WO2016092123A1 - Procédés d'obtention de matières absorbantes pour l'épuration d'eaux, matières absorbantes obtenues et leurs applications - Google Patents

Procédés d'obtention de matières absorbantes pour l'épuration d'eaux, matières absorbantes obtenues et leurs applications Download PDF

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Publication number
WO2016092123A1
WO2016092123A1 PCT/ES2014/000219 ES2014000219W WO2016092123A1 WO 2016092123 A1 WO2016092123 A1 WO 2016092123A1 ES 2014000219 W ES2014000219 W ES 2014000219W WO 2016092123 A1 WO2016092123 A1 WO 2016092123A1
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WIPO (PCT)
Prior art keywords
absorbent materials
water purification
solution
previous
materials
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PCT/ES2014/000219
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English (en)
Spanish (es)
Inventor
Rocío PÉREZ RECUERDA
Francisco Ignacio Franco Duro
José Pascual Cosp
María Del Carmen Assiego De La Riva
Francisco Alaminos Camacho
Jesús CIFUENTES MELCHOS
Manuel Jesús CASTRO DÍAZ
Mónica BENÍTEZ GUERRERO
María Isabel GONZÁLEZ TRIVIÑO
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Universidad De Málaga
Empresa Municial De Aguas De Málaga
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Publication of WO2016092123A1 publication Critical patent/WO2016092123A1/fr

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    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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

