CN104591257B - The preparation method of the micro-nano cuprous oxide powder of a kind of cubes - Google Patents
The preparation method of the micro-nano cuprous oxide powder of a kind of cubes Download PDFInfo
- Publication number
- CN104591257B CN104591257B CN201510013588.9A CN201510013588A CN104591257B CN 104591257 B CN104591257 B CN 104591257B CN 201510013588 A CN201510013588 A CN 201510013588A CN 104591257 B CN104591257 B CN 104591257B
- Authority
- CN
- China
- Prior art keywords
- oxide powder
- cuprous oxide
- micro
- cubes
- preparation
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention provides a kind of preparation method being applicable to the micro-nano cuprous oxide powder of cubes of anti-fouling ship paint, the method first prepares the copper liquor of finite concentration and pH value, stirring is preheated to 40-50 DEG C, certain density sodium sulfite solution is added fast after adding compound dispersion agent, then slowly sodium carbonate solution is dripped, control the pH value of reaction soln, and continue to be heated with stirring to 60-100 DEG C, react after 1-5 hour, by the reaction final product collected through solid-liquid separation, washing, dry, obtain the micro-nano cuprous oxide powder of cubes, wherein compound dispersion agent be gelatin and Sodium dodecylbenzene sulfonate in mass ratio 1:1 prepare.Preparation method of the present invention, simple to operate, technique is easy to control, the cuprous oxide powder obtained by the inventive method is cubes, particle diameter is between 0.4-3.0 μm, and specific surface area is little, and cupric ion release is slow, tap density is little, suspension is good, and oil number is low, is particularly suitable for being applied in anti-fouling ship paint.
Description
Technical field
The present invention relates to a kind of preparation method of Red copper oxide, particularly relate to a kind of preparation method of high pure and ultra-fine cuprous oxide powder, more specifically relate to a kind of preparation method being applicable to the micro-nano cuprous oxide powder of cubes of anti-fouling ship paint.
Background technology
Red copper oxide (Cu
2o) powder is a kind of redness or yellow Inorganic Chemicals and product, and be widely used, as being used in anti-fouling ship paint, glass porcelain glaze tinting material, organic catalyst compound, agricultural bactericide and electronic material etc., wherein more than 80% is be applied to anti-fouling ship paint.
Preventing and kill off of marine fouling organism is be engaged in the problem that boats and ships, marine biotechnology personnel and biology worker extremely pay close attention to always, especially the biodeterioration of bottom of ship, not only increase ship resistance, reduce the speed of a ship or plane, increase fuel consumption, and accelerate Ship's corrosion; In order to prevent avoiding sea-water corrosion and halobiontic attachment, conventional method is at marine surface brushing antifouling paint, and general containing bio-toxicity element in the paint of brushing, and relies on the slow releasing of this dvielement to reach the object preventing biological attachment.At present, in marine antifouling coating, apply maximum and most realistic system is Red copper oxide system superfine powdery material, because cuboidal Red copper oxide has less specific surface area, can control the rate of release of copper in anti-fouling ship paint, effect is very good.
