CN114560491A - Preparation method of copper oxide heat storage base material - Google Patents
Preparation method of copper oxide heat storage base material Download PDFInfo
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- CN114560491A CN114560491A CN202210233909.6A CN202210233909A CN114560491A CN 114560491 A CN114560491 A CN 114560491A CN 202210233909 A CN202210233909 A CN 202210233909A CN 114560491 A CN114560491 A CN 114560491A
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 49
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 49
- 238000005338 heat storage Methods 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000012141 concentrate Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 22
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 17
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 19
- 238000000354 decomposition reaction Methods 0.000 abstract description 17
- 238000002386 leaching Methods 0.000 abstract description 10
- 238000000605 extraction Methods 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052960 marcasite Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/16—Materials undergoing chemical reactions when used
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a preparation method of a copper oxide heat storage substrate material, which comprises the following steps: s1: calcining the copper concentrate and grinding the calcined product into powder; s2: adding the obtained powder into deionized water to dissolve to form a mixed solution, and filtering out impurities in the mixed solution; s3: drying the mixed solution after filtering out impurities to obtain copper sulfate crystals; s4: and calcining the copper sulfate crystals to obtain copper oxide. The copper concentrate is used as a raw material, and the copper oxide heat storage substrate material can be obtained through calcination, water leaching, drying crystallization and re-calcination decomposition, and besides deionized water, no other materials are needed to be added, so that the cost is saved, the pollution is reduced, the whole preparation process does not adopt processes such as smelting, converting, electrolysis and the like, the method is simple, the operation is simple, the energy consumption is low, and the extraction rate of copper can reach more than 95%; after calcining and leaching, the content of impurities such as iron, silicon and the like is reduced to be below 0.5%, and the purity of the copper oxide can reach above 99%.
Description
Technical Field
The invention relates to the technical field of thermochemical heat storage, in particular to a preparation method of a copper oxide heat storage substrate material.
Background
The solar thermal power generation technology provided with the heat storage system can realize self-stable power generation and play a role in peak regulation, is an important role in supporting the development of other renewable energy sources, and the heat storage is one of the most key technologies in the role. The current common heat storage forms comprise sensible heat storage, latent heat storage and thermochemical heat storage, wherein the thermochemical heat storage utilizes reversible thermochemical reaction to store/release heat, has the characteristics of larger heat storage density, wider heat storage temperature range and small energy loss, and has great development potential in the field of solar thermal power generation.
Thermochemical heat storage can be divided into a metal hydride system, an inorganic hydroxide system, a metal oxide system, an organic system, an ammonia decomposition system and a carbonate system according to the difference of reactants. The metal oxide system stores/releases heat through the oxidation-reduction reaction of the metal oxide, namely when the temperature is higher than the reduction temperature, the metal oxide performs the reduction reaction, releases oxygen and absorbs heat; when the temperature is lower than the oxidation temperature, the metal oxide undergoes an oxidation reaction, absorbs oxygen and releases heat. The system has high heat storage density and no corrosiveness, air can be used as a reactant and can transfer heat, the system is simpler, and the cost is reduced. The metal oxide systems found by the present research have more development potential: co3O4/CoO、Mn3O2/Mn3O4、CuO/Cu2O、Fe2O3and/FeO, etc. CuO/Cu2The O system has high heat storage temperature (more than 1000 ℃), high heat storage density (more than 500kJ/kg) and high reaction rate, and is an ideal heat storage base material.
At present, the method for industrially producing the copper oxide mostly uses the waste copper slag as a raw material and is obtained by the process flows of burning, melting, acid leaching, replacement and the like, the process needs to consume a large amount of acid solution and iron powder, the cost is higher, and meanwhile, the waste liquid has a large pollution effect on the environment. The method for producing copper mainly adopts pyrometallurgical copper smelting, takes copper ore as raw material, and is obtained through the technological processes of smelting, converting, electrolysis and the like, and the whole technological process also needs to consume a large amount of energy, thereby causing great pollution.