Definitions

  • the present invention relates to methods of obtaining absorbent materials for water purification. Also, the invention relates to the absorbent materials obtained and applications associated with said materials. STATE OF THE TECHNIQUE
  • Water is a limited and indispensable resource for both civilization and the environment and the life that develops in it. For this reason it is necessary to properly manage this resource, ensuring not only the availability but the quality of these waters.
  • These waters can be contaminated through different pathways that encompass natural and anthropogenic mechanisms with a variety, perhaps excessive, of contaminants.
  • pollutant that the waters have, they can be adequately purified for human consumption (drinking water) or reused for other purposes that do not require to reach the demanding conditions that a water must have to be destined for human consumption.
  • the clay minerals generally, minerals from the smectite group. These minerals have particular crystallochemical characteristics that make them have very interesting absorbent properties from an environmental point of view.
  • the crystalline structure of the smectite group minerals is based on the stacking of sheets formed by three layers.
  • Part of the Si 4+ of the tetrahedral layers (approximately 1 in 8) are isomorphically substituted by Al 3+ , generating an excess of negative charge on the surfaces of the sheets that are compensated with the existence of cations in the space between the sheets (interlaminar space).
  • the existence of these isomorphic substitutions that generate negative charges that have to be compensated, together with the location of OH groups on the surface and the existence of other structural defects provide the minerals of the smectite group with active adsorption centers that are going to confer very good adsorbent properties.
  • organo-clays have serious drawbacks. These derive, in the first place, from the uncontrolled reversibility of the adsorption process and the ease with which the alkylammonium cations of the organo-clays are released, transforming into potential contaminants.
  • the adsorbent materials object of the invention comprise, as raw material or base, clay minerals, preferably smectite minerals, more preferably dioctahedral smectite minerals (aluminum smectites) and / or trioctrahedral smectite minerals (magnesium smectites), more preferably even minerals of montmorillonite (Mont) and / or saponite (Sap), such forms obtainable from bentonites, with antagonistic crystallochemical characteristics, and whose abundance in nature makes them extremely economical.
  • clay minerals preferably smectite minerals, more preferably dioctahedral smectite minerals (aluminum smectites) and / or trioctrahedral smectite minerals (magnesium smectites), more preferably even minerals of montmorillonite (Mont) and / or saponite (Sap), such
  • Bentonites such as those referred to are very common throughout the land area, so, given that transport is one of the factors that make the product more expensive, the design of manufacturing systems should be as economical as possible to implement these systems. manufacturing where water purification is required. Indicate that montmorillonite and saponite themselves must be taken into account as part of the catalog of adsorbent materials given their excellent qualities in water purification.
  • the methods of production have been designed with the aim of generating a wide catalog of absorbent materials, economical, based on natural minerals (clays) and that are capable of removing contaminants from drinking water.
  • one of the characteristics that influence the design of the methods of obtaining it is the need to easily scale the synthesis according to the quantities required for each specific problem of purification of water for consumption.
  • the capacities of cationic change of the starting materials are determined by means of the ammonium acetate method (Sumner and Miller, 1996 ).
  • said methods of obtaining comprise a stage of delamination, after the stage, where appropriate, of conditioning (preferably by ultrasonic cavitation) that allows generating monolayers of the base or starting material ( clay ores, preferably smectite ores, more preferably dioctahedral smectite ores and / or trioctrahedral smectite ores, more preferably even Mont and / or Sap ores).
  • clay ores preferably smectite ores, more preferably dioctahedral smectite ores and / or trioctrahedral smectite ores, more preferably even Mont and / or Sap ores.
  • the invention relates to methods implemented in computer for the selection of absorbent materials for the treatment or purification of contaminated water, particularly for the selection of absorbent materials obtained by the processes for obtaining absorbent materials object of the invention.
  • These methods based on mathematical modeling, allow the selection of the most efficient and most economical type of material for the adsorption of contaminants present in waters intended for human consumption (heavy metals, organic metals, humic substances and mixtures thereof).
  • the stationary system type of complete mixture
  • the adsorbent material that is homogeneously dispersed in the water is added to achieve the removal of the contaminant
  • a system based on the use of column filters that pass the wastewater through a porous bed comprising a mixture, of suitable proportions, of sand and an adsorbent material from the catalog of materials described in the section previous.
  • Methods of obtaining the materials constituting the first object of the invention are object of the present invention, said methods comprising an ultrasonic cavitation stage, preferably high energy ultrasonic cavitation, an impregnation stage, preferably direct impregnation, and a stage of calcination); stages that allow the addition of metal oxides to the monolamines, said metal oxides, preferably iron oxides and / or aluminum oxides, providing new adsorption centers on those of the monolamines.
  • the materials, thus obtained have yields far superior to active carbon in the elimination of a large number of pollutants and a stability far superior to that of organo-clays.
  • object (second object) of the present invention are absorbent materials for the purification of water obtained by means of the obtaining procedures that constitute the first object of the invention, hereinafter referred to as oxides supported on 2: 1 monolamines of clays (OSML), comprising as base material 2: 1 monoláminas of clay minerals, preferably smectite ores, more preferably dioctahedral smectite ores and / or trioctrahedral smectite ores, more preferably even montmorillonite (Mont) and / or saponite (Sap) ores .
  • said second object extends to the intermediate materials of the obtaining processes that constitute the first object of the invention.
  • methods (third object) of the present invention are methods implemented in computer of selection of absorbent materials for the treatment or purification of contaminated water, particularly of selection of absorbent materials obtained by means of the processes of obtaining absorbent materials object of the invention.
  • Said third object extends to computer systems (for example, communication management platforms); as well as to computer programs or program instructions, more particularly to computer programs in or on carrier means, adapted to implement the methods that constitute said third object of the invention.
