WO2019003248A1 - Appareil pour l'élimination de chrome présent dans deux phases et la récupération d'énergie et procédés s'y rapportant - Google Patents

Appareil pour l'élimination de chrome présent dans deux phases et la récupération d'énergie et procédés s'y rapportant Download PDF

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Publication number
WO2019003248A1
WO2019003248A1 PCT/IN2018/050423 IN2018050423W WO2019003248A1 WO 2019003248 A1 WO2019003248 A1 WO 2019003248A1 IN 2018050423 W IN2018050423 W IN 2018050423W WO 2019003248 A1 WO2019003248 A1 WO 2019003248A1
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WO
WIPO (PCT)
Prior art keywords
sediment
anode
cathode
soil
electrons
Prior art date
Application number
PCT/IN2018/050423
Other languages
English (en)
Inventor
Prof. Raghuram CHETTY
Prof. Indumathi M NAMBI
Saranya SRIRAM
Original Assignee
INDIAN INSTITUTE OF TECHNOLOGY MADRAS (IIT Madras)
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Application filed by INDIAN INSTITUTE OF TECHNOLOGY MADRAS (IIT Madras) filed Critical INDIAN INSTITUTE OF TECHNOLOGY MADRAS (IIT Madras)
Publication of WO2019003248A1 publication Critical patent/WO2019003248A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
    • C02F1/4678—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction of metals
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46176—Galvanic cells
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/006—Electrochemical treatment, e.g. electro-oxidation or electro-osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C02F2001/46157—Perforated or foraminous electrodes
    • C02F2001/46161—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/007—Contaminated open waterways, rivers, lakes or ponds

