CN111943251A - Method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material - Google Patents
Method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material Download PDFInfo
- Publication number
- CN111943251A CN111943251A CN202010843703.6A CN202010843703A CN111943251A CN 111943251 A CN111943251 A CN 111943251A CN 202010843703 A CN202010843703 A CN 202010843703A CN 111943251 A CN111943251 A CN 111943251A
- Authority
- CN
- China
- Prior art keywords
- copper
- cuprous oxide
- tungsten alloy
- solution
- reaction
- 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
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 37
- 239000002699 waste material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910001080 W alloy Inorganic materials 0.000 title claims abstract description 34
- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002994 raw material Substances 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 61
- 239000010949 copper Substances 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 238000003756 stirring Methods 0.000 claims abstract description 33
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- 150000002500 ions Chemical class 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 18
- 150000002496 iodine Chemical class 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000006722 reduction reaction Methods 0.000 claims abstract description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 9
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 29
- -1 anilino compound Chemical class 0.000 claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 27
- 229910052802 copper Inorganic materials 0.000 claims description 27
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 13
- 229960001701 chloroform Drugs 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000000536 complexating effect Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000643 oven drying Methods 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 125000001165 hydrophobic group Chemical group 0.000 claims description 5
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 229930003268 Vitamin C Natural products 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 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000001727 glucose Nutrition 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims 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 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 5
- 239000005749 Copper compound Substances 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 4
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing cuprous oxide by using waste copper-tungsten alloy as a raw material, which comprises the following steps: (1) fully reacting the waste copper-tungsten alloy ground into powder with a nitric acid solution to obtain a copper nitrate solution; (2) then mixing the copper nitrate solution with excessive iodine salt or bromine salt solution, adding reducing agent solution with the concentration of 1-4mol/L for reduction reaction for 1-2h, continuously stirring in the reaction process, and obtaining the copper nitrate solution containing complex ions [ CuI ] after the reaction is finished2]‑Or [ CuBr ]2]‑The mixed solution of (1); adding an anilino compound C to the mixed solution6NH2Stirring R1R2R3R4R5 for 60-80min to react to generate flocculate, filtering the flocculate and cleaning with water for later use; (3) reacting the floc with an alkaline reagent to obtain high-purity Cu2And O. The preparation process is simple and time-saving, the material is economical, and the prepared cuprous oxide can ensure that the yield is more than 98 percent, the purity is about 99 percent, and the highest purity can reach 99.6 percent.
Description
Technical Field
The invention relates to the technical field of preparation and application of inorganic functional materials, in particular to a method for preparing cuprous oxide by taking waste copper-tungsten alloy as a raw material.
Background
Cuprous oxide is a P-type oxide semiconductor material, has good catalytic activity, and has the characteristics of strong adsorption property, low-temperature paramagnetism and the like. The method has wide application in numerous fields such as organic synthesis, novel energy, photolysis of water, sterilization, superconduction and the like. At present, raw materials for preparing cuprous oxide are basically copper acetate or copper nitrate, and then reducing agents such as sodium borohydride, vitamin C, formic acid, glucose and the like are used for preparing cuprous oxide by reduction, so that the production cost is increased to a certain extent. For the problem of production cost, in the prior art, there is a method for recovering and preparing cuprous oxide by using waste copper-tungsten alloy as a raw material, for example, CN201610859960.2 uses nitric acid to leach copper in the waste copper-tungsten alloy for the second time, and then uses sodium sulfite to reduce the copper nitrate to prepare cuprous oxide powder. For example, the yield can be improved by increasing the concentration of the reducing agent, but the purity of cuprous oxide is reduced due to the generation of impurity phase Cu caused by over-reduction of copper ions, and the yield is greatly reduced by decreasing the concentration of the reducing agent, so that a method for preparing high-purity and high-yield cuprous oxide by using the waste copper-tungsten alloy is needed urgently.
