• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a process for the preparation of magnetic iron oxide nanoparticles from spent coffee residues, in the absence of propionic acid, which comprises the following steps: a) Mechanochemical grinding of coffee residues together with an iron precursor (ratio 4-2), b) drying the materials obtained in stage a), c) calcination of the dried materials of stage b). The present invention also relates to the magnetic iron oxide nanoparticles obtained by the process of the present invention, and to the use thereof in oxidation reactions. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2717979A1
    申请号:ES201930227
    申请日:2019-03-12
    公开日:2019-06-26
    发明作者:Daily Rodríguez-Padrón；Alina Mariana Balu；Reyes Antonio Angel Romero；Alvarez De Sotomayor Rafael Luque
    申请人:Universidad de Cordoba；
    IPC主号:
    专利说明:

    [0001]
    [0002] PROCEDURE FOR THE PREPARATION OF MAGNETIC NANOPARTICLES OF IRON OXIDE FROM EXPOSED COFFEE WASTE.
    [0003]
    [0004] Field of the Invention
    [0005]
    [0006] The present invention falls within the general technical field of materials, and in particular refers to a process for obtaining magnetic materials from coffee waste.
    [0007]
    [0008] State of the art
    [0009]
    [0010] Coffee is one of the most popular and commercially important drinks in the world. However, this drink, highly stimulating for its caffeine content, is capable of generating a large amount of waste that can lead to harmful effects on the environment. Hence, coffee waste has attracted the attention of the scientific community in recent years, in order to find an effective way to value them.
    [0011]
    [0012] Numerous investigations have reported the presence of caffeine in the effluents of wastewater treatment plants, in surface waters, groundwater and even in marine environments. The toxic effects of this drug in various bioorganisms have been extensively investigated. These studies show that many species are quite tolerant of environmental levels of caffeine, however, current levels of caffeine are approaching the toxicity threshold for some aquatic organisms. In particular, research on marine anemones shows that caffeine contributes to the problem of coral bleaching.
    [0013]
    [0014] In this sense, many investigations have been directed towards the elimination of caffeinated residues from coffee, by means of the extraction of phenolic compounds, imidazolines and corrosion inhibitors, to the production of D-mannose and bioethanol. Similarly, coffee residues combined with bentonite have been proposed as effective adsorbents in the removal of dyes from industrial textile effluents. The use of these coffee wells for the synthesis of ZnO and carbon microspheres has also been reported.
    [0015] On the other hand, in recent years, iron oxide magnetic nanoparticles have been widely studied, among other reasons due to their easy recovery and handling, applying many synthetic approaches, such as sol-gel synthesis, sonochemical reactions, reactions hydrothermal, hydrolysis and thermolysis of precursors, synthesis by injection flow and synthesis by electrospray.
    [0016]
    [0017] In this regard, and in particular, mechanochemical methods have been used for the synthesis of magnetic iron oxide nanoparticles. However, such protocols require the addition of propionic acid, which forms an iron propionate complex that by thermal decomposition results in the iron oxide magnetic nanoparticles. The use of an additional acidic compound with corrosive properties, not only increases the cost of the synthesis of magnetic nanoparticles, but also represents an environmental problem.
    [0018]
    [0019] There is therefore a need to provide a process for obtaining magnetic nanoparticles from residues that are environmentally friendly, and that, in addition, provide a way to remove caffeinated residues such as those from coffee dispensed.
    [0020]
    [0021] Brief Description of the Invention
    [0022]
    [0023] The present invention solves the problems described in the state of the art since it provides a process for the production of magnetic nanoparticles from coffee waste, simple, fast and environmentally sustainable, which does not require the use of solvents, and which allows the easy recovery of the magnetic nanoparticles thus obtained, facilitating the reuse of the catalyst.
    [0024]
    [0025] Thus, in a first aspect, the present invention relates to a process for the preparation of magnetic iron oxide nanoparticles from spent coffee residues, in the absence of propionic acid (hereinafter, process of the present invention) , which includes the following stages:
    [0026]
    [0027] a) mechanochemical grinding of coffee waste together with an iron precursor (ratio 4-2),
    [0028]
    [0029] b) drying of the materials obtained in step a),
    [0030]
    [0031] c) calcination of the dried materials of stage b).
    [0032] In the present invention, coffee waste refers to any substance resulting after coffee processing.
    [0033]
    [0034] In a particular embodiment, the iron precursors of step a) of the process of the present invention are selected from iron (III) and ammonium citrate, and iron (III) nitrate.
    [0035]
    [0036] In a more particular embodiment, step a) of mechanochemical grinding of the process of the present invention is performed between 250-350 rpm, for 5-15 minutes, preferably performed at 300 rpm, for 10 minutes.
