JPH0393623A - Production of cuprous oxide - Google Patents
Production of cuprous oxideInfo
- Publication number
- JPH0393623A JPH0393623A JP22437989A JP22437989A JPH0393623A JP H0393623 A JPH0393623 A JP H0393623A JP 22437989 A JP22437989 A JP 22437989A JP 22437989 A JP22437989 A JP 22437989A JP H0393623 A JPH0393623 A JP H0393623A
- Authority
- JP
- Japan
- Prior art keywords
- cuprous oxide
- solution
- electrolytic solution
- electrolytic
- electrolyte
- 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.)
- Pending
Links
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 23
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000002245 particle Substances 0.000 claims abstract description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- 239000012670 alkaline solution Substances 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 13
- 230000000903 blocking effect Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000049 pigment Substances 0.000 abstract description 7
- 230000003373 anti-fouling effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000013019 agitation Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 244000062793 Sorghum vulgare Species 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
産粟≧曵剋亙立互
本発明は、金属鋼を電極とする電解による平均粒径８μ
ｍから２０μｍの亜酸化銅の製造方法に関する。[Detailed Description of the Invention] The present invention provides millet with an average grain size of 8μ by electrolysis using metal steel as an electrode.
The present invention relates to a method for producing cuprous oxide having a thickness of 20 μm to 20 μm.
且圭立且歪
亜酸化銅は船底塗料等の防汚顔料、窯業用顔料、農薬、
触媒等に巾広く使用されており、通常品は平均粒径２μ
ｍから５μｍの丸状粉で、その製法はよく知られている
。Strained cuprous oxide is used as antifouling pigments for ship bottom paints, pigments for ceramics, agricultural chemicals,
Widely used in catalysts, etc., and regular products have an average particle size of 2μ
It is a round powder with a size of 5 μm to 5 μm, and its manufacturing method is well known.
一方、本発明の方法に関する平均粒径８μｍから２０μ
ｍの亜酸化銅はレジャーボート、漁船、軍用艦艇等の防
汚性低着色顔料として用いられるもので、その製法の詳
細は公表されていない。On the other hand, the average particle size for the method of the present invention is 8 μm to 20 μm.
The cuprous oxide of M is used as an antifouling, low-coloring pigment for leisure boats, fishing boats, military ships, etc., and the details of its manufacturing method have not been made public.
例えば電解法での亜酸化銅の製法として特公昭５４−６
６３９ （特願昭５２−１３２４７９）の比較例に、？
膜電解での亜酸化鋼の作製が報告されている。For example, as a method for producing cuprous oxide using the electrolytic method,
639 (Japanese Patent Application No. 52-132479), as a comparative example?
The production of suboxide steel by membrane electrolysis has been reported.
く べ ■ ，
上述の従来の方法で得られる亜酸化銅は、丸状粉で平均
粒径２μｍから５μｍである。このものは粒径が小さく
防汚性低着色顔料用には使用出来ない。このため大粒径
亜酸化銅を簡易に製造する方法が要望されていた。この
ため発明者等らは鋭意検討した結果下記の発明をなした
。1. Cuprous oxide obtained by the conventional method described above is a round powder with an average particle size of 2 μm to 5 μm. This product has a small particle size and cannot be used as a colored pigment with low stain resistance. Therefore, there has been a need for a method for easily producing large-particle cuprous oxide. For this reason, the inventors have made the following invention as a result of intensive studies.
