WO2018104959A1 - Appareil pour la synthèse d'un système de nanoparticules pour le dessalement et procédé associé - Google Patents

Appareil pour la synthèse d'un système de nanoparticules pour le dessalement et procédé associé Download PDF

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Publication number
WO2018104959A1
WO2018104959A1 PCT/IN2017/050511 IN2017050511W WO2018104959A1 WO 2018104959 A1 WO2018104959 A1 WO 2018104959A1 IN 2017050511 W IN2017050511 W IN 2017050511W WO 2018104959 A1 WO2018104959 A1 WO 2018104959A1
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WO
WIPO (PCT)
Prior art keywords
reactor
nanoparticle system
core
chamber
receive
Prior art date
Application number
PCT/IN2017/050511
Other languages
English (en)
Inventor
Ajay Kumar Gupta
Dinesh Kumar Jagroopsingh YADAV
Mihir Kanjibhai RATHOD
Nitin Narayan SHIRSAT
Original Assignee
Arvind Envisol Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arvind Envisol Ltd. filed Critical Arvind Envisol Ltd.
Priority to CN201780075667.XA priority Critical patent/CN110049950A/zh
Publication of WO2018104959A1 publication Critical patent/WO2018104959A1/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
    • C02F1/28—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
    • 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 an apparatus for synthesis of a nanoparticle system for desalination, more specifically it relates to an apparatus for synthesis of a nanoparticle system for desalination coated with a charged species and method of manufacturing thereof.
  • 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 deploy primarily thermal properties
  • filtration, reverse osmosis, forward osmosis deploy primarily mechanical energy
  • electro- dialysis and ionic exchange may deploy combination of electrical and chemical energies.
  • Most of these techniques have their own limitations, e.g. cost and complexity, scalability, efficiency, economic viability etc.
  • the present subject matter addresses these issues and provides a solution that may not only be used for recycling industrial refuge but also generating fresh water from seawater, brackish water etc. [005]
  • the present subject matter provides solution to the above and other problems.
  • the present subject matter provides an apparatus for synthesis of a nanoparticle system for desalination and a method thereof.
  • an apparatus comprising: a reactor configured to receive a solution of metal salts and a pH controller and the reactor is configured to cause precipitation of metal salts in a pH controlled environment resulting in formation of a core; and a temperature controller coupled to the reactor wherein, the temperature controller is adapted to heat treat the solution during formation of the core; wherein the reactor is further configured to receive a charge species for coating on the core to form a
  • the apparatus further comprises an extractor configured to extract the nanoparticle system.
  • the apparatus comprises an agitator.
  • the reactor includes a first chamber wherein the first chamber is configured to receive the solution of metal salts and the pH controller and the first chamber has the agitator and the temperature controller.
  • the reactor includes a second chamber wherein the second chamber is configured to receive the core and the charge species and the second chamber has the agitator and the temperature controller.
  • the apparatus further comprises a dispenser coupled to the reactor, wherein the dispenser is configured to controllably dispense the pH controller into the reactor.
  • the extractor comprises a separator and an optimizer wherein the separator is configured to separate the nanoparticle system and the optimizer optimizes the pH value of the nanoparticle system based on the ionization value (pKa) of the ionizable group of the charged species.
  • the present subject matter provides a method of manufacturing an apparatus comprising: configuring a reactor to receive a solution of metal salts and a pH controller and to cause precipitation of metal salts in a pH controlled environment resulting in formation of a core;
  • the method comprises providing an extractor to extract the nanoparticle system.
  • the method includes providing an agitator.
  • configuring the reactor to receive the solution includes, configuring a first chamber to receive the solution of metal salts and the pH controller and providing the first chamber with providing the agitator and the temperature controller.
  • configuring the reactor to receive the charge species includes configuring a second chamber to receive the core and the charge species and providing the second chamber with the agitator and the temperature controller.
  • the method includes coupling a dispenser to the reactor, wherein the dispenser is configured to controllably dispense the pH controller into the reactor.
  • a seventh embodiment coupling the extractor configuring a separator to separate the nanoparticle system and configuring an optimizer to optimize the pH value of the nanoparticle system and the ionization value (pKa) of the ionizable group of the charged species.
  • FIG. 1 shows a block diagram of an embodiment of the present subject matter
  • FIG. 2 shows a more detailed block diagram of a reactor according to an embodiment of the present subject matter
  • FIG. 3 shows a block diagram of the reactor coupled to a dispenser according to an embodiment of the present subject matter
  • FIG. 4 shows a more detailed block diagram of an extractor according to an embodiment of the present subject matter.
  • FIG. 5 shows another more detailed block diagram of the present subject matter according to an embodiment of the present subject matter.
  • nanoparticle systems may present limitations in removing dissolved solids based on chemical characteristics. It is desirable that nanoparticle systems achieve desalination of most, if not all, salts without regards to their chemical properties. In some cases, lower valance salts present challenges during desalination. This is because charge carrying capacity of nanoparticle systems plays an important role in desalination and to desalinate lower valance salts require that nanoparticle system must have a higher charge carrying capacity.
  • 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 enhance its charge carrying capacity after its use. Thereby achieving most from the nanoparticle system
  • 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.
  • FIG. 1 shows a block diagram of an embodiment of the apparatus 100 according to the present subject matter.
  • FIG. 1 includes a reactor 101, a temperature controller 103, an inlet control 105, an agitator 111 and collectively these elements are referred to as a reactor assembly 110.
  • the FIG. 1 further shows an extractor 107 and an outlet 109.
