CN115676871B - Preparation process of nanometer copper oxide powder - Google Patents
Preparation process of nanometer copper oxide powder Download PDFInfo
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- CN115676871B CN115676871B CN202211376814.6A CN202211376814A CN115676871B CN 115676871 B CN115676871 B CN 115676871B CN 202211376814 A CN202211376814 A CN 202211376814A CN 115676871 B CN115676871 B CN 115676871B
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- 239000000654 additive Substances 0.000 claims abstract description 27
- 230000000996 additive effect Effects 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 7
- 230000002195 synergetic effect Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 53
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 229920002498 Beta-glucan Polymers 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 25
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 25
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- -1 triphenyl ester Chemical class 0.000 claims description 13
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010025 steaming Methods 0.000 claims description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 abstract description 20
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 20
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012043 crude product Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920001732 Lignosulfonate Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 150000004699 copper complex Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of nano materials, in particular to a preparation process of nano copper oxide powder; the reaction additive finished product prepared by the method is applied to the preparation process of the nanometer copper oxide powder, so that the dispersion performance of the nanometer copper oxide powder in the reaction liquid can be effectively improved, the agglomeration phenomenon of the nanometer copper oxide powder is reduced, the particle size of the prepared nanometer copper oxide powder can be effectively controlled, the morphology of the nanometer copper oxide powder is more uniform, and the grade is better; meanwhile, the yield of the nanometer copper oxide powder is relatively high; in addition, the method finally and effectively reduces the impurity content in the prepared nano copper oxide product through the synergistic cooperation of the working procedures of washing treatment, vacuum freeze drying, high-temperature sintering and the like, obviously improves the purity of the prepared nano copper oxide powder, and ensures the product quality and grade.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation process of nano copper oxide powder.
Background
Nano copper oxide is a black metal oxide and is widely used in various fields as an important inorganic material. In recent years, copper oxide is an important model compound for explaining the spectral characteristics of complex oxides due to the abnormal characteristics of copper-containing oxides in the field of high-temperature superconductivity; in the aspect of the sensor, the copper oxide nano particles are very sensitive to the external environment such as temperature, light, moisture and the like, so that the response speed, sensitivity and selectivity of the sensor can be greatly improved; the nano copper oxide has very good catalytic effect on the chemical reactions such as complete oxidation of toluene and ethanol, phenol synthesis by benzene and the like; in the battery industry, nano copper oxide can be used as an anode material of a high-performance lithium battery and a cathode material of a solar battery. In addition, the nano copper oxide powder has good application prospect in the aspects of superconductivity, sensors, chemical catalysis, batteries and the like, and can be predicted to have great application potential and market prospect in a plurality of fields.
At present, the preparation method of the nanometer copper oxide powder mainly comprises a solid phase method and a liquid phase method. The solid phase method is to mix metal salt or metal oxide fully according to the formula, grind and react fully to obtain nanometer copper oxide powder directly, or calcine and grind again to obtain superfine powder, which is a traditional pulverizing process. The powder particles prepared by the method have the advantages of no agglomeration, good filling property, low cost, large yield, simple preparation process and the like, and are still a common method so far, but have the defects of high energy consumption, low efficiency, insufficient fineness of powder, easy impurity mixing and the like. The liquid phase method is to select one or more soluble copper salts, prepare solution according to the composition of the prepared materials to enable each element to be in an ion or molecular state, select a proper precipitant or use operations such as evaporation, sublimation, hydrolysis and the like to enable copper ions to be uniformly precipitated or crystallized, and finally heat-treat the precipitation or crystallization to obtain the nano copper oxide powder. The method has the advantages of good metal selectivity, high recovery rate, renewable reagent, easy serialization and the like, and is the most extensive method for preparing the nanometer copper oxide powder in the laboratory and industry at present.
