WO2018115560A1 - Procédé de fabrication d'argiles anioniques d'aluminium et leurs dérivés à partir de scories salines issues des processus de recyclage de l'aluminium - Google Patents

Procédé de fabrication d'argiles anioniques d'aluminium et leurs dérivés à partir de scories salines issues des processus de recyclage de l'aluminium Download PDF

Info

Publication number
WO2018115560A1
WO2018115560A1 PCT/ES2017/070835 ES2017070835W WO2018115560A1 WO 2018115560 A1 WO2018115560 A1 WO 2018115560A1 ES 2017070835 W ES2017070835 W ES 2017070835W WO 2018115560 A1 WO2018115560 A1 WO 2018115560A1
Authority
WO
WIPO (PCT)
Prior art keywords
aluminum
solution
aqueous solution
salt
divalent metal
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/ES2017/070835
Other languages
English (en)
Spanish (es)
Inventor
Antonio Gil Bravo
Sophia A. Korili
Ekhine ARRIETA CHANGO
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.)
Universidad Publica de Navarra
Original Assignee
Universidad Publica de Navarra
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 Universidad Publica de Navarra filed Critical Universidad Publica de Navarra
Publication of WO2018115560A1 publication Critical patent/WO2018115560A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite

Definitions

  • the object of the invention relates to the manufacture of anionic aluminum clays and their derivatives from salt slags from the aluminum recycling processes.
  • the synthesis process will be carried out, directly and hotly using the solution containing Al 3+ , without any conditioning step and applying a new modified coprecipitation method in which pH control is not necessary.
  • the present invention relates to the obtaining of anionic aluminum clays and their derivatives, from aluminum residues, for example salt slags from the second melting processes of aluminum. By chemical attack of these residues, it is possible to extract part of the aluminum that is used directly in hot and without further treatment steps for the synthesis of anionic clays and products derived from Co 2+ , Mg 2+ , Ni 2+ , among others.
  • Salt slags are produced when salts are used to cover molten material mainly from low-quality aluminum scrap and aluminum-rich slags.
  • the molten salt reduces the melting temperature, prevents oxidation of aluminum and allows metal oxides to be easily separated from metal aluminum [2].
  • the average composition of salt slags can be summarized as: 3-9% aluminum metal; various oxides 20-50%, Al 2 0 3 , Na 2 0, K 2 0, Si0 2 and MgO, fraction referred to as non-metallic products; 50-75% fluxes, usually NaCI and KCI; and other compounds in smaller proportion; among them Nal, AI 4 C 3 , AI 2 S 3 , Si 3 P 4 , Na 2 S0 4 , Na 2 S and cryolite [3]. Some of these components result from the reaction with air and moisture, so that their formation could be minimized by good process control.
  • the amount Salt slags generated in these operations can be between 30 and 60% of the metal produced.
  • Both the amount generated, and the composition of the slags can vary widely depending on the material to be melted, the type of oven used and the mode of operation thereof and the composition of the fluxes used, among others [3-1 1]. Due to its composition and possible reaction with water, salt slags from aluminum recycling processes are classified as hazardous waste, code LER (European Waste List) 100308 [12], and must be deposited in controlled landfills or in security deposits
  • pretreatment systems for the materials to be melted such as chip drying systems and deslacado systems applied to beverage containers
  • furnace heating systems preventing the combustion of organic compounds electric heating system, plasma heating systems, electric arc heating systems
  • new smelting furnaces rotary tilting furnaces
  • Shinzato and Hypolito [19] explain that the Aluminum recycling companies in the metropolitan area of Sao Paulo (Brazil) operate using a simple method for the treatment of slags. The slag is initially crushed to release the metal part trapped in the residue. The remaining material is leached with water and the recovered material is sorted by size.
  • Particles larger than 20 mesh that is, particles that do not pass through a mesh with a nominal aperture of 0.841 mm
  • Particles smaller than 20 mesh are sold to steel manufacturers as a refractory product.
  • Liquid waste which is rich in soluble salts, is transferred to the settling tanks to separate the solid fraction. This fraction has a low Al content and is finally disposed in landfills.
  • this type of material is also used to obtain blocks by adding two parts of the residue to one part of cement and four parts of sand. The blocks thus produced have a low compressive strength. López et al.
  • [6] analyze the possibility of producing a mixture of alumina and spinel by sintering the residues produced after leaching of salt slags. Although the treatment seems simple, several stages of separation are necessary, so the overall process has a relatively high technical complexity and economic cost.
  • the process initially involves grinding the slag and carrying out the grain screening, which leads to the recovery of most of the aluminum metal found in the original material.
  • the process continues with leaching with water of the non-metallic part of the slag once it has been ground to a grain diameter of less than 500 ⁇ .