  • the apparatus 100 may synthesize of the nanoparticle system in few stages. First stage being formation of a core and second being coating of a charged species on the core to obtain the nanoparticle system. At another optional stage, the core may further be coated with a stabilizing agent prior to coating the charged species. It shall become clear to a person in the art, after reading this specification, that in some instances, technical fraternity may refer to the core as nanoparticles.
  • 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. Having an iron core offers additional advantage, which is to say, that magnetic filtration becomes easier.
  • the reactor assembly 110 may be used at multiple stages. That is to say, that the reactor 101 of the reactor assembly 110 may be first deployed in core formation, followed by coating of the charge species on the core and in some optional cases for coating the stabilizing agent on the core.
  • This feature of the subject matter is advantageous because it enables a compact and cost effective system.
  • the solution of metal salts and a pH controller is provided in a controlled manner into the reactor 101 through the inlet control 105. It shall become clear to a person in the art, after reading this specification, that there may be multiple inlet control 105 each inlet control is configured to introduce separate component of the solution.
  • the inlet control 105 for introducing metal salts and a second inlet control for introducing the pH controller.
  • the pH controller controls the core formation reaction in the reactor 101.
  • the reactor 101 is further provided with the agitator 111 and the temperature controller 103.
  • This embodiment shows a coil as the temperature controller 103 and a stirrer as the agitator 111 however, it shall become clear to a person in the art, after reading this specification, that these elements may be different than the coil or stirrer.
  • the temperature controller 103 may be a steam based controller, or may have a low conductive jacket, or ice based temperature controller.
  • agitator 111 may be a temperature based agitator or other electrical motor based agitator, shaking agitator etc. Formation of desired size of the core is achieved by sequentially supplying the pH controller and stirring and sequentially heat-treating the solution in the reactor 101.
  • the core may also be coated with a stabilizing agent.
  • the stabilizing agent may be coated prior to coating of the negatively charged species.
  • the stabilizing 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 core may be extracted.
  • the core may be deployed for coating of charged species in the reactor 101.
  • the reactor For coating the charged species the reactor
  • ionization value is the pKa value of charged species. It shall clear to a person in the art, after reading this specification, that the charged species have a number of ionizable group each ionizable group may have a different ionization value that is to say that a different pKa value. In some cases, where the charged species is a negatively charged species, for example, humic acid etc. the pH value of the nanoparticle system is kept below the pKa value of the charged species.
  • the pH value of nanoparticle system is controlled and is kept less than at least one pKa value of the negatively charged species.
  • the negatively charged species may multiple ionizable groups and each of the ionizable group may have a different pKa value.
  • the pH value of the nanoparticle system is kept below the lowest pKa value of ionizable group in the negatively charged species. This ensures that charge carrying capacity of the core or the nanoparticle system is at optimal levels, which in turn assist in improved binding of the oppositely charged ions.
  • Some other negatively charged species may be selected from poly carboxylic 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 charged species is a positively charged species, for example, Benzal koniumch loride (BKC) etc.
  • BKC Benzal koniumch loride
  • the pH value of the nanoparticle system is kept above the pKa value of the charged species.
  • Some other positively charged species may be selected from poly am ines, polyal konium sa lts, poly ethylam ine, cation ic polymers, polyamines, polypeptides, quaternary ammon ium salts, the positively charged species is any one or more of Benza lkon ium ch loride (BKC), cetyl trimethylammonium bromide (CTAB), peptides.
  • the positively charged species may have multiple ion izable groups and each of the ion izable group may have a d ifferent pKa value.
  • the pH value of the nanoparticle system is kept above the lowest pKa value of ion izable group in the positively 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 binding of the oppositely charged ions. Therefore, when the nanoparticle system is employed for the desal ination of an effluent, the TDS or the impurities of the nanoparticle system does not become counterproductive to the desal ination .
  • nanoparticle system is formed in the reactor 101.
  • the nanoparticle system may be extracted into the extractor 107 and the output nanoparticle system may be received at the outlet 109.
  • size of the nanoparticle system is in the range from 20 nanometer to 100 micrometer. Nanoparticle systems size in the a bove referred range has shown relatively better desa lination results.
  • the nanoparticles system having size below 50 m icron may be prepared .
  • the nanoparticle system may be in the form of solution, slurry, paste, sol id or powder.
  • FI G FI G.
  • FIG. 2 shows a more detailed diagram of the reactor assembly 110 according to another embodiment of the present subject matter.
  • FIG . 2 includes a first chamber 200, an agitator 201 and 211 and a temperature controller 203 and 213, an inlet control 205 and 215, a second chamber 210.
  • the first chamber 200 may be employed for core formation whereas the second chamber 210 may be employed for coating of charged species.
  • the solution of the metal salts and the pH controller may be received in the first chamber 200 for core formation through the inlet control 205.
  • the role and examples of the temperature controller 203 remain as explained previously with respect to the F IG. 1 in core formation stage.
  • the core may be coated with a stabilizing agent.
  • the core may be transferred to the second chamber 210.
  • the core may be coated with the stabilizing agent.
  • the core may be subjected to the charge coating process.
  • role of the agitator 211 role of the temperature controller 213 remains substantially similar to that described with reference to FIG . 1. It shall become clear to a person in the art, after reading this specification, that the temperature controllers 203 and 213 are shown as a coil based controller and a jacket based controller, however such depiction is only for the purpose of example and other configuration of the temperature controllers may be deployed.
  • FI G. 3 shows another embodiment of the present subject matter, wherein the pH block 300 is shown.
  • the pH block 300 may includes a dispenser 301 and an agitator 311.