Disclosure of Invention
Aiming at the problems, the invention provides the preparation method of the copper oxide heat storage base material with lower cost and less influence on the environment.
The invention provides a preparation method of a copper oxide heat storage substrate material, which comprises the following steps:
s1: calcining the copper concentrate and grinding the calcined product into powder;
s2: adding the obtained powder into deionized water to dissolve to form a mixed solution, and filtering out impurities in the mixed solution;
s3: drying the mixed solution after filtering out impurities to obtain copper sulfate crystals;
s4: and calcining the copper sulfate crystals to obtain the copper oxide.
The copper concentrate is used as a raw material, and the copper oxide heat storage substrate material can be obtained through calcination, water leaching, drying crystallization and re-calcination decomposition, and besides deionized water, no other materials are needed to be added, so that the cost is saved, the pollution is reduced, the whole preparation process does not adopt processes such as smelting, converting, electrolysis and the like, the method is simple, the operation is simple, the energy consumption is low, and the extraction rate of copper can reach more than 95%; after calcination and leaching, the content of impurities such as iron, silicon and the like is reduced to be below 0.5%, and the purity of copper oxide can reach above 99%.
In the optional technical scheme of the invention, the copper concentrate is prepared by combining the following raw materials, by mass, 0-40% of Fe, 0-42% of S, 5-100% of Cu, 0-5% of Bi, 0-3% of Si, 0-3% of Ca, 0-12% of Zn, 0-12% of Pb, 0-1% of Mn, 0-0.4% of As, 0-5% of Mg, 0-0.6% of Sb, 0-0.02% of Hg, 0-0.1% of F and 0-0.05% of Cd.
According to the technical scheme, the extraction rate of copper in the copper concentrate with the components can reach more than 95 percent through the preparation method; after calcination and leaching, the content of impurities such as iron, silicon and the like is reduced to be below 0.5%, the purity of copper oxide can reach above 99%, and the prepared copper oxide heat storage substrate material has high quality, low cost and low energy consumption.
In the optional technical scheme of the invention, the calcining temperature of the copper concentrate in the step S1 is 450-500 ℃, and the calcining time is 4-6 hours.
According to the technical scheme, in the calcining temperature interval, the main substance CuFeS in the copper concentrate2Will decompose into CuSO4And Fe2O3And preparing for effectively separating copper and iron subsequently. The calcination time is more than 4 hours, so that CuFeS can be ensured2The decomposition is thorough, but the decomposition is not too long, and unnecessary energy is wasted.
In an optional technical scheme of the invention, in the step S2, the mass ratio of the powder to the deionized water is 1: 10-1: 15.
According to the technical scheme, CuSO is easily caused by too low solid-liquid ratio4Too much water is wasted and the subsequent drying time is prolonged.
In an optional technical solution of the present invention, in the step S2, the method further includes: and putting the mixed solution into a water bath kettle, and stirring the mixed solution at constant temperature.
According to the technical scheme, the mixed solution is stirred at constant temperature, so that CuSO is improved4The dissolution rate of the preparation method shortens the preparation time, improves the preparation efficiency and reduces the production cost.
In the optional technical scheme, the stirring temperature is 60-70 ℃, the stirring time is 5-6 hours, and the rotating speed is 500-1000 r/min.
According to the technical scheme, the CuSO can be increased by higher stirring temperature4The dissolution rate of (a) shortens the dissolution and stirring time, but too high a stirring temperature may cause the water to evaporate too quickly. The appropriate rotating speed can promote CuSO4The proper stirring time can ensure the CuSO4The dissolution is complete.
In the optional technical scheme of the invention, impurities in the mixed solution are filtered and separated by a suction filter.
According to the technical scheme, impurities are removed, the purity of the copper oxide heat storage base material is improved, the suction filtration method is simple, rapid and efficient, and the preparation efficiency of the copper oxide heat storage base material is improved.
In the optional technical scheme of the invention, in the step S3, the drying temperature is 150-200 ℃, and the drying time is 3-5 hours.