The invention patent with publication number of CN 103420408A provides a preparation method of nano copper oxide, which comprises the following steps: the lignosulfonate is used as a template, copper salt and sodium hydroxide are used for solid phase reaction, and the template is removed by calcining at different temperatures to prepare the nano copper oxide. The lignosulfonate is a byproduct of pulping by a sulfurous acid method, contains rich functional groups, has good diffusivity, and utilizes the lignosulfonate as a template agent, so that the controllable technology of the nano material is realized, waste resources are fully utilized, and the pollution to the environment is reduced. The nano copper oxide synthesized by the solid phase method has the advantages of simple synthesis process, low cost, high yield, short time and less environmental pollution. However, the synthesized nano copper oxide has various shapes and poor uniformity of size granularity.
The invention patent with publication number of CN 113955795A provides a preparation method of nano copper oxide, which comprises the following steps: preparing a copper nitrate aqueous solution with the concentration of 0.01 mol/L; preparing a polyvinylpyrrolidone aqueous solution with the concentration of 3 mol/L; mixing 0.01mol/L copper nitrate aqueous solution with 3mol/L polyvinylpyrrolidone aqueous solution, and heating at 40-70 ℃ for reaction to obtain a copper complex; dripping the copper complex into the mixed alkaline aqueous solution, and stirring for reaction to obtain a crude product of nano copper oxide; and centrifuging the crude product of the nano copper oxide to obtain a precipitate, drying the precipitate in a drying oven, and cooling to room temperature to obtain a finished product of the nano copper oxide. The preparation method is simple to operate, mild in reaction condition, capable of reacting at a lower temperature, low in production cost, environment-friendly, and good in appearance of the prepared nano copper oxide. However, the nano copper oxide product prepared by the method has more impurities and relatively lower purity, and is required to be further improved-!
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation process of nano copper oxide powder, which has the advantages that the prepared nano copper oxide powder has better dispersion performance, is not easy to agglomerate, effectively controls the particle size of the prepared nano copper oxide powder, ensures that the appearance of the prepared nano copper oxide powder is more uniform and has better grade; in addition, the impurities contained in the product are better, and the product quality and grade are ensured.
The invention is realized by the following technical scheme:
the preparation process of the nanometer copper oxide powder comprises the following steps:
step one, according to 1: 1.2-1.8 of copper nitrate aqueous solution with the concentration of 0.5-0.8 g/mL and reaction additive aqueous solution with the concentration of 0.7-1.2 g/mL are mixed and dispersed uniformly, the pH value of the mixture is adjusted to 9.5-10.8 by ammonia water while stirring, the temperature of the obtained mixture is increased to 30-40 ℃, and the mixture is stirred and reacted for 50-80 min at the temperature; after the reaction is finished, the obtained reaction product is stored for standby;
step two, adding cyclohexane into a reaction kettle, stirring the cyclohexane at a speed of 150-200 r/min, stirring the cyclohexane for 10-20 min, and heating the cyclohexane to 55-65 ℃; then adding dispersant with the mass being 0.5-0.65 times of that of the reaction additive, synergistic dispersant with the volume being 1.8-2.5% of that of cyclohexane and the reaction product obtained in the step one, mixing and stirring for 5-8 hours, and then preserving the obtained colloidal particles for later use;
freezing the colloidal particles obtained in the step two at a low temperature of between 25 ℃ below zero and 5 ℃ below zero, performing low-temperature suction filtration on the colloidal particles, and washing the colloidal particles after the suction filtration is finished; after washing, vacuum freeze drying is carried out on the copper oxide powder for 25-30 h at the temperature of minus 55-minus 40 ℃, the copper oxide powder is transferred into sintering equipment for high-temperature sintering after drying, and finally the copper oxide powder is obtained.