  • the fraction which is not soluble in water is granulated and then calcined at 1500 and C in an oxidizing atmosphere to produce a mixture of a-AI 2 0 3, MgOAI 2 0 3, Si0 2 and CaOAI 2 0 3 * 2Si0 2.
  • sintered materials can be applied in cement and glass smelters, such as refractory materials, mineral wool, abrasives and ceramic fibers.
  • Yoshimura et al. [23] have proposed directly using aluminum slag to replace raw material in obtaining refractories.
  • the use of the non-metallic fraction in the production of mineral wool has been reported by O'Driscoll [24].
  • Mineral wool is an insulation product that plays an important role in the conservation of energy in residential and industrial buildings. These products absorb sound, are not flammable and do not allow the growth of mold or bacteria. All these properties are derived from its structure.
  • mineral wool is manufactured by melting natural rocks (basalt, diabasa, amphibolite) and adding certain fine-tuning materials (limestone, dolomite, as well as olivine) and alumina.
  • the typical chemical composition of mineral wool is in the range of 45-48% Si0 2 ; 18% Al 2 0 3 , 10% Fe 2 0 3 , 10% CaO and 10% MgO.
  • the main source of alumina is bauxite.
  • the alumina recovered from aluminum slags can be a good alternative as a raw material in those formulations of materials that use natural alumina [26]. This is the case of materials from the treatment of salt slags that are marketed under several names.
  • Oxiton® (BUS, Germany) is used as raw material for refractory materials.
  • the mineralogical components of this material are a-AI 2 0 3 and MgO (64-75%), with the following physical properties: a specific density 2.95 g / cm 3 ; particle size between 10 and 20 ⁇ and a melting point greater than 1680 e C.
  • the areas that can be applied include ceramics, refractories, cement, glass, mineral wool, ceramic fibers, cast iron steel and mixtures and abrasives.
  • Oxiton® can replace up to 25% of the alumina used in cement formulations.
  • Valoxy® (RVA, La Vignette, Les Islettes, France), a solid with a chloride content of less than 0.5%, has been used in the synthesis of a borosilicate glass composite material that can be used in a wide range of applications [27].
  • Valoxy® is an aluminum oxide-based material marketed by the company RVA [28] that contains about 70% alumina and is offered as a substitute for bauxite / alumina in non-metallurgical applications such as cement production, binders, bricks, aluminates and refractories. This material is classified by the French environmental authorities as not dangerous. Paval® (Befesa, Sevilla, Spain) has been used as raw material for the manufacture of cement, refractory material and ceramics [29]. It is a solid that contains alumina and halite, and that can be combined with calcium hydroxide to produce a stable and insoluble compound known as Friedel salt ( ⁇ 3 4 ⁇ 2 ⁇ 2 ⁇ 6 ⁇ 10 ⁇ 2 ⁇ ). The material resulting from the cement / waste mixture shows lower mechanical strength and greater total porosity.
  • Bajare et al. [36] have produced light aggregates of expanded clay from a clay with a high carbonate content and varying proportions of non-metallic fraction (from 0 to 37.5%). These aggregates were treated at a temperature between 1 150 and 1270 e C to remove impurities and to produce a material rich in Al 2 0 3 and spinel. The authors observed an important effect of the composition and heat treatment on the properties of the material such as density and porous structure. The results indicate that the bulk density of aggregates at the maximum expansion temperature is between 0.4 and 0.6 g / cm 3 . Valorization of aluminum present in salt slags:
  • the magnesium aluminate In an initial treatment at acidic pH, the magnesium aluminate is dissolved without dissolving by filtration. The pH of the solution is raised between 9.5 and 12 to precipitate the magnesium oxide, which is also filtered off. As the pH of the remaining liquid approaches neutrality, alumina trihydrate precipitates, resulting in a pure product. It is worth highlighting the large number of stages that have this type of treatment, which implies a certain technical complexity and could be an inconvenience from the point of view of its industrialization.
  • Natural clays are components of sedimentary rocks of the earth's crust that are essentially composed of hydrated aluminum / magnesium silicates, laminar or fibrous structure, which may contain other elements such as iron, calcium, sodium, potassium or others. Its great adsorption capacity and its applications in catalytic processes, such as the Houdry process, has been a cause of interest on the part of the industry, which has been developing variants of natural clays. They have advantageous properties such as low cost, versatility of use, simple handling, among others, which make them useful materials to be key parts in environmentally friendly processes.
  • Clays are used for the manufacture of cements, they are used for the degreasing of fabrics and skins, for the discoloration of fats and oils, for oil refining and as a base for paints and rubbers. They have a great importance in agriculture, since many soils contain high amounts of clay materials, which characterizes the key properties of the soil: structure, texture, water retention, etc.