  • the computer program may be in the form of source code, object code or an intermediate code between source code and object code, such as partially compiled form, or in any other form suitable for use in the implementation of the methods constituting said third object of the invention.
  • the carrier medium can be any entity or device capable of carrying the program.
  • the carrier medium may comprise a storage medium, such as a ROM, for example a CD ROM or a semiconductor ROM, or a magnetic recording medium, for example a floppy disc or a hard disk.
  • the carrier means can be a transmissible carrier medium such as an electrical or optical signal that can be transmitted via electrical or optical cable or by radio or other means.
  • the carrier medium may be constituted by said cable or other device or medium.
  • the The carrier means may be an integrated circuit in which the computer program is encapsulated (embedded), said integrated circuit being adapted to perform, or to be used in carrying out the methods constituting said third object of the invention.
  • aspects of said third object of the invention are computer systems that implement said methods implemented in computer of selection of absorbent materials, as well as computer programs, storage media readable by computer systems, and transmissible signals capable of making a computer system carry out said methods implemented in computer selection of absorbent materials.
  • a fourth object of the invention relates to the use of the materials that constitute the second object of the invention, or of the intermediate materials of the obtaining procedures that constitute the first object of the invention, or of the methods implemented in computer selection of absorbent materials constituting the third object of the invention (including aspects of said third object) in the treatment or purification of contaminated water.
  • - Cation exchange capacity the minerals of the smectite group have adsorption centers, in which cations are retained, which are generated either by the isomorphic replacement of elements with different loads or by the presence of structural defects. These cations can be exchanged for others that are in an aqueous solution.
  • the cationic exchange capacity expresses the number of moles of adsorbed positively charged ions that can be exchanged per unit of dry mass of smectite. 2: 1 monolamines: The crystalline structure of the smectite group minerals is based on the stacking of sheets formed by three layers.
  • the sheets of the smectite group minerals are formed by two tetrahedral layers and an octahedral layer. Hence, they are called 2: 1 sheets to differentiate them from other minerals such as those of the kaolinite group (1: 1) whose structure is based on the stacking of sheets formed by two layers, one octahedral and one tetrahedral.
  • Step 1. Ultrasonic cavitation. Dispersion and delamination to monolmina.
  • an ultrasonic system is used, preferably a high energy ultrasonic system, more preferably a high energy ultrasonic system that works continuously at 20kHz and 1000W.
  • a high energy ultrasonic system preferably a high energy ultrasonic system that works continuously at 20kHz and 1000W.
  • the adequate dispersion of the clay particle packages, preferably smectites, which are naturally aggregated in the starting samples, and in turn the total delamination of the dispersed particles in monolilamines 2: 1 is achieved. In this way, all adsorbent centers are exposed on the external surface.
  • reactors preferably cylindrical conical-based reactors (to favor the collection of materials), more preferably reactors made of an economic material that, in addition it must be inert in the chemical conditions in which the different reactions are to be carried out and must allow, directly, scaling depending on the amount of material to be synthesized.
  • the resulting aqueous suspension is kept under stirring in the reactors, preferably for 24 hours, more preferably with the aid of a 0.5 hp agitator with a 600 rpm output speed reducer and with a rod and propeller made of a material resistant to the physical-chemical conditions in which the impregnation takes place.
  • the same agitator can be used for the washing process at a suitable speed, particularly at 125 rpm in the preferred embodiment described in this section.
  • a suitable speed particularly at 125 rpm in the preferred embodiment described in this section.
  • 4 h in the preferred embodiment described in this section it is left to decant for a suitable time, preferably for 20 h, the liquid remaining on the deposited solid is removed and this process is repeated until the wash water has a suitable conductivity, preferably less than 10 ⁇ / ⁇ .
  • the material obtained from the previous stages is a mixed suspension of the 2: 1 monollamines impregnated with the reactive material and a large amount of water.
  • This suspension must be dried in its entirety, for example with the help of a dryer by thermal convection transmission (at 70 ° C in a preferred embodiment; stationary or continuous, depending on the quantity to be manufactured) and allowing the samples to be dried homogeneously in the entrance of a furnace in which the impregnated sheets will be calcined to anchor the reagents on the surface and transform them into new absorbent active centers. Ovens will be used for this.
  • the materials are ground, for example in industrial ball mills, preferably inside cylinders (of sizes depending on the amount of material to be ground) with steel spheres (preferably> 10 mm in diameter ) that rotate at constant speed, for example with the help of rollers, until the dispersed particles are obtained. It is important to keep track of the grinding process since excessive grinding leads to the amorphousization of the material and the formation of hard aggregates that would nullify the adsorbent properties of the synthesized materials.
  • the size of this ball mill will be, where appropriate, directly scalable to the amount of material to be manufactured.
  • FeSML-Mont, FeSML-Sap The reactive solutions consist of aqueous solutions of FeCl3-6H 2 0 with the amount of equivalents that mark the cationic exchange capacities of smectites that are used as raw material.
  • FeOSML-Mont, FeOSML-Sap To prepare the precursor solution it is necessary to prepare two solutions containing the amounts of FeCl3-6H 2 0, on the one hand (solution
  • adsorption isotherms were determined for the different synthesized adsorbent materials, as well as the starting materials (Mont and Sap) and an active carbon commercial. These isotherms that describe the performance of these materials in the adsorption of contaminants. Although the isotherms obtained in the case of the removal of Ni (II), As (III) and Cd (II) are presented as an example, adsorption isotherms at 25 ° C have been determined for a large number of contaminants.
  • the synthesized materials have adsorbent properties markedly superior to those of active carbon.
  • said methods implemented in computer of selection of absorbent materials comprise the following steps: 1. Choice of adsorption system.
  • the method implemented in computer of selection of absorbent materials is based on mathematical modeling by adsorption isotherms that relate the amount of contaminant absorbed by the material against the amount of contaminant which remains untained once equilibrium is reached, particularly the amount in mg of contaminant absorbed per g of adsorbent material (qe) versus that of contaminant that remains untapped expressed in mg / L (Ce) once equilibrium is reached.