Disclosure of Invention
The invention aims to provide a method for preparing cuprous oxide by using waste copper-tungsten alloy as a raw material, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing cuprous oxide by using waste copper-tungsten alloy as a raw material comprises the following steps:
(1) firstly, grinding the waste copper-tungsten alloy into micron-sized particles, pouring the micron-sized particles into a nitric acid solution with the concentration of 2-5mol/L for reaction for 50-70min, continuously stirring in the reaction process to ensure that the reaction is fully carried out, and filtering impurity tungsten and removing impurity tungsten to obtain a copper nitrate solution for later use after the reaction is finished;
(2) mixing a copper nitrate solution with an excessive iodine salt or bromine salt solution, adding a reducing agent solution with the concentration of 1-4mol/L to perform reduction reaction for 1-2h, continuously stirring in the reaction process, and obtaining the copper nitrate solution containing complex ions [ CuI ] after the reaction is finished2]-Or [ CuBr ]2]-The mixed solution of (1); adding an anilino compound C to the mixed solution6NH2Stirring R1R2R3R4R5 for 60-80min to react to generate flocculate, filtering the flocculate and cleaning with water for later use;
this step adds an iodide salt or bromide salt to the solution of copper ions and a reducing agent for reaction, here exemplified by an iodide salt due to an electric pairCu2+/CuI/I-Has an electrode potential of about 0.86V, which is much higher than that of Cu2+Cu (0.337V) and Cu2+/Cu+(0.519V), so that iodine ions are introduced into the reduction reaction solution of copper ions, and Cu is caused to occur at the time of reduction reaction2+It is easier for electrons to form CuI precipitates rather than being reduced to Cu or Cu2O, and simultaneously CuI and iodide ions continue to coordinate to generate complex ions [ CuI ] due to excessive iodide salt2]-The specific reaction formula is as follows. This has promoted the reaction of bivalent copper to monovalent copper and has gone on one hand for monovalent copper's content is higher in the product, has promoted the productivity, and on the other hand can be protected monovalent copper with iodide ion complex that generates, has avoided monovalent copper and reductant direct contact in the solution to lead to it to continue to be reduced into the problem of Cu, has promoted the utilization ratio of copper source, has avoided the waste of raw and other materials. The action principle of bromine salt is similar to that of iodine salt, and electricity is paired with Cu2+/CuBr/Br-Is about 0.67V.
Cu2++2I-+e-＝[CuI2]-
The above first step reaction is a one-step protection method in the step, and although monovalent copper can be effectively protected, the first step reaction contains complex ions [ CuI ] of monovalent copper2]-Still dispersed in the solution, thereby adding anilino compound C6NH2R1R2R3R4R5 and complex ion [ CuI2]-The reaction is carried out as a two-step protection method of the step. The anilino compound is slightly soluble in water, lone pair electrons contained in amino groups of the anilino compound are easily paired with the monovalent copper to form a coordination bond, and iodine ions in complex ions are replaced to form insoluble flocs, so that the monovalent copper compound is effectively separated out from a solution to facilitate subsequent reaction, and the monovalent copper is still protected under the action of the anilino compound, and the specific action principle is shown in figure 1.
(3) Pouring the cleaned flocculate into a mixed solution of an alkaline reagent with the hydroxide radical concentration of 1-10mol/L and trichloromethane, and stirring for reacting for 3-5h to obtain Cu2Precipitating with oxygen, filtering, washing with water, and oven drying to obtain final productHigh purity Cu2O。
The reaction in step (2) is to obtain a monovalent copper compound with higher yield and purity, and the reaction in this step is to convert all the monovalent copper in the flocs into Cu2O, the conversion of the monovalent copper compound is realized, and the specific reaction formula is as follows.
[Cu(C6NH2R1R2R3R4R5)I]2n+2nOH-＝nCu2O+2nI-+nH2O+2nC6NH2R1R2R3R4R5
Furthermore, the particle size of the micron-sized powder particles is 0.5-10 μm.
The waste copper-tungsten alloy is ground into powder so as to fully perform the stirring reaction with the nitric acid solution, thereby improving the utilization rate of the copper source.
Further, the molar ratio of copper in the micron-sized powder particles to nitrate in the nitric acid solution is (0.5-1.4): 1.
the Cu in the scrap copper tungsten alloy can be fully reacted in the preferred molar ratio range, while too much or too little nitric acid can result in the waste of one of the reactants.