  • Anionic clays are also known as double laminar hydroxides, mixed metal hydroxides or hydrotalcite-type compounds, because the diffraction patterns of many anionic clays are similar to those of the latter mineral. They are laminar materials of similar structure to that of brucite (mineral magnesium hydroxide), in which part of the Mg 2+ cations have been replaced by trivalent Al 3+ cations, which generates an excess load that must be compensated by the incorporation of anions and water in the interlaminar space.
  • brucite mineral magnesium hydroxide
  • interlaminar anions are usually carbonates, but others are also possible, such as N0 3 “ , OH “ , CI “ , Br “ , ⁇ , S0 4 2 “ , Si0 3 2” , Cr0 4 2 “ , B0 3 2 “ , MnO 4 -, HGa0 3 2” , HV0 4 2 “ , CI0 3 ⁇ CI0 4 ⁇ I0 3 ⁇ S 2 0 3 2 -, W0 4 2” , [Fe (CN) 6 ] 3 " , [Fe (CN) 6 ] 4 " , (PMo 12 O 40 ) 3 -, (PW 12 O 40 ) 3 -, V 10 O 26 6 -, Mo 7 0 24 6” , etc.
  • the Mg 2+ cation can be substituted, in part or in its entirety, by other divalent cations, such as: Cu 2+ , Ni 2+ , Zn 2+ , Co 2+ and Ca 2+ , resulting in derivatives of the anionic clays.
  • M (ll) is a divalent cation (Me 2+ )
  • M (lll) is a trivalent cation (Me 3+ )
  • A is a charge anion n
  • x is a rational number between 0.2 and 4, determines the charge density in each layer and the anion exchange capacity
  • n represents the negative electronic charge of the interlaminar anion and is an integer that can vary between -1 to -8
  • m represents the water molecules present as hydration water or as water present in the interlaminar region and is a rational number between 0 and 10, where A, x, n and m are such that the formula meets the rule of neutrality of its total charge.
  • Anionic clays exhibit the ability of anion adsorption and diffusion properties and ion exchange, together with a basic surface that makes them important materials for many current applications, including clinical applications related to controlled drug delivery.
  • Coprecipitation involves the addition of two solutions.
  • One of them contains cationic precursors, that is, the divalent Me 2+ cations (such as Mg 2+ ) together with the trivalent Me 3+ cations (generally Al 3+ ); and the other solution contains the precipitating agent (usually sodium hydroxide) together with a compound containing the interlaminar anion.
  • the precipitating agent usually sodium hydroxide
  • the ratio divalent cation to trivalent cation (Me 2 7Me 3+ ) has a great influence on the properties of the solid, given that instead of the double hydroxide structure the mixture of simple hydroxides can be obtained. Different documents can be found where examples of application of this procedure or variants thereof are given.
  • U.S. Pat. US4454244 refers to synthetic minerals formed by expanded layers that are the product of anion exchange reactions between certain layered minerals and polyanions, as well as the methods for the production of said minerals.
  • Example 3 of said document describes a process in which two solutions are prepared, a first solution containing the divalent cations Mg 2+ and Zn 2+ and the anion N0 3 " , and a second alkaline solution (NaOH) acting as The two solutions are mixed by adding them dropwise simultaneously to a container while maintaining the pH at approximately 10.
  • a solid is obtained which after its separation, washing and drying is said to correspond to a material whose formula is indicated as Zn x Al y (OH) 2x- + 3y-nz-z (N0 3 ) .tH 2 0, and whose structure is hydrotalcite type.
  • U.S. patent application Published under US2005261381 A1 refers to compositions of nanoparticles of anionic clays, stable colloidal dispersions of nanoparticles of anionic clays and methods for preparing the latter. The possibility of mixing saline solutions of metal cations with a base in the high shear mixing zone is considered.
  • Example 4 the mixed solution containing the metal salts (Mg (N0 3 ) 2 and AI (N0 3 ) 3 ) is initially added to the particle formation vessel and subsequently added dropwise. drop the basic solution of NaOH, with vigorous stirring, until the pH becomes 10, continuing with stirring and then let stand.
  • Example 6 which is described herein as coprecipitation synthesis, the addition to the vessel of the mixed solution with the metal salts and the addition of the NaOH precipitating solution are performed simultaneously and dropwise; The NaOH solution is added in sufficient proportion to keep the pH near 10.
  • Galindo and collaborators [45] have proposed a process for the preparation of hydrotalcite-like materials in which waste from the aluminum tertiary industry is started, specifically fine dust dispersions from the bag filters used in management of the gaseous effluent that is produced in the milling of aluminum slags.