At present, prepare ultrafine cuprous oxide powder and mainly contain solid phase method, liquid phase method and electrolytic process.Solid phase method and electrolytic process prepare high-purity superfine Cu
2o has certain limitation, and liquid phase method can prepare that particle diameter is little, purity is high and the powder of good dispersity.Liquid phase method is generally with Cu
2+salt is raw material, with S-WAT, hydrazine hydrate, oxammonium sulfate, glucose, rongalite etc. for reductive agent, obtains Red copper oxide, and utilize simple method by redox reaction, prepares the ultra-fine Cu of morphology controllable
2o is the problem that those skilled in the art endeavour to study.Chinese patent application (CN104030339A) discloses a kind of preparation method of cubes cuprous nano material, the method take cupric sulfate pentahydrate as copper source, glucose is reductive agent, liquid phase reduction and hydrothermal method is used to obtain the Red copper oxide material of cubes pattern, because the method adds highly basic in reaction solution, easily cause local ph too high, the Red copper oxide specific surface area of preparation is larger, be unfavorable for the control of pattern, be not suitable for for anti-fouling ship paint, in addition, adopt glucose as reductive agent, cost is too high, from industrialization angle, unpractical.Chinese patent (101412530A) discloses a kind of preparation method utilizing organic addition for controlling external morphology of cuprous oxide crystal, the method utilizes Sodium.alpha.-hydroxypropionate as mantoquita complexing agent and reductive agent, cuprous oxide crystal is prepared under thermal and hydric environment, the morphology Control of Red copper oxide is realized by the kind and dosage controlling organic additive, wherein add acetone and can prepare cubical Red copper oxide, but the method needs the amount of the organic solvent added larger, and organic solvent is inflammable, explosive and poisonous, give and produce, store, transport, use and bring very large danger and difficulty.In addition, liquid phase reduction is raw material mainly with copper sulfate, high due to raw materials cost, limit liquid phase reduction process of industrialization, and printed-wiring board (PWB) (PCB) is the basic element of character of electronic product, along with the fast development of electronics and information industry, the demand of printed-wiring board (PWB) is also in continuous growth, in printed-wiring board (PWB) making processes, the Copper Foil of 80% ~ 90% is removed through etching solution, after in etching solution, cupric ratio acquires a certain degree, etching solution cannot meet making needs and become waste liquid, how these devil liquor recovery are utilized, also be the problem that present invention applicant endeavours to study.
Summary of the invention
For solving above Problems existing, the object of this invention is to provide a kind of with low cost, produce and prepare the method for the micro-nano cuprous oxide powder of cubes efficiently.
For realizing above object, the preparation method of the micro-nano cuprous oxide powder of cubes of the present invention, in turn includes the following steps:
(1) Cu is prepared
2+the copper liquid that concentration is 80-120g/L, pH value is 2.5-3.5, stirs copper liquid and is preheated to 40-50 DEG C;
(2) sodium carbonate, S-WAT are dissolved in the water respectively, form sodium carbonate solution and sodium sulfite solution;
(3) first in copper liquid, add compound dispersion agent, then add sodium sulfite solution fast, then slowly drip sodium carbonate solution, control the pH of reaction soln at 3.0-5.0, continue stir and be heated to 60-100 DEG C;
(4) react after 1-5 hour, by the reaction final product collected through solid-liquid separation, washing, drying, obtain the micro-nano cuprous oxide powder of cubes;
Wherein the compound dispersion agent of step (2) be gelatin and Sodium dodecylbenzene sulfonate in mass ratio 1:1 prepare, the sodium sulfite solution concentration of step (2) is 180-220g/L.
In order to cost-saving, reach the object of waste reclaimation, environmental protection and energy saving, above-mentioned copper liquid is the mixed solution of printed-wiring board (PWB) restored acid etching waste liquor and alkaline etched waste liquid simultaneously.
More stable in order to ensure the pH value of reaction soln, the preferred 180-220g/L of concentration of the sodium carbonate solution in above-mentioned steps (3).
In order to better control reaction times and economic benefit, in aforesaid method, the mass ratio of copper liquid, compound dispersion agent, sodium sulfite solution and sodium carbonate solution controls at 1 ︰ 0.01-0.02 ︰ 2.5-3.5 ︰ 0.5-1.0.
The drying of above-mentioned steps (4) is vacuum-drying, and temperature controls at 30 ~ 70 DEG C.
In order to avoid the introducing of other impurity, the pH value of above-mentioned steps (1) copper liquid controls preferably by dropping sodium carbonate.
