CN104402037B - A kind of method of preparing nano cuprous oxide from printed substrate copper-contained sludge - Google Patents

A kind of method of preparing nano cuprous oxide from printed substrate copper-contained sludge Download PDF

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Publication number
CN104402037B
CN104402037B CN201410581394.4A CN201410581394A CN104402037B CN 104402037 B CN104402037 B CN 104402037B CN 201410581394 A CN201410581394 A CN 201410581394A CN 104402037 B CN104402037 B CN 104402037B
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printed substrate
substrate copper
contained sludge
mud
cuprous oxide
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CN201410581394.4A
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CN104402037A (en
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修福荣
齐莹莹
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Fujian University of Technology
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Fujian University of Technology
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

The invention discloses a kind of method of preparing nano cuprous oxide from printed substrate copper-contained sludge; first by printed substrate copper-contained sludge drying and dehydrating; then mud is added in moving electric reaction unit; control the conditions such as current density, protective agent concentration, solid-to-liquid ratio, auxiliary reagent and reaction time; after reaction finishes, catholyte centrifugation is obtained to nanometer Cu2O material. The present invention proposes a kind of eco-friendly, almost nano cuprous oxide (the Cu that reclaims preparation high added value from printed substrate copper-contained sludge of non-secondary pollution2O) method of material. Cu2O is an important p-type metal oxide semiconductor material, and directly bandwidth is 2.2eV. Cu2O nano particle has excellent optics and magnetic force character, has broad application prospects at aspects such as catalyst, solar cell, gas sensor and cathode material for lithium ion battery.

