CN102153129A - Method and device for continuously synthesizing spherical micro-nano cuprous oxide powder - Google Patents
Method and device for continuously synthesizing spherical micro-nano cuprous oxide powder Download PDFInfo
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- CN102153129A CN102153129A CN2011100837243A CN201110083724A CN102153129A CN 102153129 A CN102153129 A CN 102153129A CN 2011100837243 A CN2011100837243 A CN 2011100837243A CN 201110083724 A CN201110083724 A CN 201110083724A CN 102153129 A CN102153129 A CN 102153129A
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000000843 powder Substances 0.000 title claims abstract description 42
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 39
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 78
- 239000008103 glucose Substances 0.000 claims abstract description 22
- 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 abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 12
- 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 7
- 238000000926 separation method Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 2
- 238000011437 continuous method Methods 0.000 claims 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract 3
- 239000011259 mixed solution Substances 0.000 abstract 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 230000011218 segmentation Effects 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention provides a method for continuously synthesizing spherical micro-nano cuprous oxide powder, and a segmented pipe type reactor for realizing the method, belonging to the technical field of nanometer materials. The method includes the steps as follows: fully mixing copper sulfate solution with sodium hydroxide solution by a pipeline and then leading the mixed solution to enter the pipe type reactor for preheating; adding glucose solution in the mixed solution; later leading the mixed system to pass through a segment or a serial-connection multi-pipe type reactor so as to raise temperature to 50-70 DEG C in a continuous or gradient way; and filtering the mixed system after oxidation reduction in the pipe type reactor, washing the mixed system with water and ethanol in sequence, conducting vacuum drying, and finally obtaining the spherical micro-nano cuprous oxide powder. The spherical micro-nano cuprous oxide powder obtained by the method is within the range of 0.5-2Mum in particle size and smooth on surface, has a cubic phase in crystal form, and has high uniformity of particle size distribution, excellent dispersivity, good sphericity and high purity. The method is easy to control in synthesizing process, low in cost, energy-saving and environment-friendly, and beneficial to industrialized production.
Description
Technical field
The invention belongs to technical field of nano material, relate to the synthetic method of the micro-nano cuprous oxide powder of a kind of sphere, relate in particular to the method for the micro-nano cuprous oxide powder of a kind of continuous synthesizing spherical; The present invention also relates to the device of the micro-nano cuprous oxide powder of continuous synthesizing spherical simultaneously.
Background technology
Red copper oxide (Cu
2O) powder has purposes widely in industrial and agricultural production.As: in coatings industry, be used as boats and ships priming paint and be used to prevent that marine organisms from adhering to; On agricultural, be used as sterilant; On electronic industry, can be used as barretter with copper.The Red copper oxide ultrafine powder can also be used as photo-thermal catalyzer, smoke-inhibiting flame retardant material, electrode materials, the microelectronic circuit printing key intermediate material of electrocondution slurry, information storage material etc.So, controlled in the serialization production and the size of industrial realization Red copper oxide ultrafine powder, be to have suitable realistic meaning and economic interests.
In the field of synthetic Red copper oxide micro mist, a large amount of documents and patent disclosure have been arranged synthetic various Red copper oxide micro-and nano-particles or crystal with certain how much symmetrical structures.But, less always about the document of synthesizing spherical (circle) Red copper oxide micro-nano powder material, and mostly be the interstitial water thermal synthesis of adopting tank reactor.
Sugimoto(Journal of Colloid and Interface Science, 189 (1997), pp.167) having adopted with CuO is precursor, uses hydrazine hydrate to synthesize the Red copper oxide spherical particle of being reunited and being formed by a large amount of ultrafine particulates as reductive agent.This method is at first with CuSO
4Be raw material, add excessive alkali lye, through heating and stirring have obtained pure CuO gel for a long time.With the CuO purifying, be dispersed in the sol system that obtains CuO in the gelatinum then, and then add reductive agent, obtained the extremely narrow Cu of size distribution
2The O spherical particle.Certainly also other bibliographical informations have been arranged and synthesized spheric Red copper oxide particulate, but in these documents, all adopted a large amount of tensio-active agents to control pattern, and the reaction times is longer, temperature also often higher (employing hydrothermal method).The particle that these methods are synthesized is often reunited seriously, and size distribution is good inadequately.And these methods all adopt the batch production method of kettle type crystallization reactor, can not continuous production, and the consistence control difficulty between batch.In addition, when adopting the kettle type crystallization reactor, because the special growth mechanism of Red copper oxide, system is always exploded repeatedly and is generated superfine little Red copper oxide particulate, in case and after these particulates generations, owing to back mixing, the superfine small particle that has generated is in order to reduce surface energy again, be adsorbed in long macroparticle surface of the residence time in the system, thereby cause shape, the size of reunion and particle uncontrollable fully.
