CN110385443A - A kind of preparation method of acid system Nanometer Copper colloidal sol - Google Patents
A kind of preparation method of acid system Nanometer Copper colloidal sol Download PDFInfo
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- CN110385443A CN110385443A CN201910698066.5A CN201910698066A CN110385443A CN 110385443 A CN110385443 A CN 110385443A CN 201910698066 A CN201910698066 A CN 201910698066A CN 110385443 A CN110385443 A CN 110385443A
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- copper
- colloidal sol
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- nanometer copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
Abstract
The present invention relates to a kind of preparation methods of acid system Nanometer Copper colloidal sol, belong to nanometer copper product and copper catalyst technical field.Preparation including copper solution, the preparation of dispersing agent, the preparation of sodium hydroxide solution, the preparation of reducing agent, the preparation of copper colloidal sol, copper solution is mixed with dispersant solution and is stirred, is then directly sufficiently stirred to react or sodium hydroxide solution is added dropwise into the mixed liquor of copper chloride solution and dispersing agent and obtains Nanometer Copper colloidal sol with reducing agent mixing；Copper colloidal sol, which can load, prepares catalyst on different carriers, 80 mesh~400 mesh active carbons are added and are loaded, and the nanometer copper catalyst that active carbon is carrier can be obtained.The invention has the advantages that realizing easy, the cost effective method for preparing Nanometer Copper colloidal sol, overcome the factors such as low temperature, anoxybiotic, alkaline condition needed for tradition prepares the material, epigranular, the stabilization of Nanometer Copper, catalytic performance are good in the different carriers nanometer copper catalyst prepared according to demand.
Description
Technical field
The present invention relates to nanometer copper product and copper catalyst technical fields, and in particular to a kind of acid system Nanometer Copper colloidal sol
Preparation method.
Background technique
Compared with common metal, nano metal has excellent performance in terms of chemistry, optics, electricity and catalysis, in crowd
In more metal nano materials, copper nano material have the advantages that price it is relatively low, using wide, raw material are extensive.Meanwhile copper is made
For catalyst, it is widely applied in many fields.
The performance of nanometer copper product depends primarily on the partial size, pattern and stability of Nanometer Copper.Partial size is smaller, specific surface area
Bigger, the performance showed is better.So to obtain excellent copper product in the preparation process of Nanometer Copper colloidal sol, it must
Stability, the uniformity of particle and the different sizes for being suitble to different purposes of palpus strict control copper colloidal sol.
Currently, the preparation of copper colloidal sol mainly carries out under alkaline condition, by adding akaline liquid in oxytropism copper solution
Come make solution from acidity become alkalinity, then in alkaline environment carry out reduction reaction be made Nanometer Copper colloidal sol.Alkaline system system
Standby copper colloidal sol needs strict control pH, it is desirable that relatively finer.
Summary of the invention
The present invention provides a kind of preparation method of acid system Nanometer Copper colloidal sol, is made under acid system using electronation
Standby Nanometer Copper colloidal sol out, while the copper colloidal sol prepared can load to the catalyst that different purposes are prepared in different matrix.
The technical solution adopted by the present invention is that, comprising the following steps:
(1) using Copper dichloride dihydrate as raw material, deionized water is that solvent configures copper chloride solution, and dispersion is added into solution
Agent polyvinylpyrrolidone, obtains acid solution A after being sufficiently stirred or a small amount of sodium hydroxide solution of addition obtains acid system
Kocide SD colloid B, wherein the concentration of copper chloride is 4mM/L~48mM/L, polyvinylpyrrolidone and Copper dichloride dihydrate
Mass ratio be 1:1~30:1；
(2) compound concentration is 0.5g/L~2g/L solution of potassium borohydride as C solution；
(3) isometric solution A or Kocide SD colloid B are thoroughly mixed under normal temperature conditions with C solution, are obtained
Nanometer Copper colloidal sol D；
The invention also includes:
(4) be added according to load factor 0.5~5% into Nanometer Copper colloidal sol D 80 mesh~400 mesh active carbons or other carriers into
Row load, then can be obtained a nanometer copper catalyst through being separated by solid-liquid separation.