Description

A kind of method of preparing nano cuprous oxide from printed substrate copper-contained sludge
Technical field
The invention belongs to waste recovery processing technology field, specifically, the present invention relates toA kind of method of preparing nano cuprous oxide from printed substrate copper-contained sludge.
Background technology
In recent years, along with the development of electronics industry, printed substrate manufacturing industry development poleFor rapidly. In the production process of printed substrate, can produce a large amount of acid waste water. OrderBefore, conventionally adopt neutralization precipitation processing for this class waste water, produce thus a large amount of cuprics,The mud of the heavy metals such as iron. This type of moisture percentage in sewage sludge approximately 65%～80%, pH is 6.8～9.8Between, copper content is between 1%～5%. This type of copper-contained sludge belongs to hazardous waste, withMeaning is stacked and is disposed and easily causes leaching ability of heavy metal, and again enters water body or soil and makeBecome secondary pollution. On the other hand, due to copper content opening far above copper mine in this type of mudAdopt grade, therefore any disposal certainly will cause the significant wastage of resource.
At present, the technique that reclaims copper from printed substrate copper-contained sludge can be divided into heatReason technology and the large class of chemical treatment method two. Heat treatment technics energy consumption is higher and easily causeA large amount of Air Pollutant Emission. Chemical treatment mainly comprises that acidleach, ammonia soak, ultrasonic waveAccelerate acidleach, electrochemical deposition etc. Above-mentioned chemical treatment method also exists selectively low,Secondary pollution problems. What is more important, current existing technical method is all to returnThe concentrated solution of receiving metallic copper simple substance, copper-containing compound or metal copper ion is target,Cause reclaiming value-added content of product not high. Therefore, the friendly type of development environment from trackSelective recovery copper prepare high value added product in the plate copper-contained sludge of road, has wideProspect.
The relative deficiency existing for prior art, proposes the present invention.
Summary of the invention
The object of the invention is to propose a kind of environmental friendliness, almost non-secondary pollution from printingBrush wiring board copper-contained sludge is directly prepared the nano cuprous oxide (Cu of high added value2O) materialThe method of material.
Technical scheme provided by the invention is: one is received from the preparation of printed substrate copper-contained sludgeThe method of rice cuprous oxide, comprises the following steps:
A) baking oven that printed substrate copper-contained sludge is placed in to 105 degree is dried to constant weight, cooling;
B) cooled mud is added in moving electric reaction unit, moving electric reaction unit is three Room reactionsDevice, is respectively anode chamber, mud room, cathode chamber, anode chamber, mud room and cathode chamber twoBetween two, separate with amberplex, auxiliary reagent is watery hydrochloric acid or dilute sulfuric acid, concentration controlAt 0.5mol/L-1mol/L, controlling reaction solid-to-liquid ratio is 1:20-1:40 grams per milliliter, protectionThe interpolation concentration of agent is controlled at 5-50g/L, controls moving electric reaction condition, and current density is controlled at10-40mA/cm2, the reaction time is controlled at 1-6 hour, mud room and negative electrode in course of reactionDistrict keeps permanent by magnetic agitation stirs, and mixing speed is 1500-2000rpm; Protective agent is for poly-Vinylpyrrolidone;
Step c) react and finish after, take out catholyte centrifugation, use immediately 30% (v/v)Water/alcohol mixeding liquid rinses gained nanometer Cu2O particle three times, removes water miscible impurity and productThe protective agent of product adsorption;
Steps d) by the nanometer Cu obtaining2O product is dry under room temperature vacuum.
The invention has the beneficial effects as follows:
The present invention proposes a kind of eco-friendly, almost non-secondary pollution from printed substrateIn copper-contained sludge, reclaim the nano cuprous oxide (Cu of preparation high added value2O) method of material.Cu2O is an important p-type metal oxide semiconductor material, and directly bandwidth is 2.2eV.Cu2O nano particle has excellent optics and magnetic force character, catalyst, solar cell,The aspect such as gas sensor and cathode material for lithium ion battery has broad application prospects.
Brief description of the drawings
When considered in conjunction with the accompanying drawings, by the detailed description with reference to below, can be more completeUnderstand well the present invention and easily learn wherein many advantages of following, but described hereinAccompanying drawing be used to provide a further understanding of the present invention, form a part of the present invention, thisThe schematic description and description of invention is used for explaining the present invention, does not form the present inventionImproper restriction, wherein:
Fig. 1 is that printed substrate copper-contained sludge of the present invention is prepared high added value nanometer Cu2O materialProcess chart;
Fig. 2 is that (in figure, PVP is polyethylene pyrrole for moving electric reaction unit schematic diagram in the present inventionPyrrolidone);
The nanometer Cu that Fig. 3 prepares2The XRD diffraction analysis collection of illustrative plates of O particle;
The Cu that Fig. 4 prepares2The transmission electron microscope picture of O nano particle.
Detailed description of the invention
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, belowThe present invention is further detailed explanation with detailed description of the invention by reference to the accompanying drawings.
Embodiment 1:
As shown in Figure 1, the one of the present embodiment is prepared nanometer from printed substrate copper-contained sludgeThe method of cuprous oxide, comprises the following steps:
A) baking oven that printed substrate copper-contained sludge is placed in to 105 degree is dried to constant weight, cooling;
B) cooled mud is added in moving electric reaction unit, moving electric reaction unit is three Room reactionsDevice (as shown in Figure 2), is respectively anode chamber, mud room, cathode chamber, anode chamber,Mud room and cathode chamber separate with amberplex between any two, auxiliary reagent be watery hydrochloric acid orDilute sulfuric acid, concentration is controlled at 0.5mol/L, and controlling reaction solid-to-liquid ratio is 1:40 grams per milliliter,Protectant interpolation concentration is controlled at 50g/L, controls moving electric reaction condition, current density controlAt 40mA/cm2, the reaction time is controlled at 4 hours, mud room and cathodic region in course of reactionKeep permanent by magnetic agitation and stir, mixing speed is 2000rpm; Protective agent is polyethylene pyrrolePyrrolidone;
Step c) react and finish after, take out catholyte centrifugation, use immediately 30% (v/v)Water/alcohol mixeding liquid rinses gained nanometer Cu2O particle three times, removes water miscible impurity and productThe protective agent of product adsorption;
Steps d) by the nanometer Cu obtaining2O product is dry under room temperature vacuum.
Finally, the nanometer Cu of acquisition2After O product is dry under room temperature vacuum, carry out XRD diffractionAnalyze and transmission electron microscope sign, analysis result is shown in respectively Fig. 3 and Fig. 4. Fig. 3 shows acquisitionProduct is the Cu of cube crystalline phase2O. Fig. 4 can find out, Cu2O nano particle approximate regulationSpherical, and high degree of dispersion, thering is uniformity highly, average-size is 10nm.
Embodiment 2:
As shown in Figure 1, the one of the present embodiment is prepared nanometer from printed substrate copper-contained sludgeThe method of cuprous oxide, comprises the following steps:
A) baking oven that printed substrate copper-contained sludge is placed in to 105 degree is dried to constant weight, cooling;
B) cooled mud is added in moving electric reaction unit, moving electric reaction unit is three Room reactionsDevice (as shown in Figure 2), is respectively anode chamber, mud room, cathode chamber, anode chamber,Mud room and cathode chamber separate with amberplex between any two, auxiliary reagent be watery hydrochloric acid orDilute sulfuric acid, concentration is controlled at 1mol/L, and controlling reaction solid-to-liquid ratio is 1:20 grams per milliliter, protectsThe interpolation concentration of protecting agent is controlled at 5g/L, controls moving electric reaction condition, and current density is controlled at10mA/cm2, the reaction time is controlled at 1 hour, and in course of reaction, mud room and cathodic region are usedMagnetic agitation keeps permanent and stirs, and mixing speed is 1500rpm; Protective agent is polyethylene pyrrolesAlkane ketone;
Step c) react and finish after, take out catholyte centrifugation, use immediately 30% (v/v)Water/alcohol mixeding liquid rinses gained nanometer Cu2O particle three times, removes water miscible impurity and productThe protective agent of product adsorption;
Steps d) by the nanometer Cu obtaining2O product is dry under room temperature vacuum.
Finally, the nanometer Cu of acquisition2After O product is dry under room temperature vacuum, carry out XRD diffractionAnalyze and transmission electron microscope sign. Result shows that the product obtaining is the Cu of cube crystalline phase2O。Cu2ONano particle approximate regulation spherical, and high degree of dispersion, have the uniformity of height, averageBe of a size of 50nm.
Embodiment 3:
As shown in Figure 1, the one of the present embodiment is prepared nanometer from printed substrate copper-contained sludgeThe method of cuprous oxide, comprises the following steps:
A) baking oven that printed substrate copper-contained sludge is placed in to 105 degree is dried to constant weight, cooling;
B) cooled mud is added in moving electric reaction unit, moving electric reaction unit is three Room reactionsDevice (as shown in Figure 2), is respectively anode chamber, mud room, cathode chamber, anode chamber,Mud room and cathode chamber separate with amberplex between any two, auxiliary reagent be watery hydrochloric acid orDilute sulfuric acid, concentration is controlled at 1mol/L, and controlling reaction solid-to-liquid ratio is 1:30 grams per milliliter, protectsThe interpolation concentration of protecting agent is controlled at 30g/L, controls moving electric reaction condition, and current density is controlled at20mA/cm2, the reaction time is controlled at 6 hours, and in course of reaction, mud room and cathodic region are usedMagnetic agitation keeps permanent and stirs, and mixing speed is 1600rpm; Protective agent is polyethylene pyrrolesAlkane ketone;
Step c) react and finish after, take out catholyte centrifugation, use immediately 30% (v/v)Water/alcohol mixeding liquid rinses gained nanometer Cu2O particle three times, removes water miscible impurity and productThe protective agent of product adsorption;
Steps d) by the nanometer Cu obtaining2O product is dry under room temperature vacuum.
Finally, the nanometer Cu of acquisition2After O product is dry under room temperature vacuum, carry out XRD diffractionAnalyze and transmission electron microscope sign. Result shows that the product obtaining is the Cu of cube crystalline phase2O。Cu2ONano particle approximate regulation spherical, and high degree of dispersion, have the uniformity of height, averageBe of a size of 30nm.
The explanation of above example is just for helping to understand core concept of the present invention; Meanwhile,For one of ordinary skill in the art, according to thought of the present invention, in detailed description of the inventionAnd all will change in range of application, in sum, this description should not be understoodFor limitation of the present invention.