Further, the preparation method of the reaction additive comprises the following steps:
i, putting beta-1, 3-glucan into N, N-dimethylformamide with the mass being 5-8 times of that of the beta-1, 3-glucan, stirring and dissolving the beta-1, 3-glucan under the oil bath condition of 80-90 ℃, and preserving heat for reaction for 30-40 min after full dissolution; adding sodium azide with the mass of 3.0-3.5 times of beta-1, 3-glucan into the obtained product components after the reaction is finished, mechanically mixing uniformly, adding triphenyl ester with the mass of 0.4-0.6% of beta-1, 3-glucan and tetrachloromethane with the mass of 1.5-3 times into the mixture respectively, and carrying out heat preservation reaction for 40-60 min at the temperature of 80-90 ℃; after the reaction is finished, methanol is used for carrying out precipitation treatment, then methanol, ethanol and deionized water are respectively used for carrying out centrifugal washing on the obtained precipitate for 2-3 times, and then drying treatment is carried out, so that the obtained solid micro powder is stored for later use;
II, dissolving the solid micro powder obtained in the step I into dimethyl sulfoxide according to the solid-to-liquid ratio of 0.08-0.15 g/mL, then adding sodium tetrahydroborate with the molar weight of 0.08-0.15 times that of the dimethyl sulfoxide into the dimethyl sulfoxide, stirring the mixture at constant temperature in an oil bath kettle at 60-75 ℃ for reaction for 10-20 hours, and after the reaction is finished, adding absolute ethyl alcohol with the volume of 0.3-0.6 times that of the dimethyl sulfoxide into the mixture, and continuing the reaction for 3-5 hours; centrifuging the obtained product components, dialyzing for 2-4 days, and finally performing rotary evaporation and freeze-drying to obtain product powder for later use;
III, dissolving proper amount of ethylenediamine tetraacetic acid in dimethyl sulfoxide according to the dosage ratio of 0.06-0.12 g/mL, adding proper amount of mixed components into the mixture, respectively adding N, N-diisopropylethylamine with the molar weight of 0.9-1.3 times of that of the ethylenediamine tetraacetic acid and product powder with the mass of 0.55-0.75 times of that of the ethylenediamine tetraacetic acid into the mixture after the mixture is uniformly mixed and dispersed, continuously introducing nitrogen into the mixture, and carrying out heat preservation reaction for 60-80 hours at the temperature of 50-65 ℃; and (3) purifying the reaction product after the reaction is finished, and finally obtaining the reaction additive finished product.
Further, when ammonia water is added in the first step, stirring treatment is carried out on the ammonia water at a stirring rate of 800-1200 r/min, and the concentration of the ammonia water solution is 6-8 mol/L; the dropping speed of the ammonia water is 3-8 mL/min.
Further, the mixed components in the step III are compounded by 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide, and the dosage of the two components is 1.0 to 1.5 times and 1.2 to 1.4 times of the molar quantity of the ethylenediamine tetraacetic acid.
Further, the dispersant used in the second step is any one of cetyltrimethylammonium chloride and cetyltrimethylammonium bromide.
Further, the synergistic dispersant used in the second step is n-butanol.
Furthermore, the washing process in the third step adopts absolute ethyl alcohol with the temperature of minus 18 ℃ to minus 15 ℃ for washing, and the washing times are 3 to 4 times.
Further, the sintering temperature in the high-temperature sintering in the third step is set to be 450-550 ℃, and the sintering time is set to be 3-5 hours.
Further, the purification treatment procedure in the step III is as follows: the method comprises the steps of firstly carrying out dialysis treatment in a distillation environment, and then carrying out spin-steaming freeze-drying treatment.
The beneficial effects of the invention are as follows:
in the invention, beta-1, 3-glucan, sodium azide, triphenyl ester and the like are taken as starting materials, and are subjected to chemical reaction to prepare the solid micro powder. Then solid micro powder, sodium tetrahydroborate and the like are used as raw materials, the solid micro powder, the sodium tetrahydroborate and the like are subjected to chemical reaction to form a crude product of the product powder, and the crude product of the obtained product powder is subjected to the processes of centrifugal separation, rotary evaporation and freeze drying of a dialysis machine and the like to prepare the finished product of the product powder. And then taking the prepared product powder and ethylenediamine tetraacetic acid, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, N-hydroxysuccinimide and the like as raw materials, and finally preparing a reaction additive finished product through the chemical reaction generated by the raw materials. The prepared reaction additive finished product is applied to the preparation process of the nanometer copper oxide powder, so that the dispersion performance of the nanometer copper oxide powder in the reaction liquid can be effectively improved, the agglomeration phenomenon of the nanometer copper oxide powder is reduced, the particle size of the prepared nanometer copper oxide powder can be effectively controlled, the appearance of the nanometer copper oxide powder is more uniform, and the grade is better. Meanwhile, the yield of the nanometer copper oxide powder is relatively high. In addition, the method finally and effectively reduces the impurity content in the prepared nano copper oxide product through the synergistic cooperation of the working procedures of washing treatment, vacuum freeze drying, high-temperature sintering and the like, obviously improves the purity of the prepared nano copper oxide powder, and ensures the product quality and grade.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of the nano copper oxide powder produced by the present invention;
