CN104495907A - Method for producing ultrafine cuprous oxide by microwave calcination of copper oxalate - Google Patents
Method for producing ultrafine cuprous oxide by microwave calcination of copper oxalate Download PDFInfo
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- CN104495907A CN104495907A CN201410712844.9A CN201410712844A CN104495907A CN 104495907 A CN104495907 A CN 104495907A CN 201410712844 A CN201410712844 A CN 201410712844A CN 104495907 A CN104495907 A CN 104495907A
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- rotary kiln
- cuprous oxide
- cupric oxalate
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- oxide powder
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a method for producing ultrafine cuprous oxide by microwave calcination of copper oxalate. The method comprises the following steps: drying, crushing and screening copper oxalate particles, and then putting into a material bin of a microwave rotary kiln according to a certain feeding amount; opening microwaves, starting to heat and calcine, simultaneously introducing oxygen, controlling an atmosphere in the rotary kiln, calcining for a certain time, returning into the rotary kiln, crushing and screening to obtain ultrafine cuprous oxide powder. The obtained powder has the particle size of 0.3-1.2mu m. The process has the advantages of low energy consumption, small product particle size, high purity, no production of three wastes and capability of greatly improving the production efficiency, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of method that ultrafine cuprous oxide produced by microwave calcination cupric oxalate.Belong to technical field of material.
Background technology
Red copper oxide (Cu
2o) powder is a kind of redness or yellow industrial chemicals and product, is industrially widely used, as being used as marine antifouling priming paint, glass porcelain glaze tinting material, organic catalyst compound and electronic material etc.Superfine powdery material, particularly nanometer grade powder usually have the excellent properties that bulk material does not have, and such as high catalytic property, unusual electromagnetism and optical property etc., therefore prepare the Cu of specified particle diameter and pattern
2o particle has more wide market outlook and potential value.
Cu
2o powder is of many uses, is used as marine antifouling priming paint and prevents marine organisms to be attached to hull bottom in coatings industry; Red glass and red enamel tinting material is used as in glass and ceramic industry; Agriculturally be used as sterilant; Cu
2o has semiconductor property, and electronic industry makes barretter with it and copper.It also can be used as coating, plastic and glass surface modifying material and organic industry catalyzer etc.In addition, ultra-fine Cu
2o also can make photo-thermal catalyzer, flame-retardant smoke inhibition material etc.
In addition, Cu
2o is a kind of important metal oxide p-type semiconductor, and band gap is 2.2eV, and this makes it promise to be solar energy converting to be the material of electric energy or chemical energy, it is reported, Cu
2water decomposition can be O by O under visible light
2and H
2.At present, ultra-fine Cu
2o powder is just as intermediate prepared by laminated ceramic capacitor (MLCC) copper termination copper powder.Due to rising violently of precious metal price, current most of MLCC has replaced the precious metals such as palladium-silver as its electrode materials with base metals such as copper nickel.One of preparation method of copper electrode copper powder is and uses suitable reductive agent reduction Cu
2+.Directly by Cu
2+when being reduced into copper, because intermediate reaction is many, gained copper powder size is uneven.One of terms of settlement is exactly first by Cu
2+be reduced into ultra-fine Cu
2o intermediate, and then by Cu
2o powder is reduced into copper powder, because copper powder is by ultra-fine Cu
2o mono-step generates, and intermediate steps is few, makes particle diameter more easy to control.In addition, Cu
2o also can be used as in the proofwater hydrogen anode that conductive auxiliary agent joins in alkaline hydrogen oxygen fuel cell, to reduce its ohmic polarization, adds Cu
2o is better than adding graphite material greatly.With Cu
2o is the sintering metal of base is one of possible surrogate of the non-burning anode material of electrolysis of aluminum.
Common Cu
2o technology of preparing mainly contains solid phase method, liquid phase method and electrolytic process three kinds.Along with going deep into of research and development, Cu
2the preparation method of O constantly brings forth new ideas, and various pattern and the different product of particle diameter impel ultra-fine Cu
2o powder application scope constantly expands, and less particle diameter, higher purity and various pattern will be Cu
2o finds more purposes.As patent CN87106540.1 proposes the technique that a kind of pressurized hydrogen also prepared Red copper oxide originally, the cuprous oxide powder granularity of final preparation can < 1.0um, purity > 98%, and pattern is that class is spherical.But there is problem: 1. react at high temperature under high pressure, energy consumption is large; 2. autoclave requires higher to equipment and human users; 3. produce a large amount of waste water containing ammonia nitrogen and heavy metal and need process.If the patent No. is the method that CN97100952.X proposes uv-radiation and prepares ultrafine cuprous oxide powder, adopt the buffered soln of ultraviolet radiation soluble copper salt at normal temperatures and pressures, can obtain the cuprous oxide powder of 10-100nm, but this technique is not suitable for scale operation.
The maximum feature of solid state reaction is temperature of reaction convenient operation and control. in addition, do not use solvent, highly selective, high yield in addition, saves the energy, the features such as synthesis technique is simple.And the shortcoming that general solid reaction process prepares Red copper oxide is that energy consumption is huge, three-waste pollution is serious, and it is high to be not easy obtained purity, and the Red copper oxide that particle is little, production efficiency is low.