According to the technical scheme, under the temperature interval and the drying time, the complete water evaporation can be ensured, the copper oxide is obtained, the drying time is shortened, and the drying efficiency is improved.
In the optional technical scheme of the invention, in the step S4, the calcining temperature is 600-650 ℃, and the calcining time is 4-5 hours.
According to the technical scheme, the CuSO can be promoted in the temperature range4The calcination time is favorable for ensuring thorough decomposition, the calcination temperature and the calcination time take account of the decomposition speed and the decomposition degree, and the CuSO is improved4The decomposition efficiency of (a).
In an optional technical scheme of the invention, the powder mainly comprises CuSO4Powder and Fe2O3And (3) powder.
According to the technical scheme, the CuSO4The powder is soluble in deionized water, Fe2O3The powder exists in the deionized water in a solid form, so that solid-liquid separation can be conveniently carried out, a copper sulfate solution with higher purity is obtained, and the purity of copper oxide is improved.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a copper oxide heat storage substrate material according to an embodiment of the present invention.
Fig. 2 is an XRD pattern of the powder obtained in step S1 in the embodiment of the present invention.
Fig. 3 is an XRD pattern of copper oxide obtained in step S4 in the embodiment of the present invention.
Fig. 4 is a thermogravimetric analysis (TG) chart of the copper oxide obtained in step S4 in the embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
The invention provides a preparation method of a copper oxide heat storage substrate material, which comprises the following steps:
s1: calcining the copper concentrate and grinding the calcined product into powder;
s2: adding the obtained powder into deionized water to dissolve to form a mixed solution, and filtering out impurities in the mixed solution;
s3: drying the mixed solution after filtering out impurities to obtain copper sulfate crystals;
s4: and calcining the copper sulfate crystals to obtain the copper oxide.
The copper concentrate is used as a raw material, and the copper oxide heat storage substrate material can be obtained through calcination, water leaching, drying crystallization and re-calcination decomposition, and besides deionized water, no other materials are needed to be added, so that the cost is saved, the pollution is reduced, the whole preparation process does not adopt processes such as smelting, converting, electrolysis and the like, the method is simple, the operation is simple, the energy consumption is low, and the extraction rate of copper can reach more than 95%; after calcining and leaching, the content of impurities such as iron, silicon and the like is reduced to be below 0.5%, and the purity of the copper oxide can reach above 99%. On the other hand, the copper content of the copper concentrate is higher, the extraction rate of the copper oxide is improved, and the production cost is reduced.
In a preferred embodiment of the invention, the copper concentrate is composed of the following raw materials, by mass, 48.24% of Fe, 23.4% of S, 16.73% of Cu, 4.06% of Bi, 2.39% of Si, 2.28% of Ca, 1.92% of Zn, 0.57% of Pb, and 0.41% of Mn.
By adopting the mode, the extraction rate of copper in the copper concentrate with the components can reach more than 95 percent through the preparation method; after calcination and leaching, the content of impurities such as iron, silicon and the like is reduced to be below 0.5%, the purity of copper oxide can reach above 99%, and the prepared copper oxide heat storage substrate material has high quality, low cost and low energy consumption.
In a preferred embodiment of the present invention, in step S1, the calcined product is ground to have an average particle size of about 20 to 200 μm, which is advantageous for increasing the dissolution rate of the powder and improving the production efficiency.
In a preferred embodiment of the present invention, the calcination temperature of the copper concentrate in step S1 is 450 to 500 ℃, and the calcination time is 4 to 6 hours. In the calcination temperature interval, the main substance CuFeS in the copper concentrate2Will decompose into CuSO4And Fe2O3To follow-upAnd preparing for effectively separating copper and iron. The calcination time is more than 4 hours, so that CuFeS can be ensured2The decomposition is thorough, but the decomposition is not too long, and unnecessary energy is wasted.