FIG. 2 is a first view angle high magnification Scanning Electron Microscope (SEM) of the SEM of FIG. 1;
fig. 3 is a second view angle SEM of the SEM of fig. 1.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation process of the nanometer copper oxide powder comprises the following steps:
step one, according to 1:1.2, respectively mixing and dispersing a copper nitrate aqueous solution with the concentration of 0.5g/mL and a reaction additive aqueous solution with the concentration of 0.7g/mL uniformly, regulating the pH value to 9.5 by ammonia water while stirring, then heating the obtained mixed solution to 30 ℃, and stirring and reacting for 50min at the temperature; after the reaction is finished, the obtained reaction product is stored for standby; wherein, when ammonia water is added, stirring treatment is carried out on the ammonia water at a stirring rate of 800r/min, and the concentration of the ammonia water solution is 6mol/L; the dropping speed of the ammonia water is 3mL/min
Step two, adding cyclohexane into a reaction kettle, stirring the cyclohexane at a speed of 150r/min, stirring the cyclohexane for 10 to 20min, and heating the cyclohexane to 55 ℃; then adding hexadecyl trimethyl ammonium chloride with the mass being 0.5 times of that of the reaction additive and n-butanol with the volume being 1.8 percent of cyclohexane and the reaction product obtained in the step one with the volume being 2.5 percent respectively into the reaction additive, mixing and stirring the mixture for 5 hours, and then preserving the obtained colloidal particles for later use;
freezing the colloidal particles obtained in the step two at a low temperature of minus 25 ℃, carrying out low-temperature suction filtration on the colloidal particles, and washing the colloidal particles for 3 times by adopting absolute ethanol with a temperature of minus 18 ℃ after the suction filtration is finished; after washing, vacuum freeze drying is carried out on the copper oxide powder for 25 hours at the temperature of minus 55 ℃, the copper oxide powder is transferred into sintering equipment after drying is finished, and high-temperature sintering is carried out for 3 hours at the temperature of 450 ℃, and finally the copper oxide powder is obtained.
The preparation method of the reaction additive comprises the following steps:
i, putting beta-1, 3-glucan into N, N-dimethylformamide with the mass being 5 times of that of the beta-1, 3-glucan, stirring and dissolving the beta-1, 3-glucan under the oil bath condition of 80 ℃, and carrying out heat preservation reaction for 30min after full dissolution; adding sodium azide with the mass of 3.0 times of beta-1, 3-glucan into the obtained product components after the reaction is finished, mechanically mixing uniformly, adding triphenyl ester with the mass of 0.4 percent of beta-1, 3-glucan and tetrachloromethane with the mass of 1.5 times into the mixture respectively, and carrying out heat preservation reaction for 40min at 80 ℃; after the reaction is finished, carrying out precipitation treatment on the precipitate by using methanol, and then respectively carrying out centrifugal washing on the obtained precipitate by using methanol, ethanol and deionized water for 2 times, and then carrying out drying treatment, wherein the obtained solid micro powder is stored for later use;
II, dissolving the solid micro powder obtained in the step I into dimethyl sulfoxide according to the solid-to-liquid ratio of 0.08g/mL, then adding sodium tetrahydroborate with the molar quantity of 0.08 times that of the dimethyl sulfoxide into the mixture, stirring the mixture at constant temperature in an oil bath at 60 ℃ for reaction for 10 hours, and adding absolute ethyl alcohol with the volume of 0.3 times that of the dimethyl sulfoxide into the mixture after the reaction is finished, and continuing the reaction for 3 hours; centrifuging the obtained product component, dialyzing for 2 days, and spin-evaporating and lyophilizing to obtain product powder;
III, dissolving proper amount of ethylenediamine tetraacetic acid in dimethyl sulfoxide according to the dosage ratio of 0.06g/mL, adding proper amount of mixed components into the mixture, respectively adding N, N-diisopropylethylamine with the molar weight being 0.9 times of that of the ethylenediamine tetraacetic acid and product powder with the mass being 0.55 times of that of the ethylenediamine tetraacetic acid into the mixture after the mixture is uniformly mixed and dispersed, continuously introducing nitrogen into the mixture, and carrying out heat preservation reaction for 60 hours at the temperature of 50 ℃; after the reaction is finished, dialyzing the mixture in a distillation environment, and then performing rotary steaming freeze-drying treatment on the mixture to obtain a reaction additive finished product; wherein, the mixed component is compounded by 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide with the same molar weight as ethylenediamine tetraacetic acid and N-hydroxysuccinimide with the molar weight which is 1.2 times that of ethylenediamine tetraacetic acid.