The preparation method of the micro-nano cuprous oxide powder of cubes of the present invention, utilize S-WAT reduction bivalent cupric ion, in liquid-phase reduction process, sodium carbonate solution is adopted to regulate the pH value of reaction soln, avoid the big ups and downs of reacting solution pH value, adopt gelatin and Sodium dodecylbenzene sulfonate (SDBS) as compound dispersion agent, control copper liquid and the concentration of S-WAT and the temperature of each step by strict simultaneously, make the Red copper oxide of acquisition not only smooth surface be easy to cleaning, and can particle diameter that effectively controlled oxidization is cuprous and pattern.Preparation method of the present invention, simple to operate, technique is easy to control, the cuprous oxide powder obtained by the inventive method is cubes, particle diameter is between 0.4-3.0 μm, and specific surface area is little, and cupric ion release is slow, tap density is little, suspension is good, and oil number is low, is particularly suitable for being applied in anti-fouling ship paint.In addition, the present invention also provides a new technological approaches for the recycling of circuit board etching liquid, more greatly can reduce the cost that liquid phase reduction prepares Red copper oxide, be conducive to the process of industrialization promoting Red copper oxide.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the embodiment of the present invention 1 gained Red copper oxide.
Fig. 2 is the stereoscan photograph of the embodiment of the present invention 2 gained Red copper oxide.
Fig. 3 is the stereoscan photograph of the embodiment of the present invention 3 gained Red copper oxide.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further described; but these embodiments are also not used to limit the scope of the invention; under the prerequisite not departing from theory of the present invention, to the change in copper liquid source or the replacement of reductive agent, protection scope of the present invention all should be belonged to.
Embodiment 1
(1) printed-wiring board (PWB) restored acid etching waste liquor and alkaline etched waste liquid are mixed by a certain percentage, the pH controlling the rear copper liquid of mixing, 3.0, adopts method that is concentrated or moisturizing to be mixed with Cu
2+concentration is the copper liquid A of 100g/L;
(2) sodium carbonate, S-WAT are dissolved in the water respectively, are mixed with the sodium sulfite solution C that sodium carbonate solution B that concentration is 200g/L and concentration are 200g/L;
(3) get 500mL solution A stir and be preheated to 50 DEG C, add the compound dispersion agent of 0.8g, compound dispersion agent is gelatin and the Sodium dodecylbenzene sulfonate of mass ratio 1:1;
(4) 750mL solution C added fast in the solution of step (3), slowly drip solution B, the pH value controlling reaction soln is 4.5, continues stir and be heated to 90 DEG C;
(5) react after 2 hours, the reaction final product collected is filtered, after water or washing with alcohol twice, dries at 40 DEG C with vacuum drying oven, obtain bright red, cubes cuprous oxide powder product that particle diameter is 1.5-2.1um, Fig. 1 is shown in by the photo of its scanning electronic microscope.
Embodiment 2
(1) mixed by a certain percentage with alkaline etched waste liquid by printed-wiring board (PWB) restored acid etching solution, the pH controlling the rear copper liquid of mixing, 3.0, adopts method that is concentrated or moisturizing to be mixed with Cu
2+concentration is the copper liquid A of 120g/L;
(2) sodium carbonate, S-WAT are dissolved in the water respectively, are mixed with the sodium sulfite solution C that sodium carbonate solution B that concentration is 210g/L and concentration are 200g/L.
(3) get 500mL solution A stir and be preheated to 45 DEG C, add the compound dispersion agent of 0.5g, compound dispersion agent is gelatin and the Sodium dodecylbenzene sulfonate of mass ratio 1:1;
(4) 700mL solution C added fast in the solution of step (3), slowly drip solution B, the pH value controlling reaction soln is 4.5, continues to be heated with stirring to 83 DEG C;
(5) react after 2.5 hours, the reaction final product collected is filtered, after water or washing with alcohol twice, dries at 40 DEG C with vacuum drying oven, obtain bright red, cubes cuprous oxide powder product that particle diameter is 1.1-1.8um, Fig. 2 is shown in by the photo of its scanning electronic microscope.