Further, the iodine salt or bromine salt can be one or a mixture of potassium iodide, sodium bromide and potassium bromide.
Further, the content of the excess iodine salt or bromine salt should be controlled so that the anion and Cu in the copper nitrate solution are in the same2+In a molar ratio of (1.5-5): 1.
i in the preferred molar ratio range-Or Br-Can be complexed with CuI generated by monovalent copper to generate [ CuI2]-The complex ions will dissolve in the aqueous solution, while too little iodide or bromide will cause the formation of CuI precipitate, monovalent copper will be reduced to Cu by direct contact with the reducing agent in solution, and too much iodide or bromide will reduce the rate of reaction.
Further, the reducing agent solution can be one or more of sodium sulfite, ascorbic acid, sodium hypophosphite, sodium citrate, hydrazine hydrate, sodium borohydride, vitamin C, formic acid and glucose.
Further, the R1, R2, R3, R4 and R5 groups in the anilino compound are hydrophobic groups; the hydrophobic group can be a combination of any five of a hydrogen group, an alkyl group having 1 to 10 carbon atoms.
The hydrophobic group in the anilino compound can ensure that the anilino compound can be effectively separated out after CuI forms a coordination compound, and if the anilino compound is hydrophilic, the solubility of the anilino compound in an aqueous solution can be increased, so that the loss of a copper source is caused.
Further, the anilino compound is complexed with a complexing ion [ CuI2]-Or [ CuBr ]2]-In a molar ratio of (2-4): 1.
a slight excess of anilino compound may sufficiently replace the iodide or bromide ions.
Further, the alkaline reagent is one or more of sodium hydroxide, potassium hydroxide, barium hydroxide and ammonia water, and the volume ratio of the water in the alkaline reagent to the trichloromethane is 1: (0.8-2).
Appropriate amount of trichloromethane can dissolve lipophilic anilino compound in the flocculate, so that the alkaline reagent is fully contacted with CuI and reacts to obtain Cu2O。
Further, the drying temperature is 60-70 ℃ and the drying time is 15-25 min; the stirring speed is 500-3000 r/min.
Compared with the prior art, the invention has the following beneficial effects:
(1) the univalent copper compound prepared by the two-step protection method is protected by iodide ions or bromide ions and anilino compounds in the whole process, so that the problem that the univalent copper is reduced into Cu due to over-strong reducibility of a reducing agent in the reduction reaction process is solved, and the final product Cu is improved2The purity of O.
(2) The invention utilizes the electric pair Cu2+/CuI/I-Or Cu2+/CuBr/Br-Has higher electrode potential by introducing excessive bromine salt or iodine salt and controlling iodine or bromine ion and Cu2+In a molar ratio of (1.5-5): 1, on the one hand, the generated monovalent copper is indirectly protected, and on the other handFace promotes Cu2The yield of O avoids the waste of raw materials.
(3) The materials such as bromine salt, iodine salt, nitric acid and the like used in the invention have wide sources and low prices, the preparation process is simple and time-saving, the waste utilization can be realized only by low cost, and the product with high yield can be obtained, thus the invention has wide application prospect.
Drawings
FIG. 1 is a schematic representation of the reaction of a complex ion of the present invention with an anilino compound.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The invention provides a method for preparing cuprous oxide by using waste copper-tungsten alloy as a raw material, which comprises the following steps:
(1) firstly, grinding waste copper-tungsten alloy into micron-sized particles, pouring the particles into a nitric acid solution with the concentration of 2mol/L for reaction for 50min, continuously stirring in the reaction process to ensure that the reaction is fully carried out, and filtering impurity tungsten and removing impurity tungsten to obtain a copper nitrate solution for later use after the reaction is finished;
(2) mixing a copper nitrate solution with an excessive iodine salt solution, adding a reducing agent solution with the concentration of 1mol/L for reduction reaction for 2 hours, continuously stirring the reaction process, and obtaining the copper nitrate solution containing complex ions [ CuI ] after the reaction is finished2]-The mixed solution of (1); adding an anilino compound C to the mixed solution6NH2Stirring R1R2R3R4R5 for 60min to react to generate flocculate, filtering the flocculate and cleaning with water for later use;
(3) pouring the cleaned flocculate into a mixed solution of an alkaline reagent with the hydroxide radical concentration of 1mol/L and trichloromethane, stirring and reacting for 5 hours to obtain Cu2Precipitating with oxygen, filtering, washing with water, oven drying,finally obtaining high-purity Cu2O。
Wherein the particle size of the micron-sized powder particles is 0.5 mu m; the molar ratio of copper in the micron-sized powder particles to nitrate in the nitric acid solution is 0.5: 1; the iodine salt is potassium iodide; the content of the excess iodonium salt should be controlled in such a way that the iodonium ion and Cu in the copper nitrate solution are controlled2+In a molar ratio of 1.5: 1; the reducing agent solution is sodium sulfite; the anilino compound is mesitylene; the anilino compound is complexed with a complexing ion [ CuI2]-In a molar ratio of 2: 1; the alkaline reagent is sodium hydroxide, and the volume ratio of water to trichloromethane in the alkaline reagent is 1: 0.8; the drying temperature is 60 ℃ and the drying time is 15 min; the stirring speed is 500 r/min.