  • the pH block 300 may have a temperature controller and some other additional element.
  • the pH block 300 may be configured to receive the pH controller such as NaOH etc.
  • the inlet control 205 may be coupled to the outlet of the pH block.
  • the reactor assembly no may be configured to controllably receive the pH controller from the pH block 300.
  • FIG. shows a more detailed diagram of the exactor 117 according to one embodiment of the present subject matter.
  • the extractor 117 comprises an optimizer 427, an agitator 411, and a separator 417 having a magnet 403.
  • pH of the nanoparticle system may be adjusted according the ionization value (pKa) of the charge species and the type of the charge species. The adjustment of the pH value is discussed previously with reference to FIG 1.
  • the nanoparticle system may be then extracted using the magnetic extractor 417.
  • extracted nanoparticle system may be again subjected to the optimizer 27 until the nanoparticle system reach at a desired pH level.
  • the optimizer 427 becomes advantageous when nanoparticles are recovered from a desalination process and are desired to be recycled in the desalination process again.
  • the output becomes advantageous when nanoparticles are recovered from a desalination process and are desired to be recycled in the desalination process again.
  • nanoparticle system may be received at the outlet 109.
  • extractor 117 is a magnet based extractor, however one or more of other extractors such as, filtration-based, centrifugation-based, sedimentation-based etc. may also be deployed at this stage. Magnet based extractors are of interest when the core is of a magnetic material.
  • FIG. 5 shows another more detailed block diagram of the apparatus of the present subject matter.
  • the apparatus includes the reactor assembly 110, the pH block 300, and the extractor 107.
  • the construction and functions of the reactor assembly 110, the pH block 300, and the extractor 107 is substantially same as described with reference to the previous figures.
  • the reactor assembly 110 shows additional features, such as the temperature controller 503 is shown as a steam based temperature controller, further a temperature probe 553 is shown in the figure.
  • various valves for controlling in and out flow of the solution, core, charged species, nanoparticles system and temperature controlling agents such as steam, cold water, liquid nitrogen etc are not shown in the FIG 5.
  • One of the embodiments of the present subject matter may be understood as follows.
  • demineralized water of about 1500 liters is supplied to the first chamber 200 which is part of the reactor assembly 110.
  • weight of about 18-20 kg of ferrous sulphate and about 20 kg of ferric chloride is added to the first chamber 200.
  • the ferrous suphate and the ferric chloride are the metal salts.
  • the agitator 201 may be actuated to dissolve the ferrous sulphate and ferric chloride.
  • the dissolution of metal salt may generate heat, the temperature controller 203 or 503, a temperature probe 533 and may be used to ensure that the temperature remains within the desired range.
  • the temperature of about 50 degree Celsius is maintained using the temperature controller 203 or 503, and the temperature probe 533.
  • a dose of NaOH solution from pH block 300 may be supplied to the first chamber 200.
  • the NaOH in the present case acts as the pH controller.
  • the NaOH is 2M NaOH and sufficient quantity of the 2M NaOH is supplied to the first chamber 200 to ensure that the pH level of the solution of the first chamber is controlled in a level ranging from 8 through 11.
  • the temperature of the solution in the first chamber is maintained at around 50 degree calcius.
  • the solution of the first chamber 200 is controllably heat treated using the temperature controller 203, 503, and temperature probe 553.
  • humic acid is supplied to the second chamber 200 and agitated for up to 2-6 hours at an ambient temperature, resulting in coating of the charge species on the core and formation of the nanoparticle system.
  • the solution may be then supplied to the extractor 117 where the solution may be further treated for pH adjustment and the nanoparticle system are extracted for use in desalination. In some additional step the nanoparticle system may be washed and pH treatment may be repeated.
  • the present subject matter provides, a method of manufacturing the apparatus of the present subject matter.
  • the method of manufacturing the apparatus 100 includes a number of steps. While a number of steps become apparent from the discussion with reference to the FIG. i through FIG. 5, solely for the sake of completeness following describes the method. FIG. i through FIG. 5 are collectively referenced in the following discussion and the reference numerals corresponding elements may be referred accordingly.
  • the reactor 101 is configured.
  • the reactor assembly 110 may be configured.
  • the reactor 101 and reactor assembly 110 may be provided with one or more inlets including the control inlet 105, 205, 215.
  • the reactor assembly 110 is configured to cause precipitation of meta l salts in a pH and temperature controlled environment resu lting in formation of a core.
  • the reactor assembly no may be provided with a temperature controller 103, 203, 213.
  • the method provides the extractor 107 to extract the nanoparticle system.
  • the agitator 201, 211, 111,311, 411 may be provided .
  • the reactor assembly may be configured to couple the first cham ber 200 and the second cham ber 210.
  • the pH block 300 is configured and coupled to the reactor assem bly 110 and at one stage the extractor 107 is configured and coupled to the reactor assem bly 110.
  • the nanoparticle system so prepared has capa bi l ity to capture the oppositely charged ions of an effluent, when it is mixed with the effluent.
  • the effluent may have a number of d issolved sol ids and have h igh Total D issolved Sol ids (TDS) concentration.
  • the effluent may be an infrastructure l effluent or any solution that needs to be subjected to desa lination, removal of hardness and toxic heavy metal ions etc. Such solution may include, but not l im ited to industrial refuse, sea water, salty water, brackish water.
  • the nanoparticle system bound with the ions can then be separated through fi ltration, sed imentation, magnetical ly, centrifugation, osmosis or any other means leaving beh ind the water with sign ificantly reduced TDS .
  • the present subject matter has demonstrated up to 90% of targeted TDS desal ination from the effluent of industrial grade, that is to say an effluent having TDS upto 100,000 ppm or more.
  • the present subject matter provides a desalination process that requires m ⁇ l external energy and also the process is su bstantial ly independent of ion type and its va lances.
  • the su bj ect matter has demonstrated improved removal of ions such as sod ium, potassium, calcium, a luminum, magnesium, arsen ic, lead etc.