    [0037]
    [0038] In another particular embodiment, step b) of drying, of the process of the present invention, is carried out at a temperature between 80-120 ° C for 18-30 hours. Preferably step b) is carried out at 100 ° C, for at least 24 hours. In another particular embodiment, the calcination step c) of the process of the present invention is carried out under a nitrogen atmosphere, in a temperature range between 300-800 ° C.
    [0039]
    [0040] In another aspect, the present invention relates to the iron oxide magnetic nanoparticles obtained by the process of the present invention (hereinafter, magnetic nanoparticles of the present invention), characterized in that they have a mesoporous structure, with a diameter between 15-22 nm and a surface area of 20 m2 / g.
    [0041]
    [0042] The structure of the magnetic nanocomposites has been investigated by X-ray diffraction analysis. All samples can be indexed in two phases, maghemite and hematite (Fe2Ü3), with a clear increase in the hematite phase by increasing the calcination temperature. The magnetic susceptibility data are in accordance with the XRD results mentioned above for the synthesized materials and confirm their magnetic characteristics. The magnetic susceptibility decreases with the increase in calcination temperature, however, it is notable that even at calcination temperatures of 800 ° C, the material retains its magnetic characteristics.
    [0043]
    [0044] The textural properties of synthesized nanomaterials have been investigated by the analysis of adsorption isotherms of N2. The materials analyzed show a certain mesoporosity, with diameters ranging between 15 and 22 nm. The surface area values were found around 20 m2 / g for the six materials, being slightly lower with the increase in calcination temperature.
    [0045] In another aspect, the present invention relates to the use of the magnetic nanoparticles of the present invention, as catalysts.
    [0046]
    [0047] More particularly, it refers to the use of the nanoparticles of the present invention in oxidation reactions, more particularly in the oxidation of isoeugenol to vanillin, both using conventional and microwave heating.
    [0048]
    [0049] In another particular embodiment, it refers to the use of the nanoparticles of the present invention in the oxidation of diphenyl sulfide.
    [0050]
    [0051] Description of the figures
    [0052]
    [0053] Figure 1: Shows the X-ray diffractograms for the different compounds of the invention: A: Fe2O3-Coffee-T1, B: Fe2O3-Coffee -T2, C: Fe2O3-Coffee-T3, D: Fe2O3-Coffee-T4, E: Fe2O3-Coffee-T5 and F: Fe2O3-Coffee-T6.
    [0054]
    [0055] Figure 2: Shows the adsorption-desorption Isotherms of: A: Fe2O3-Coffee-T1, B: Fe2O3-Coffee -T2, C: Fe2O3-Coffee-T3, D: Fe2O3-Coffee-T4, E: Fe2O3-Coffee- T5 and F: Fe2O3-Coffee-T6.
    [0056]
    [0057] Figure 3. TEM micrographs of the Fe2O3-Coffee-T1 compound, A: High resolution TEM microscopy at 10 nm scale, B: TEM microscopy at 50 nm scale.
    [0058]
    [0059] Figure 4. SEM micrographs of Fe2O3-Coffee-T 1 materials, A: SEM microscopy at 1 pm scale B: SEM microscopy at 10 pm scale.
    [0060]
    [0061] Figure 5. XPS spectra of Fe2O3-Coffee-T materials 1. A: Preliminary spectrum in the entire link energy region, B: Spectrum deconvolved in the Fe 2p region, the bands correspond to the typical spectrum of the species of Faith (111).
    [0062]
    [0063] Figure 6. Scheme of the oxidation reaction of isoeugenol to vanillin with conventional heating.
    [0064]
    [0065] Figure 7. Scheme of the reaction of vanillin production in microwaves.
    [0066] Detailed description of the invention
    [0067] Example 1: Synthesis of Fe2O3-Coffee-T1 materials,
    [0068]
    [0069] The Fe2O3-Coffee-T1 material was synthesized using coffee waste expended in an amount comprised between 2-4 g and iron (III) citrate and ammonium in an amount comprised between 1-2 g, as an iron precursor. The synthesis was carried out in a ball mill (Retsch PM100 model), at 300 rpm for 15 min.
    [0070]
    [0071] The material obtained in the previous step was dried at 100 ° C for 24 h in an oven and finally calcined in an atmosphere of N2 at 300 ° C.
    [0072]
    [0073] The above procedure was repeated in the same way, varying only the calcination temperature, so that the following compounds were obtained as shown in Table 1.
    [0074]
    [0075]
    [0076]
    [0077]
    [0078] Table 1: products obtained based on the calcination temperature and magnetic susceptibility of each of the compounds of the present invention.