Example two
The invention provides a method for preparing cuprous oxide by using waste copper-tungsten alloy as a raw material, which comprises the following steps:
(1) firstly, grinding waste copper-tungsten alloy into micron-sized particles, pouring the particles into a nitric acid solution with the concentration of 5mol/L for reaction for 50min, continuously stirring in the reaction process to ensure that the reaction is fully carried out, and filtering impurity tungsten and removing impurity tungsten to obtain a copper nitrate solution for later use;
(2) mixing a copper nitrate solution with an excessive iodine salt solution, adding a reducing agent solution with the concentration of 4mol/L to perform reduction reaction for 1h, continuously stirring the reaction process, and obtaining the copper nitrate solution containing complex ions [ CuI ] after the reaction is finished2]-The mixed solution of (1); adding an anilino compound C to the mixed solution6NH2Stirring R1R2R3R4R5 for 80min to react to generate flocculate, filtering the flocculate and cleaning with water for later use;
(3) pouring the cleaned flocculate into a mixed solution of an alkaline reagent with the hydroxide radical concentration of 10mol/L and trichloromethane, stirring and reacting for 3 hours to obtain Cu2Precipitating with O, filtering the precipitate, washing with water, and oven drying to obtain high-purity Cu2O。
Wherein the particle size of the micron-sized powder particles is 10 mu m; the mole of copper in the micron-sized powder particles and nitrate radical in nitric acid solutionThe ratio is 1.4: 1; the iodine salt is potassium iodide; the content of the excess iodonium salt should be controlled in such a way that the iodonium ion and Cu in the copper nitrate solution are controlled2+In a molar ratio of 5: 1; the reducing agent solution is sodium sulfite; the anilino compound is mesitylene; the anilino compound is complexed with a complexing ion [ CuI2]-In a molar ratio of 4: 1; the alkaline reagent is sodium hydroxide, and the volume ratio of water to trichloromethane in the alkaline reagent is 1: 2; the drying temperature is 70 ℃ and the drying time is 25 min; the stirring speed is 3000 r/min.
EXAMPLE III
The invention provides a method for preparing cuprous oxide by using waste copper-tungsten alloy as a raw material, which comprises the following steps:
(1) firstly, grinding waste copper-tungsten alloy into micron-sized particles, pouring the particles into a nitric acid solution with the concentration of 3mol/L for reaction for 60min, continuously stirring in the reaction process to ensure that the reaction is fully carried out, and filtering impurity tungsten and removing impurity tungsten to obtain a copper nitrate solution for later use after the reaction is finished;
(2) mixing copper nitrate solution with excessive iodine salt solution, adding reducing agent solution with the concentration of 2mol/L for reduction reaction for 1.5h, continuously stirring in the reaction process, and obtaining the copper nitrate solution containing complex ions [ CuI ] after the reaction is finished2]-The mixed solution of (1); adding an anilino compound C to the mixed solution6NH2Stirring R1R2R3R4R5 for 70min to react to generate flocculate, filtering the flocculate and cleaning with water for later use;
(3) pouring the cleaned flocculate into a mixed solution of an alkaline reagent with the hydroxyl concentration of 4mol/L and trichloromethane, and stirring for reacting for 4 hours to obtain Cu2Precipitating with O, filtering the precipitate, washing with water, and oven drying to obtain high-purity Cu2O。
Wherein the particle size of the micron-sized powder particles is 3 μm; the molar ratio of copper in the micron-sized powder particles to nitrate in the nitric acid solution is 1.2: 1; the iodine salt is potassium iodide; the content of the excess iodonium salt should be controlled in such a way that the iodonium ion and Cu in the copper nitrate solution are controlled2+In a molar ratio of 3: 1; the reducing agent solution is sodium sulfite(ii) a The anilino compound is mesitylene; the anilino compound is complexed with a complexing ion [ CuI2]-In a molar ratio of 3: 1; the alkaline reagent is sodium hydroxide, and the volume ratio of water to trichloromethane in the alkaline reagent is 1: 1.5; the drying temperature is 65 ℃ and the drying time is 20 min; the stirring speed is 1000 r/min.