且且曵曵炭
本発明の方法は、（１）ＮａＣｌ及び酸化防止剤を含む
水溶液を電解液とし、両極を銅材とし、陰極を隔膜室内
に配置した電解槽において、隔膜室内に電解液ｐＨ調整
用酸又はアルカリ溶液を給液し、かつ不活性ガスによる
撹拌及び空気遮断を行って、電解液ｐＨ９．０から１１
．０で電解し、平均粒径８μｍから２０μｍの形状のも
のを得ることを特徴とする亜酸化銅の製造方法。（２）
電解液温を５０℃から１０７℃とすることを特徴とする
上記（１）記載の亜酸化鋼の製造方法。（３）電解槽底
面ｌｍｌあたり０ ． Ｉ Ｑ ／ｍｉｎから５Ｑ／Ｉ
Ｉｉｎの流速で不活性ガスを吹き込むことを特徴とする
上記（１）記載の亜酸化銅の製造方法。（４）不活性ガ
スでの空気遮断に代えて、電解液面を多数個の球形のプ
ラスチックの中空体で覆うことを特徴とする上記（１）
記載の亜酸化銅の製造方法。を提供するものである。The method of the present invention includes (1) an electrolytic cell in which an aqueous solution containing NaCl and an antioxidant is used as an electrolyte, both electrodes are made of copper, and a cathode is arranged in a diaphragm chamber; The pH of the electrolytic solution is adjusted from 9.0 to 11 by supplying an acid or alkaline solution for adjustment, stirring with an inert gas, and blocking air.
．． 1. A method for producing cuprous oxide, which comprises electrolyzing at 0 to obtain cuprous oxide having an average particle size of 8 to 20 μm. (2)
The method for producing suboxide steel according to (1) above, characterized in that the temperature of the electrolyte is 50°C to 107°C. (3) 0.0% per ml on the bottom of the electrolytic cell. IQ/min to 5Q/I
The method for producing cuprous oxide according to (1) above, characterized in that the inert gas is blown in at a flow rate of Iin. (4) In the above (1), the electrolyte surface is covered with a large number of spherical plastic hollow bodies instead of blocking air with an inert gas.
The method for producing cuprous oxide described above. It provides:
ベ
本発明者等は、ＮａＣｌ及び酸化防止剤を含む水溶液を
電解液とし、両極を銅材とし、陰極を隔膜室内に配置し
た電解槽において、諸条件を詳細に検討した結果、電解
液中のＮａＣｌ濃度及び酸化防止剤濃度、電解液ｐＨ及
び調整方法、電解電流密度、電解液温度及び撹伴方法、
酸化防止策等を適切に選択することによって、平均粒径
８μｍから２０μｍの亜酸化銅が得られる事を見出した
。The inventors of the present invention have investigated the various conditions in detail for an electrolytic cell in which an aqueous solution containing NaCl and an antioxidant is used as the electrolyte, both electrodes are made of copper, and the cathode is placed in the diaphragm chamber. NaCl concentration and antioxidant concentration, electrolyte pH and adjustment method, electrolytic current density, electrolyte temperature and stirring method,
It has been found that cuprous oxide having an average particle size of 8 μm to 20 μm can be obtained by appropriately selecting anti-oxidation measures and the like.
以下に本発明の方法及び条件について詳述する。The method and conditions of the present invention will be explained in detail below.
電解液中のＮａＣ１の濃度は、高い程好ましいが実施の
面から３から５Ｍｏｌ／Ｌが好ましい。電解液温は、高
いほど好ましいが、５０℃から１０７℃が好ましい。こ
れは、低温側では粒径が小さく一方、亜酸化鋼の製造に
おいては、酸化防止剤として、グリセリン、砂糖を用い
る。本発明の方法においても酸化防止策は必要で酸化防
止剤の添加に加えて、電解液と空気との接触を断つ為に
、不活性ガスでの液面のシールが最も効果的である。The concentration of NaCl in the electrolytic solution is preferably as high as possible, but from a practical standpoint, it is preferably 3 to 5 Mol/L. The higher the electrolyte temperature is, the more preferable it is, and preferably from 50°C to 107°C. This has a small particle size at low temperatures, while glycerin and sugar are used as antioxidants in the production of suboxidized steel. Anti-oxidation measures are also necessary in the method of the present invention, and in addition to adding an antioxidant, sealing the liquid surface with an inert gas is most effective in order to cut off contact between the electrolyte and air.