    [0079]
    [0080] Next, we proceeded to characterize the catalysts obtained by the X-ray diffraction technique, magnetic susceptibility measurements, confirming these results, the magnetic properties of the synthesized iron oxide (Figures 1-5). The data showed that the compounds of the present invention presented a corresponding crystalline structure with a mixture of the maghemite and hematite phases, according to their magnetic properties and the magnetic susceptibility obtained (254 * 10-6 m3Kg-1) (table 1) . The presence of iron species in its oxidized form, with a 3+ oxidation state was confirmed by X-ray photoelectronic spectroscopy. In addition, the compounds presented good textural properties, with a surface area of 20 m2 / g.
    [0081] Example 2: use of the compounds of the present invention in the oxidation reaction of isoeugenol to vanillin.
    [0082]
    [0083] The compounds were used in the oxidation reaction of isoeugenol to vanillin by conventional heating, reaching a conversion of 67%. Oxidation of isoeugenol to vanillin was performed using 0.8 ml of isoeugenol, 1.2 ml of H2O2 as an oxidizing agent, 8 ml of acetonitrile (CH3CN) as solvent and 0.1 g of the synthesized catalyst (0.01 g / ml ). The reaction mixture was stirred at 90 ° C for 24 hours using a multiple synthesis system (Carousel reaction station, Radleys Discovery Technologies Ltd., Saffron Walden, United Kingdom). During the reaction, samples were taken every 30 minutes and characterized by gas chromatography. The reactions were also carried out in microwaves using the CEM-Discover system with a power of 300 W, for 30 min, obtaining a conversion of 80% (tables 2 and 3).
    [0084]
    [0085]
    [0086]
    [0087]
    [0088] Table 2: Catalytic activity of the compounds of the present invention in the vanilla production reaction with conventional heating in first, second, third and fourth use.
    [0089]
    [0090]
    [0091]
    [0092]
    [0093] Table 3: Catalytic activity of the compounds of the present invention in the microwave vanilla production reaction for 10 and 30 minutes.
    [0094] Example 3: use of the compounds of the present invention in the diphenyl sulfide oxidation reaction.
    [0095]
    [0096] Next, the use of the compounds of the present invention was carried out in the diphenyl sulfide oxidation reaction, with selective formation of the corresponding sulfoxide. The reaction was carried out in the microwave using the CEM-Discover system with a power of 300 W, for 60 min, using 0.084 mL of diphenyl sulfide, 0.057 mL of H2O2 as oxidizing agent, 2 mL of ethanol as solvent and 0.02 g of the synthesized catalyst. During the reaction, samples were taken every 15 minutes and characterized by gas chromatography. After the reaction time, a conversion of 71% was obtained with the selective formation of diphenyl sulfoxide (See Table 4).
    [0097]
    [0098]
    [0099]
    [0100]
    [0101] Table 4: Catalytic activity of the compounds of the present invention in the diphenylsulfide oxidation reaction.
    权利要求:
    Claims (10)
    [1]
    1. Procedure for the preparation of magnetic iron oxide nanoparticles from waste coffee dispensed, in the absence of propionic acid, which comprises the following steps:
    a) mechanochemical grinding of coffee waste together with an iron precursor (ratio 4-2)
    b) drying of the materials obtained in step a),
    c) calcination of the dried materials of stage b).
    [2]
    2. The method according to claim 1, wherein the iron precursors are selected from iron citrate citrate (III) and ammonium, and iron nitrate (III).
    [3]
    3. Method according to any of claims 1-2, wherein step a) of mechanochemical grinding is performed between 250-350 rpm, for 5-15 minutes.
    [4]
    4. Method according to any of the preceding claims, wherein step b) of drying is carried out at a temperature between 80-120 ° C for 18-30 hours.
    [5]
    5. Method according to any of the preceding claims, wherein the step c) of calcination is carried out under a nitrogen atmosphere, in a temperature range between 300-800 ° C.
    [6]
    6. Magnetic iron oxide nanoparticles obtained by a method according to any of claims 1-5, characterized in that they have a mesoporous structure, with a diameter between 15-22 nm and a surface area of 20 m2 / g.
    [7]
    7. Use of the iron oxide magnetic nanoparticles of claim 6 as catalysts.
    [8]
    8. Use of the iron oxide magnetic nanoparticles of claim 6, in oxidation reactions.
    [9]
    9. Use of magnetic nanoparticles according to claim 8, in the oxidation of isoeugenol to vanillin.
    [10]
