CN104928724A - Method for electrolytically preparing dendritic fine copper powder in oxalic acid - Google Patents
Method for electrolytically preparing dendritic fine copper powder in oxalic acid Download PDFInfo
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- CN104928724A CN104928724A CN201510391482.2A CN201510391482A CN104928724A CN 104928724 A CN104928724 A CN 104928724A CN 201510391482 A CN201510391482 A CN 201510391482A CN 104928724 A CN104928724 A CN 104928724A
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- copper powder
- fine copper
- oxalic acid
- negative electrode
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 216
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 235000006408 oxalic acid Nutrition 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 241000555268 Dendroides Species 0.000 claims description 66
- 238000002360 preparation method Methods 0.000 claims description 32
- 239000008151 electrolyte solution Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 25
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- 238000003795 desorption Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000007670 refining Methods 0.000 claims description 9
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000009790 rate-determining step (RDS) Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to a method for electrolytically preparing dendritic fine copper powder in oxalic acid, and belongs to the technical field of nonferrous metallurgy. The method comprises the steps that the oxalic acid is added into pure water to form an oxalic acid solution with the concentration 0.1-0.5 mol/L, then an auxiliary reagent is added according to the mole ratio 1:1 of the oxalic acid and the auxiliary reagent in the oxalic acid solution, and an electrolyte is obtained after even mixing; the electrolyte is heated to 20-50 DEG C, then a fine copper anode and a titanium chip cathode are placed in the electrolyte for electrolysis, and then the fine copper powder can be deposited on the cathode; the fine copper powder deposited on the cathode is taken down and washed for three times by using the pure water, 60-80 DEG C vacuum drying is performed, and then the dendritic fine copper powder with the granularity 10-20 micrometers is obtained. According to the method for electrolytically preparing the dendritic fine copper powder in the oxalic acid, the fine copper powder which is narrow in granularity distribution range can be obtained through an easy method, and an electrolyte system is friendly to environment, low in cost and easy to get.
Description
Technical field
The present invention relates to a kind of method of electrolytic preparation dendroid fine copper powder in oxalic acid, belong to non-ferrous metallurgy technology field.
Background technology
Copper powder has good conduction, heat conductance and compactibility, plasticity-and sintering character, is the indispensable and irreplaceable metal powder materials in field such as automobile, space flight and aviation, machinery, chemical industry, the energy and 3C industry.Along with the development of science and technology, copper powder is changed to functional material by metal powder material, and particularly in recent years, along with the development of 3D printing technique, copper powder becomes a kind of important printing raw material, has the irreplaceable effect of other powder.
Copper powder preparation method is roughly divided into Physical, solution phase chemical reduction and electrolytic process three major types, and Physical is divided into again physical evaporation-condensation method, mechanical disruption method and atomization etc.Physical evaporation-condensation method can prepare that sphericity is high, antioxidant property better and the tiny copper powder of particle diameter, but the particle size distribution of copper powder is comparatively large, and equipment used is very expensive, and production cost is high.The copper powder particle size skewness that mechanical disruption legal system is standby, reunite comparatively serious, pattern is difficult to control, and be easily oxidized, and the production cycle is long, and energy consumption is large, is restricted in the high-end copper powder of production.Copper powder prepared by atomization is spherical in shape, and particle diameter is usually at micron order.Solution phase chemical reduction can prepare the more tiny copper powder of particle diameter, and the size-grade distribution of copper powder can be controlled, but need the reductive agent selecting to be applicable to, in aqueous the compound of copper, cupric ion or cuprous ion etc. are reduced to copper powder, in preparation process, required reagent type is many, operation is comparatively complicated, and by the restriction of reductive agent kind and cost, and the reductive agent commonly used as NaBH
4, xitix, glucose, Hypophosporous Acid, 50, quinhydrones, formaldehyde, some have toxicity in hydrazine hydrate etc., some are expensive, so can only prepare a small amount of copper powder on a small scale, should not carry out fairly large industrial production.The advantages such as the copper powder produced due to electrolytic process has that purity is high, specific surface area is large, compressibility and good moldability are the main stream approach of producing copper powder at present.In the aqueous solution, electrolysis production copper powder is usually using copper sulfate+sulfuric acid as electrolytic solution, and need in the electrolytic solution of low copper ion concentration and high acid concentration during electrolysis, control cathode current density is at 1200 ~ 2000A/m
2condition under carry out, to make the concentration polarization of cathode surface cupric ion, impel the generation of copper powder.The concentration polarization of cupric ion must cause cathodic polarization and cathode surface that violent liberation of hydrogen side reaction occurs, like this when carrying out electrolytic copper powder, current efficiency only about 30%, need to consume a large amount of electric energy, low current efficiency not only reduces the output of unit time copper powder, also substantially increases the preparation cost of copper powder simultaneously.