Example 2
The preparation process of the nanometer copper oxide powder comprises the following steps:
step one, according to 1:1.5, respectively mixing and dispersing a copper nitrate aqueous solution with the concentration of 0.6g/mL and a reaction additive aqueous solution with the concentration of 1.0g/mL uniformly, regulating the pH value to 10.3 by ammonia water while stirring, then heating the obtained mixed solution to 35 ℃, and stirring and reacting for 70min at the temperature; after the reaction is finished, the obtained reaction product is stored for standby; wherein, when ammonia water is added, stirring treatment is carried out on the ammonia water at a stirring rate of 1000r/min, and the concentration of the ammonia water solution is 7mol/L; the dropping speed of the ammonia water is 5mL/min;
step two, adding cyclohexane into a reaction kettle, stirring the cyclohexane at a speed of 180r/min, stirring the cyclohexane for 15min, and heating the cyclohexane to 60 ℃; then adding hexadecyl trimethyl ammonium bromide with the mass being 0.6 times of that of the reaction additive and n-butanol with the volume being 2.0 percent of cyclohexane and the reaction product obtained in the step one, mixing and stirring the reaction products for 6 hours, and then preserving the obtained colloidal particles for later use;
freezing the colloidal particles obtained in the step two at a low temperature of-15 ℃, performing low-temperature suction filtration, and washing the colloidal particles with absolute ethanol at a temperature of-16 ℃ for 3 times after the suction filtration is finished; after washing, vacuum freeze drying is carried out on the copper oxide powder for 28 hours at the temperature of minus 45 ℃, the copper oxide powder is transferred into sintering equipment to be sintered for 4 hours at the high temperature of 500 ℃ after drying, and finally the copper oxide powder is obtained.
The preparation method of the reaction additive comprises the following steps:
i, putting beta-1, 3-glucan into N, N-dimethylformamide with the mass being 6 times of that of the beta-1, 3-glucan, stirring and dissolving the beta-1, 3-glucan under the oil bath condition of 85 ℃, and preserving heat for reaction for 35min after full dissolution; adding sodium azide with the mass of 3.2 times of beta-1, 3-glucan into the obtained product components after the reaction is finished, mechanically mixing uniformly, adding triphenyl ester with the mass of 0.5 percent of beta-1, 3-glucan and tetrachloromethane with the mass of 2.5 times into the mixture, and carrying out heat preservation reaction for 50 minutes at the temperature of 85 ℃; after the reaction is finished, carrying out precipitation treatment on the precipitate by using methanol, and then respectively carrying out centrifugal washing on the obtained precipitate by using methanol, ethanol and deionized water for 3 times, and then carrying out drying treatment, wherein the obtained solid micro powder is stored for later use;
II, dissolving the solid micro powder obtained in the step I into dimethyl sulfoxide according to the solid-to-liquid ratio of 0.1g/mL, then adding sodium tetrahydroborate with the molar quantity of 0.12 times that of the dimethyl sulfoxide into the mixture, stirring the mixture at constant temperature in an oil bath at 70 ℃ for reaction for 15 hours, and adding absolute ethyl alcohol with the volume of 0.5 times that of the dimethyl sulfoxide into the mixture after the reaction is completed, and continuing the reaction for 4 hours; centrifuging the obtained product component, dialyzing for 3 days, and spin-evaporating and lyophilizing to obtain product powder;
III, dissolving proper amount of ethylenediamine tetraacetic acid in dimethyl sulfoxide according to the dosage ratio of 0.09g/mL, adding proper amount of mixed components into the mixture, respectively adding N, N-diisopropylethylamine with the molar weight being 1.2 times of that of the ethylenediamine tetraacetic acid and product powder with the mass being 0.65 times of that of the ethylenediamine tetraacetic acid into the mixture after the mixture is uniformly mixed and dispersed, continuously introducing nitrogen into the mixture, and carrying out heat preservation reaction for 70 hours at the temperature of 60 ℃; after the reaction is finished, dialyzing the mixture in a distillation environment, and then performing rotary steaming freeze-drying treatment on the mixture to obtain a reaction additive finished product; wherein, the mixed components in the step III are compounded by 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide, and the dosage of the two components is 1.2 times and 1.3 times of the molar quantity of the ethylenediamine tetraacetic acid respectively.
