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WO2018104957A1 - Système de nanoparticules anioniques pour dessalement et procédé associé - Google Patents

Système de nanoparticules anioniques pour dessalement et procédé associé Download PDF

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Publication number
WO2018104957A1
WO2018104957A1 PCT/IN2017/050509 IN2017050509W WO2018104957A1 WO 2018104957 A1 WO2018104957 A1 WO 2018104957A1 IN 2017050509 W IN2017050509 W IN 2017050509W WO 2018104957 A1 WO2018104957 A1 WO 2018104957A1
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WO
WIPO (PCT)
Prior art keywords
nanoparticle
core
desal
ination
negatively charged
Prior art date
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Ceased
Application number
PCT/IN2017/050509
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English (en)
Inventor
Ajay Kumar Gupta
Dinesh Kumar Jagroopsingh YADAV
Mihir Kanjibhai RATHOD
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arvind Envisol Pvt Ltd
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Arvind Envisol Pvt Ltd
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Priority to CN201780075668.4A priority Critical patent/CN110049816A/zh
Publication of WO2018104957A1 publication Critical patent/WO2018104957A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
    • C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
    • 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
    • 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
    • C02F2103/08—Seawater, e.g. for desalination
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/08—Nanoparticles or nanotubes

Definitions

  • the present subject matter generally relates to nanoparticles system. More specifically the subject matter relates to an anionic nanoparticles system coated. Even more specifically the subject matter relates to an anionic nanoparticle system for desalination and method of desalination.
  • One of the water recycling challenge is desalination.
  • Conventional desalination processes generally exploit one or many of thermal, mechanical, electrical and chemical properties for desalination.
  • evaporation and crystallization exploit primarily thermal properties
  • filtration, reverse osmosis, forward osmosis exploit primarily mechanical properties.
  • electro-dialysis and ionic exchange may deploy combination of electrical and chemical properties.
  • Most of these techniques have their own limitations, e.g. cost and complexity, scalability, efficiency, economic viability etc.
  • the present subject matter provides solution to the above and other problems.
  • the present subject matter provides an anionic nanoparticle system for desalination and a method of desalination thereof.
  • Some of the problems faced by nanoparticle based desalination systems are: low efficiency; poor quality of desalination; high time and iteration requirements.
  • One of the reasons for such limitations is the charge carrying capacity of the nanoparticles and problems associated with the process required for enhancing charge carrying capacity.
  • the present subject matter provides a solution to at least these limitations by control lably enhancing the charge carrying capacity of the nanoparticles while ensuring that the resulting nanoparticle system, also significantly improves the desalination process.
  • the present subject matter not only enables desalination but also provides easy recyclability of the nanoparticle system thereby providing a solution that is efficient, cost effective and of interest in industrial application.
  • the present subject matter provides a nanoparticle based desalination system comprising: a nanoparticle system having a core and a negatively charged species coated on the core, wherein the pH value of the nanoparticle system is less than at least one pKa value of the negatively charged species and the nanoparticle system is configured to cause desalination of positively charged ions from an effluent.
  • the core includes any one or more of, transition elements, second group elements, third group elements, fourth group element and fifth group elements.
  • the core is a metallic core including metal oxide core, an iron core and iron oxide core.
  • the negatively charged species is selected from poly carboxylic acid, poly sulphonic acid.
  • the negatively charged species is any one or more of humic acid, Ethylenediaminetetraaceticacid (EDTA), Diethylenetriaminepentaacetic (DTPA), citric acid.
  • the size of the nanoparticle system is below 100 microns.
  • the size of the nanoparticle system is between 20 nm to 10 microns.
  • the nanoparticle system is in the form of any one of: solution, slurry, paste, solid and powder.
  • the pH value of the nanoparticle system is below7 and is lowerthan the lowest pKa value of the negatively charged species.
  • the core is coated with a stabilizing agent.
  • the stabilizing agent is any one of polymer, surfactant, reducing agent, and chelating agent.
  • the stabilizing agent is dextran or
  • the effluent has positively charged ions.
  • the negatively charged nanoparticles bind to positively charged ions present in the effluent causing desalination.
  • the present subject matter provides, a desalination method.
  • the desalination method comprising: supplying a nanoparticle system to an effluent, wherein the nanoparticle system having a core and a negatively charged species coated on the core, wherein the pH value of the nanoparticle system is lessthan at least one pKa value of the negatively charged species causing desalination by binding the nanoparticles system and cations present in the effluent.
  • the core includes any one or more of, transition elements, second group elements, third group elements, fourth group element and fifth group elements.