Example four
The invention provides a method for preparing cuprous oxide by using waste copper-tungsten alloy as a raw material, which comprises the following steps:
(1) firstly, grinding waste copper-tungsten alloy into micron-sized particles, pouring the particles into a nitric acid solution with the concentration of 3mol/L for reaction for 60min, continuously stirring in the reaction process to ensure that the reaction is fully carried out, and filtering impurity tungsten and removing impurity tungsten to obtain a copper nitrate solution for later use after the reaction is finished;
(2) mixing a copper nitrate solution with an excessive bromine salt solution, adding a reducing agent solution with the concentration of 2mol/L to perform reduction reaction for 1.5h, continuously stirring the reaction process, and obtaining the copper nitrate solution containing complex ions [ CuBr ] after the reaction is finished2]-The mixed solution of (1); adding an anilino compound C to the mixed solution6NH2Stirring R1R2R3R4R5 for 70min to react to generate flocculate, filtering the flocculate and cleaning with water for later use;
(3) pouring the cleaned flocculate into a mixed solution of an alkaline reagent with the hydroxyl concentration of 4mol/L and trichloromethane, and stirring for reacting for 4 hours to obtain Cu2Precipitating with O, filtering the precipitate, washing with water, and oven drying to obtain high-purity Cu2O。
Wherein the particle size of the micron-sized powder particles is 3 μm; the molar ratio of copper in the micron-sized powder particles to nitrate in the nitric acid solution is 1.2: 1; the bromine salt is potassium bromide; the content of the excess bromine salt should be controlled so that the bromide ions and Cu in the copper nitrate solution are in the excess2+In a molar ratio of 3: 1; the reducing agent solution is sodium sulfite; the anilino compound is mesitylene; the anilino compound is complexed with a complexing ion [ CuBr ]2]-In a molar ratio of 3: 1; the alkaline reagent is sodium hydroxide and the alkaline reagentThe volume ratio of water to trichloromethane is 1: 1.5; the drying temperature is 65 ℃ and the drying time is 20 min; the stirring speed is 1000 r/min.
The electrode potential in the present invention is obtained by assembling each pair of electrodes and a standard hydrogen electrode into a galvanic cell and measuring the electromotive force of each galvanic cell, and since the electrode potential of the standard hydrogen electrode is defined as 0V, the measured electromotive force is the electrode potential of each pair of electrodes, wherein each electrode is in a standard state, the concentration is 1mol/L in the case of an ionic solution, 100kPa in the case of a gas, and the temperature is 298.15K. In order to test the superiority and inferiority of the preparation methods of the examples, the yield and purity of each cuprous oxide were respectively tested by the present invention. The method for testing the yield is to calculate the mass ratio of the product cuprous oxide to the copper element in the raw material waste copper-tungsten alloy, wherein the method for testing the quality of the cuprous oxide in the product and the quality of the copper element in the waste copper-tungsten alloy is to fully react and dissolve the copper in the product by using 5mol/L nitric acid, calculate the mass difference before and after the reaction, and calculate the quality of the copper element in the cuprous oxide by using the atomic mass ratio; and the purity is obtained by calculating the ratio of the mass difference of the product before and after dissolution to the product mass, in order to verify the purity of the cuprous oxide, the invention also tests an experiment for cuprous oxide photocatalytic explanation of methyl orange, wherein the usage amount of the product is 0.05g, the reaction time is 3h, the concentration of the methyl orange is 5mg/L, and the purity of the cuprous oxide in the product can be judged by calculating the degradation rate of the methyl orange.