Definitions

  • the present invention relates to wastewater and sediment remediation particularly to an apparatus and methods of reduction of Cr(VI) to Cr (III) from dual phases.
  • Dredging is the most common traditional ex-situ method widely reported in the literatures for removing the contaminated sediments.
  • several physico-chemical and biological technologies such as chemical precipitation, pump and treat, in-situ solidification /stabilization, soil flushing, electro kinetic remediation and bioremediation have emerged in depolluting the sediments.
  • the process limitation that exists with several of these techniques is that either they cause secondary contamination, or expensive or require lengthy time scales for complete remediation.
  • An alternative to this could contemplate reduction of metal ions from dual phase (i.e. both the underlying sediment phase and overlying water phase) with an economically viable technology to overcome the existing scenario.
  • Another challenge is the effective utilization of waste generated with organic matter as an alternate to conventional energy resources.
  • the generated waste with high organic loading find their way to the sediment and or the water phase increasing in the ratio of N, P, K leading to eutrophication many a times.
  • a typical example to this can be animal waste management, which aims in best utilizing the nutrients for energy recovery.
  • the essential nutrients in theses wastes, if not managed properly can deteriorate the quality of water and soil.
  • the combined process described above may undermine the resilience in the societal face as environmental threats, if not remediated.
  • MFC microbial fuel cells
  • the MFC s employ the microorganisms as the biocatalyst to oxidize a natural organic matter at anode and simultaneously reduce a metal ion at cathode with energy output.
  • sediment-MFC sediment-MFC
  • SMFC s have been investigated over the decades as an alternate source of energy especially in the remote areas where the access to basic power is denied. The greater challenge here, which still remains unanswered is that, the twofold benefit of these fuel cells to bridge the gap between the energy and the environment sectors.
  • the main object of the invention is to disclose an apparatus and methods for reduction of Cr(VI)to Cr (III) from both sediment and water phase through an electrochemical driven process without the use of additional power.
  • It is yet another object of the invention is to reduce a carcinogenic metal ion from both the sediment and the overlying supernatant phase.
  • an electrochemical apparatus for simultaneous power production and remediation of Cr contaminated wetland having a bottom sediment layer and an overlying water surface comprising of:
  • the natural dissolved oxygen separates the anode and cathode
  • the anaerobic oxidation of an organic material (electron donor) in the soil phase generates the necessary electrons and protons
  • the electrons travel via the conductive wire and the protons are exchanged via the soil-water
  • FIG. 1 Schematic representation of single chambered membrane free soil water electrolytic cell .
  • FIG. 2 Effect of urea concentration on Cr removal from (a) electrolyte phase (b) sediment phase
  • FIG. 3 Effect of initial metal ion concnetration and removal efficiency at optimized urea concentration as organic matter (a) from electrolyte phase (b) from soil phase
  • FIG. 4 Power density curves with 1000 ppm Cr in dual phase (a) urea as organic matter (b) cow dung as organic matter DETAILED DESCRIPTION OF THE INVENTION
  • the schematic of the sediment water electrolytic apparatus is depicted in Figure 1.
  • the apparatus (100) has an anode (1) and a cathode (2) .
  • the anode (1) submerged in the wetland soil, the cathode (2) suspended in the water phase of the wetland, the said anode and cathode are in-turn connected to a constant load (3) .
  • the natural dissolved oxygen separates the anode and cathode.
  • the anaerobic oxidation of an organic material (electron donor) in the soil phase generates the necessary electrons and protons, the electrons travel via the conductive wire and the protons are exchanged via the soil-water interface.
  • the electrons extracted from the sediment treat wastewater contaminated with metals, and the Cr (VI) in the sediment scavenge partial electrons released from the organic matter oxidation and accepts them to reduce to Cr (III) .
  • the anode (1) and cathode (2) may be optionally connected to the current collector (4) and storage means through the resistor (3) to collect and store current.
  • the instant invention also has an added advantage of oxidizing a wasteful organic matter as an electron source, achieving the benefit of cleaning up sediments rich in organic loading.
  • urea is chosen an organic contaminant, as an electron donor in the soil. Cow urine, cow dung etc. can also be used in place of urea .
  • SWEC sediment water electrolytic cell
  • Ni based electrodes acts as anode and carbon-based electrodes (carbon felt) as cathode.
  • the present invention reduces hexavalent chromium (Cr-VI) with an organic waste as electron donor through a unique sediment-water membrane free electrolytic cell (SWEC) .
  • the carcinogenic metal ion is reduced from both the sediment and the overlying supernatant phase.
  • Low cost Ni foam and carbon felt is employed as anode and cathode, respectively.
  • Urea is chosen as a representative nitrogenous organic waste which is added as an electron source in the sediment.
  • the source of urea could be from the urea manufacturing plant, or the fecal discharge from any mammalian body (both human and animals), dialysis unit and fertilizer or agricultural runoff.
  • the primary objective is to depollute the Cr(VI) contaminated sediment and the overlying water phase through an electrochemical driven process.
  • the invention is further described by means of an example .
  • the electrodes, Ni foam and carbon felt were procured from Sigma Aldrich and AVCARD respectively.
  • the fresh electrodes were rinsed with MilliQ water, oven dried at 80 °C and used.
  • the Cr(VI) as the catholyte was prepared using K2Cr20 (oven dried for 2 h at 110 °C) in 0.5 M H 2 S0 4 with pH maintained between 1 and 2.
  • Standard Cr solution of desired concentrations was prepared from a stock solution.
  • Sodium bentonite was employed as the model clay component.
  • Micro scale soil studies were conducted with soil packed in the reactor vessel and homogenized with freshly prepared Cr(VI) solutions of the desired concentrations (viz, 50 to 1000 ppm) .
  • the soil was equilibrated with the spiked Cr of desired concentration for 24 hours.
  • Samples of sediment and the aliquot were drawn at equal time periods and the concentration of metal ion was calculated in the soil and liquid phases separately.
  • the sediment samples were digested as per the USEPA 3060A protocol for the alkaline Cr (VI) digestion. Consecutively, both the sample phases were analyzed using calorimetric 1, 5 diphenylcarbaz ide method for absorption at 540 nm. All the experiments were carried out connecting a 1000 ohm resistance as a constant load with Ni wire as current collector at ambient temperature and pressure in triplicates and the mean values are reported. All the chemicals used were of analytical grade.
  • the fundamental process mechanism for the reduction of Cr (VI) from both the phases may be attributed as follows.
  • the quasi reversible oxidation of the transition metal anode Ni +2 to Ni +3 marks the spontaneous oxidation of urea (electron donor) to render electron flow from the submerged anode compartment.
  • the Cr(VI)in the sediment partially utilize these electrons and probably could have reduced to Cr(III) .
  • the electron that travel across the sediment water interface are utilized by the Cr(VI) in the supernatant. This marks the beginning of dual phase reduction of the metal ion.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Treatment Of Sludge (AREA)