しかし、電槽、ポンプ槽、貯槽などの液面を多数個の球
状のプラスチックなどの中空体でシールする方法であっ
ても目的の亜酸化銅粉が得られる．以下、実施例で詳述
する。However, the desired cuprous oxide powder can also be obtained by sealing the liquid surface of a battery container, pump tank, storage tank, etc. with a large number of hollow bodies such as spherical plastic. This will be explained in detail in Examples below.
叉轟盟工
ＮａＣｌ濃度５Ｍｏｌ／Ｌ，グーリセリン１ ０ｇ／Ｌ
の水溶液を電解液とし、隔膜ボックスを内装した電槽を
用い、両極とも有効面１０ｃ＋ｎＸ１０ａｎの銅板とし
、陰極は隔膜ボックス内に配置し、電槽底部より窒素ガ
スをｌｍｌ当たり０ ．９ Ｑ ／＋ａｉｎの速度で吹
き込む方法で、液温のみを５０℃から１０７℃に変化さ
せ、電流密度３ ０ ０ Ａ／ｒｄ，電解時間１０時間
を一定とし電解を行った。なお、いずれの場合でも、電
解中はｐＨコントローラーにて、酸及びアルカリを隔膜
ボックス内に添加し、電解液のｐＨは９．５からｔｏ，
５に保った。液面は窒素ガスでシールした。得られた亜
酸化銅の粒径は走査型電子顕微鏡（５０００倍）で観察
し、粒径は光透過法で測定し第１表の結果を得た。NaCl concentration 5Mol/L, Glycerin 10g/L
The electrolyte is an aqueous solution of 100 ml, a diaphragm box is used inside the container, both electrodes are copper plates with an effective surface of 10 c + n x 10 an, the cathode is placed inside the diaphragm box, and nitrogen gas is supplied from the bottom of the container at a rate of 0. Electrolysis was carried out by blowing at a rate of 9 Q/+ain while changing only the liquid temperature from 50°C to 107°C, keeping the current density at 300 A/rd, and the electrolysis time constant at 10 hours. In any case, during electrolysis, acid and alkali are added into the diaphragm box using a pH controller, and the pH of the electrolytic solution is adjusted from 9.5 to
I kept it at 5. The liquid level was sealed with nitrogen gas. The particle size of the cuprous oxide obtained was observed using a scanning electron microscope (5,000 times magnification), and the particle size was measured using a light transmission method, and the results shown in Table 1 were obtained.
第 １ 表
液温６０℃、電流密度３ ０ ０Ａ／ｎｌ．液面を直径
約５閣のプラスチックボールでシール（窒素シールに代
えて）した以外は総て実施例１同様に行って、平均粒径
１０．９μｍの正八面体の亜酸化銅粉を得た。1st surface liquid temperature 60°C, current density 300A/nl. The same procedure as in Example 1 was repeated except that the liquid level was sealed with a plastic ball having a diameter of approximately 5 mm (instead of a nitrogen seal), to obtain octahedral cuprous oxide powder with an average particle size of 10.9 μm.
井一較一銭
液温４０℃、他の条件は実施例ｌと同一に行った。得ら
れた亜酸化銅の平均粒径は５μｍで好ましくない。The liquid temperature was 40° C., and the other conditions were the same as in Example 1. The average particle size of the cuprous oxide obtained was 5 μm, which is not preferable.
且映坐立果
実施例から明らかなように本発明の方法によって、防汚
性低着色顔料用として有用な、平均粒径８μｍから２０
μｍの正八面体の亜酸化銅が得られる。As is clear from the Examples, the method of the present invention produces particles with an average particle diameter of 8 μm to 20 μm, which are useful as antifouling, low-color pigments.
A regular octahedral cuprous oxide of μm size is obtained.