Through comparative experiments on the four groups of examples, the cuprous oxide with excellent purity and performance can be prepared in each group of examples, and specific data are shown in table 1. The cuprous oxide prepared by the method can ensure that the yield is more than 98%, the purity is about 99%, the methyl orange has higher purity according to the degradation rate, wherein the purity of the third example is 99.6% at most, and the catalytic performance is optimal.
TABLE 1
Comparative example 1: the difference from example three is that potassium iodide is replaced by potassium chloride. Due to Cu2+/CuCl/Cl-About 0.55V, which is comparable to Cu+The electrode potential of/Cu (0.52V) is relatively close, so [ CuCl ] exists in the reduction reaction process2]-But also accompanied by the formation of elemental Cu, resulting in Cu in the product2The purity of O is reduced.
Comparative example 2: the difference from example three is that potassium iodide was replaced with potassium nitrate. Since the introduced potassium nitrate does not participate in the reaction, the reaction is carried out on the final Cu2The yield and purity of O are not improved, so that the yield and purity are greatly reduced.
Comparative example 3: the difference from the third embodiment is that Cu2+The molar ratio to iodide ion is 3: 1. cu is caused because excessive copper ions cause the formation of CuI precipitates, which are subsequently reduced to copper2The O purity is reduced.
Comparative example 4: the difference from example three is that the reaction was carried out without addition of an iodide salt. Electric pair Cu due to lack of high electrode potential2+/CuI/I-Function, no generation of transitional complex ions [ CuI2]-The reaction with subsequent anilino compound can not be carried out, and simultaneously, a large amount of simple substance Cu is generated during the reduction reaction, so that the final product Cu is reduced2Both the yield and purity of O will decrease.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing cuprous oxide by using waste copper-tungsten alloy as a raw material is characterized by comprising the following steps:
(1) firstly, grinding the waste copper-tungsten alloy into micron-sized particles, pouring the micron-sized particles into a nitric acid solution with the concentration of 2-5mol/L for reaction for 50-70min, continuously stirring in the reaction process to ensure that the reaction is fully carried out, and filtering impurity tungsten and removing impurity tungsten to obtain a copper nitrate solution for later use after the reaction is finished;
(2) mixing a copper nitrate solution with an excessive iodine salt or bromine salt solution, adding a reducing agent solution with the concentration of 1-4mol/L to perform reduction reaction for 1-2h, continuously stirring in the reaction process, and obtaining the copper nitrate solution containing complex ions [ CuI ] after the reaction is finished2]-Or [ CuBr ]2]-The mixed solution of (1); adding an anilino compound C to the mixed solution6NH2Stirring R1R2R3R4R5 for 60-80min to react to generate flocculate, filtering the flocculate and cleaning with water for later use;
(3) pouring the cleaned flocculate into a mixed solution of an alkaline reagent with the hydroxide radical concentration of 1-10mol/L and trichloromethane, and stirring for reacting for 3-5h to obtain Cu2Precipitating with O, filtering the precipitate, washing with water, and oven drying to obtain high-purity Cu2O。
2. The method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material according to claim 1, characterized by comprising the following steps: the grain size of the micron-sized powder particles is 0.5-10 mu m.
3. The method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material according to claim 1, characterized by comprising the following steps: the molar ratio of copper in the micron-sized powder particles to nitrate in the nitric acid solution is (0.5-1.4): 1.
4. the method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material according to claim 1, characterized by comprising the following steps: the iodine salt or bromine salt can be one or a mixture of potassium iodide, sodium bromide and potassium bromide.
5. The method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material according to claim 1, characterized by comprising the following steps: the content of the excess iodine salt or bromine salt should be controlled so that the anion and Cu in the copper nitrate solution are in the same2+In a molar ratio of (1.5-5): 1.