  • biparametric equations such as Langmuir, Freundlich, Dubinin-Radushkevich, Temkin, Brunauer-Emmet-Teller, Sips and Toth are used.
  • the method implemented in computer of selection of absorbent materials manages information about some of the variables that control the design of the filtering columns, such as material selection with higher yield, amount of adsorbent and adsorbent / sand ratio of the porous bed depending on the concentration of pollutant, the flow rate and the total volume of water to be purified, and finally the diameter and height of the column.
  • column adsorption models such as Thomas, Yoon-Nelson, Adams-Bohart (BDST), Wang and Wolborska-Pustelnik are used.
  • the method implemented in computer of selection of absorbent materials includes access by computer means to an updateable database related to the type of clay, pollutant and water, adsorption balance and economic cost of synthesis of the different adsorbents.
  • the scheme of the operation of the computer program is described in Figure 6.
  • the step of choosing the adsorption system allows the user of the method implemented in the computer of selection of absorbent materials to choose the appropriate adsorption system, particularly choosing between a column filter system and a stationary system.
  • the problem identification stage allows the user to define or identify the type of pollutant, its initial or incoming concentration, its desired final or exit concentration, the type of water to be treated or treated, and the volume and flow of said water to Debug or treat.
  • the selected adsorption system is the column filter system:
  • the expected result is modeled, based on the parameters and variables defined in the step of identifying the problem, of the use of each available absorbent material based on the experimental data, and / or, where appropriate, theoretical, available in relation to each available absorbent material as well as each contaminant, said experimental data, and / or, where appropriate, theorists, stored in a database.
  • the maternal models implemented are column adsorption models such as Thomas, Yoon-Nelson, Adams-Bohart (BDST), Wang and Wolborska-Pustelnik.
  • the adsorption system selected is the stationary system:
  • the modeling is based on the mathematical modeling by adsorption isotherms that relate the amount of contaminant absorbed by the material to the amount of contaminant that remains without retaining once equilibrium is reached, using biparametric equations such as Langmuir, Freundlich, Dubinin-Radushkevich, Temkin, Brunauer- Emmet-Teller, Sips and Toth.
  • the result of the different modeling and graphic adjustments is statistically analyzed, particularly by means of the chi2 statistical test, generating a list of the different absorbent materials available indicative of the efficiency of each absorbent material in relation to the problem identified and the adsorption system chosen.
  • Said list may also contain indication of the concentration, or particularly of the amount (depending on the parameters defined in the problem identification stage), of absorbent material to be used to purify or treat the water defined in the problem identification stage. and obtain, depending on the rest of the parameters and variables defined in said problem identification stage, the desired final or exit concentration of the contaminant for which it is desired to apply the method implemented in computer of selection of absorbent materials.
  • the list of absorbent materials may in turn contain an indication of the economic cost associated with the amount of each available absorbent material, so that the list may be indicative of the efficiency / cost ratio of the available absorbent materials.
  • the method implemented in computer of selection of absorbent materials can allow, in relation to the information related to economic costs, the definition and / or update of the parameters and variables determinants of said economic costs, such as the acquisition or acquisition price of the absorbent material (including base or starting material and, where appropriate, reagents), economic cost associated with its transportation, electricity cost associated with its acquisition and / or use, etc.
  • the evaluation and decision stage provides an indication of the efficiency in relation to all available absorbent materials, particularly the most efficient absorbent material and, where appropriate, an indication of the concentration or necessary amount of said absorbent material, and, where appropriate, the height of the bed to be used (depending on the amount of absorbent material), as well as, where appropriate, indication of the efficiency / cost ratio.
  • the method implemented in computer of selection of absorbent materials object of the invention can be implemented in a computer system, said computer system comprising for said implementation (a) a configuration module, (b) a processing module, (c) a module of storage, and (d) a decision module.
  • a configuration module for said implementation
  • a processing module for said implementation
  • a module of storage for said implementation
  • a decision module for said implementation
  • the configuration module is responsible for the execution of the stages of choosing the adsorption system and identifying the problem as well as, where appropriate, allowing the definition and / or updating of the parameters and variables that determine the economic costs associated to the quantities to be used of the different absorbent materials available, particularly of the economic costs associated to the quantity to be used of the absorbent material that would allow the adsorption process to be the most efficient;
  • the processing module is responsible for the execution of the modeling and data processing stage
  • the storage module comprises a database that is accessed by computer means and comprises experimental, and / or, where appropriate, theoretical data, available in relation to each available absorbent material as well as each contaminant;
  • the decision module is responsible for the execution of the evaluation and decision stage.
  • the method implemented in computer of selection of absorbent materials adjusts the data previously implemented in the database to the different isotherms and determines which of them has less chi2 for each clay studied and the necessary amount of these:
  • the software selects the one that is most efficient, in this case FeSML-Mont, and the necessary amount would be 0.066 g / 1.
  • the final concentration obtained by means of a stationary system turns out to be 10,146 ppb, thus validating the software.
  • Case 2 To reduce a Ni (II) contamination from 100 ppb to 20 ppb, 0.028 g / 1 of FeOSML-Mont clay would be needed.
  • Case 3 For a contamination of Pb (II), from 100 ppb to 10 ppb, 0.0166 g / 1 of FeSML-Mont clay would be needed.
  • Case 6 To treat a flow rate of 30 L / min of 50 ppb of Cu (II) and obtain a treated volume of 2000 L with 2 ppb of Cu (II), a bed with a 1000: 1 ratio of sand will be required: FeSML-Mont clay, intimately mixed, with a total height of 1.75 m, corresponding to one or several columns of 22 cm in diameter.
  • Case 7 A bed with a 1000: 1 sand ratio will be required: FeSML-Sap clay of 1.7 m total height and 21 cm in diameter to treat 15 L / min of 100 ppb of Cu (II) and obtain a treated volume 10000 L with 10 ppb of Cu (II).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

L'invention concerne des procédés d'obtention de matières absorbantes pour l'épuration d'eaux, les matières absorbantes obtenues et leurs applications. L'invention concerne des procédés d'obtention de matières absorbantes à partir de minéraux d'argile, de préférence des smectites, préférablement des smectites dioctahédriques et/ou trioctahédriques, de préférence encore de la montmorillonite et/ou de la saponite, comprenant des étapes suivantes : (1) dispersion et délamination de la matière de départ ; (2) imprégnation des monocouches de la matière de départ avec une solution réactive comprenant des oxydes métalliques ajoutés en quantité égale aux équivalents correspondant à la capacité d'échange cationique calculée pour ladite matière de départ ; (3) décantation et lavage ; (4) séchage et calcination ; et (5) broyage. L'invention concerne également les matières absorbantes obtenus, les matières intermédiaires desdits procédés et les applications de ces matières de départ, intermédiaires ou finales, dans l'épuration ou le traitement des eaux.
PCT/ES2014/000219 2014-12-10 2014-12-17 Procédés d'obtention de matières absorbantes pour l'épuration d'eaux, matières absorbantes obtenues et leurs applications WO2016092123A1 (fr)

Applications Claiming Priority (2)

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ESP201401005 2014-12-10
ES201401005A ES2532520B1 (es) 2014-12-10 2014-12-10 Métodos de obtención de materiales absorbentes para depuración de aguas, materiales absorbentes obtenidos v aplicaciones de los mismos

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WO2016092123A1 true WO2016092123A1 (fr) 2016-06-16

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005102930A1 (fr) * 2004-04-26 2005-11-03 Albemarle Netherlands B.V. Procede de preparation d'une argile anionique contenant un additif
ES2332651T3 (es) * 2003-11-20 2010-02-10 S.A. Minera Catalano-Aragonesa Composicion ecologica para el tratamiento y purificacion de aguas residuales.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2332651T3 (es) * 2003-11-20 2010-02-10 S.A. Minera Catalano-Aragonesa Composicion ecologica para el tratamiento y purificacion de aguas residuales.
WO2005102930A1 (fr) * 2004-04-26 2005-11-03 Albemarle Netherlands B.V. Procede de preparation d'une argile anionique contenant un additif

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HUANG, SHU ET AL.: "Complexes of polydopamine-modifiedclay and ferric ions as the framework for pollutant-absorbingsupramolecular hydrogels.", LANGMUIR, vol. 29, no. 4, 2013, pages 1238 - 1244 *
SÁNCHEZ MOTTA, TATIANA ET AL.: "Utilización of microondasy ultrasonidos in the preparación of hectoritas mesoporosaspara su aplicación como soportes of catalizadoresde cobre in the reacción catalítica of hidrogenólisisde glicerol a 1, 2-propanodiol.", TESIS DOCTORAL UNIVERSITATROVIRA I VIRGILI., 16 October 2014 (2014-10-16), Retrieved from the Internet <URL:http://global.tesisenred.net/handle/10803/52797> *

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ES2532520B1 (es) 2015-12-22

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