Embodiment 3
(1) mixed by a certain percentage with alkaline etched waste liquid by printed-wiring board (PWB) restored acid etching solution, the pH controlling the rear copper liquid of mixing, 2.5, adopts method that is concentrated or moisturizing to be mixed with Cu
2+concentration is the copper liquid A of 90g/L;
(2) sodium carbonate, S-WAT are dissolved in the water respectively, are mixed with the sodium sulfite solution C that sodium carbonate solution B that concentration is 190g/L and concentration are 200g/L;
(3) get 500mL solution A stir and be preheated to 50 DEG C, add the compound dispersion agent of 1g, compound dispersion agent is gelatin and the Sodium dodecylbenzene sulfonate of mass ratio 1:1;
(4) 800mL solution C joined fast in the solution of step (3), slowly drip solution B, controlling reaction soln pH is 3.5, continues stir and be heated to 100 DEG C;
(5) react after 4 hours, the reaction final product collected is filtered, after water or washing with alcohol twice, dries at 40 DEG C with vacuum drying oven, obtain bright red, cubes cuprous oxide powder product that particle diameter is 0.4-1.5um, Fig. 3 is shown in by the photo of its scanning electronic microscope.
The product that above-described embodiment 1-3 is obtained, its Cu
2+yield is all more than 99%.
The product obtained by above-described embodiment 1-3, according to industrial standard HG/T2961-2010 detection method detects, and detected result is as following table:
As can be seen from the above table, this product obtained by invention preparation method, high purity 98%, indices all meets the high-quality product standard of industrial standards HG/T2961-2010.
Claims (6)
1. a preparation method for the micro-nano cuprous oxide powder of cubes, in turn includes the following steps:
(1) Cu is prepared
2+the copper liquid that concentration is 80-120g/L, pH value is 2.5-3.5, stirs copper liquid and is preheated to 40-50 DEG C;
(2) sodium carbonate, S-WAT are dissolved in the water respectively, form sodium carbonate solution and sodium sulfite solution;
(3) first in copper liquid, add compound dispersion agent, then add sodium sulfite solution fast, then slowly drip sodium carbonate solution, control the pH of reaction soln at 3.0-5.0, continue stir and be heated to 60-100 DEG C;
(4) react after 1-5 hour, by the reaction final product collected through solid-liquid separation, washing, drying, obtain the micro-nano cuprous oxide powder of cubes;
Wherein the compound dispersion agent of step (2) be gelatin and Sodium dodecylbenzene sulfonate in mass ratio 1:1 prepare, the sodium sulfite solution concentration of step (2) is 180-220g/L.
2. the preparation method of the micro-nano cuprous oxide powder of cubes according to claim 1, is characterized in that: described copper liquid is the mixed solution of printed-wiring board (PWB) restored acid etching waste liquor and alkaline etched waste liquid.
3. the preparation method of the micro-nano cuprous oxide powder of cubes according to claim 1 and 2, is characterized in that: the concentration of the sodium carbonate solution in described step (3) is 180-220g/L.
4. the preparation method of the micro-nano cuprous oxide powder of cubes according to claim 3, it is characterized in that: in described method, the mass ratio of copper liquid, compound dispersion agent, sodium sulfite solution and sodium carbonate solution controls at 1 ︰ 0.01-0.02 ︰ 2.5-3.5 ︰ 0.5-1.0.
5. the preparation method of the micro-nano cuprous oxide powder of cubes according to claim 4, is characterized in that: the drying of described step (4) is vacuum-drying, and temperature controls at 30 ~ 70 DEG C.