6. the method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material according to claim 1, characterized by comprising the following steps: the reducing agent solution can be one or more of sodium sulfite, ascorbic acid, sodium hypophosphite, sodium citrate, hydrazine hydrate, sodium borohydride, vitamin C, formic acid and glucose.
7. The method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material according to claim 1, characterized by comprising the following steps: the R1, R2, R3, R4 and R5 groups in the anilino compound are hydrophobic groups; the hydrophobic group can be a combination of any five of a hydrogen group, an alkyl group having 1 to 10 carbon atoms.
8. The method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material according to claim 1, characterized by comprising the following steps: the anilino compound is complexed with a complexing ion [ CuI2]-Or [ CuBr ]2]-In a molar ratio of (2-4): 1。
9. The method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material according to claim 1, characterized by comprising the following steps: the alkaline reagent is one or more of sodium hydroxide, potassium hydroxide, barium hydroxide and ammonia water, and the volume ratio of the water in the alkaline reagent to the trichloromethane is 1: (0.8-2).
10. The method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material according to claim 1, characterized by comprising the following steps: the drying temperature is 60-70 ℃ and the drying time is 15-25 min; the stirring speed is 500-3000 r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010843703.6A CN111943251B (en) | 2020-08-20 | 2020-08-20 | Method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010843703.6A CN111943251B (en) | 2020-08-20 | 2020-08-20 | Method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111943251A true CN111943251A (en) | 2020-11-17 |
| CN111943251B CN111943251B (en) | 2021-07-02 |
Family
ID=73358695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010843703.6A Active CN111943251B (en) | 2020-08-20 | 2020-08-20 | Method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111943251B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364056A (en) * | 1999-06-25 | 2002-08-14 | 阿奇化工公司 | Pyrithione biocides enhanced by silver, copper, or zinc ions |
| CN103435090A (en) * | 2013-08-02 | 2013-12-11 | 浙江理工大学 | Grinding production method of nano cuprous chloride |
| US9850389B1 (en) * | 2017-03-22 | 2017-12-26 | King Saud University | Synthesis of bimetallic oxide nanocomposites using poly (ionic liquid) |
| CN108328677A (en) * | 2018-03-08 | 2018-07-27 | 河海大学 | A kind of Multifunctional environment friendly composite material and preparation method and application |
| CN108971513A (en) * | 2018-10-12 | 2018-12-11 | 圣戈莱（北京）科技有限公司 | A kind of nano copper particle and its inexpensive environmentally protective preparation method |
| CN109536991A (en) * | 2018-12-14 | 2019-03-29 | 天津大学 | A kind of application of the preparation method and cuprous oxide of loose porous cuprous oxide material in electro-catalysis reduction carbon dioxide |
| CN110396705A (en) * | 2019-08-07 | 2019-11-01 | 中国科学院合肥物质科学研究院 | The method of the porous silver of electrodeposited nanocrystalline |
| KR102054784B1 (en) * | 2017-11-02 | 2019-12-11 | 숙명여자대학교산학협력단 | Porous metal organic framework with fibrous structure and method for preparing the same |
| CN111420664A (en) * | 2020-03-11 | 2020-07-17 | 惠州学院 | Preparation method of flaky cuprous oxide/cobaltous oxide nanocomposite and application of flaky cuprous oxide/cobaltous oxide nanocomposite in catalyzing ammonia borane hydrolysis hydrogen production |
-
2020
- 2020-08-20 CN CN202010843703.6A patent/CN111943251B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364056A (en) * | 1999-06-25 | 2002-08-14 | 阿奇化工公司 | Pyrithione biocides enhanced by silver, copper, or zinc ions |
| CN103435090A (en) * | 2013-08-02 | 2013-12-11 | 浙江理工大学 | Grinding production method of nano cuprous chloride |
| US9850389B1 (en) * | 2017-03-22 | 2017-12-26 | King Saud University | Synthesis of bimetallic oxide nanocomposites using poly (ionic liquid) |
| KR102054784B1 (en) * | 2017-11-02 | 2019-12-11 | 숙명여자대학교산학협력단 | Porous metal organic framework with fibrous structure and method for preparing the same |