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

La présente invention concerne un appareil et son procédé de fabrication. L'appareil comprend un réacteur conçu pour recevoir une solution de sels métalliques et un dispositif de régulation du pH. Le réacteur est conçu pour provoquer la précipitation de sels métalliques dans un environnement à pH régulé conduisant à la formation d'un cœur. Un dispositif de régulation de la température est couplé au réacteur. Le dispositif de régulation de la température est conçu pour traiter thermiquement la solution pendant la formation du cœur. Le réacteur est en outre conçu pour recevoir une espèce de charge destinée à revêtir le cœur pour former un système de nanoparticules. Le système de nanoparticules a une surface chargée et la valeur de pH du système de nanoparticules est basée sur au moins une valeur d'ionisation (pKa) du groupe ionisable de l'espèce chargée. Le système de nanoparticules est conçu pour provoquer le dessalement d'un effluent.
PCT/IN2017/050511 2016-12-09 2017-11-04 Appareil pour la synthèse d'un système de nanoparticules pour le dessalement et procédé associé WO2018104959A1 (fr)

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CN201780075667.XA CN110049950A (zh) 2016-12-09 2017-11-04 用于脱盐的纳米颗粒体系的合成用装置及其方法

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IN201621042074 2016-12-09
IN201621042074 2016-12-09

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WO2018104959A1 true WO2018104959A1 (fr) 2018-06-14

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CN113385044B (zh) * 2021-05-31 2023-03-07 天津大学 基于静电强化反应表面偏析方法制备的纳滤膜及其应用

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