Patent CN101560674A carries out electrolytic preparation and goes out median size at the copper powder of about 20 μm in super gravity field, increases Cu by hypergravity
2+to the rate of diffusion of electrode surface, reduce electrode surface Cu
2+concentration polarization, improve current efficiency to 55% ~ 74% of electrolytic copper powder.Patent CN101007354A uses ultrasonic membrane electrolysis directly to carry out in-pulp electrolysis with copper ore concentrates, prepare granularity and be less than 4 μm of superfine cupper powders, metallurgical and materials processing flow process can be shortened, the copper powder that the method obtains mostly is spherical, but because raw material is copper ore concentrates, complicated component, gained copper powder is 98.8% containing Cu.Patent CN 101717971B utilizes the mixing solutions of copper sulfate, phosphoric acid, gelatin and benzotriazole as electrolytic solution, at 300 ~ 800A/m
2current density under, electrolytic preparation goes out particle diameter at the fine copper powder of 2.5 ~ 7.5 μm, and current efficiency is 17% ~ 45%, and power consumption is generally higher than 15000 (kWh) copper powder per ton.The ChCl-Urea eutectic solvent type ionic liquid that contriver once adopted choline chloride 60 and urea mixing congruent melting to be formed is as ionogen, take fine copper as anode, titanium sheet or stainless steel plate be negative electrode, electrolysis has gone out dendroid fine copper powder, and the current density controlled during electrolysis is only 50A/m
2, and current efficiency can reach 95%.It is wide that ChCl-Urea eutectic solvent type ionic liquid has electrochemical window, the feature of stable system, but the cost ratio oxalic acid of raw materials wants high.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the invention provides a kind of method of electrolytic preparation dendroid fine copper powder in oxalic acid.The method obtains the narrow fine copper powder of particle size distribution by simple method, and electrolyte system environmental friendliness, cheap and easy to get, and significantly reduce power consumption and the production cost of electrolysis production copper powder, the present invention is achieved through the following technical solutions.
A method for electrolytic preparation dendroid fine copper powder in oxalic acid, its concrete steps are as follows:
Step 1, in pure water, adding oxalic acid, to form concentration be the oxalic acid solution of 0.1 ~ 0.5mol/L, is then that 1:1 adds auxiliary reagent according to the mol ratio of oxalic acid and auxiliary reagent in oxalic acid solution, obtains electrolytic solution after mixing;
Step 2, electrolytic solution step 1 obtained are heated to 20 ~ 50 DEG C, then pure copper anode and titanium sheet negative electrode being placed in electrolytic solution, is (1 ~ 2) in the area ratio stirring, control anode and negative electrode: 1, cathode and anode spacing is 20 ~ 50mm, DC current flow density is 50 ~ 300A/m
2electrolysis 30 ~ 120min under condition, can deposit fine copper powder on negative electrode;
Step 3, to take off step 2 negative electrode deposits fine copper powder, clean 3 times with pure water, through 60 ~ 80 DEG C of vacuum-dryings, obtain the dendroid fine copper powder that granularity is 10 ~ 20 μm.
Auxiliary reagent in described step 1 is one or several arbitrary proportion mixtures in ammoniacal liquor, ammonium chloride, ammonium sulfate, monoammonium sulfate.
The standard cathode copper that in described step 2, pure copper anode is aqueous electrolysis refining institute output or Cu-CATH-1.
In described step 2, titanium sheet negative electrode is TA1 or TA2.
In described step 3, negative electrode depositing the process that fine copper powder takes off is: after being taken out from electrolyzer by the negative electrode of deposition fine copper powder, put into pure water quickly, carry out ultrasonic desorption, dispersion, cleaning through ultrasonic cleaner, ultrasonic time is 10 ~ 60min.
The invention has the beneficial effects as follows:
(1) the present invention is compared with traditional aqueous system electrolytic copper powder, and current efficiency significantly improves, and is up to 90.5%, and power consumption significantly reduces, and lowest energy consumption is 2994 (kWh) t
-1, this technology can adopt lower current density 50 ~ 300A/m
2, traditional aqueous electrolytic copper powder is then 1200 ~ 2000A/m
2.