Summary of the invention
The objective of the invention is provides the micro-nano cuprous oxide powder serialization of a kind of sphere synthetic method in order to overcome the problem that prior art exists.
Another object of the present invention provides a kind of device---segmentation tubular reactor of realizing spherical micro-nano cuprous oxide powder serialization synthetic method.
The method of the micro-nano cuprous oxide powder of the continuous synthesizing spherical of the present invention is to enter tubular reactor by pipeline after with copper-bath and sodium hydroxide solution thorough mixing to carry out preheating; In mixing solutions, add glucose solution again; Mixed system is carried out continuously or gradient increased temperature to 50～70 ℃ through one section or placed in-line multistage tubular reactor; Mixed system carries out redox reaction after solid-liquid separation is washed at tubular reactor, and drying obtains spherical micro-nano cuprous oxide powder.
In described copper-bath, sodium hydroxide solution and the glucose solution, its mol ratio can be by the chemical reaction amount than estimation.Consider finishing and economic benefit of reaction, the mol ratio of copper sulfate, sodium hydroxide and glucose is for being controlled at 1:0.55:2.55～1:1:8.
The concentration of described copper-bath is 0.1 ~ 0.4mol/L.
The concentration of described sodium hydroxide solution is 0.25 ~ 1.0mol/L.
The concentration of described glucose solution is 0.05 ~ 0.2mol/L.
The preheating temperature of mixing solutions degree in tubular reactor of described copper sulfate and sodium hydroxide is controlled at 20 ~ 30 ℃.
The temperature of reaction of the initial section of described mixed system is controlled at 30 ~ 35 ℃, and the latter end temperature of reaction is controlled at 50～70 ℃.
The bore of tubular reactor and the flow velocity of tube fluid have determined the state of tube fluid.The internal diameter of tubular reactor pipeline and flow velocity, can be according to the yield target of reaction and guarantee time that reaction mixture stop in pipeline and in pipeline the mobile rate request decide, generally can precipitation polymerization not take place in pipeline and reactant can be reacted by thorough mixing as long as guarantee particle, caliber is too thin, copper sulfate mixes the back system status with sodium hydroxide be gel, resistance is bigger, and power consumption is big, is easy to generate obstruction; Caliber is too big, and the radial temperature produces than big-difference, has also increased energy consumption and equipment cost indirectly, and it is inhomogeneous to make that reaction produces.Therefore, the internal diameter of tubular reactor is better in 2 ~ 12mm scope; Copper-bath and sodium hydroxide solution enter tubular reactor with the speed of 20～120ml/min respectively to be mixed; Glucose solution enters in the tubular reactor with the speed of 20～120ml/min; The flow velocity of three's mixed system in tubular reactor is 60 ~ 360ml/min; The reactor pipe range was advisable at 22min ~ 40min with the residence time of mixed system.
Described solid-liquid separation can be by conventional separation method, as filtering centrifugation etc.
Described washing can water, the washing of pure equal solvent.The powder that washing obtains can carry out drying by the drying means of routine, also can utilize rare gas element for example to carry out drying under the nitrogen protection, as long as guarantee that Red copper oxide is not oxidized.Adopt vacuum-drying, it is better that temperature is controlled at 30～70 ℃ of effects.
The present invention realizes the tubular reactor of the method for the micro-nano cuprous oxide powder of continuous synthesizing spherical, comprises Y-pipe successively, tubular reactor and discharge nozzle; Described tubular reactor is at least two sections series connection, and between Y-pipe and the tubular reactor, pass through pipe connection between the placed in-line tubular reactor; Pipeline between first, second section tubular reactor is provided with the material input tube.Tubular reactor both can be that horizontal positioned also can vertically be placed, and considered the fluidic characteristic, and mode from top to bottom is better.
The present invention is 0.5 μ m ~ 2 μ m by the size scope of the spherical cuprous oxide powder of sectional temperature-controlled tubular reactor synthetic, and its smooth surface, and size distribution is quite even, good dispersion, and soccer star's degree is fine.The X diffraction confirms that its diffraction peak corresponds respectively to the crystal face diffraction peak of (110), (111), (200), (220), (311), (222), the spherical cuprous oxide powder that preparation is described is cube phase, and the assorted peak that does not have other, illustrate that the synthetic cuprous oxide powder is purer, do not have the existence of impurity such as cupric oxide or copper.