Claims (1)

1. a method of preparing nano cuprous oxide from printed substrate copper-contained sludge, its feature existsIn, formed by following steps:
A) printed substrate copper-contained sludge is placed in to the baking oven of 105 DEG C and dries to constant weight, cooling;
B) cooled mud is added in moving electric reaction unit, moving electric reaction unit is that three Room are anti-Answer device, be respectively anode chamber, mud room, cathode chamber, anode chamber, mud room and negative electrodeChamber separates with amberplex between any two, and auxiliary reagent is watery hydrochloric acid or dilute sulfuric acid, denseDegree is controlled at 0.5mol/L-1mol/L, and controlling reaction solid-to-liquid ratio is 1:20-1:40 grams per milliliter,Protectant interpolation concentration is controlled at 5 or 50g/L, and protective agent is polyvinylpyrrolidone,Control moving electric reaction condition, current density is controlled at 40mA/cm2, the reaction time is controlledAt 1-6 hour, in course of reaction, mud room and cathode chamber keep permanent stirring by magnetic agitation,Mixing speed is 1500-2000rpm;
Step c) react and finish after, take out catholyte centrifugation, use immediately 30% (v/v)Water/alcohol mixeding liquid rinses gained nanometer Cu2O particle three times, removes water miscible impurityProtective agent with product surface absorption;
Steps d) by the nanometer Cu obtaining2O product is dry under room temperature vacuum.
CN201410581394.4A 2014-10-24 2014-10-24 A kind of method of preparing nano cuprous oxide from printed substrate copper-contained sludge Expired - Fee Related CN104402037B (en)

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CN106390908A (en) * 2016-06-03 2017-02-15 福建工程学院 Apparatus and method for preparing heavy metal adsorbent from sludge of circuit board industry

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1434151A (en) * 2003-02-27 2003-08-06 华中师范大学 Method for preparing nano copper protoxide material by metal copper anodic oxidation method
CN101658941A (en) * 2009-09-24 2010-03-03 无锡市霄鹰环境科技有限公司 Technology for extracting copper powder from waste materials generated in circuit board manufacturing plants by compound extraction method
CN101928098B (en) * 2010-04-22 2012-07-25 江苏技术师范学院 Method for preparing cuprous oxide powder by copper-contained electroplating sludge pressurizing hydrogen reduction

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1434151A (en) * 2003-02-27 2003-08-06 华中师范大学 Method for preparing nano copper protoxide material by metal copper anodic oxidation method
CN101658941A (en) * 2009-09-24 2010-03-03 无锡市霄鹰环境科技有限公司 Technology for extracting copper powder from waste materials generated in circuit board manufacturing plants by compound extraction method
CN101928098B (en) * 2010-04-22 2012-07-25 江苏技术师范学院 Method for preparing cuprous oxide powder by copper-contained electroplating sludge pressurizing hydrogen reduction

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Recovery of copper and lead from waste printed circuit boards by supercritical water oxidation combined with electrokinetic process";Fu-Rong Xiu et al.;《Journal of Hazardous Materials》;20081031;第165卷;第1002–1007页 *
"Size-controlled preparation of Cu2O nanoparticles from waste printed circuit boards by supercritical water combined with electrokinetic process"，;Fu-Rong Xiu et al.，;《Journal of Hazardous Materials》;20120713;第233–234卷;第200–206页 *
"纳米氧化亚铜电化学法制备及光催化研究进展";陈善亮等;《环境化学》;20110531;第30卷(第5期);第976-982页 *

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