Abstract

L'invention concerne une configuration de cellule électrolytique pour simultanément traiter un déchet organique azoté présent dans le sédiment et réduire la quantité d'un ion métallique carcinogène à la fois dans le sédiment et la phase de surnageant sus-jacente. L'invention concerne plus précisément un appareil et des procédés pour réduire le chrome hexavalent (Cr+6) en un état non toxique inférieur, c'est-à-dire Cr+3 avec un déchet organique. La source d'urée pourrait provenir de l'installation de fabrication d'urée ou de l'évacuation fécale de n'importe quel corps de mammifère (aussi bien de l'homme que d'animaux), d'une unité de dialyse et d'un engrais ou d'un lessivage de terres cultivées.
PCT/IN2018/050423 2017-06-30 2018-06-27 Appareil pour l'élimination de chrome présent dans deux phases et la récupération d'énergie et procédés s'y rapportant WO2019003248A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IN201741023125 2017-06-30
IN201741023125 2017-06-30
IN201841004785 2018-02-08
IN201841004785 2018-02-08

Publications (1)

Publication Number Publication Date
WO2019003248A1 true WO2019003248A1 (fr) 2019-01-03

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109912176A (zh) * 2019-04-17 2019-06-21 中国地质大学（北京） 一种底泥有机质稳定化的反应器和方法
CN110395805A (zh) * 2019-07-30 2019-11-01 盐城工学院 一种强化水平潜流湿地微生物电化学装置
WO2021032804A1 (fr) 2019-08-21 2021-02-25 Carl Zeiss Vision International Gmbh Verre de lunettes à effet de filtre pour la lumière bleue et lunettes
CN116040787A (zh) * 2023-01-12 2023-05-02 郑州轻工业大学 一种生物电化学人工湿地系统及其应用
WO2023213268A1 (fr) * 2022-05-05 2023-11-09 集美大学 Appareil électrochimique végétal pour la restauration écologique concernant la pollution des rivières et des lacs, et son procédé d'utilisation

Non-Patent Citations (6)

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B. ASHRAF ALI ET AL.: "Electrolytic Degradation of Uric Acid Using Nickel Electrodes in an Unpartitioned and Partitioned Batch Cell", INTERNATIONAL JOURNAL OF CHEMICAL ENGINEERING AND PROCESSING, vol. 2, no. 1, 2016 *
E.P.L ROBERTS ET AL.: "Chromium removal using a porous carbon felt cathode", JOURNAL OF APPLIED ELECTROCHEMISTRY, vol. 32, no. 10, October 2002 (2002-10-01), pages 1091 - 1099, XP055570010 *
GUPTAS ET ET AL.: "Simultaneous Cr(VI) Reduction and Bioelectricity Generation using Microbial Fuel Cell based on Alumina-Nickel Nanoparticles-dispersed Carbon Nanofiber Electrode", CHEMICAL ENGINEERING JOURNAL, vol. 307, 1 January 2017 (2017-01-01), pages 729 - 738, XP029774753 *
XAFENIAS N ET AL.: "Evaluating hexavalent chromium reduction and electricity production in microbial fuel cells with alkaline cathodes", INT. JOURNAL OF ENVIRONMENT SCIENCE AND TECHNOLOGY, vol. 12, no. 8, August 2015 (2015-08-01), pages 2435 - 2446, XP055570004 *
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YU B ET AL.: "Remediation of chromium-slag leakage with electricity cogeneration via a urea-Cr(VI) cell", SCIENTIFIC REPORTS 4, vol. 4, no. 1, 2014, XP055570001 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109912176A (zh) * 2019-04-17 2019-06-21 中国地质大学（北京） 一种底泥有机质稳定化的反应器和方法
CN110395805A (zh) * 2019-07-30 2019-11-01 盐城工学院 一种强化水平潜流湿地微生物电化学装置
CN110395805B (zh) * 2019-07-30 2024-01-23 盐城工学院 一种强化水平潜流湿地微生物电化学装置
WO2021032804A1 (fr) 2019-08-21 2021-02-25 Carl Zeiss Vision International Gmbh Verre de lunettes à effet de filtre pour la lumière bleue et lunettes
WO2023213268A1 (fr) * 2022-05-05 2023-11-09 集美大学 Appareil électrochimique végétal pour la restauration écologique concernant la pollution des rivières et des lacs, et son procédé d'utilisation
CN116040787A (zh) * 2023-01-12 2023-05-02 郑州轻工业大学 一种生物电化学人工湿地系统及其应用
CN116040787B (zh) * 2023-01-12 2023-08-08 郑州轻工业大学 一种生物电化学人工湿地系统及其应用

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