The present invention relatively and prior art have the following advantages:
1, utilize the multistage tubular reactor to realize the synthetic continuously of spherical micro-nano cuprous oxide powder, and reaction mass in reaction tubes because the whole pushing effect of fluidic, be difficult for producing back mixing, after blast generates imperceptible Red copper oxide particulate, the no adsorbable or big cuprous oxide particle of interferential, automatically assemble generating the extremely narrow Red copper oxide particulate of monodispersity, effectively prevented the back mixing of reaction mass, the state of system is relatively easily stable.
2, by sectional temperature-controlled adapting to the more special process of growth of Red copper oxide crystallite, thereby obtain single dispersion, do not reunite, the good cuprous oxide powder of sphericity; By regulating heat-up rate and alkali lye add-on, can control the size of spherical cuprous oxide powder.
3, do not need to add any tensio-active agent, environmentally friendly, aftertreatment also is easier to relatively, thereby has reduced production cost.
4, tubular reactor is simple in structure, and the equipment input is low establishes, and helps industry and changes into product.
5, the entire reaction course temperature is lower, has saved the energy.
6, system is controlled easily, when system meets accident disturbance, only needs system status is regulated.When tubular reactor when section inner control or reinforced condition breaks down fluctuation sometime, back mixing influences end product quality, owing to the entire reaction material can not take place along with fluid advances forward in pipe, as long as remove one section reaction product this moment, thereby the product of back is exerted an influence.
Description of drawings
Fig. 1 is the structure iron of tubular reactor of the present invention and the process flow sheet of continuous synthesizing spherical cuprous oxide powder
Solution A---copper-bath; Solution B---NaOH solution; Solution C---glucose solution;
T
1, T
2, T
3, T
4, T
5, T
6---be respectively first, second, third and fourth, five, six sections temperature that tubular reactor is controlled;
Fig. 2 is the photo of the scanning electronic microscope of embodiment 1 gained sample;
Fig. 3 is the photo of the scanning electronic microscope of embodiment 2 gained samples;
Fig. 4 is the photo of the scanning electronic microscope of embodiment 3 gained samples;
Fig. 5 is the XRD figure spectrum of embodiment 1,2,3 gained samples;
Fig. 6 is the photo of the scanning electronic microscope of embodiment 4 gained samples;
Fig. 7 is the photo of the scanning electronic microscope of embodiment 5 gained samples.
Embodiment
Below by specific embodiment the structure of tubular reactor of the present invention and the technology of continuous synthesizing spherical cuprous oxide powder are described further.
Embodiment 1
A kind of sectional type tubular reactor (referring to Fig. 1) comprises Y-pipe successively, placed in-line six sections tubular type reactor heatings and discharge nozzle; Between Y-pipe and the tubular type reactor heating, pass through pipe connection between the placed in-line tubular type reactor heating; Pipeline between first, second section tubular type reactor heating is provided with the material input tube.The bore of tubular reactor is got 4mm, and the pipe total length is 85m, and removing first section pipe range is 10m, and all the other segmentations are all 15m.
The technology of continuous synthesizing spherical cuprous oxide powder:
(1) cupric sulfate pentahydrate, sodium hydroxide, glucose are dissolved in respectively in the deionized water, are mixed with the sodium hydroxide solution B of copper-bath A, 0.55mol/L of 0.2mol/L and the glucose solution C of 0.11mol/L.
(2) with solution A and solution B respectively with the speed constant-flux pump of 20ml/min, squeeze in first section tubular reactor the temperature T of first section tubular reactor of control by Y-pipe
1At 30 ℃.
(3), add in the reaction system by the pipeline that is arranged between first section and the second section tubular reactor with the speed of solution C with 20ml/min;
(4) mixture system enters in five sections tubular reactors of back successively with the speed of 60ml/min, and controls the temperature of reaction (T of each section
2, T
3, T
4, T
5, T
6) respectively at 40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃.
(5) the reaction final product of discharge nozzle collection is used distilled water wash three times after filtration, after alcohol is washed twice again, with drying down at 35 ℃ in the vacuum drying oven, obtains spherical cuprous oxide powder product.
The photo of the scanning electronic microscope of sample is seen Fig. 2; The XRD figure spectrum is seen a among Fig. 5, and compares with standard diagram, is confirmed that it is the Red copper oxide of cube phase.
The structure of sectional type tubular reactor is with embodiment 1.
The technology of continuous synthesizing spherical cuprous oxide powder:
(1) cupric sulfate pentahydrate, sodium hydroxide, glucose are dissolved in respectively in the deionized water, are mixed with the sodium hydroxide solution B of copper-bath A, 0.80mol/L of 0.2mol/L and the glucose solution C of 0.11mol/L.