Claims (4)
し、両極を銅材とし、陰極を隔膜室内に配置した電解槽
において、隔膜室内に電解液ｐＨ調整用酸又はアルカリ
溶液を給液し、かつ不活性ガスによる撹拌及び空気遮断
を行って、電解液ｐＨ９．０から１１．０で電解し、平
均粒径８μｍから２０μｍの形状のものを得ることを特
徴とする亜酸化銅の製造方法。(1) In an electrolytic cell in which an aqueous solution containing NaCl and an antioxidant is used as an electrolyte, both electrodes are made of copper, and a cathode is placed in a diaphragm chamber, an acid or alkaline solution for adjusting the electrolyte pH is supplied into the diaphragm chamber, A method for producing cuprous oxide, which comprises stirring with an inert gas and blocking air, electrolyzing the electrolytic solution at pH 9.0 to 11.0, and obtaining particles having an average particle size of 8 μm to 20 μm.
とする特許請求の範囲第１項記載の亜酸化銅の製造方法
。(2) The method for producing cuprous oxide according to claim 1, characterized in that the temperature of the electrolyte is 50°C to 107°C.
５ｌ／ｍｉｎの流速で不活性ガスを吹き込むことを特徴
とする特許請求の範囲第１項記載の亜酸化銅の製造方法
。(3) The method for producing cuprous oxide according to claim 1, characterized in that inert gas is blown at a flow rate of 0.1 l/min to 5 l/min per 1 m^2 of the bottom surface of the electrolytic cell.
数個の球形のプラスチックの中空体で覆うことを特徴と
する特許請求の範囲第１項記載の亜酸化銅の製造方法。(4) The method for producing cuprous oxide according to claim 1, characterized in that instead of blocking air with an inert gas, the electrolyte surface is covered with a large number of spherical plastic hollow bodies.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22437989A JPH0393623A (en) | 1989-09-01 | 1989-09-01 | Production of cuprous oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22437989A JPH0393623A (en) | 1989-09-01 | 1989-09-01 | Production of cuprous oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0393623A true JPH0393623A (en) | 1991-04-18 |
Family
ID=16812834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22437989A Pending JPH0393623A (en) | 1989-09-01 | 1989-09-01 | Production of cuprous oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0393623A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000234072A (en) * | 1998-12-17 | 2000-08-29 | Chugoku Marine Paints Ltd | Antifouling paint composition, antifouling coating, ship or submarine structure coated therewith, and antifouling method of outer board of ship and submarine structure |
| WO2011010663A1 (en) * | 2009-07-22 | 2011-01-27 | 日本化学工業株式会社 | Particles coated with cuprous oxide, method for producing same, and antifouling coating material containing the particles coated with cuprous oxide |
| RU2570086C2 (en) * | 2014-04-01 | 2015-12-10 | федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Южно-Российский государственный политехнический университет (НПИ) имени М.И. Платова" | Method of obtaining copper (i) oxide |
| CN105905936A (en) * | 2016-04-14 | 2016-08-31 | 青岛大学 | Cuprous oxide nanocrystalline assembly |
-
1989
- 1989-09-01 JP JP22437989A patent/JPH0393623A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000234072A (en) * | 1998-12-17 | 2000-08-29 | Chugoku Marine Paints Ltd | Antifouling paint composition, antifouling coating, ship or submarine structure coated therewith, and antifouling method of outer board of ship and submarine structure |
| WO2011010663A1 (en) * | 2009-07-22 | 2011-01-27 | 日本化学工業株式会社 | Particles coated with cuprous oxide, method for producing same, and antifouling coating material containing the particles coated with cuprous oxide |
| JP2011042559A (en) * | 2009-07-22 | 2011-03-03 | Nippon Chem Ind Co Ltd | Particle coated with cuprous oxide and method for producing the same, and antifouling coating material containing the particle coated with cuprous oxide |
| RU2570086C2 (en) * | 2014-04-01 | 2015-12-10 | федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Южно-Российский государственный политехнический университет (НПИ) имени М.И. Платова" | Method of obtaining copper (i) oxide |
| CN105905936A (en) * | 2016-04-14 | 2016-08-31 | 青岛大学 | Cuprous oxide nanocrystalline assembly |
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