6. the preparation method of the micro-nano cuprous oxide powder of cubes according to claim 1 and 2, is characterized in that: the pH value of described step (1) copper liquid controls preferably by dropping sodium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510013588.9A CN104591257B (en) | 2015-01-12 | 2015-01-12 | The preparation method of the micro-nano cuprous oxide powder of a kind of cubes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510013588.9A CN104591257B (en) | 2015-01-12 | 2015-01-12 | The preparation method of the micro-nano cuprous oxide powder of a kind of cubes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104591257A CN104591257A (en) | 2015-05-06 |
| CN104591257B true CN104591257B (en) | 2016-01-06 |
Family
ID=53117375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510013588.9A Active CN104591257B (en) | 2015-01-12 | 2015-01-12 | The preparation method of the micro-nano cuprous oxide powder of a kind of cubes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104591257B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105400955A (en) * | 2015-11-19 | 2016-03-16 | 湖南力泓新材料科技股份有限公司 | Method for removing copper ions in zinc sulfate solution |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249276C (en) * | 2003-07-11 | 2006-04-05 | 华中师范大学 | Method for preparing stable nanometer cuprous oxide whiskers with chemical precipitation method |
| CN102390861A (en) * | 2011-08-17 | 2012-03-28 | 金川集团有限公司 | Method for preparing cuprous oxide powder |
| CN103112883B (en) * | 2012-12-10 | 2015-03-04 | 浙江理工大学 | Method for preparing superfine cuprous oxide powder |
| CN103043703B (en) * | 2013-01-05 | 2014-06-11 | 河北工业大学 | Preparation method of hollow Cu2O cubic box |
-
2015
- 2015-01-12 CN CN201510013588.9A patent/CN104591257B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104591257A (en) | 2015-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101532096B (en) | A recovery method of tin in tin-stripping waste liquid | |
| CN104386679A (en) | Method for preparing graphene oxide and graphene | |
| CN101524763A (en) | Method for preparing submicron spherical copper powder | |
| CN110923448B (en) | Preparation method for obtaining high-purity praseodymium oxide and neodymium oxide by singly separating praseodymium-neodymium enrichment | |
| CN111635994A (en) | Method for recovering copper from acidic copper-containing etching solution and preparing cuprous oxide | |
| CN103388076A (en) | Method for recovering elementary substance arsenic from arsenic sulfide slag | |
| CN105817645A (en) | Ultra-pure silver powder preparation method capable of controlling particle size | |
| CN104591257B (en) | The preparation method of the micro-nano cuprous oxide powder of a kind of cubes | |
| CN104291331A (en) | Selectively oxidized graphene material and preparation method thereof | |
| CN106082297B (en) | A kind of preparation method of 20~60 microns of gadolinium oxides of medium particle diameter | |
| CN105366713B (en) | A kind of method utilizing stannum waste residue to produce high-purity sodium stannate | |
| CN103303964A (en) | Method for producing food-grade copper sulfate by smelting byproduct-copper sulfate | |
| CN103979600B (en) | A kind of preparation method of ultrafine copper oxide powder | |
| CN110143675A (en) | Industrial circulating cooling water system without phosphorus prefilming agent and preparation method thereof | |
| CN114408943B (en) | Method for preparing cuprous thiocyanate nanoparticles through solid-phase synthesis | |
| CN110479267A (en) | A kind of photochemical catalyst of degradation of organic substances impurity and application | |
| Guo et al. | Recovery of copper from printed circuit board (PCB) acidic etching wastewater: Ammonia regulates the crystallization of high valued copper salt | |
| CN104591256B (en) | A kind of method that cuprous oxide is prepared under copper chloride system | |
| CN1105682C (en) | Process for Preparing nm-class cobalt oxide | |
| CN108178174B (en) | Method for preparing sapphire-grade high-purity aluminum oxide by using aluminum anodic oxidation waste liquid | |
| CN108500290A (en) | A kind of preparation method of sheet cobalt powder | |
| US20220324718A1 (en) | Method for preparing basic copper carbonate | |
| CN112850772A (en) | Method for preparing calcium sulfate by using calcium-containing waste liquor of fluorite ore | |
| CN109399693A (en) | A kind of preparation process of high-purity nano-zinc oxide | |
| WO2022141045A1 (en) | Preparation method for electronic-grade copper chloride dihydrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |