CN101879606A - Submicron copper powder and method for preparing same by sulfuric acid-process chemical reduction - Google Patents
Submicron copper powder and method for preparing same by sulfuric acid-process chemical reduction Download PDFInfo
- Publication number
- CN101879606A CN101879606A CN 201010225280 CN201010225280A CN101879606A CN 101879606 A CN101879606 A CN 101879606A CN 201010225280 CN201010225280 CN 201010225280 CN 201010225280 A CN201010225280 A CN 201010225280A CN 101879606 A CN101879606 A CN 101879606A
- Authority
- CN
- China
- Prior art keywords
- copper
- copper powder
- sulfate
- solution
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000003638 chemical reducing agent Substances 0.000 title abstract description 14
- 238000006722 reduction reaction Methods 0.000 title abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 230000002829 reductive effect Effects 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 7
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 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 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 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 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000000084 colloidal system Substances 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 3
- 239000000243 solution Substances 0.000 abstract 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- 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 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000012850 discrimination method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000010303 mechanochemical reaction Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 238000009692 water atomization Methods 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Images
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention provides a method for preparing submicron copper powder by sulfuric acid-process chemical reduction. The method comprises the following steps of: adding sulfuric acid into the mixed solution of solution of soluble sulfate and solution of colloid; adding iron sheets into the mixed solution for performing a reaction to generate high-reducibility hydrogen; adding anhydrous cupric sulfate or blue vitriol twice into the mixed solution; controlling temperature and stirring speed under the action of the high-reducibility hydrogen; and reducing copper ions into copper atoms. In the method, high-activity and low-cost hydrogen is taken as a reducing agent, so that cost is lowered and yield is increased; particle control technology is adopted, so that the obtained copper powder has fine particles, high purity and high oxidation resistance; and micro copper powder is suitable for industrial mass production and wider product use.
Description
Technical field
The present invention relates to a kind of submicron metal and preparation method thereof, particularly a kind of copper powder in submicro and prepare the method for this copper powder with the sulfuric acid process electronation.
Background technology
Super-fine material is 20th century new function basic materials that grow up of the mid-80, and the superfine metal material is one of them important branch.At present, because submicron particle has advantages of high activity under ultra tiny state, how so that the metal super-fine material is not had a strict definition, the powder from several nanometers to several thousand nanometers all can be referred to as superfine metal powder material.Because the superfine metal material exists small-size effect, surface interface effect, quantum scale effect and quantum tunneling effect etc., make it have the many character different of meter, many specific performances and great potential using value are arranged in fields such as mechanics, electricity, magnetics and chemistry with the identical component conventional material.
Copper powder in submicro has metallic copper favorable conductive, heat conduction, anti-corrosion, any surface finish and advantage such as nonmagnetic, as high performance-price ratio basic function powder body material, be widely used in modern high-tech field such as space flight, microelectronics, chemistry, biology, medicine, mechanical break-in reparation, great exploitation potential for its.
Preparation method about the micron copper powder is a lot, generally speaking, is divided into chemical method and physical method two big classes.Physical method such as eddy-current heating gas phase vapor method, gamma-radiation method, plasma method, water atomization etc., chemical method such as electrolysis, mechanochemical reaction, ammonium salt discrimination method, liquid phase chemical reduction method etc.Wherein the liquid phase chemical reduction method is to adopt the reducing agent with certain reducing power, bivalent cupric ion in the solution is reduced to zero-valent state, by controlling the powder that various technological parameters obtain different-grain diameter rank, pattern, the kind of reducing agent is a lot, and commonly used have hydrazine hydrate, ascorbic acid, formaldehyde, inferior sodium phosphate and a KBH4 etc.
No matter be that a kind of preparation method, the advantage of himself is all arranged, but also have problems more or less.With regard to the physics method, gas phase steam method equipment complexity, cost height; Gamma-radiation method product is difficult to collect; The plasma method capacity usage ratio is low; The product granularity of water atomization preparation is big, and formability is poor.With regard to chemical method, the copper powder of mechanochemical reaction preparation is inhomogeneous, and particle diameter distributes wide, easily introduces impurity; The electrolysis energy consumption is big, the cost height; Ammonium salt discrimination method productive rate is low excessively; Though liquid phase chemical reduction method equipment is simple, easy suitability for industrialized production, but present employed reducing agent or severe toxicity is arranged, cost is too high, and difficult treatment, yield are low again after the preparation, causes price can not to be in any more and market can't be accepted, particularly copper nanoparticle very easily is oxidized into cupric oxide, preservation is all very difficult with use, so copper nanoparticle never can be realized suitability for industrialized production, considerable restraint has been received in the application of copper nanoparticle.
Summary of the invention
At the deficiencies in the prior art, the invention provides the method that a kind of sulfuric acid process electronation prepares copper powder in submicro, gained copper powder particle is thin, purity is high, oxidation resistance is strong.
The technical scheme for preparing the employing of this micron copper powder is as follows:
(1), earlier prepare sulfate liquor soluble sulphate is dissolved in water, make the total concentration of its contained sulfate radical and metal cation be controlled at 50～550g/L, described soluble sulphate is a sulfate soluble in water;
(2), the preparation colloidal solution will add in the water soluble organic substance in the entry, stirring and evenly mixing is mixed with the colloidal solution that concentration is 15～150g/L, described water soluble organic substance is selected from one or more in glucose, urea, citric acid, the water soluble starch;
(3), step (1), (2) two kinds of solution are mixed back add industrial sulphuric acids by volume at 8～15: 1, make solution P H be adjusted to 0.1～1.5 behind the stirring and evenly mixing, solution proportion is 1.2～1.6; Be warming up to 45～85 ℃ then;
(4), in step (3) gained solution, add earlier iron sheet or iron powder after the oil removing, produce fresh high reductive hydrogen;
(5), according to the copper powder weight that will prepare, calculate the amount of required copper sulphate or cupric sulfate pentahydrate, add total amount 1～12% earlier, utilize the high reproducibility of hydrogen and the catalytic action of temperature that bivalent cupric ion is reduced to copper atom, slaking 0.5～18 minute forms the copper nanoparticle crystal seed;
(6), continue slowly to add remaining copper sulphate or cupric sulfate pentahydrate, the hydrogen that is produced with step (4) fully reacts the generation copper atom, by control mixing speed 35～50rpm and 20～30 minutes curing times, on the copper nanoparticle crystal seed and connect and grow into the submicron copper powder particles, be the present invention.
Wherein the described soluble sulphate of step (1) is a hydrosulphate soluble in water, optional one or more collocation in aluminum sulfate, ferrous sulfate, zirconium sulfate, manganese sulfate etc., and ratio does not each other have special requirement.
Wherein the amount of step (3) adding industrial sulphuric acid is to work as solution P H0.1～1.5 behind the stirring and evenly mixing, and solution proportion is 1.2～1.6 o'clock volume numbers that consumed.
Wherein the amount of the added iron of step (4) must guarantee to react the hydrogen capacity of generation, copper ion can be reduced into elemental copper.That is to say in the preparation process and should estimate the amount of required iron again, thereby guarantee to have enough hydrogen that bivalent cupric ion is reduced into copper atom according to the quality of the prepared required reducing agent hydrogen of copper powder quality estimation.
The copper powder of the present invention's traditional handicraft production more in the market has following characteristics:
● particle is thin: at 0.1～3.0um, industrial production copper powder average grain diameter is not less than 8 microns now;
● the purity height: chemical method is produced copper powder purity height, can reach more than 99.94%;
● size distribution is more concentrated;
● finer particles, the ball-type degree of copper powder is just good more;
● the copper powder oxidation resistance that sour environment is produced down is stronger.
In August, 2009, arrange the special messenger to deliver to the national metal powder material laboratory inspection of Central South University of Changsha product of the present invention, show under the Electronic Speculum that (energy spectrum analysis copper content reaches 99.94% for copper powder size 0.1～3.0 micron (major part concentrates on 0.5～1.5 micron), shape convergence ball-type, particle diameter even (referring to the electromicroscopic photograph of Central South University's detection) and purity height, in the market purity preferably electrolytic copper powder have only 99.8%), energy spectrum analysis figure sees Figure of description 1.
Non-oxidizability through this copper powder in submicro after the anti-oxidant treatment also can improve greatly, test confirms that uncovered placement does not still have obvious oxidation stain phenomenon after testing after 10 days in humid air below 60 ℃, what solved copper powder in submicro deposits and uses a difficult problem, for the large-scale industrial production of copper powder in submicro has thoroughly been paved road with using.
The present invention is aspect the suitability for industrialized production of product, utilize the advantage of liquid phase chemical reduction method, prepare copper powder in submicro with the sulfuric acid process electronation, under sour environment, generate high activity hydrogen as low cost on the one hand by industrial sulphuric acid and iron reaction, efficient reducing agent, expensive to substitute, poisonous, the traditional chemical reducing agent of difficult treatment again after the reduction particularly, such as hydrazine hydrate, ascorbic acid, formaldehyde, material such as inferior sodium phosphate and KBH4, bivalent cupric ion in the copper sulphate is reduced to copper atom, adopt temperature in the control solution on the other hand, means control reaction speeds such as total ion degree and colloid concentration, thereby reach the purpose that control generates copper powder particle size, this particle control technology has overcome the drawback that the traditional chemical reducing process can only be produced copper nanoparticle, being beneficial to the product that solves copper nanoparticle reclaims and an anti-oxidant difficult problem, also broken through modern industry and produced copper powder and can not surpass 2500 purpose quality bottlenecks, the functional metal base material that product of the present invention is become really have extensive use and high using value.
Acidoid solution behind the isolated by filtration copper powder in submicro can be recycling, and the ferrous sulfate heptahydrate of by-product is freezing can directly to be used as iron fertilizer and the raw material of producing iron oxide after separating, and belongs to recycling economy, cleaner production, saving cost.
The invention has the beneficial effects as follows this method adopt high activity cheaply hydrogen be reducing agent, reduced cost, improved recovery rate, adopted the particle control technology, make that gained copper powder particle is thin, purity is high, oxidation resistance is strong, purposes is more extensive.This micron copper powder is applicable to industrialized production, belongs to recycling economy and clearer production technology, saves production cost, and is accepted by market easily.
Figure of description accompanying drawing 1 detects the energy spectrum analysis figure of purity of the present invention
Specific embodiment (totally 2 examples)
Embodiment 1 preparation 500 gram copper powder in submicro
Preparation as follows:
(1), preparation sulfate liquor 20000ml is dissolved in water ferrous sulfate, making the total concentration of its contained sulfate radical and ferrous ion is 500g/l;
(2), preparation colloidal solution 2000ml, add the water stirring and evenly mixing in the water soluble organic substance and be mixed with the colloidal solution that concentration is 100g/L, described water soluble organic substance is selected from glucose, citric acid, water soluble starch combination, and three's gross weight is 200 grams, and proportionate relationship does not limit mutually;
(3), will step (1), (2) two kinds of solution mix the back and add industrial sulphuric acids, regulator solution PH to 0.8, solution proportion is 1.32, stirring and evenly mixing is warmed up to 55 ℃;
(4), in step (3) solution, add iron sheet after the oil removing, produce fresh high activity hydrogen;
(5), required cupric sulfate pentahydrate 2000g, add 7.5% i.e. 150 grams of total amount earlier, utilize the high reproducibility of hydrogen that bivalent cupric ion is reduced to copper atom according to the copper powder Mass Calculation that will prepare, and slaking 6 minutes, the copper nanoparticle crystal seed formed;
((6), continuation slowly add remaining cupric sulfate pentahydrate 1850 grams, the hydrogen reaction that continues to be produced with step (4) becomes copper atom, on the copper nanoparticle crystal seed and connect and grow into the ultra tiny copper powder particle of sub-micron, treat that it fully reacts, by control mixing speed (40rpm) and 20 minutes curing times,, the bivalent cupric ion Restore All in the solution is 0.1～3.0 micron of the present invention's copper powder for the ultra-fine copper particle.
Embodiment 2 preparations 1000 gram micron copper powders
Preparation as follows:
(1), preparation sulfate liquor 30000ml is dissolved in water the sulfate of solubility, making its contained sulfate radical and metal cation is that the total concentration of aluminium ion, ferrous ion, manganese ion is 250g/L, the sulfate of solubility is selected from aluminum sulfate, ferrous sulfate, manganese sulfate, and three's ratio is unrestricted;
(2), preparation colloidal solution 2000ml, add the water stirring and evenly mixing in the water soluble organic substance and be mixed with the colloidal solution that concentration is 100g/L, described water soluble organic substance is selected from urea, water soluble starch combination, both gross weights are 200 grams, proportionate relationship does not limit mutually;
(3), will step (1), (2) two kinds of solution mix the back and add industrial sulphuric acids, regulator solution PH to 0.1, solution proportion is 1.28; Stirring and evenly mixing is warmed up to 48 ℃ then;
(4), iron powder, the fresh high activity hydrogen of generation earlier after the adding oil removing;
(5), required cupric sulfate pentahydrate 4000 grams, adding total amount 2.5% earlier is 100g, utilizes the high reproducibility of hydrogen that the cupric particle is reduced to copper atom, and slaking 1～18 minute, forms the copper nanoparticle crystal seed according to the copper powder Mass Calculation that will prepare;
(6), continue slowly to add remaining cupric sulfate pentahydrate, the hydrogen reaction that is produced with step (4) becomes copper atom, on the copper nanoparticle crystal seed and connect and grow into the ultra tiny copper powder particle of sub-micron, treat that it fully reacts, by control mixing speed (25rpm) and curing time (20 minutes), the bivalent cupric ion Restore All in the solution is 0.1～3.0 micron of the present invention's copper powder for the ultra-fine copper particle.
Claims (4)
1. copper powder in submicro is characterized in that adopting following method to be prepared:
(1), earlier prepare sulfate liquor soluble sulphate is dissolved in water, make the total concentration of its contained sulfate radical and metal cation be controlled at 50～550g/L, described soluble sulphate is a sulfate soluble in water;
(2), the preparation colloidal solution will add in the water soluble organic substance in the entry, stirring and evenly mixing is mixed with the colloidal solution that concentration is 15～150g/L, described water soluble organic substance is selected from one or more in glucose, urea, citric acid, the water soluble starch;
(3), step (1), (2) two kinds of solution are mixed back add industrial sulphuric acids by volume at 8～15: 1, make solution PH be adjusted to 0.1～1.5 behind the stirring and evenly mixing, solution proportion is 1.2～1.6; Be warming up to 45～85 ℃ then;
(4), in step (3) gained solution, add earlier iron sheet or iron powder after the oil removing, produce fresh high reductive hydrogen;
(5), according to the copper powder weight that will prepare, calculate the amount of required copper sulphate or cupric sulfate pentahydrate, add 1～12% of total amount earlier, utilize the high reproducibility of hydrogen and the catalytic action of temperature that bivalent cupric ion is reduced to copper atom, slaking 0.5～18 minute forms the copper nanoparticle crystal seed;
(6), continue slowly to add remaining copper sulphate or cupric sulfate pentahydrate, the hydrogen that is produced with step (4) fully reacts the generation copper atom, by control mixing speed 35～50rpm and 20～30 minutes curing times, on the copper nanoparticle crystal seed and connect and grow into the submicron copper powder particles, be the present invention.
2. copper powder in submicro as claimed in claim 1 is characterized in that step (1) soluble sulphate is selected from ferrous sulfate.
3. copper powder in submicro as claimed in claim 1 is characterized in that step (1) soluble sulphate is selected from the combination of aluminum sulfate, manganese sulfate, ferrous sulfate.
4. copper powder in submicro as claimed in claim 1 is characterized in that step (6) mixing speed is 35～50rpm, and the curing time is 20～30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102252808A CN101879606B (en) | 2010-07-13 | 2010-07-13 | Submicron copper powder and method for preparing same by sulfuric acid-process chemical reduction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102252808A CN101879606B (en) | 2010-07-13 | 2010-07-13 | Submicron copper powder and method for preparing same by sulfuric acid-process chemical reduction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101879606A true CN101879606A (en) | 2010-11-10 |
| CN101879606B CN101879606B (en) | 2011-09-28 |
Family
ID=43051815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102252808A Active CN101879606B (en) | 2010-07-13 | 2010-07-13 | Submicron copper powder and method for preparing same by sulfuric acid-process chemical reduction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101879606B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103203456A (en) * | 2013-04-15 | 2013-07-17 | 河北钢铁股份有限公司邯郸分公司 | Method for manufacturing iron-copper alloy from regenerated iron oxide red of cold-rolling waste acid |
| CN103831431A (en) * | 2012-11-26 | 2014-06-04 | 苏州钻石金属粉有限公司 | Method for preparing conductive copper powder |
| CN112916864A (en) * | 2021-01-21 | 2021-06-08 | 范期奎 | Water-phase copper nanocrystal and preparation method and application thereof |
| CN114734050A (en) * | 2022-04-01 | 2022-07-12 | 浙江旭德新材料有限公司 | Preparation machine and preparation method of superfine pure copper powder for thermal spraying technology |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034689A (en) * | 1987-12-09 | 1989-08-16 | 中国科学院化工冶金研究所 | The preparation method of submicron metal |
| CN1600478A (en) * | 2003-09-28 | 2005-03-30 | 中国科学院过程工程研究所 | Fabricating copper powder from water slurry of sulfide of copper through hydrogen reduction |
| US20080264205A1 (en) * | 2006-12-16 | 2008-10-30 | Taofang Zeng | Method for Making Nanoparticles |
| CN101386076A (en) * | 2008-10-24 | 2009-03-18 | 北京科技大学 | Preparation method of prealloy powder for nano level oxide dispersion strengthened metal |
-
2010
- 2010-07-13 CN CN2010102252808A patent/CN101879606B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034689A (en) * | 1987-12-09 | 1989-08-16 | 中国科学院化工冶金研究所 | The preparation method of submicron metal |
| CN1600478A (en) * | 2003-09-28 | 2005-03-30 | 中国科学院过程工程研究所 | Fabricating copper powder from water slurry of sulfide of copper through hydrogen reduction |
| US20080264205A1 (en) * | 2006-12-16 | 2008-10-30 | Taofang Zeng | Method for Making Nanoparticles |
| CN101386076A (en) * | 2008-10-24 | 2009-03-18 | 北京科技大学 | Preparation method of prealloy powder for nano level oxide dispersion strengthened metal |
Non-Patent Citations (2)
| Title |
|---|
| 《四川有色金属》 20030630 廖戎等 纳米铜粉的制备研究 , 第02期 2 * |
| 《材料导报》 20090125 宋永辉等 微混效应对化学法制备超细铜粉的影响分析 , 第02期 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103831431A (en) * | 2012-11-26 | 2014-06-04 | 苏州钻石金属粉有限公司 | Method for preparing conductive copper powder |
| CN103203456A (en) * | 2013-04-15 | 2013-07-17 | 河北钢铁股份有限公司邯郸分公司 | Method for manufacturing iron-copper alloy from regenerated iron oxide red of cold-rolling waste acid |
| CN112916864A (en) * | 2021-01-21 | 2021-06-08 | 范期奎 | Water-phase copper nanocrystal and preparation method and application thereof |
| CN114734050A (en) * | 2022-04-01 | 2022-07-12 | 浙江旭德新材料有限公司 | Preparation machine and preparation method of superfine pure copper powder for thermal spraying technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101879606B (en) | 2011-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| LIU et al. | Preparation of Cu nanoparticles with NaBH4 by aqueous reduction method | |
| CN103231072B (en) | Preparation method of silicon dioxide/silver core-shell composite powder for high temperature electronic paste | |
| CN104999076B (en) | The method that one kettle way prepares the controllable silver-colored copper-clad nano-powder of shell thickness | |
| CN101347841B (en) | Method for preparing high tap density silver powder with controllable graininess | |
| CN103273083B (en) | A kind of preparation method of gold nano grain | |
| CN102633307A (en) | Method for hydrothermally preparing mono-dispersed hollow magnetic nanometer particles | |
| CN101554664A (en) | Method for preparing nano-scale silver powder | |
| CN103128308A (en) | Method for preparing compact silver-coated copper powder by using one pot method | |
| CN105436517A (en) | Method for preparing metal powder by utilizing nano crystal seed induction | |
| CN101879606B (en) | Submicron copper powder and method for preparing same by sulfuric acid-process chemical reduction | |
| CN101049976A (en) | Method for preparing superfine even Fe2O3 | |
| CN100408704C (en) | Method for producing nano-magnetic FeO particle by iron extracted and utilized in tin tails | |
| CN102583576A (en) | Method for preparing paramagnetic Fe3O4 nanoparticles by using iron tailings | |
| CN104014808B (en) | Crystal seeding growth prepares the method for monodisperse superfine nickel powder and micro-reaction system thereof | |
| CN101279377A (en) | Method for preparing spherical superfine copper powder | |
| CN1776014A (en) | Method for cladding honeycomb metal cobalt or cobalt alloy on nickel or nickel alloy powder surface | |
| CN104096850A (en) | Method for preparing superfine spherical silver powder by reducing silver-ammonia complex with aminophenol | |
| CN102699348A (en) | Method of preparing micron-sized spherical high-purity nickel powder | |
| LIU et al. | Effects of reaction parameters on preparation of Cu nanoparticles via aqueous solution reduction method with NaBH4 | |
| CN104625082A (en) | Nanometer nickel powder preparation method | |
| CN106670450A (en) | Copper silver coaxial nanowire with high length-diameter ratio and preparation method thereof | |
| CN104478699A (en) | Preparation method of high-purity superfine cobalt oxalate powder | |
| CN103691965A (en) | Preparation method for copper/silver heterojunction nano-particles | |
| CN105397104B (en) | A kind of method based on liquid complexing reduction method for preparing nanometer Zero-valent Iron | |
| CN108579760A (en) | A kind of carbon-coated dilval nanocatalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHONGQING TAILU TECHNOLOGY DEVELOPMENT CO., LTD. Free format text: FORMER OWNER: JI WEIQUN Effective date: 20120629 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 400060 NANAN, CHONGQING TO: 400039 JIULONGPO, CHONGQING |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20120629 Address after: 400039 Chongqing Jiulongpo Yuzhou Road No. 18 (Shiqiaopu) high Kam No. 18 Patentee after: Chongqing Tailu Technology Development Co., Ltd. Address before: Huilong road 400060 Chongqing Nan'an District No. 66 Building 1 unit 1 3-2 Patentee before: Ji Weiqun |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Submicron copper powder and method for preparing same by sulfuric acid-process chemical reduction Effective date of registration: 20170314 Granted publication date: 20110928 Pledgee: Chongqing bridge financing Company Limited by Guarantee Pledgor: Chongqing Tailu Technology Development Co., Ltd. Registration number: 2017990000195 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20180508 Granted publication date: 20110928 Pledgee: Chongqing bridge financing Company Limited by Guarantee Pledgor: Chongqing Tailu Technology Development Co., Ltd. Registration number: 2017990000195 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Submicron copper powder and method for preparing same by sulfuric acid-process chemical reduction Effective date of registration: 20180511 Granted publication date: 20110928 Pledgee: Chongqing bridge financing Company Limited by Guarantee Pledgor: Chongqing Tailu Technology Development Co., Ltd. Registration number: 2018110000007 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PM01 | Change of the registration of the contract for pledge of patent right |
Change date: 20181012 Registration number: 2018110000007 Pledgee after: Chongqing Longshang financing Company Limited by Guarantee Pledgee before: Chongqing bridge financing Company Limited by Guarantee |
|
| PM01 | Change of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20190719 Granted publication date: 20110928 Pledgee: Chongqing Longshang financing Company Limited by Guarantee Pledgor: Chongqing Tailu Technology Development Co., Ltd. Registration number: 2018110000007 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Submicron copper powder and method for preparing same by sulfuric acid-process chemical reduction Effective date of registration: 20200525 Granted publication date: 20110928 Pledgee: Chongqing Longshang financing Company Limited by Guarantee Pledgor: CHONGQING TAILU TECHNOLOGY DEVELOPMENT Co.,Ltd. Registration number: Y2020500000007 |