Example 3
The preparation process of the nanometer copper oxide powder comprises the following steps:
step one, according to 1:1.8, respectively mixing and dispersing a copper nitrate aqueous solution with the concentration of 0.8g/mL and a reaction additive aqueous solution with the concentration of 1.2g/mL uniformly, regulating the pH value to 10.8 by ammonia water while stirring, then heating the obtained mixed solution to 40 ℃, and stirring and reacting for 80min at the temperature; after the reaction is finished, the obtained reaction product is stored for standby; wherein, when ammonia water is added, stirring treatment is carried out on the ammonia water at a stirring rate of 1200r/min, and the concentration of the ammonia water solution is 8mol/L; the dropping speed of the ammonia water is 8mL/min;
step two, adding cyclohexane into a reaction kettle, stirring the cyclohexane at a speed of 200r/min, stirring the cyclohexane for 20min, and heating the cyclohexane to 65 ℃; then adding hexadecyl trimethyl ammonium chloride with the mass being 0.65 times of that of the reaction additive and n-butanol with the volume being 2.5 percent of cyclohexane and the reaction product obtained in the step one, mixing and stirring the mixture for 8 hours, and then preserving the obtained colloidal particles for later use;
freezing the colloidal particles obtained in the step two at a low temperature of-5 ℃, performing low-temperature suction filtration, and washing the colloidal particles with absolute ethanol at a temperature of-15 ℃ for 4 times after the suction filtration is finished; after washing, vacuum freeze drying is carried out on the copper oxide powder for 30 hours at the temperature of minus 40 ℃, the copper oxide powder is transferred into sintering equipment for high-temperature sintering for 5 hours at the temperature of 550 ℃ after drying, and finally the copper oxide powder is obtained.
The preparation method of the reaction additive comprises the following steps:
i, putting beta-1, 3-glucan into N, N-dimethylformamide with the mass being 8 times of that of the beta-1, 3-glucan, stirring and dissolving the beta-1, 3-glucan under the oil bath condition of 90 ℃, and carrying out heat preservation reaction for 40min after full dissolution; adding sodium azide with the mass of 3.5 times of beta-1, 3-glucan into the obtained product components after the reaction is finished, mechanically mixing uniformly, adding triphenyl ester with the mass of 0.6 percent of beta-1, 3-glucan and tetrachloromethane into the mixture respectively, and carrying out heat preservation reaction for 60 minutes at 90 ℃; after the reaction is finished, carrying out precipitation treatment on the precipitate by using methanol, and then respectively carrying out centrifugal washing on the obtained precipitate by using methanol, ethanol and deionized water for 3 times, and then carrying out drying treatment, wherein the obtained solid micro powder is stored for later use;
II, dissolving the solid micro powder obtained in the step I into dimethyl sulfoxide according to the solid-to-liquid ratio of 0.15g/mL, then adding sodium tetrahydroborate with the molar quantity of 0.15 times that of the dimethyl sulfoxide into the mixture, stirring the mixture at constant temperature in an oil bath at 75 ℃ for reaction for 20 hours, and adding absolute ethyl alcohol with the volume of 0.6 times that of the dimethyl sulfoxide into the mixture after the reaction is finished, and continuing the reaction for 5 hours; centrifuging the obtained product component, dialyzing for 4 days, and spin-evaporating and lyophilizing to obtain product powder;
III, dissolving proper amount of ethylenediamine tetraacetic acid in dimethyl sulfoxide according to the dosage ratio of 0.12g/mL, adding proper amount of mixed components into the mixture, respectively adding N, N-diisopropylethylamine with the molar weight being 1.3 times of that of the ethylenediamine tetraacetic acid and product powder with the mass being 0.75 times of that of the ethylenediamine tetraacetic acid into the mixture after the mixture is uniformly mixed and dispersed, continuously introducing nitrogen into the mixture, and carrying out heat preservation reaction for 80 hours at the temperature of 65 ℃; after the reaction is finished, dialyzing the mixture in a distillation environment, and then performing rotary steaming freeze-drying treatment on the mixture to obtain a reaction additive finished product; wherein, the mixed components are compounded by 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide, and the dosage of the two components is 1.5 times and 1.4 times of the molar quantity of the ethylenediamine tetraacetic acid respectively.