Solution A of the present invention or colloid B are acidity, and pH is between 3~6；
Polyethylene of dispersing agent pyrrolidones is one of model K15, K30, K90 or several in step (1) of the present invention
Kind, the mass fraction of sodium hydroxide is 0.5%-1%.
Nanometer Copper granularity is 10nm in Nanometer Copper colloidal sol D of the present invention, and the load factor of copper is 0.5~5%.
Step (4) other carriers of the present invention are resin.
The present invention first passes through dropwise addition sodium hydroxide and obtains Kocide SD colloid, is then obtained by reduction Kocide SD colloid
To Nanometer Copper colloidal sol, sodium hydroxide can also be added without and form Kocide SD colloid, direct-reduction copper chloride obtains Nanometer Copper colloidal sol.
The invention has the advantages that using common medicament for reducing agent, using mantoquita as oxidant, under water phase acid system also
Former copper chloride finally obtains Nanometer Copper colloidal sol.Colloidal solution is stably dispersed in by above step nano copper particle obtained
In, partial size is 10nm or so, and Nanometer Copper catalysis can be obtained in addition, Nanometer Copper colloidal sol is supported on active carbon or other matrixes
Agent, the nano copper particle after load are highly stable.The Nanometer Copper colloidal sol that the present invention obtains is a kind of efficient, feasible method, tool
Have wide practical use.Easy reaction of the present invention, it is economic and environment-friendly, reproducible.
Detailed description of the invention
Fig. 1 is the grain size analysis volume distribution map of 1 Nanometer Copper colloidal sol of the embodiment of the present invention；
Fig. 2 is the high power transmission electron microscope picture of product made from the embodiment of the present invention 1；
Fig. 3 is the grain size analysis volume distribution map of 2 Nanometer Copper colloidal sol of the embodiment of the present invention；
Fig. 4 is the high power transmission electron microscope picture of product made from the embodiment of the present invention 2；
Fig. 5 is the grain size analysis volume distribution map of 3 Nanometer Copper colloidal sol of the embodiment of the present invention；
Fig. 6 is the high power transmission electron microscope picture of product made from the embodiment of the present invention 3.
Specific embodiment
Embodiment 1
(1) preparation of copper solution
0.1736g Copper dichloride dihydrate is weighed, 100mL deionized water dissolving is added, is then transferred to constant volume in volumetric flask
To 250mL, the copper chloride solution of 4mM/L is obtained, takes 40mL spare；
(2) preparation of dispersing agent
It is that 1:1 ratio column weigh dispersion according to the mass ratio of polyethylene of dispersing agent base pyrrolidones and 40mL Copper dichloride dihydrate
Agent, be then dissolved in 10mL deionized water be sufficiently stirred it is spare；
(3) preparation of sodium hydroxide solution
A certain amount of sodium hydroxide is taken, is dissolved in a certain amount of deionized water, preparing mass fraction is that 0.5% sodium hydroxide is molten
Liquid is spare；
(4) preparation of reducing agent
Preparing 50mL concentration is that 0.5g/L solution of potassium borohydride is spare as reducing agent；
(5) preparation of copper colloidal sol
40mL copper solution is mixed with 10mL dispersant solution, stirs under the revolving speed of 400r/min, is then added dropwise
Sodium hydroxide solution adjusts pH range to 3.9 or so, then mixes to be sufficiently stirred with 50mL reducing agent by the 50mL solution and (stir
Speed 400r/min) reaction 30min obtain Nanometer Copper colloidal sol, as shown in the grain size analysis volume distribution map of Fig. 1 Nanometer Copper colloidal sol,
Copper particle degree is in 10nm or so；
(6) load of Nanometer Copper colloidal sol prepares catalyst
80 mesh~400 mesh active carbons are added into Nanometer Copper colloidal sol according to load factor 0.5% or other carriers are loaded,
Different carriers nanometer copper catalyst can be obtained in load 1h~2h, as shown in Fig. 2, nanometer can be observed by high power transmission electron microscope
Copper is supported on the state in active carbon.
Embodiment 2
(1) preparation of copper solution
8.3328g Copper dichloride dihydrate is weighed, 100ml deionized water dissolving is added, is then transferred to constant volume in volumetric flask
To 500mL, the copper chloride solution of 96mM/L is obtained, takes 40mL spare；
(2) preparation of dispersing agent
It is the column weighing point of 10:1 ratio according to the mass ratio of polyethylene of dispersing agent base pyrrolidones and 40mL Copper dichloride dihydrate
Powder, be then dissolved in 10mL deionized water be sufficiently stirred it is spare；
(3) preparation of sodium hydroxide solution
A certain amount of sodium hydroxide is taken, is dissolved in a certain amount of deionized water, preparation mass fraction is 0.75% sodium hydroxide
Solution for standby；
(4) preparation of reducing agent
Preparing 50mL concentration is that 1g/L solution of potassium borohydride is spare as reducing agent；
(5) preparation of copper colloidal sol
40mL copper solution is mixed with 10mL dispersant solution, stirs under the revolving speed of 600r/min, is then added dropwise
Sodium hydroxide solution adjusts pH range to 4.2, then mixes the 50mL solution with 50mL reducing agent and (mixing speed is sufficiently stirred
600r/min) reaction 60min obtains Nanometer Copper colloidal sol, as shown in the grain size analysis volume distribution map of Fig. 3 Nanometer Copper colloidal sol, copper particle
Degree is in 10nm or so；
(6) activated carbon supported copper colloidal sol prepares catalyst
80 mesh~400 mesh active carbons are added into copper colloidal sol according to load factor 1.0% or other carriers are loaded, load
Different carriers nanometer copper catalyst can be obtained in 1h.It is supported on as shown in figure 4, Nanometer Copper can be observed by high power transmission electron microscope
State in active carbon.
Embodiment 3
(1) preparation of copper solution
24.9984g Copper dichloride dihydrate is weighed, 100ml deionized water dissolving is added, is then transferred to constant volume in volumetric flask
To 500mL, the copper chloride solution of 288mM/L is obtained, takes 40mL spare；
(2) preparation of dispersing agent
It is the column weighing point of 30:1 ratio according to the mass ratio of polyethylene of dispersing agent base pyrrolidones and 40mL Copper dichloride dihydrate
Powder, be then dissolved in 10mL deionized water be sufficiently stirred it is spare；
(3) preparation of sodium hydroxide solution
A certain amount of sodium hydroxide is taken, is dissolved in a certain amount of deionized water, preparing mass fraction is that 1.0% sodium hydroxide is molten
Liquid is spare；
(4) preparation of reducing agent
Preparing 50mL concentration is that 2g/L solution of potassium borohydride is spare as reducing agent；
(5) preparation of copper colloidal sol
40mL copper solution is mixed with 10mL dispersant solution, stirs under the revolving speed of 1000r/min, is then added dropwise
Sodium hydroxide solution adjusts pH range to 5.6, then mixes the 50mL solution with 50mL reducing agent and (mixing speed is sufficiently stirred
1000r/min) reaction 60min obtains Nanometer Copper colloidal sol, as shown in the grain size analysis volume distribution map of Fig. 5 Nanometer Copper colloidal sol, copper
Granularity is in 10nm or so；
(6) activated carbon supported copper colloidal sol prepares catalyst
80 mesh~400 mesh active carbons are added into copper colloidal sol according to load factor 1.0% or other carriers are loaded, load
Different carriers nanometer copper catalyst can be obtained in 1h, is supported on as shown in fig. 6, Nanometer Copper can be observed by high power transmission electron microscope
State in active carbon.
Embodiment 4
(1) preparation of copper solution
0.1736g Copper dichloride dihydrate is weighed, 100mL deionized water dissolving is added, is then transferred to constant volume in volumetric flask
To 250mL, the copper chloride solution of 4mM/L is obtained, takes 40mL spare；
(2) preparation of dispersing agent
It is that 1:1 ratio column weigh dispersion according to the mass ratio of polyethylene of dispersing agent base pyrrolidones and 40mL Copper dichloride dihydrate
Agent, be then dissolved in 10mL deionized water be sufficiently stirred it is spare；
(3) preparation of reducing agent
Preparing 50mL concentration is that 0.5g/L solution of potassium borohydride is spare as reducing agent；
(4) preparation of copper colloidal sol
40mL copper solution is mixed with 10mL dispersant solution, is sufficiently stirred under the revolving speed of 400r/min, then will
(mixing speed 400r/min), which is sufficiently stirred, in the mixing of the 50mL solution and 50mL reducing agent reacts 30min and obtains Nanometer Copper colloidal sol,
With the granularity of nano particle size instrument detection Nanometer Copper in 10nm or so；
(5) load of Nanometer Copper colloidal sol prepares catalyst
80 mesh~400 mesh active carbons are added into Nanometer Copper colloidal sol according to load factor 0.5% or other carriers are loaded,
Different carriers nanometer copper catalyst can be obtained in load 1h~2h.
Claims (6)
1. a kind of preparation method of acid system Nanometer Copper colloidal sol, which comprises the following steps:
(1) using Copper dichloride dihydrate as raw material, deionized water is that solvent configures copper chloride solution, and it is poly- that dispersing agent is added into solution
Vinyl pyrrolidone, obtains acid solution A after being sufficiently stirred or a small amount of sodium hydroxide solution of addition obtains acid system hydrogen-oxygen
Change copper colloid B, wherein the concentration of copper chloride is 4mM/L~48mM/L, the matter of polyvinylpyrrolidone and Copper dichloride dihydrate
Amount is than being 1:1~30:1；
(2) compound concentration is 0.5g/L~2g/L solution of potassium borohydride as C solution；
(3) isometric solution A or Kocide SD colloid B are thoroughly mixed under normal temperature conditions with C solution, obtain nanometer
Copper colloidal sol D.
2. a kind of preparation method of acid system Nanometer Copper colloidal sol as described in claim 1, which is characterized in that further include:
(4) 80 mesh~400 mesh active carbons are added into Nanometer Copper colloidal sol D according to load factor 0.5~5% or other carriers is born
It carries, a nanometer copper catalyst then can be obtained through being separated by solid-liquid separation.
3. a kind of preparation method of acid system Nanometer Copper colloidal sol according to claim 1, it is characterised in that: described is molten
Liquid A or colloid B is acidity, and pH value is between 3~6.
4. a kind of preparation method of acid system Nanometer Copper colloidal sol according to claim 1, it is characterised in that: the step
(1) polyethylene of dispersing agent pyrrolidones is one or more of model K15, K30, K90 in, and the mass fraction of sodium hydroxide is
0.5%-1%.
5. a kind of preparation method of acid system Nanometer Copper colloidal sol according to claim 1, it is characterised in that: the nanometer
Nanometer Copper granularity is 10nm in copper colloidal sol D, and the load factor of copper is 0.5~5%.
6. a kind of preparation method of acid system Nanometer Copper colloidal sol according to claim 2, it is characterised in that: step (4)
Other carriers are resin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115739082A (en) * | 2022-12-09 | 2023-03-07 | 长春黄金研究院有限公司 | Preparation of carbon-based nano copper oxide catalyst and method for treating cyanide-containing wastewater |
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2019
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115739082A (en) * | 2022-12-09 | 2023-03-07 | 长春黄金研究院有限公司 | Preparation of carbon-based nano copper oxide catalyst and method for treating cyanide-containing wastewater |
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Application publication date: 20191029 |