CN106673049B - A kind of preparation method of porous graduation ball active oxidation copper powder - Google Patents
A kind of preparation method of porous graduation ball active oxidation copper powder Download PDFInfo
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- CN106673049B CN106673049B CN201710038740.8A CN201710038740A CN106673049B CN 106673049 B CN106673049 B CN 106673049B CN 201710038740 A CN201710038740 A CN 201710038740A CN 106673049 B CN106673049 B CN 106673049B
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Abstract
The invention belongs to no ammonia process rapidly and efficiently to prepare porous graduation ball active oxidation copper technology, and in particular to a kind of preparation method of porous graduation ball active oxidation copper powder.The features such as extensively, process flow is simple for raw material selection of the present invention, easy to operate, and product is easy to wash, and less investment, low energy consumption, and space-time yield is high.The method that the present invention uses makes copper ion concentration 40-80 g/L in copper salt solution 1) to prepare copper salt solution；2) lye is prepared, Na ion concentration 20-60 g/L in lye is made；3) in the case where temperature is 60-90 DEG C, copper salt solution is added in lye, reaction to neutrality, i.e. pH=7 while stirring in 20-30min, then is aged 25-35min；4) it filters, with pure water 3 times；5) dry and heat resolve obtains porous graduation ball active copper oxide.
Description
One, technical field
The invention belongs to no ammonia process rapidly and efficiently to prepare porous graduation ball active oxidation copper technology, and in particular to Yi Zhongduo
The preparation method of hole graduation ball active oxidation copper powder.
Two, background technique:
Currently, the cupric oxide powder size in catalytic field requires generally in nano-level, the copper oxide of the scale just has
High specific surface area (20~50m2/ g), but complex process, production capacity are small, easy to reunite during the preparation process for nano oxidized copper powder,
And surfactant is generally added, this will reduce the purity and catalytic activity of copper oxide, and be added when washing organic molten
Agent.
Prepare that cupric oxide powder technique is excessively complicated, and environmental pollution is serious, and obtained copper oxide is due to the effects of reuniting folder
Miscellaneous impurity content is higher, and product is generally unformed, and solution rate relatively slow (generally more than 40s) even cannot be completely molten
Solution.
Plating-grade copper oxide generally requires copper oxide to have still to have high solution rate in the electrolytic solution.But it is traditional activated
When system cupric oxide powder preparation: solution prepare complex or even to use complex device and technique (such as number of patent application
CN201010207485.3；201410612009.8)；And it to be filtered or be centrifuged, be dried, be calcined, is crushed, sieved and obtain most
Finished product.In active copper oxide preparation process, many techniques have all used ammonium hydroxide (such as number of patent application
201210336633.0；CN201210559066.5；201410550840.5；) or surfactant CN201410721949.0
(number of patent application CN201210123571.5), which adds technology difficulties and wastewater treatment difficulty.
Three, summary of the invention
The present invention provides a kind of preparation method of porous graduation ball active oxidation copper powder, easy to operate, space-time yield
It is high.
To achieve the above object, the technical solution adopted by the present invention are as follows: the porous graduation ball active oxidation copper powder of one kind
Preparation method, it is characterised in that: it is described the preparation method comprises the following steps:
1) copper salt solution is prepared, copper ion concentration 40-80g/L in copper salt solution is made；
2) lye is prepared, Na ion concentration 20-60g/L in lye is made；
3) in the case where temperature is 60-90 DEG C, copper salt solution is added in lye while stirring in 20-30min, reaction is extremely
Neutrality, i.e. pH=7, then it is aged 25-35min；
4) it filters, with pure water 3 times；
5) dry and heat resolve obtains porous graduation ball active copper oxide.
The drying temperature is 120 DEG C, and the temperature of heat resolve is 400 DEG C.
Compared with prior art, the invention has the advantages that and effect:
1, copper salt solution of the present invention is prepared simply and concentration is big, is increased output efficiency, is reduced the dosage of water, reduce waste water
Treating capacity and its difficulty；
2, present invention preparation resulting product granularity is larger, is easy to wash and wash free of losses, metal recovery rate height；
3, the entire technical process mechanism of the present invention is clear, and technological operation is simple, can utilize raw material to the greatest extent, save original
Material, reaction end is easily controllable, while reducing environmental pollution, effectively that surfactant, ammonium hydroxide is not added in preparation process
Production capacity is promoted, by taking nano cupric oxide as an example as a comparison, the market price of nano cupric oxide is in 200,000/ton or so, and the technique produces
Copper oxide cost in 60,000/ton hereinafter, this will substantially reduce downstream producer operating cost；
4, the present invention obtains the parameter of product: oxidation copper content is greater than 95%, and anion-content is less than 0.03%, specific surface
Product BET is 15~25m2/ g, apparent density can be adjusted between 0.7~1.5g/mL, in the dilute sulfuric acid that magneton quickly stirs
Middle solution rate 25-40s, pattern are micron particles (diameter 20-70 μ made of micron bar (diameter 500nm, 2 μm of length) accumulation
M),
5, product of the present invention solution rate 25-40s in the dilute sulfuric acid that magneton quickly stirs, meets making for active copper oxide
With performance, meanwhile, it is also equipped with the performance of nano oxidized copper products, alternative nano cupric oxide is widely used in electroplating technology, urges
Agent and catalyst carrier.
Four, Detailed description of the invention:
The porous graduation ball active copper oxide preparation technology flow chart of Fig. 1；
SEM picture (a: evenly dispersed spherical sample figure of the porous graduation ball active oxidation copper sample of Fig. 2；B: sample
Porous graded structure figure)；
The XRD diagram (monoclinic system) of the porous graduation ball active oxidation copper sample of Fig. 3.
Five, specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Referring to Fig. 1, it is a kind of it is porous graduation ball active oxidation copper powder the preparation method comprises the following steps:
1) copper salt solution is prepared, copper ion concentration 40-80g/L in copper salt solution is made；
2) lye is prepared, Na ion concentration 20-60g/L in lye is made；
3) in the case where temperature is 60-90 DEG C, copper salt solution is added in lye while stirring in 20-30min, reaction is extremely
Neutral (the ratio between sodium ion and copper ion amount of substance are 2:1), i.e. pH=7, then it is aged 25-35min；
4) it filters, with pure water 3 times；
5) dry and heat resolve obtains porous graduation ball active copper oxide.
The drying temperature is 120 DEG C, and the temperature of heat resolve is 400 DEG C.
Reaction mechanism of the invention:
(1) initial reaction stage, a small amount of copper ion, which is added in alkaline medium, firstly generates navy blue tetrahydroxy conjunction copper complex ion
Solution, and solution is clarified；
(2) as copper ion concentration increases, copper ion generate Kocide SD flocculent deposit, but this be deposited in strong basicity by
It is extremely unstable in hydrothermal solution, it decomposes generate nano cupric oxide nucleus rapidly；
(3) as copper ion concentration further increases, solution ph will continue to reduce, and basic carbonate is quickly generated in solution
Copper precipitating, newly-generated basic copper carbonate precipitating can be coated on the surface of nano cupric oxide, send out the nucleus in step (2) quickly
It educates and grows up；
(4) continuously adding with mantoquita, solution ph further decrease, and it is heavy that a small amount of copper carbonate is quickly generated in solution
It forms sediment, nucleus is made further to grow up, until solution is neutrality, reaction terminates；
(5) the complicated intermediate that above-mentioned reaction obtains passes through active oxygen that is dry and thermally decomposing to generate porous graduation ball
Change copper products.
Embodiment 1:
Weigh 107.2g CuCl2·H2O is dissolved in pure water and is made into 1L solution (Cu2+Concentration is 40g/L), weigh 106g
NaHCO3It is dissolved in pure water and is made into 1.2L solution (Na+Ion concentration 24.5g/L), by NaHCO3Solution is added in the beaker of 3L, machine
Under the conditions of being preheated to 85 DEG C and keeping the reaction temperature, CuCl is added in tool stirring2Solution adds in 30min, pH=7.Ageing
Half an hour.
It filters, 50mL pure water 3 times.
Powder drying and thermal decomposition after washing obtain porous graduation ball active copper oxide.
The drying temperature is 120 DEG C, and the temperature of heat resolve is 400 DEG C.
Embodiment 2:
Weigh 266.4g Cu (NO3)2·3H2O is dissolved in pure water and is made into 1L solution (Cu2+Concentration is 70g/L), weigh 118.5g
Na2CO3It is dissolved in pure water and is made into 1.2L solution (Na+Ion concentration 43g/L), by Na2CO3Solution is added in the beaker of 3L, mechanical
Under the conditions of being preheated to 75 DEG C and keeping the reaction temperature, Cu (NO is added in stirring3)2Solution adds in 30min, pH=7.Ageing
Half an hour.
It filters, 50mL pure water 3 times.
Powder drying and thermal decomposition after washing obtain porous graduation ball active copper oxide.
The drying temperature is 120 DEG C, and the temperature of heat resolve is 400 DEG C.
Embodiment 3:
Weigh 236g Cu (SO4)2·5H2O is dissolved in pure water and is made into 1L solution (Cu2+Concentration is 60g/L), it weighs respectively
19.2g sodium hydroxide and 51.2g Na2CO3It is dissolved in pure water and is made into 1.2L solution (Na+Ion concentration 36.8g/L), by above-mentioned alkalinity
Mixed solution is added in the beaker of 3L, mechanical stirring, and under the conditions of being preheated to 65 DEG C and keeping the reaction temperature, Cu is added
(SO4)2Solution adds in 30min, pH=7.It is aged half an hour.
It filters, 50mL pure water 3 times.
Powder drying and thermal decomposition after washing obtain porous graduation ball active copper oxide.
The drying temperature is 120 DEG C, and the temperature of heat resolve is 400 DEG C.
Referring to fig. 2, this is the SEM picture of most preferred embodiment 2, and the product pattern is that micron bar is (straight as we can see from the figure
Micron spheric granules (20-70 μm of diameter, as shown in Figure 2 a) made of accumulation diameter 500nm, 2 μm of length, as shown in Figure 2 b).
Referring to Fig. 3, this is the XRD diagram of most preferred embodiment 2, from the figure, it can be seen that the product is in 2 θ=32.51 °,
35.54°,38.91°,46.26°,48.71°,53.48°,58.26°,61.52°,66.44°,67.91°,72.37°,75.24°
There is stronger diffraction maximum at place.Discovery is mutually retrieved by object: the 48-1548 sample in the product and PDF card coincide, and is monoclinic system.
In conclusion only present pre-ferred embodiments, are not intended to limit the scope of the present invention.
Claims (1)
1. a kind of preparation method of porous graduation ball active oxidation copper powder, it is characterised in that: it is described the preparation method comprises the following steps:
1) CuSO is weighed4·5H2O or Cu(NO3)2·3H2O prepares copper salt solution, makes copper ion concentration 70 in copper salt solution
g/L；
2) lye is prepared, 43 g/L of Na ion concentration in lye is made, the lye is sodium carbonate pure water solution；
3) it is 65-85 DEG C in temperature, copper salt solution is added in lye while stirring in 30 min, reaction to neutrality, i.e.,
PH=7, then it is aged 30 min；
4) it filters, with pure water 3 times；
5) it is dried at 120 DEG C and is heated to 400 DEG C and decomposes to obtain porous graduation ball active copper oxide, described porous point
The specific surface area BET of grade ball active copper oxide is 15-25m2/ g, apparent density can be adjusted between 0.7-1.5g/mL
Whole, the solution rate 25-40s in the dilute sulfuric acid that magneton quickly stirs, pattern is micron particles made of micron bar accumulation, institute
Stating micron bar diameter is 500nm, and length is 2 μm, and the diameter of the micron particles is 20-70 μm.
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| CN109970092B (en) * | 2017-12-27 | 2021-09-21 | 广州科城环保科技有限公司 | Preparation method of high-bulk-density basic copper carbonate |
| CN109337088B (en) * | 2018-11-23 | 2019-08-02 | 西安工业大学 | A method of monodisperse cubic crystal PCPs material is prepared by raw material of copper formate |
| CN111330601B (en) * | 2020-03-14 | 2022-11-22 | 西安工业大学 | Preparation method of cuprous oxide composite material with core-shell structure |
| CN111330600B (en) * | 2020-03-14 | 2021-09-03 | 西安工业大学 | Preparation method of cuprous oxide composite material with porous structure |
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| CN105084410B (en) * | 2015-08-15 | 2016-09-14 | 淮北师范大学 | A kind of preparation method of the micro-nano hierarchy of the spherical CuO of controllable |
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Non-Patent Citations (2)
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| Formation Process of Cu2(OH)2CO3 and CuO Hierarchical Nanostructures by Assembly of Hydrated Nanoparticles;Jinhe Sun等;《Journal of Nanoscience and Nanotechnology》;20091231;第9卷;第5903–5909页 |
| 氧化铜、碱式碳酸铜纳米矿物的合成及其表面络合研究;孙和云;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20130415;第14-21页 |
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