  • the method includes extracting the nanoparticles system from the effluent.
  • the core of the nanoparticle system is an iron based core and includes magnetic extraction.
  • the extracting includes one or more of filtration, centrifugation, sedimentation, magnetic separation.
  • method includes purifying the nanoparticle system for reuse in the desalination.
  • the purifying includes acidifying the nanoparticles system and removing desalinated salts from the nanoparticles.
  • the negatively charged species is selected from poly carboxylic acid, poly sulphonic acid.
  • nanoparticle systems are expensive. Therefore it is required that most is achieved prior to trashing such nanoparticle systems. Hence recyclability of the nanoparticle systems is desirable. In fact, most desirable is a nanoparticle system that may be substantially perpetually used. However, desalination process poisons the nanoparticle system quickly and effective recyclability may not be achieved.
  • the present subject matter provides not only recyclability but also provides possibility of multiple rounds to charging of nanoparticle system to enhancing its charge carrying capacity after its use.
  • the present subject matter addresses the above and other problems and offer many advantages, including but not limited to, simplifying desalination process, reduced energy consumption, enablement desalination process for industrial application, recyclability of nanoparticle systems, effective desalination substantially independent of valances of the salts, enablement of the system for application in: industrial refuse, sea water, salty water, brackish water, removal of hardness and toxic heavy metal ions etc.
  • the present subject matter provides nanoparticle system having a core.
  • the core includes any one or more of, transition elements, second group elements, th ird group elements, fourth group element and fifth group elements.
  • the core is a meta ll ic core includ ing metal oxide core, an iron core and iron oxide core. Having an iron core offers add itional advantage, wh ich is to say, that magnetic fi ltration becomes easier.
  • the core is coated with a negatively charged species.
  • the negatively charged species may be selected from poly carboxyl ic acid, poly sulphon ic acid etc. Some other examples of the negatively charged species may include hum ic acid, E DTA, DTPA, citric acid etc.
  • the pH va lue of nanoparticle system is controlled and is kept less than at least one pKa value of the ioniza ble groups present in negatively charged species.
  • the negatively charged species may have mu ltiple ionizable groups and each of the ion izable group may have a pKa value.
  • the pKa value of one ion izable group may be d ifferent than the pKa value of other ion izable groups in the negatively charged species.
  • the pH value of the nanoparticle system is kept below the lowest pKa value in the negatively charged species.
  • the pH va lue of the nano particle system is kept below the hig hest pKa value in the negatively charged species. Th is ensures that charge carrying capacity of the core or the nanoparticle system is at optima l levels, wh ich in turn assist in improved bind ing of the oppositely charged ions.
  • Size of the nanoparticle system is in the range from 20 nanometer to 100 micrometer. Nanoparticle systems size in the above referred range has shown relatively better desalination results. I n one em bod iment, for practicing the subject matter, the nanoparticles system having size below 50 m icron may be prepared . In some examples, the nanoparticle system may be in the form of solution, slurry, paste, sol id or powder.
  • the core may also be coated with a sta bi l izing agent.
  • the stabi l izing agent may be coated prior to coating of the negatively charged species.
  • the sta bi lizing agent may be a polymer, a surfactant, a reducing agent or a chelating agent.
  • the stabilizing agent may be dextran or PVP. The stabilizing agent assists in ensuring that the core remains stable during the coating and desalination process.
  • the nanoparticle system so prepared has capability to capture the oppositely charged ions of an effluent, when it is mixed with the effluent.
  • the effluent may have a number of dissolved solids and have high Total Dissolved Solids (TDS) concentration.
  • the effluent may be an industrial effluent or any solution that needs to be subjected to desalination, removal of hardness and toxic heavy metal ions etc. Such solution may include, but not limited to industrial refuse, sea water, salty water, brackish water.
  • the nanoparticle system when mixed with the effluent binds with the oppositely charged ions of the TDS solution.
  • the nanoparticle system bound with the ions can then be separated through filtration, sedimentation, magnetically, centrifugation, osmosis or any other means leaving behind the water with significantly reduced TDS.
  • the present subject matter has demonstrated up to 90% of targeted TDS desalination from the effluent of industrial grade, that isto say an effluent having TDS upto 100,000 ppm or more.
  • the present subject matter provides a desalination process that requires minimal external energy and also the process is substantially independent of ion type and its valances.
  • the subject matter has demonstrated improved removal of ions such as sodium, potassium, calcium, aluminum, magnesium, arsenic, lead etc.
  • the present subject matter further provides a desalination method using the nanoparticle system of the present subject matter.
  • the nanoparticle system is supplied to an effluent.
  • the nanoparticle system is prepared as taught herein.
