
参考例 ２
実施例１により調整した塩化第一銅食塩錯体水
溶液2000mlとNaOH400ｇ／の組成の苛性ソー
ダ水溶液227mlとを窒素雰囲気下でPHを10.0に一
定に保持しつつ、反応温度55℃、反応時間60分で
同時に滴下反応させた。得られた亜酸化銅は美麗
な赤紫色であり、収量141.5ｇ平均粒径は4.6μで
ある。[Table] Added water to make 15. Then this liquid was heated to 60℃
Heat the metal in batches with copper metal in a nitrogen stream.
Contact was made for 5 hours with Cu precipitated, and all the copper in the solution was dissolved as a cuprous chloride salt complex. The composition of this cuprous chloride salt complex aqueous solution is as follows. Cu ion 63g/Salt 250g/Free hydrochloric acid 5g/Example 2 Basic copper carbonate 738g Salt 3.9Kg 35% Hydrochloric acid 1.730Kg was added with water to make 15. This liquid was heated to 50°C to oxidize the cuprous ions and dissolve them all into cupric chloride. The composition of this aqueous saline chloride solution is 28.25 g of Cu ions/260 g of common salt/8 g of free hydrochloric acid. Next, this solution was heated to 60° C. and brought into contact with metallic copper in the same manner as in Example 1 in a carbon dioxide gas flow to convert all the cupric chloride in the solution into cuprous chloride.
The composition of the cuprous chloride saline solution is as follows. Cu ion 56.5g/Salt 260g/35% Hydrochloric acid 8g/Example 3 Copper oxide 638.4g Salt 3.6Kg 35% Hydrochloric acid 1.843Kg and water are added to make 15. The composition of this liquid is 34 g of Cu ions/240 g of common salt/4 g of free hydrochloric acid. Next, this liquid was heated to 55°C and brought into contact with metallic copper packed in a packed tower in an argon gas stream, thereby converting the copper in the solution into a solution of a cuprous chloride salt complex. The composition of this cuprous chloride salt complex aqueous solution is as follows. Cu ion 68g / Salt 240g / Free hydrochloric acid 4g / Example 4 Basic copper chloride 273.3g Copper oxide 376g Salt 4.05Kg 35% Hydrochloric acid Add water to 1.53Kg to make 15. The composition of this liquid is Cu ions 30g/salt 270g/free hydrochloric acid 7g/. Next, this solution was heated to 60° C. and brought into contact with metallic copper under a nitrogen stream, so that all the copper in the solution was converted into a cuprous chloride salt aqueous solution. The composition of this cuprous chloride salt complex aqueous solution is as follows. Cu ion 60g / Salt 270g / Free hydrochloric acid 7g / Reference example 1 15 cuprous chloride salt complex aqueous solution prepared according to Example 1 was placed in an autoclave with an internal volume of 20,
When free hydrochloric acid was neutralized and 95% by weight of the copper content was neutralized with 30% by weight of caustic soda containing 565g of NaOH at a temperature of 90 to 100°C, a fine powder slurry consisting mainly of cuprous hydroxide was obtained. I was able to get it. This slurry, which is mainly composed of cuprous hydroxide, has a pH of 9.0 and is aged at 138°C under heating and pressure of 1.8 kg/cm 2 for 20 hours to produce a slurry with a uniform particle size of 2.5 μm in average particle size. We were able to obtain copper oxide products. The amount of cuprous oxide obtained was 1004 g, with a yield of 99.3%. In addition, the obtained cuprous oxide had uniform particles and a deep red color.Also, when it was applied to an iron plate coated with ship bottom paint using the formulation specified in JISK5630, its performance was extremely excellent. be. Reference Example 2 2000 ml of the cuprous chloride salt complex aqueous solution prepared according to Example 1 and 227 ml of a caustic soda aqueous solution having a composition of 400 g of NaOH were heated under a nitrogen atmosphere at a reaction temperature of 55°C and a reaction time of 60 while keeping the pH constant at 10.0. Dropwise reaction was carried out simultaneously within minutes. The cuprous oxide obtained was a beautiful reddish-purple color, with a yield of 141.5g and an average particle size of 4.6μ.
Claims (1)
銅、水酸化銅及び表面の一部が化学的に腐食され
ている金属銅粉末から選ばれる水不溶性の銅化合
物の１種又は２種以上に食塩及び塩酸を添加し
て、塩化第二銅食塩水溶液又はそのススラリーと
し、次いで金属銅と接触させることを特徴とする
塩化第一銅食塩錯体水溶液の製造方法。 ２ 塩化第一銅食塩錯体水溶液の液組成が銅50〜
75ｇ／、食塩230〜280ｇ／及び遊離塩酸２〜
10ｇ／である特許請求の範囲第１項記載の塩化
第一銅食塩錯体水溶液の製造方法。[Claims] 1. A water-insoluble copper compound selected from copper carbonate, basic copper chloride, basic copper carbonate, copper oxide, copper hydroxide, and metallic copper powder whose surface is partially chemically corroded. A method for producing a cuprous chloride salt complex aqueous solution, which comprises adding common salt and hydrochloric acid to one or more of the above to form a cupric chloride salt aqueous solution or a slurry thereof, and then bringing the mixture into contact with metallic copper. 2 The liquid composition of the cuprous chloride salt complex aqueous solution is copper 50~
75g/, salt 230~280g/and free hydrochloric acid 2~
10 g/method for producing a cuprous chloride salt complex aqueous solution according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5238881A JPS57170825A (en) | 1981-04-09 | 1981-04-09 | Manufacture of aqueous solution of cuprous chloride- salt complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5238881A JPS57170825A (en) | 1981-04-09 | 1981-04-09 | Manufacture of aqueous solution of cuprous chloride- salt complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57170825A JPS57170825A (en) | 1982-10-21 |
| JPS6112849B2 true JPS6112849B2 (en) | 1986-04-10 |
Family
ID=12913415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5238881A Granted JPS57170825A (en) | 1981-04-09 | 1981-04-09 | Manufacture of aqueous solution of cuprous chloride- salt complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57170825A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100380035B1 (en) * | 2000-05-10 | 2003-04-14 | 서안켐텍 주식회사 | Process for purifying cuprous chloride using the mixture of methyl acetate and methanol |
| JP5134473B2 (en) * | 2008-09-04 | 2013-01-30 | 住友精化株式会社 | Production method of adsorbent |
| JP5578608B2 (en) * | 2010-03-17 | 2014-08-27 | 住友精化株式会社 | Carbon monoxide gas purification method |
-
1981
- 1981-04-09 JP JP5238881A patent/JPS57170825A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57170825A (en) | 1982-10-21 |
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