Comparative example 1: the preparation process of the nano copper oxide powder provided in this example is substantially the same as that of example 1, and the main difference is that: in this example, equal amounts of citric acid were used instead of the reaction additive.
Comparative example 2: the preparation process of the nano copper oxide powder provided in this example is substantially the same as that of example 1, and the main difference is that: in this example, equal amounts of malic acid were used instead of the reaction additive.
Comparative example 3: the preparation process of the nano copper oxide powder provided in this example is substantially the same as that of example 1, and the main difference is that: in this example, the same amount of tartaric acid was used instead of the reaction additive.
Sample testing: the nano copper oxide powder samples prepared in examples 1 to 3 and comparative examples 1 to 3 were each examined, and the obtained examination data were recorded in the following tables:
| nano copper oxide particle size/nm | Yield/%of nano copper oxide | Purity/%of nano copper oxide | |
| Example 1 | 68 | 98.9 | 99.52 |
| Example 2 | 62 | 98.7 | 99.63 |
| Example 3 | 73 | 97.2 | 99.57 |
| Comparative example 1 | 112 | 87.6 | 93.6 |
| Comparative example 2 | 116 | 85.3 | 93.9 |
| Comparative example 3 | 122 | 86.8 | 92.8 |
The comparison and analysis of the related data in the table show that the prepared nano copper oxide powder has better dispersion performance and is not easy to agglomerate, the particle size of the prepared nano copper oxide powder is effectively controlled, the morphology of the prepared nano copper oxide powder is more uniform, and the grade is better; in addition, the impurities contained in the product are better, and the product quality and grade are ensured. Therefore, the preparation process of the nanometer copper oxide powder provided by the invention has wider market prospect and is more suitable for popularization.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. The preparation process of the nanometer copper oxide powder is characterized by comprising the following steps of:
step one, according to 1: 1.2-1.8 of copper nitrate aqueous solution with the concentration of 0.5-0.8 g/mL and reaction additive aqueous solution with the concentration of 0.7-1.2 g/mL are mixed and dispersed uniformly, the pH value of the mixture is adjusted to 9.5-10.8 by ammonia water while stirring, the temperature of the obtained mixture is increased to 30-40 ℃, and the mixture is stirred and reacted for 50-80 min at the temperature; after the reaction is finished, the obtained reaction product is stored for standby;
step two, adding cyclohexane into a reaction kettle, stirring the cyclohexane at a speed of 150-200 r/min, stirring the cyclohexane for 10-20 min, and heating the cyclohexane to 55-65 ℃; then adding dispersant with the mass being 0.5-0.65 times of that of the reaction additive, synergistic dispersant with the volume being 1.8-2.5% of that of cyclohexane and the reaction product obtained in the step one, mixing and stirring for 5-8 hours, and then preserving the obtained colloidal particles for later use;
freezing the colloidal particles obtained in the step two at a low temperature of between 25 ℃ below zero and 5 ℃ below zero, performing low-temperature suction filtration on the colloidal particles, and washing the colloidal particles after the suction filtration is finished; after washing, vacuum freeze drying is carried out on the copper oxide powder for 25 to 30 hours at the temperature of between 55 ℃ below zero and 40 ℃ below zero, the copper oxide powder is transferred into sintering equipment for high-temperature sintering after drying is finished, and finally the copper oxide powder is obtained;
the preparation method of the reaction additive comprises the following steps:
i, putting beta-1, 3-glucan into N, N-dimethylformamide with the mass being 5-8 times of that of the beta-1, 3-glucan, stirring and dissolving the beta-1, 3-glucan under the oil bath condition of 80-90 ℃, and preserving heat for reaction for 30-40 min after full dissolution; adding sodium azide with the mass of 3.0-3.5 times of beta-1, 3-glucan into the obtained product components after the reaction is finished, mechanically mixing uniformly, adding triphenyl ester with the mass of 0.4-0.6% of beta-1, 3-glucan and tetrachloromethane with the mass of 1.5-3 times into the mixture respectively, and carrying out heat preservation reaction for 40-60 min at the temperature of 80-90 ℃; after the reaction is finished, methanol is used for carrying out precipitation treatment, then methanol, ethanol and deionized water are respectively used for carrying out centrifugal washing on the obtained precipitate for 2-3 times, and then drying treatment is carried out, so that the obtained solid micro powder is stored for later use;
II, dissolving the solid micro powder obtained in the step I into dimethyl sulfoxide according to the solid-to-liquid ratio of 0.08-0.15 g/mL, then adding sodium tetrahydroborate with the molar weight of 0.08-0.15 times that of the dimethyl sulfoxide into the dimethyl sulfoxide, stirring the mixture at constant temperature in an oil bath kettle at 60-75 ℃ for reaction for 10-20 hours, and after the reaction is finished, adding absolute ethyl alcohol with the volume of 0.3-0.6 times that of the dimethyl sulfoxide into the mixture, and continuing the reaction for 3-5 hours; centrifuging the obtained product components, dialyzing for 2-4 days, and finally performing rotary evaporation and freeze-drying to obtain product powder for later use;
III, dissolving proper amount of ethylenediamine tetraacetic acid in dimethyl sulfoxide according to the dosage ratio of 0.06-0.12 g/mL, adding proper amount of mixed components into the mixture, respectively adding N, N-diisopropylethylamine with the molar weight of 0.9-1.3 times of that of the ethylenediamine tetraacetic acid and product powder with the mass of 0.55-0.75 times of that of the ethylenediamine tetraacetic acid into the mixture after the mixture is uniformly mixed and dispersed, continuously introducing nitrogen into the mixture, and carrying out heat preservation reaction for 60-80 hours at the temperature of 50-65 ℃; purifying the reaction product after the reaction is finished, and obtaining a reaction additive finished product;
the mixed components in the step III are compounded by 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide, and the dosage of the mixed components is 1.0 to 1.5 times and 1.2 to 1.4 times of the molar quantity of the ethylenediamine tetraacetic acid;
the dispersing agent used in the second step is any one of cetyl trimethyl ammonium chloride and cetyl trimethyl ammonium bromide;
and in the second step, the synergistic dispersing agent is n-butanol.
2. The process for preparing the nanometer copper oxide powder according to claim 1, which is characterized in that: stirring the ammonia water at a stirring rate of 800-1200 r/min when adding the ammonia water in the first step, wherein the concentration of the ammonia water solution is 6-8 mol/L; the dropping speed of the ammonia water is 3-8 mL/min.
3. The process for preparing the nanometer copper oxide powder according to claim 1, which is characterized in that: in the washing process of the step three, absolute ethyl alcohol with the temperature of minus 18 ℃ to minus 15 ℃ is adopted for washing, and the washing times are 3 to 4.
4. The process for preparing the nanometer copper oxide powder according to claim 1, which is characterized in that: the sintering temperature in the high-temperature sintering in the step three is set to be 450-550 ℃ and the sintering time is set to be 3-5 h.
5. The process for preparing nano copper oxide powder according to claim 1, wherein the purification treatment procedure in the step iii is as follows: the method comprises the steps of firstly carrying out dialysis treatment in a distillation environment, and then carrying out spin-steaming freeze-drying treatment.
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