  • the effluent generally has both the cations and the anions that are needed to be desalinated.
  • the effluent has alkaline pH.
  • the nanoparticle system being negatively charged binds with the cations of the effluent.
  • the nanoparticle system along with the cations may be then filtered from the effluent.
  • magnetic separation may be employed for separating nanoparticle system from the effluent.
  • the nanoparticle system bound with cations of the effluent may be cleaned and filtered for redeployment in further desalination process.
  • Example - 1 An Example for Development of Core of a Nanoparticle System:
  • a standard solution of 0.1 M ferric chloride (FeCI 3 ) and 0.1 M ferrous sulphate (FeS0 4 ) may be prepared while ensuring that the solution is stirred constantly.
  • concentrated NaOH solution may be added to the above solution under constant stirring and temperature of range about 30°C to 6o°C.
  • the rate of addition of NaOH may be kept slow enough to increase the pH of the solution to alkaline around 8-11 and the color of the solution turns into coke black.
  • Sequential heating of the above mixture may be carried out at different temperatures over a period of time.
  • the solution may be heated to 6o-70°C for 15-30 minutes and then at 75-85 ⁇ for 15-30 minutes and final heating up to 90 - ioo°C for 30-60 minutes.
  • a known concentration of polymer such as Dextran or PVP (ranging 2 to 20 grams) may be added before addition of NaOH solution to the solution under constant stirring.
  • the solution is then cooled to room temperature and cleaned with demineralized water. Cleaning may be performed 2-3 times or as many times as required to obtained the core.
  • the core obtained, in an optional step, may be characterized for the size distribution.
  • Example - 2 An Example of Coating of A Charged Species on the Core:
  • the core obtained in the Example 1 may be further coated with a negatively charged species.
  • the negatively charged species may be poly carboxylic acid, poly sulphonic acid or alike. More specifically, the negatively charged species may be humic acid, EDTA, DTPA, citric acid or alike.
  • a humic acid is coated on the core. While coating the negatively charged species it is ensured that the pH value of the nanoparticle system is less than the pKa values of the negatively charged species. This is achieved by acidifying the nanoparticle system. In some examples, acid such HCI, sulphuric acid, nitric acid, etc may be used for controlling pH value.
  • the pH value of the nanoparticle system may be adjusted to keep the value within acidic range.
  • the pH value may be adjusted by incubating the nanoparticle system for about 2 hours.
  • the nanoparticle system may be purified with DM water. While adjusting the pH value of the nanoparticle system it is ensured that the total dissolved solids in the nanoparticle system remain may below 1000 ppm. In some other embodiments, dissolved solids in the nanoparticle system may remain below 200.
  • humic acid and core are mixed and stirred for about 2-4 hours at the temperature between 30-50 °C. From the mixture excess salts are removed to obtain the nanoparticle system.
  • the present subject matter also provides recycling of nanoparticles system. According to this aspect the present subject matter provides extracting used nanoparticles system from the refuge and cleaning the nanoparticle system. The nanoparticles system may then be further coated with the negatively charged species, as in this case humic acid by mixing and stirring in a temperature controlled environment as taught above. In an optional step, the nanoparticle system may be tested for efficiency for cation removal.
  • Example - 3 Example of Measurement of Core Size:
  • the nanoparticle system size characteristics may be determined using Malvern Zetasizer Nano ZS.
  • the present example data obtained in show in the below appended Table 1.
  • Example - Example of TDS reduction from Effluent:
  • an effluent having NaCI and TDS around 980 ppm and alkaline pH in nature where treated for desalination using the method of the present subject matter.
  • Table 2 shows results of sequential treatment according to the present subject matter.
  • pH of the nanoparticle system is kept around 3.0 (i.e. below the pKa values of all ionizable groups in the humic acid).
  • Table 3 further shows results of TDS reduction in effluent containing
  • NaCI in varying concentration between 1000 - 100,000 ppm and the effluent having alkaline pH.
  • Example - 6 Another Example of TDS reduction from Effluent, wherein the Multiple Salts are Present in the Effluent:
  • the present subject matter provides cation reduction up to 84%.
  • the effluent has TDS upto 1000 ppm and has salts such Calcium chloride, magnesium chloride, sodium chloride, aluminium sulphate etc.
  • the effluent has pH in alkaline range.
  • the nanoparticle system has demonstrated effective treatment of an effluent having variety of ions, first group ions, second group ions, third group ions, fourth group ions, fifth group ions, effectively and substantially covering entire range of ions of the periodic table.
  • Example - 7 Another Example of TDS reduction experiments with different coating ligands -
  • the present subject matter provides nanoparticle system having coating of a negatively charged species.
  • a coating of any one or more of citric acid, EDTA or DTPA i.e. polycarboxylic acids
  • effluent having about 1000 ppm of NaCI salts and pH of in alkaline range desalination of cations upto 60-80% is achieved.
  • higher the carboxylic acid moieties in the coating materials result in better binding of nanoparticle systems and salt and therefore results in better desalination.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Abstract