Summary of the invention
The object of this invention is to provide a kind of method that ultrafine cuprous oxide produced by microwave calcination cupric oxalate.By adopting microwave heating, control heat-up rate simultaneously, make cupric oxalate slow, utilize simultaneously and pass into oxygen to control the weak oxide atmosphere in kiln, achieve the preparation of Red copper oxide, because the granularity of cupric oxalate presoma is thinner, and rotary kiln is in continuous rotation, make among material process moves up and down, the decomposition accelerating cupric oxalate makes production efficiency greatly improve, and the Red copper oxide particle obtained thinner evenly, because rotary kiln is sealed environment, and discharging adopts vacuum feeder discharging, gas is outer again after adopting sack cleaner to collect dust to be arranged, stop the pollution of waste gas, rotary kiln hearth inner lining refractory ceramics, avoiding other impurity introduces in cuprous oxide powder, the Red copper oxide purity obtained is higher, and microwave heating can make cupric oxalate particle internal and external temperature raise simultaneously, avoid Conventional calcination mode temperature and conduct mode into internal batch from outward, energy consumption reduces greatly.Thus solving the shortcoming that general solid reaction process prepares Red copper oxide, energy consumption reduces greatly, basic three-waste free pollution, and the cuprous oxide powder purity of preparation is high, and particle is little, and production efficiency also substantially increases.
The present invention realizes in the following way:
1) be, by particle diameter that the cupric oxalate of 0.5-20 μm is dried to moisture and is less than 1wt%, then fragmentation is for subsequent use after sieving;
2), the cupric oxalate material of drying is dropped in microwave rotary kiln feed bin according to the 10-35% of thorax volume in rotary kiln;
3), open microwave heating, regulate rotary kiln rotating speed 2-10 rev/min simultaneously, rotary kiln temperature with 20-100 DEG C/min ramp to 500-600 DEG C;
4) pass into oxygen, in control kiln, oxygen accounts for the volume of all gas is between 5-25%, and the total time that control material stops in rotary kiln is 10-120min, and oxygen can be pure oxygen or the oxygen containing inert atmosphere;
5) fragmentation of product process, excessively the 150-350 mesh sieve that go out rotary kiln obtain cuprous oxide powder.The Red copper oxide granularity of final preparation is between 0.3-1.2um.
The reaction mechanism that ultrafine cuprous oxide prepared by calcining cupric oxalate is as follows:
4CuC
2O
4+O
2→Cu
2O+8CO
2
The present invention has the following advantages:
1. the granularity due to cupric oxalate presoma is comparatively thin, and rotary kiln is in continuous rotation, and make among material process moves up and down, the decomposition accelerating cupric oxalate makes production efficiency greatly improve, and the Red copper oxide particle obtained thinner evenly.
2. because rotary kiln is sealed environment, and discharging adopts vacuum feeder discharging, and gas is outer again after adopting sack cleaner to collect dust to be arranged, and has stopped the pollution of waste gas.
3. rotary kiln hearth inner lining refractory ceramics, avoid other impurity and introduce in cuprous oxide powder, the Red copper oxide purity obtained is higher.
4. and microwave heating can make cupric oxalate particle internal and external temperature raise simultaneously, avoid Conventional calcination mode temperature and conduct mode into internal batch from outward, energy consumption reduces greatly.
Embodiment
Embodiment 1:
1) be, by particle diameter that to be dried to moisture be 0.5wt% for the cupric oxalate of 2 μm, then fragmentation is sieved;
2), the cupric oxalate material of drying is dropped in microwave rotary kiln feed bin according to 15% of thorax volume in rotary kiln;
3), open microwave heating, regulate rotary kiln rotating speed 8 revs/min, rotary kiln temperature is with 30 DEG C/min ramp to 510 DEG C simultaneously;
4) pass into pure oxygen, in control kiln, oxygen accounts for the volume of all gas is between 12%, and the total time that control material stops in rotary kiln is 60min;
5) fragmentation of product process, excessively 200 mesh sieves that go out rotary kiln obtain cuprous oxide powder.The cuprous oxide powder particle diameter finally obtained is 0.8um.
Embodiment 2:
1) be, by particle diameter that to be dried to moisture be 0.8wt% for the cupric oxalate of 0.5 μm, then fragmentation is for subsequent use after sieving;
2), the cupric oxalate material of drying is dropped in microwave rotary kiln feed bin according to 20% of thorax volume in rotary kiln;
3), open microwave heating, regulate rotary kiln rotating speed 8 revs/min, rotary kiln temperature is with 80 DEG C/min ramp to 500 DEG C simultaneously;
4) pass into the oxygen containing inert nitrogen gas, in control kiln, oxygen accounts for the volume of all gas is between 13%, and the total time that control material stops in rotary kiln is 40min;
5) fragmentation of product process, excessively 300 mesh sieves that go out rotary kiln obtain cuprous oxide powder.The cuprous oxide powder particle diameter finally obtained is 0.65um.