(2) electrolytic solution oxalic acid of the present invention has reductibility, makes the copper powder produced in electrolytic process not easily oxidized, serves obvious antioxygenation.
(3) copper powder size that prepared by the present invention is 10 ~ 20 μm, epigranular, and pattern is dendroid, has suitability widely.
(4) raw material oxalic acid of the present invention is general chemical product and raw material, and daily for washing composition, SYNTHETIC OPTICAL WHITNER etc., inexpensive, nontoxic pollution-free, also can be recycled, and auxiliary reagent is common chemical reagent.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is the dendroid fine copper powder SEM photo figure A that the embodiment of the present invention 4 prepares;
Fig. 3 is the dendroid fine copper powder SEM photo figure B that the embodiment of the present invention 4 prepares;
Fig. 4 is the particle size distribution figure of the dendroid fine copper powder that the embodiment of the present invention 4 prepares.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, its concrete steps are as follows:
Step 1, in pure water, adding oxalic acid, to form concentration be the oxalic acid solution of 0.1mol/L, is then that 1:1 adds auxiliary reagent according to the mol ratio of oxalic acid and auxiliary reagent in oxalic acid solution, obtains electrolytic solution after mixing; Wherein auxiliary reagent is 1.2g ammonium chloride;
Step 2,220mL electrolytic solution step 1 obtained are heated to 40 DEG C, then pure copper anode and titanium sheet negative electrode are placed in electrolytic solution, stir speed (S.S.) be 500r/min, the area ratio controlling anode and negative electrode is 1:1, cathode and anode spacing is 50mm, DC current flow density is 75A/m
2electrolysis 120min under condition, can deposit fine copper powder on negative electrode; Wherein pure copper anode is the standard cathode copper of aqueous electrolysis refining institute output, and titanium sheet negative electrode is TA1;
Step 3, to take off step 2 negative electrode deposits fine copper powder, 3 times are cleaned with pure water, through 80 DEG C of vacuum-drying 2h, obtain the dendroid fine copper powder that granularity is 11 ~ 18 μm, wherein negative electrode depositing the process that fine copper powder takes off is: after being taken out from electrolyzer by the negative electrode of deposition fine copper powder, put into pure water quickly, carry out ultrasonic desorption, dispersion, cleaning through ultrasonic cleaner, ultrasonic time is 10min.
The dendroid fine copper powder pattern prepared is dendroid, and copper powder particle size is even.Direct current consumption is 3059 (kWh) t
-1, current efficiency is 83.5%.
Embodiment 2
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, its concrete steps are as follows:
Step 1, in pure water, adding oxalic acid, to form concentration be the oxalic acid solution of 0.2mol/L, is then that 1:1 adds auxiliary reagent according to the mol ratio of oxalic acid and auxiliary reagent in oxalic acid solution, obtains electrolytic solution after mixing; Wherein auxiliary reagent is 2.4g ammonium chloride;
Step 2,220mL electrolytic solution step 1 obtained are heated to 40 DEG C, then pure copper anode and titanium sheet negative electrode are placed in electrolytic solution, stir speed (S.S.) be 500r/min, the area ratio controlling anode and negative electrode is 1:1, cathode and anode spacing is 50mm, DC current flow density is 75A/m
2electrolysis 120min under condition, can deposit fine copper powder on negative electrode; Wherein pure copper anode is the standard cathode copper of aqueous electrolysis refining institute output, and titanium sheet negative electrode is TA1;
Step 3, to take off step 2 negative electrode deposits fine copper powder, 3 times are cleaned with pure water, through 80 DEG C of vacuum-drying 2h, obtain the dendroid fine copper powder that granularity is 12 ~ 16 μm, wherein negative electrode depositing the process that fine copper powder takes off is: after being taken out from electrolyzer by the negative electrode of deposition fine copper powder, put into pure water quickly, carry out ultrasonic desorption, dispersion, cleaning through ultrasonic cleaner, ultrasonic time is 10min.
The dendroid fine copper powder pattern prepared is dendroid, and copper powder particle size is even.Direct current consumption is 3039 (kWh) t
-1, current efficiency is 86.0%.
Embodiment 3
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, its concrete steps are as follows:
Step 1, in pure water, adding oxalic acid, to form concentration be the oxalic acid solution of 0.3mol/L, is then that 1:1 adds auxiliary reagent according to the mol ratio of oxalic acid and auxiliary reagent in oxalic acid solution, obtains electrolytic solution after mixing; Wherein auxiliary reagent is 3.5g ammonium chloride;
Step 2,220mL electrolytic solution step 1 obtained are heated to 40 DEG C, then pure copper anode and titanium sheet negative electrode are placed in electrolytic solution, stir speed (S.S.) be 500r/min, the area ratio controlling anode and negative electrode is 1:1, cathode and anode spacing is 50mm, DC current flow density is 75A/m
2electrolysis 120min under condition, can deposit fine copper powder on negative electrode; Wherein pure copper anode is the standard cathode copper of aqueous electrolysis refining institute output, and titanium sheet negative electrode is TA1;
Step 3, to take off step 2 negative electrode deposits fine copper powder, 3 times are cleaned with pure water, through 80 DEG C of vacuum-drying 2h, obtain the dendroid fine copper powder that granularity is 12 ~ 18 μm, wherein negative electrode depositing the process that fine copper powder takes off is: after being taken out from electrolyzer by the negative electrode of deposition fine copper powder, put into pure water quickly, carry out ultrasonic desorption, dispersion, cleaning through ultrasonic cleaner, ultrasonic time is 10min.
The dendroid fine copper powder pattern prepared is dendroid, and copper powder particle size is even.Direct current consumption is 3011 (kWh) t
-1, current efficiency is 87.1%.
Embodiment 4
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, its concrete steps are as follows:
Step 1, in pure water, adding oxalic acid, to form concentration be the oxalic acid solution of 0.4mol/L, is then that 1:1 adds auxiliary reagent according to the mol ratio of oxalic acid and auxiliary reagent in oxalic acid solution, obtains electrolytic solution after mixing; Wherein auxiliary reagent is 4.7g ammonium chloride;
Step 2,220mL electrolytic solution step 1 obtained are heated to 40 DEG C, then pure copper anode and titanium sheet negative electrode are placed in electrolytic solution, stir speed (S.S.) be 500r/min, the area ratio controlling anode and negative electrode is 1:1, cathode and anode spacing is 50mm, DC current flow density is 75A/m
2electrolysis 120min under condition, can deposit fine copper powder on negative electrode; Wherein pure copper anode is the standard cathode copper of aqueous electrolysis refining institute output, and titanium sheet negative electrode is TA1;
Step 3, to take off step 2 negative electrode deposits fine copper powder, 3 times are cleaned with pure water, through 80 DEG C of vacuum-drying 2h, obtain the dendroid fine copper powder that granularity is 12 ~ 19 μm, wherein negative electrode depositing the process that fine copper powder takes off is: after being taken out from electrolyzer by the negative electrode of deposition fine copper powder, put into pure water quickly, carry out ultrasonic desorption, dispersion, cleaning through ultrasonic cleaner, ultrasonic time is 10min.
As shown in Figures 2 and 3, the particle size distribution figure of dendroid fine copper powder as shown in Figure 4 for the dendroid fine copper powder SEM photo figure that the present embodiment prepares.
The dendroid fine copper powder pattern prepared is dendroid, and copper powder particle size is even.Direct current consumption is 3004 (kWh) t
-1, current efficiency is 89.2%.
Embodiment 5
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, its concrete steps are as follows:
Step 1, in pure water, adding oxalic acid, to form concentration be the oxalic acid solution of 0.5mol/L, is then that 1:1 adds auxiliary reagent according to the mol ratio of oxalic acid and auxiliary reagent in oxalic acid solution, obtains electrolytic solution after mixing; Wherein auxiliary reagent is 5.9g ammonium chloride;
Step 2,220mL electrolytic solution step 1 obtained are heated to 40 DEG C, then pure copper anode and titanium sheet negative electrode are placed in electrolytic solution, stir speed (S.S.) be 500r/min, the area ratio controlling anode and negative electrode is 1:1, cathode and anode spacing is 50mm, DC current flow density is 75A/m
2electrolysis 120min under condition, can deposit fine copper powder on negative electrode; Wherein pure copper anode is the standard cathode copper of aqueous electrolysis refining institute output, and titanium sheet negative electrode is TA1;
Step 3, to take off step 2 negative electrode deposits fine copper powder, 3 times are cleaned with pure water, through 80 DEG C of vacuum-drying 2h, obtain the dendroid fine copper powder that granularity is 15 ~ 20 μm, wherein negative electrode depositing the process that fine copper powder takes off is: after being taken out from electrolyzer by the negative electrode of deposition fine copper powder, put into pure water quickly, carry out ultrasonic desorption, dispersion, cleaning through ultrasonic cleaner, ultrasonic time is 10min.
The dendroid fine copper powder pattern prepared is dendroid, and copper powder particle size is even.Direct current consumption is 2994 (kWh) t
-1, current efficiency is 89.7%.
Embodiment 6
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, its concrete steps are as follows:
Step 1, in pure water, adding oxalic acid, to form concentration be the oxalic acid solution of 0.4mol/L, is then that 1:1 adds auxiliary reagent according to the mol ratio of oxalic acid and auxiliary reagent in oxalic acid solution, obtains electrolytic solution after mixing; Wherein auxiliary reagent is 4.7g ammonium chloride;
Step 2,220mL electrolytic solution step 1 obtained are heated to 20 DEG C, then pure copper anode and titanium sheet negative electrode are placed in electrolytic solution, stir speed (S.S.) be 500r/min, the area ratio controlling anode and negative electrode is 1:1, cathode and anode spacing is 50mm, DC current flow density is 75A/m
2electrolysis 120min under condition, can deposit fine copper powder on negative electrode; Wherein pure copper anode is the standard cathode copper of aqueous electrolysis refining institute output, and titanium sheet negative electrode is TA1;
Step 3, to take off step 2 negative electrode deposits fine copper powder, 3 times are cleaned with pure water, through 80 DEG C of vacuum-drying 2h, obtain the dendroid fine copper powder that granularity is 11 ~ 20 μm, wherein negative electrode depositing the process that fine copper powder takes off is: after being taken out from electrolyzer by the negative electrode of deposition fine copper powder, put into pure water quickly, carry out ultrasonic desorption, dispersion, cleaning through ultrasonic cleaner, ultrasonic time is 10min.
The dendroid fine copper powder pattern prepared is dendroid, and copper powder particle size is even.Direct current consumption is 3024 (kWh) t
-1, current efficiency is 84.2%.
Embodiment 7
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, its concrete steps are as follows:
Step 1, in pure water, adding oxalic acid, to form concentration be the oxalic acid solution of 0.4mol/L, is then that 1:1 adds auxiliary reagent according to the mol ratio of oxalic acid and auxiliary reagent in oxalic acid solution, obtains electrolytic solution after mixing; Wherein auxiliary reagent is 4.70g ammonium chloride;
Step 2,220mL electrolytic solution step 1 obtained are heated to 50 DEG C, then pure copper anode and titanium sheet negative electrode are placed in electrolytic solution, stir speed (S.S.) be 500r/min, the area ratio controlling anode and negative electrode is 1:1, cathode and anode spacing is 50mm, DC current flow density is 75A/m
2electrolysis 120min under condition, can deposit fine copper powder on negative electrode; Wherein pure copper anode is the standard cathode copper of aqueous electrolysis refining institute output, and titanium sheet negative electrode is TA1;
Step 3, to take off step 2 negative electrode deposits fine copper powder, 3 times are cleaned with pure water, through 80 DEG C of vacuum-drying 2h, obtain the dendroid fine copper powder that granularity is 10 ~ 17 μm, wherein negative electrode depositing the process that fine copper powder takes off is: after being taken out from electrolyzer by the negative electrode of deposition fine copper powder, put into pure water quickly, carry out ultrasonic desorption, dispersion, cleaning through ultrasonic cleaner, ultrasonic time is 10min.
The dendroid fine copper powder pattern prepared is dendroid, and copper powder particle size is even.Direct current consumption is 3011 (kWh) t
-1, current efficiency is 90.2%.
Embodiment 8
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, in rate-determining steps 2 process, the stirring velocity of electrolytic preparation copper powder is 100r/min, and all the other steps, condition, parameter are all identical with embodiment 4.Dendroid fine copper powder epigranular, size range is 12 ~ 17 μm.Direct current consumption is 3018 (kWh) t
-1, current efficiency is 88.3%.
Embodiment 9
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, in rate-determining steps 2 process, the stirring velocity of electrolytic preparation copper powder is 700r/min, and all the other steps, condition, parameter are all identical with embodiment 4.Dendroid fine copper powder epigranular, size range is 13 ~ 20 μm, and pattern is dendroid.Direct current consumption is 3010 (kWh) t
-1, current efficiency is 88.9%.
Embodiment 10
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, in rate-determining steps 2 process, the DC current flow density of electrolytic preparation copper powder is 50A/m
2, all the other steps, condition, parameter are all identical with embodiment 4.Dendroid fine copper powder epigranular, size range is 11 ~ 18 μm, and pattern is dendroid.Direct current consumption is 2984 (kWh) t
-1, current efficiency is 82.9%.
Embodiment 11
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, in rate-determining steps 2 process, the DC current flow density of electrolytic preparation copper powder is 300A/m
2, all the other steps, condition, parameter are all identical with embodiment 4.Dendroid fine copper powder epigranular, size range is 12 ~ 19 μm, and pattern is dendroid.Direct current consumption is 3112 (kWh) t
-1, current efficiency is 90.5%.
Embodiment 12
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, prepare 0.4mol/L oxalic acid solution in step 1, add the ammoniacal liquor auxiliary reagent of 1.65ml, massfraction 25%, all the other steps, condition, parameter are all identical with embodiment 4.Dendroid fine copper powder epigranular, size range is 12 ~ 17 μm, and pattern is dendroid.Direct current consumption is 3012 (kWh) t
-1, current efficiency is 89.5%.
Embodiment 13
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, prepare 0.4mol/L oxalic acid solution in step 1, add the ammonium sulfate auxiliary reagent of 11.6g, all the other steps, condition, parameter are all identical with embodiment 4.Dendroid fine copper powder epigranular, size range is 12 ~ 19 μm, and pattern is dendroid.Direct current consumption is 3142 (kWh) t
-1, current efficiency is 87.5%.
Embodiment 14
As shown in Figure 1, be somebody's turn to do the method for electrolytic preparation dendroid fine copper powder in oxalic acid, prepare 0.4mol/L oxalic acid solution in step 1, add the monoammonium sulfate auxiliary reagent of 10g, all the other steps, condition, parameter are all identical with embodiment 4.Dendroid fine copper powder epigranular, size range is 11 ~ 16 μm, and pattern is dendroid.Direct current consumption is 3187 (kWh) t
-1, current efficiency is 86.2%.
Below by reference to the accompanying drawings the specific embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (5)
1. the method for electrolytic preparation dendroid fine copper powder in oxalic acid, is characterized in that concrete steps are as follows:
Step 1, in pure water, adding oxalic acid, to form concentration be the oxalic acid solution of 0.1 ~ 0.5mol/L, is then that 1:1 adds auxiliary reagent according to the mol ratio of oxalic acid and auxiliary reagent in oxalic acid solution, obtains electrolytic solution after mixing;
Step 2, electrolytic solution step 1 obtained are heated to 20 ~ 50 DEG C, then pure copper anode and titanium sheet negative electrode being placed in electrolytic solution, is (1 ~ 2) in the area ratio stirring, control anode and negative electrode: 1, cathode and anode spacing is 20 ~ 50mm, DC current flow density is 50 ~ 300A/m
2electrolysis 30 ~ 120min under condition, can deposit fine copper powder on negative electrode;
Step 3, to take off step 2 negative electrode deposits fine copper powder, clean 3 times with pure water, through 60 ~ 80 DEG C of vacuum-dryings, obtain the dendroid fine copper powder that granularity is 10 ~ 20 μm.
2. the method for electrolytic preparation dendroid fine copper powder in oxalic acid according to claim 1, is characterized in that: the auxiliary reagent in described step 1 is one or several arbitrary proportion mixtures in ammoniacal liquor, ammonium chloride, ammonium sulfate, monoammonium sulfate.
3. the method for electrolytic preparation dendroid fine copper powder in oxalic acid according to claim 1, is characterized in that: the standard cathode copper that in described step 2, pure copper anode is aqueous electrolysis refining institute output or Cu-CATH-1.
4. the method for electrolytic preparation dendroid fine copper powder in oxalic acid according to claim 1, is characterized in that: in described step 2, titanium sheet negative electrode is TA1 or TA2.
5. the method for electrolytic preparation dendroid fine copper powder in oxalic acid according to claim 1, it is characterized in that: in described step 3, negative electrode depositing the process that fine copper powder takes off is: after the negative electrode of deposition fine copper powder is taken out from electrolyzer, put into pure water quickly, carry out ultrasonic desorption, dispersion, cleaning through ultrasonic cleaner, ultrasonic time is 10 ~ 60min.
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