(2) with solution A and solution B respectively with the speed constant-flux pump of 20ml/min, squeeze in first section tubular reactor the temperature T of first section tubular reactor of control by Y-pipe
1At 25 ℃.
(3), add in the reaction system by the pipeline that is arranged between first section and the second section tubular reactor with the speed of solution C with 20ml/min;
(4) mixture system enters in five sections tubular reactors of back successively with the speed of 60ml/min, and controls the temperature of reaction (T of each section
2, T
3, T
4, T
5, T
6) respectively at 40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃.
(5) the reaction final product of discharge nozzle collection is used distilled water wash three times after filtration, after alcohol is washed twice again, with drying down at 35 ℃ in the vacuum drying oven, obtains spherical cuprous oxide powder product.
The photo of the scanning electronic microscope of sample is seen Fig. 3; The XRD figure spectrum is seen the b among Fig. 5, and compares with standard diagram, is confirmed that it is the Red copper oxide of cube phase.
The structure of sectional type tubular reactor is with embodiment 1.
(1) cupric sulfate pentahydrate, sodium hydroxide, glucose are dissolved in respectively in the deionized water, are mixed with the sodium hydroxide solution B of copper-bath A, 0.60mol/L of 0.2mol/L and the glucose solution C of 0.11mol/L.
(2) with solution A and solution B respectively with the speed constant-flux pump of 20ml/min, squeeze in first section tubular reactor the temperature T of first section tubular reactor of control by Y-pipe
1At 30 ℃.
(3), add in the reaction system by the pipeline that is arranged between first section and the second section tubular reactor with the speed of solution C with 20ml/min;
(4) mixture system enters in five sections tubular reactors of back successively with the speed of 60ml/min, and controls the temperature of reaction (T of each section
2, T
3, T
4, T
5, T
6) respectively at 50 ℃, 55 ℃, 60 ℃, 65 ℃ and 70 ℃.
(5) the reaction final product of discharge nozzle collection is used distilled water wash three times after filtration, after alcohol is washed twice again, with drying down at 35 ℃ in the vacuum drying oven, obtains spherical cuprous oxide powder product.
The photo of the scanning electronic microscope of sample is seen Fig. 4; The XRD figure spectrum is seen the c among Fig. 5, and compares with standard diagram, is confirmed that it is the Red copper oxide of cube phase.
Embodiment 4
A kind of sectional type tubular reactor (referring to Fig. 1) comprises Y-pipe successively, placed in-line six sections tubular type reactor heatings and discharge nozzle; Between Y-pipe and the tubular type reactor heating, pass through pipe connection between the placed in-line tubular type reactor heating; Pipeline between first, second section tubular type reactor heating is provided with the material input tube.The bore of tubular reactor is got 4mm, and the pipe total length is 160m, and removing first section pipe range is 10m, and all the other segmentations are all 30m.
(1) cupric sulfate pentahydrate, sodium hydroxide, glucose are dissolved in respectively in the deionized water, are mixed with the sodium hydroxide solution B of copper-bath A, 0.60mol/L of 0.2mol/L and the glucose solution C of 0.11mol/L.
(2) with solution A and solution B respectively with the speed constant-flux pump of 40ml/min, squeeze in first section tubular reactor the temperature T of first section tubular reactor of control by Y-pipe
1At 30 ℃.
(3), add in the reaction system by the pipeline that is arranged between first section and the second section tubular reactor with the speed of solution C with 40ml/min;
(4) mixture system enters in five sections tubular reactors of back successively with the speed of 120ml/min, and controls the temperature of reaction (T of each section
2, T
3, T
4, T
5, T
6) respectively at 50 ℃, 55 ℃, 60 ℃, 65 ℃ and 70 ℃.
(5) the reaction final product of discharge nozzle collection is used distilled water wash three times after filtration, after alcohol is washed twice again, with drying down at 35 ℃ in the vacuum drying oven, obtains spherical cuprous oxide powder product.
The photo of the scanning electronic microscope of sample is seen Fig. 6.
Embodiment 5
A kind of sectional type tubular reactor (referring to Fig. 1) comprises Y-pipe successively, placed in-line six sections tubular type reactor heatings and discharge nozzle; Between Y-pipe and the tubular type reactor heating, pass through pipe connection between the placed in-line tubular type reactor heating; Pipeline between first, second section tubular type reactor heating is provided with the material input tube.The bore of tubular reactor is got 8mm, and the pipe total length is 85m, and removing first section pipe range is 10m, and all the other segmentations are all 15m.