    10. Use of magnetic nanoparticles according to claim 8, in the oxidation of diphenyl sulfide.
    类似技术:
    公开号 | 公开日 | 专利标题
    Yang et al.2016|MIL-53 |-graphene nanocomposites: efficient visible-light photocatalysts for the selective oxidation of alcohols
    Lin et al.2016|Efficient elimination of caffeine from water using Oxone activated by a magnetic and recyclable cobalt/carbon nanocomposite derived from ZIF-67
    Wang et al.2020|3D hierarchical H2-reduced Mn-doped CeO2 microflowers assembled from nanotubes as a high-performance Fenton-like photocatalyst for tetracycline antibiotics degradation
    Lam et al.2016|A review on photocatalytic application of g-C3N4/semiconductor | nanocomposites towards the erasure of dyeing wastewater
    Stan et al.2015|Enhanced photocatalytic degradation properties of zinc oxide nanoparticles synthesized by using plant extracts
    Wang et al.2018|Frustrated lewis pairs accelerating CO2 reduction on oxyhydroxide photocatalysts with surface lattice hydroxyls as a solid‐state proton donor
    Lin et al.2016|Synthesis of a SrFeO 3− x/gC 3 N 4 heterojunction with improved visible-light photocatalytic activities in chloramphenicol and crystal violet degradation
    Vinoth et al.2017|Bismuth oxyiodide incorporated reduced graphene oxide nanocomposite material as an efficient photocatalyst for visible light assisted degradation of organic pollutants
    Cazetta et al.2016|Synthesis and application of N–S-doped mesoporous carbon obtained from nanocasting method using bone char as heteroatom precursor and template
    AU2016378991B2|2020-09-17|Photocatalytic composite material for the decomposition of air pollutants
    Sudarsanam et al.2014|An efficient noble metal-free Ce–Sm/SiO 2 nano-oxide catalyst for oxidation of benzylamines under ecofriendly conditions
    Ren et al.2020|Self-templated synthesis of Co 3 O 4 hierarchical nanosheets from a metal–organic framework for efficient visible-light photocatalytic CO 2 reduction
    He et al.2021|Metal-organic framework-derived nanomaterials in environment related fields: Fundamentals, properties and applications
    Ismael et al.2018|Solid state route for synthesis of YFeO3/g-C3N4 composites and its visible light activity for degradation of organic pollutants
    Kumar et al.2021|Vacancy engineering in semiconductor photocatalysts: implications in hydrogen evolution and nitrogen fixation applications
    Wang et al.2018|Adsorptive catalysis of hierarchical porous heteroatom-doped biomass: from recovered heavy metal to efficient pollutant decontamination
    Zhao et al.2018|Magnetic N-doped Co–carbon composites derived from metal organic frameworks as highly efficient catalysts for p-nitrophenol reduction reaction
    Singhal et al.2013|Enhanced photocatalytic degradation of methylene blue using/MWCNT composite synthesized by hydrothermal method
    GingaŞu et al.2017|Green synthesis of cobalt ferrite nanoparticles using plant extracts
    Bastami et al.2016|Preparation of magnetic photocatalyst nanohybrid decorated by polyoxometalate for the degradation of a pharmaceutical pollutant under solar light
    Khare et al.2016|Solvent-free oxidation of cyclohexane over covalently anchored transition-metal salicylaldimine complexes to α-zirconium phosphate using tert-butylhydroperoxide
    Liang et al.2020|Sodium dodecyl sulfate-decorated MOF-derived porous Fe2O3 nanoparticles: High performance, recyclable photocatalysts for fuel denitrification
    Chouchene et al.2020|Graphitic carbon nitride/SmFeO3 composite Z-scheme photocatalyst with high visible light activity
    ES2717979B2|2020-01-29|PROCEDURE FOR THE PREPARATION OF MAGNETIC IRON NANOPARTICLES FROM IRON FROM EXPENDED COFFEE WASTE.
    Kohantorabi et al.2021|Photocatalytic activation of peroxymonosulfate | by novel mesoporous Ag/ZnO@ NiFe2O4 nanorods, inducing radical-mediated acetaminophen degradation under UVA irradiation
    同族专利:
    公开号 | 公开日
    ES2717979B2|2020-01-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    BR102017011633A2|2017-06-01|2018-12-18|Universidade Federal Do Espírito Santo|green chemical synthesis process of gold, silver, copper and iron nanoparticles using coffee as reducing and stabilizing agent.|
    法律状态:
    2019-06-26| BA2A| Patent application published|Ref document number: 2717979 Country of ref document: ES Kind code of ref document: A1 Effective date: 20190626 |
    2020-01-29| FG2A| Definitive protection|Ref document number: 2717979 Country of ref document: ES Kind code of ref document: B2 Effective date: 20200129 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201930227A|ES2717979B2|2019-03-12|2019-03-12|PROCEDURE FOR THE PREPARATION OF MAGNETIC IRON NANOPARTICLES FROM IRON FROM EXPENDED COFFEE WASTE.|ES201930227A| ES2717979B2|2019-03-12|2019-03-12|PROCEDURE FOR THE PREPARATION OF MAGNETIC IRON NANOPARTICLES FROM IRON FROM EXPENDED COFFEE WASTE.|
    [返回顶部]