In a preferred embodiment of the present invention, in step S2, the mass ratio of the powder to the deionized water is 1:10 to 1: 15. CuSO is easily caused by too low solid-to-liquid ratio4The copper oxide heat storage substrate material cannot be completely dissolved, and the excessive solid-liquid ratio wastes water resources, prolongs the subsequent drying time and reduces the preparation efficiency of the copper oxide heat storage substrate material.
In a preferred embodiment of the present invention, step S2 further includes: and putting the mixed solution into a water bath kettle, and stirring the mixed solution at constant temperature.
By the mode, the mixed solution is stirred at constant temperature, and CuSO is improved4The dissolution rate of the preparation method shortens the preparation time, improves the preparation efficiency and reduces the production cost.
In a preferred embodiment of the invention, the stirring temperature is 60-70 ℃, the stirring time is 5-6 hours, and the rotating speed is 500-1000 r/min. The higher stirring temperature can increase CuSO4The dissolution rate of (a) shortens the dissolution and stirring time, but too high a stirring temperature may cause the water to evaporate too quickly. The appropriate rotating speed can promote CuSO4The proper stirring time can ensure the CuSO4The dissolution is complete.
In a preferred embodiment of the present invention, the impurities in the mixed solution are separated by suction filtration using a suction filtration machine. The impurity removal improves the purity of the copper oxide heat storage substrate material, and the suction filtration method is simple, rapid and efficient, and is beneficial to improving the preparation efficiency of the copper oxide heat storage substrate material. In some embodiments, the impurities in the mixed liquid may be separated by other solid-liquid separation methods, and the present invention is not limited to the suction filtration method of the suction filter exemplified in the embodiments of the present invention, and the method for separating impurities is not limited in the present invention.
In a preferred embodiment of the present invention, in step S3, the drying temperature is 150 to 200 ℃ and the drying time is 3 to 5 hours. Under the temperature interval and the drying time, the complete water evaporation can be ensured, the copper oxide is obtained, the drying time is shortened, and the drying efficiency is improved.
In a preferred embodiment of the present invention, in step S4, the calcination temperature is 600 to 650 ℃, and the calcination time is 4 to 5 hours. Under the temperature range, the CuSO is promoted4The calcination time is favorable for ensuring thorough decomposition, the calcination temperature and the calcination time take account of the decomposition speed and the decomposition degree, and the CuSO is improved4The decomposition efficiency of (a).
In a preferred embodiment of the invention, the powder consists essentially of CuSO4Powder and Fe2O3And (3) powder. CuSO4The powder is soluble in deionized water, Fe2O3The powder exists in the deionized water in a solid form, so that solid-liquid separation can be conveniently carried out, a copper sulfate solution with higher purity is obtained, and the purity of copper oxide is improved; the copper concentrate can simplify the preparation process of copper oxide, reduce the preparation energy consumption and the production cost, and remove CuSO from powder4Powder and Fe2O3The powder also contains small amounts of other impurities.
The following description will explain the preparation method of the copper oxide heat storage substrate material of the present invention by using specific examples.
Selecting copper concentrate ore produced by the Limited liability company of the mining industry of the Hill of the Tongling sheep, wherein the main elements of the copper concentrate ore comprise the following components:
| element name | Fe | S | Cu | Bi | Si | Ca | Zn | Pb | Mn |
| Content (mass%) | 48.24 | 23.40 | 16.73 | 4.06 | 2.39 | 2.28 | 1.92 | 0.57 | 0.41 |
As shown in fig. 1, a method for preparing a copper oxide heat storage substrate material by using copper concentrate as a raw material comprises four steps of calcining, leaching by adding water, drying, crystallizing and decomposing, and specifically comprises the following steps:
s1 calcination
40g of copper concentrate (CuFeS) are weighed out2、FeS2) Placing in a box furnace, heating from normal temperature to 480 ℃ at the speed of 10 ℃/min, and calcining for 6 hours at 480 ℃. As shown in FIG. 2, the XRD pattern of the powder obtained in step S1, the powder being mainly copper sulfate (CuSO)4) And iron oxide (Fe)2O3) And the like, and the powder is ground by a ball mill to have an average particle diameter of about 20 to 200 μm.