(1) cupric sulfate pentahydrate, sodium hydroxide, glucose are dissolved in respectively in the deionized water, are mixed with the sodium hydroxide solution B of copper-bath A, 0.60mol/L of 0.2mol/L and the glucose solution C of 0.11mol/L.
(2) with solution A and solution B respectively with the speed constant-flux pump of 80ml/min, squeeze in first section tubular reactor the temperature T of first section tubular reactor of control by Y-pipe
1At 30 ℃.
(3), add in the reaction system by the pipeline that is arranged between first section and the second section tubular reactor with the speed of solution C with 80ml/min;
(4) mixture system enters in five sections tubular reactors of back successively with the speed of 240ml/min, and controls the temperature of reaction (T of each section
2, T
3, T
4, T
5, T
6) respectively at 50 ℃, 55 ℃, 60 ℃, 65 ℃ and 70 ℃.
(5) the reaction final product of discharge nozzle collection is used distilled water wash three times after filtration, after alcohol is washed twice again, with drying down at 35 ℃ in the vacuum drying oven, obtains spherical cuprous oxide powder product.
The photo of the scanning electronic microscope of sample is seen Fig. 7.
Claims (10)
1. the method for the micro-nano cuprous oxide powder of continuous synthesizing spherical is characterized in that: enter tubular reactor by pipeline after with copper-bath and sodium hydroxide solution thorough mixing and carry out preheating; In mixing solutions, add glucose solution again; Mixed system is carried out continuously or gradient increased temperature to 50～70 ℃ through one section or placed in-line multistage tubular reactor; Mixed system carries out redox reaction in tubular reactor after solid-liquid separation is washed, and drying obtains spherical micro-nano cuprous oxide powder;
In described copper-bath, sodium hydroxide solution and the glucose solution, the mol ratio of copper sulfate, sodium hydroxide and glucose is 1:0.55:2.55～1:1:8.
2. the continuous method of the micro-nano cuprous oxide powder of synthesizing spherical according to claim 1, it is characterized in that: the concentration of described copper-bath is 0.1 ~ 0.4mol/L.
3. the continuous method of the micro-nano cuprous oxide powder of synthesizing spherical according to claim 1, it is characterized in that: the concentration of described sodium hydroxide solution is 0.25 ~ 1.0mol/L.
4. the continuous method of the micro-nano cuprous oxide powder of synthesizing spherical according to claim 1, it is characterized in that: the concentration of described glucose solution is 0.05 ~ 0.2mol/L.
5. the continuous method of the micro-nano cuprous oxide powder of synthesizing spherical according to claim 1, it is characterized in that: the preheating temperature of mixing solutions degree in tubular reactor of described copper sulfate and sodium hydroxide is controlled at 20 ~ 30 ℃.
6. the continuous method of the micro-nano cuprous oxide powder of synthesizing spherical according to claim 1, it is characterized in that: the temperature of reaction of the initial section of described mixed system is controlled at 30 ~ 35 ℃, and the latter end temperature of reaction is controlled at 50～70 ℃.
7. the continuous method of the micro-nano cuprous oxide powder of synthesizing spherical according to claim 1, it is characterized in that: the internal diameter of described tubular reactor is 2 ~ 12mm; Described copper-bath and sodium hydroxide solution enter tubular reactor with the speed of 20～120ml/min respectively to be mixed; Described glucose solution enters in the tubular reactor with the speed of 20～120ml/min; The flow velocity of described mixed system in tubular reactor is 60 ~ 360ml/min; It is 22min ~ 40min that the pipe range of tubular reactor can make the residence time of mixed system in reactor.
8. the continuous method of the micro-nano cuprous oxide powder of synthesizing spherical according to claim 1, it is characterized in that: described drying is vacuum-drying, drying temperature is controlled at 30～70 ℃.
9. realize the tubular reactor of the method for the micro-nano cuprous oxide powder of the described continuous synthesizing spherical of claim 1, it is characterized in that: comprise Y-pipe successively, tubular reactor and discharge nozzle; Described tubular reactor is at least two sections series connection, and between Y-pipe and the tubular reactor, pass through pipe connection between the placed in-line tubular reactor; Pipeline between first, second section tubular reactor is provided with the material input tube.
10. as tubular reactor as described in the claim 9, it is characterized in that: the internal diameter of described tubular reactor is at 2 ~ 12mm.
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| CN110092408A (en) * | 2019-05-12 | 2019-08-06 | 广东工业大学 | A kind of method of continuous production copper oxide |
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