Embodiment 3:
1) be, by particle diameter that to be dried to moisture be 0.3wt% for the cupric oxalate of 8 μm, then fragmentation is for subsequent use after sieving;
2), the cupric oxalate material of drying is dropped in microwave rotary kiln feed bin according to 12% of thorax volume in rotary kiln;
3), open microwave heating, regulate rotary kiln rotating speed 8 revs/min, rotary kiln temperature is with 25 DEG C/min ramp to 600 DEG C simultaneously;
4) pass into the oxygen containing inert nitrogen gas, in control kiln, oxygen accounts for the volume of all gas is between 13%, and the total time that control material stops in rotary kiln is 90min;
5) fragmentation of product process, excessively 300 mesh sieves that go out rotary kiln obtain cuprous oxide powder.The cuprous oxide powder particle diameter finally obtained is 1.0um.
Claims (5)
1. a method for ultrafine cuprous oxide produced by microwave calcination cupric oxalate, it is characterized in that: it realizes in the following way,
1) be, for subsequent use after the dry fragmentation of cupric oxalate of 0.5-20 μm is sieved by particle diameter;
2), dried material is dropped in microwave rotary kiln feed bin according to certain feeding quantity;
3), open microwave heating, regulate rotary kiln rotating speed 2-10 rev/min simultaneously, rotary kiln temperature with 20-100 DEG C/min ramp to 500-600 DEG C;
4) pass into oxygen, in control kiln, oxygen accounts for the volume of all gas is between 5-25%, and the total time that control material stops in rotary kiln is 10-120min;
5) go out the product process fragmentation of rotary kiln, sieving obtains cuprous oxide powder.
2. the method for cuprous oxide powder produced by microwave calcination cupric oxalate according to claim 1, it is characterized in that: described drying is dried to by cupric oxalate water content to be less than 1wt%.
3. the method for cuprous oxide powder produced by microwave calcination cupric oxalate according to claim 1, it is characterized in that: described feeding quantity is the 10-35% that cupric oxalate powder volume accounts for whole kiln internal volume.
4. the method for cuprous oxide powder produced by microwave calcination cupric oxalate according to claim 1, it is characterized in that: described oxygen can pure oxygen or the oxygen containing inert atmosphere.
5. the method for cuprous oxide powder produced by microwave calcination cupric oxalate according to claim 1, it is characterized in that: the described sieve number of sieving is 150-350 order.
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| CN201410712844.9A CN104495907A (en) | 2014-11-28 | 2014-11-28 | Method for producing ultrafine cuprous oxide by microwave calcination of copper oxalate |
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| CN201410712844.9A CN104495907A (en) | 2014-11-28 | 2014-11-28 | Method for producing ultrafine cuprous oxide by microwave calcination of copper oxalate |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935662A (en) * | 2006-10-19 | 2007-03-28 | 浙江大学 | Nano crystal constructed porous copper oxide aggregate and its preparing method |
| KR20100104415A (en) * | 2009-03-17 | 2010-09-29 | 한국과학기술연구원 | Preparation method of nano-size metal oxide powders |
| CN102115147A (en) * | 2011-03-28 | 2011-07-06 | 许昌学院 | Chemical method for preparing copper oxide crystals with biological micro-nano structures by thermal decomposition |
| WO2013002728A1 (en) * | 2011-06-27 | 2013-01-03 | National University Of Singapore | Synthesis of mesoporous transition metal oxides as anode materials |
-
2014
- 2014-11-28 CN CN201410712844.9A patent/CN104495907A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935662A (en) * | 2006-10-19 | 2007-03-28 | 浙江大学 | Nano crystal constructed porous copper oxide aggregate and its preparing method |
| KR20100104415A (en) * | 2009-03-17 | 2010-09-29 | 한국과학기술연구원 | Preparation method of nano-size metal oxide powders |
| CN102115147A (en) * | 2011-03-28 | 2011-07-06 | 许昌学院 | Chemical method for preparing copper oxide crystals with biological micro-nano structures by thermal decomposition |
| WO2013002728A1 (en) * | 2011-06-27 | 2013-01-03 | National University Of Singapore | Synthesis of mesoporous transition metal oxides as anode materials |
Non-Patent Citations (3)
| Title |
|---|
| B. DONKOVA ET AL.: ""Review Thermal—magnetic investigation of the decomposition of copper oxalate—a precursor for catalysts"", 《JOURNAL OF MATERIALS SCIENCE》, vol. 40, 31 December 2005 (2005-12-31), pages 3881 - 3886, XP019210563, DOI: doi:10.1007/s10853-005-0487-0 * |
| R. D. SCHMIDT-WHITLEY ET AL.: ""GROWTH AND MICROSTRUCTURAL CONTROL OF SINGLE CRYSTAL CUPROUS OXIDE Cu2O"", 《JOURML OF CRYSTAL GROWTH》, vol. 23, 31 December 1974 (1974-12-31), pages 113 - 120, XP001303807 * |
| 彭金辉等: "《微波煅烧技术及其应用》", 31 March 2013, article "《微波煅烧技术及其应用》", pages: 87 - 102 * |
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Application publication date: 20150408 |