| CN108328677A (en) * | 2018-03-08 | 2018-07-27 | 河海大学 | A kind of Multifunctional environment friendly composite material and preparation method and application |
| CN108971513A (en) * | 2018-10-12 | 2018-12-11 | 圣戈莱（北京）科技有限公司 | A kind of nano copper particle and its inexpensive environmentally protective preparation method |
| CN109536991A (en) * | 2018-12-14 | 2019-03-29 | 天津大学 | A kind of application of the preparation method and cuprous oxide of loose porous cuprous oxide material in electro-catalysis reduction carbon dioxide |
| CN110396705A (en) * | 2019-08-07 | 2019-11-01 | 中国科学院合肥物质科学研究院 | The method of the porous silver of electrodeposited nanocrystalline |
| CN111420664A (en) * | 2020-03-11 | 2020-07-17 | 惠州学院 | Preparation method of flaky cuprous oxide/cobaltous oxide nanocomposite and application of flaky cuprous oxide/cobaltous oxide nanocomposite in catalyzing ammonia borane hydrolysis hydrogen production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111943251B (en) | 2021-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104999076B (en) | The method that one kettle way prepares the controllable silver-colored copper-clad nano-powder of shell thickness | |
| CN109675603A (en) | A kind of carbon-supported catalysts and its preparation method and application of silica protection | |
| CN104070180B (en) | A kind of production method of solar cell conductive silver slurry high density silver powder | |
| CN107498064A (en) | A kind of preparation method of high temperature electric slurry ultra-fine copper galactic nucleus shell composite powder | |
| CN102745662B (en) | Preparation method of amorphous iron phosphate | |
| CN102784643B (en) | Ternary copper catalyst prepared from copper powder recovered from waste organic silicon contacts and preparation method thereof | |
| CN109876865A (en) | A kind of preparation of the polyacid Base Metal organic frame of intercalation configuration and catalytic performance | |
| CN101367557A (en) | Novel method for synthesis of tetrammine platinum hydrogen nitrate (II) | |
| CN104084598A (en) | Production method for solar cell high-density monodisperse silver powder | |
| CN110233271A (en) | A kind of carbon-based formic acid catalyst for preparing hydrogen of layered nitride and preparation method thereof | |
| CN102897739A (en) | Novel process for preparing battery-grade iron phosphate material by using iron hydroxide | |
| CN113753965A (en) | Cobalt hydroxide synthesis method and cobalt hydroxide | |
| CN104625082A (en) | Nanometer nickel powder preparation method | |
| CN100387383C (en) | Preparation method of ultra-fine nickel powder | |
| CN106513706B (en) | A kind of preparation method for being used for Nano Silver nucleus in ball shape silver powder production technology | |
| CN115449835A (en) | Preparation method of carbon fiber-loaded copper-nickel alloy nanoparticle nitrate transamination catalyst | |
| CN102350362A (en) | Nanometer catalyst for silicon tetrachloride hydrogenation reaction and preparation method thereof | |
| KR101061600B1 (en) | Manufacturing method of cobalt powder | |
| CN111584884A (en) | Microwave preparation method of fuel cell binary alloy catalyst | |
| CN111943251B (en) | Method for preparing cuprous oxide by using waste copper-tungsten alloy as raw material | |
| CN114436348A (en) | Synthetic method of platinum salt electroplated dinitroso diammine platinum | |
| CN104649261A (en) | Method for catalytic reduction of graphene oxide | |
| CN113638005A (en) | Preparation method and application of efficient and bifunctional heterostructure full-electrolysis water-electricity catalyst | |
| CN110480027B (en) | Method for preparing two-dimensional ultrathin silicon wafer loaded with silver nanoparticles | |
| CN102328094A (en) | Method for preparing ultrafine silver powder with uniform particle size |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210618 Address after: Room 516, building 3, Xiangti Business Plaza, high tech Zone, Suzhou, Jiangsu 215000 Applicant after: Suzhou Wigner Information Technology Co.,Ltd. Address before: 215000 418 Huoju Road, high tech Zone, Suzhou City, Jiangsu Province Applicant before: Tan Fen |
|
| TA01 | Transfer of patent application right |