La présente invention concerne un système de dessalement à base de nanoparticules et procédé de dessalement correspondant. La présente invention concerne un système de nanoparticule qui comporte un noyau et une espèce chargée négativement enrobant le noyau. La valeur du pH du système de nanoparticule est inférieure aux valeurs de pKa de l'espèce chargée négativement. Le système de nanoparticule est configuré pour provoquer le dessalement d'ions chargés positivement provenant d'un effluent.
PCT/IN2017/050509 2016-12-09 2017-11-04 Système de nanoparticules anioniques pour dessalement et procédé associé Ceased WO2018104957A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201780075668.4A CN110049816A (zh) 2016-12-09 2017-11-04 用于脱盐的阴离子纳米颗粒体系及其方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN201621042076 2016-12-09
IN201621042076 2016-12-09

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WO2018104957A1 true WO2018104957A1 (fr) 2018-06-14

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102423696A (zh) * 2011-09-02 2012-04-25 中国科学院新疆理化技术研究所 腐植酸修饰的纳米四氧化三铁的制备方法及用途
WO2013074669A1 (fr) * 2011-11-14 2013-05-23 The University Of Chicago Système de dessalement et de filtration à base de nanoparticules
CN103752281A (zh) * 2014-01-21 2014-04-30 南京林业大学 一种磁性腐殖酸纳米材料及其制备方法和应用
WO2015177391A1 (fr) * 2014-05-19 2015-11-26 Consejo Superior De Investigaciones Científicas (Csic) Électrolyte nanostructuré utile pour le dessalement par osmose directe, procédé d'obtention de l'électrolyte et utilisations associées

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102423696A (zh) * 2011-09-02 2012-04-25 中国科学院新疆理化技术研究所 腐植酸修饰的纳米四氧化三铁的制备方法及用途
WO2013074669A1 (fr) * 2011-11-14 2013-05-23 The University Of Chicago Système de dessalement et de filtration à base de nanoparticules
CN103752281A (zh) * 2014-01-21 2014-04-30 南京林业大学 一种磁性腐殖酸纳米材料及其制备方法和应用
WO2015177391A1 (fr) * 2014-05-19 2015-11-26 Consejo Superior De Investigaciones Científicas (Csic) Électrolyte nanostructuré utile pour le dessalement par osmose directe, procédé d'obtention de l'électrolyte et utilisations associées

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JING-FU LIU ET AL.: "Coating Fe304 Magnetic Nanoparticles with Humic Acid for High Efficient Removal of Heavy Metals in Water", ENVIRON. SCI. TECHNOL., vol. 42, 2008, pages 6949 - 6954, XP055490965 *

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