The main chemical reaction formulae of the above reactions include:
CuFeS2+O2＝＝CuSO4+Fe2O3+SO2↑；
FeS2+O2＝＝Fe2O3+SO2↑。
s2, adding water to leach
Grinding the powder obtained in step S1 (CuSO)4、Fe2O3Etc.) is added into 400ml deionized water (the solid-liquid ratio is 1:10), heated to 60 ℃ in a water bath kettle and stirred for 4 hours, after that, the filtration is carried out for 2 times by a suction filter, and the solid-liquid separation is carried out;
the obtained residue mainly contains ferric oxide (Fe)2O3) And silicon dioxide (SiO)2) The method can be used for extracting iron oxide and improving the utilization rate of copper concentrate; the main component of the filtrate is CuSO4The process proceeds to step S3 to dry the crystals.
S3, drying and crystallizing
The filtrate obtained in step S2 was put in a drying oven and dried at 150 ℃ for 3 hours to obtain copper sulfate crystals.
S4, decomposition
And (4) putting the copper sulfate crystal obtained in the step S3 into a box furnace, calcining for 4 hours at 600 ℃, and grinding by using a ball mill to obtain copper oxide (CuO) powder. The reaction formula in step S4 is mainly: CuSO4＝＝CuO+SO2↑。
As shown in fig. 3, the copper sulfate crystals were of higher purity with no apparent impurities. As shown in fig. 4, the redox performance of the copper oxide powder was substantially identical to that of the commercially available copper oxide powder.
The copper oxide powder was weighed to obtain 8.113g of copper oxide powder, and the copper extraction rate was about 97%.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements 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 preparation method of a copper oxide heat storage substrate material is characterized by comprising the following steps:
s1: calcining the copper concentrate and grinding the calcined product into powder;
s2: adding the obtained powder into deionized water to dissolve to form a mixed solution, and filtering out impurities in the mixed solution;
s3: drying the mixed solution after filtering out impurities to obtain copper sulfate crystals;
s4: and calcining the copper sulfate crystals to obtain copper oxide.
2. The method for preparing a copper oxide heat storage base material according to claim 1, wherein the copper concentrate is composed of the following raw materials, by mass, 0-40% of Fe, 0-42% of S, 5-100% of Cu, 0-5% of Bi, 0-3% of Si, 0-3% of Ca, 0-12% of Zn, 0-12% of Pb, 0-1% of Mn, 0-0.4% of As, 0-5% of Mg, 0-0.6% of Sb, 0-0.02% of Hg, 0-0.1% of F, 0-0.05% of Cd.
3. The method for preparing the copper oxide heat storage substrate material as claimed in claim 1, wherein the calcination temperature of the copper concentrate in step S1 is 450-500 ℃ and the calcination time is 4-6 hours.
4. The method for preparing the copper oxide heat storage substrate material as claimed in claim 1, wherein in step S2, the mass ratio of the powder to the deionized water is 1:10 to 1: 15.
5. The method for preparing copper oxide heat storage base material according to claim 1, wherein step S2 further comprises: and putting the mixed solution into a water bath kettle, and stirring the mixed solution at constant temperature.
6. The preparation method of the copper oxide heat storage substrate material as claimed in claim 5, wherein the stirring temperature is 60-70 ℃, the stirring time is 5-6 hours, and the rotation speed is 500-1000 r/min.
7. The method for preparing a copper oxide heat storage base material according to claim 5, wherein impurities in the mixed liquid are separated by suction filtration with a suction filter.
8. The method for preparing a copper oxide heat storage substrate material as claimed in claim 1, wherein in step S3, the drying temperature is 150-200 ℃ and the drying time is 3-5 hours.
9. The method for preparing the copper oxide heat storage substrate material as claimed in claim 1, wherein in step S4, the calcination temperature is 600-650 ℃ and the calcination time is 4-5 hours.
10. The method of making copper oxide heat storage base material of claim 1 wherein the powder comprises CuSO4Powder and Fe2O3And (3) powder.
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