  • the authors prepare stable solutions of Al 3+ from said dispersions and undergo their conventional coprecipitation process at pH 10 with magnesium chloride hexahydrate.
  • the structure of the materials obtained is generally of low crystallinity, with the presence of small spherical agglomerates due to the synthesis carried out, their properties depend on the presence of iron, as well as on the carbonate and chloride content.
  • the present invention provides a solution to that problem.
  • the present invention is based on a process of preparing anionic clays of divalent cations, Me 2+ , and containing Al 3+ as a trivalent cation, by a modified coprecipitation process.
  • the proposed method is based on an aqueous solution containing aluminum that comes from the attack, with acid or basic solutions, of salt slags generated in the recycling of scrap and aluminum by-products.
  • the process of the invention is a modified coprecipitation process in which a solution containing the divalent cation Me 2+ is prepared separately together with the precipitating agent and the anion intended to compensate for the laminar load.
  • the invention relates to a method for the preparation of anionic clays from salt slags from aluminum recycling processes comprising the steps of: a) contacting the salt slag with an aqueous solution acidic or basic; b) let the solution react with the salt slag; c) separating the salt slag from the aqueous solution with resulting Al 3+ ; d) add the aqueous solution of step c), dropwise and hot, onto a solution containing divalent cations together with a precipitating agent and the anions intended to occupy the interlaminar zone; e) Allow to react at least until the solution is finished adding with the aluminum and for a maximum of 6 hours.
  • the method comprises the additional steps of: f) separating the solid formed in e) from the supernatant; g) subject the solid obtained in f) to heat treatment.
  • the invention relates to an anionic clay obtained by the above method.
  • Fig. 1 N 2 adsorption-desorption isotherms of Ni: AI anionic clays with a 2: 1 molar ratio, treated at various heating temperatures, 200, 300 and 400 e C.
  • Fig. 2 Difractog X-ray branches representative of the anionic clays of Ni: AI and Co: AI synthesized with a 2: 1 molar ratio.
  • Fig. 3 Adsorption-desorption isotherms of N 2 of the anionic clays of Co: AI with a 2: 1 molar ratio, treated at various heating temperatures, 200, 300 and 400 e C.
  • the present invention comprises a new method of synthesis of anionic clays that directly and hotly uses the aqueous solution from the extraction of Al 3+ from a salt slag.
  • the starting material saline slag
  • solutions of acids or bases to extract aluminum, taking into account the time and temperature of treatment as variables.
  • This first stage of treatment of the starting material was already described in a previous patent, specifically the Spanish Patent ES2350435 [47], directed to the use of the salt slag once treated.
  • said treatment conditions were used to activate a residue from the aluminum industry, specifically a salt slag from a second fusion process of aluminum, and use it as an adsorbent.
  • the aluminum extracted in this activation process is used for use in the synthesis of other products, using the solution obtained as supernatant directly and hot in the process of activating the residue.
  • the conventional method of coprecipitation, by which an anionic clay can be obtained from an aluminum solution is not applicable in this case.
  • the solution containing the aluminum also contains the divalent cation together with the anion intended to compensate for the laminar load, while the precipitating agent (generally sodium hydroxide) is supplied from another solution.
  • the precipitating agent generally sodium hydroxide
  • the invention requires a modification of the coprecipitation method, according to which the solution containing the divalent cation together with the precipitating agent and the anion intended to compensate for the laminar load is prepared separately. It is this solution that is reacted by adding on it drop by drop, hot, the supernatant containing Al 3+ as it has been obtained from the salt slag, without any intermediate preparation step, with the additional advantage that it is not necessary to control the pH of the reaction, unlike previously established methods.
  • This procedure allows to reduce the number of stages necessary for the synthesis of the hydroxide, since all the methods known in the state of the art require one or more intermediate stages in which the aluminum is separated from the solution containing it, in the form of some salt, before it can be used in the synthesis of hydroxide. In addition, it does not require pH control during mixing and resting of the coprecipitating solutions.
  • the aluminum extraction process as already mentioned, was described in Spanish patent ES2350435 and consists in contacting an aluminum salt slag with an aqueous, acidic or alkaline solution. The conditions under which this stage of contact with the slag or extraction of aluminum can be carried out can be any, as long as they give rise to the extraction of aluminum.
  • the temperature of the contact process is generally the ambient temperature, but it can be in the range between 20 e C and the reflux temperature, which will be about 100 e C at a pressure of 101, 33 kPa (1 atmosphere).
  • the pressure at which this stage is carried out may be atmospheric pressure, but it can also be carried out at higher pressures.
  • the contact time depends largely on the reaction temperature, but is generally in the range of 0 to 2 hours.
  • this extraction stage a) is carried out in a container with stirring although, optionally and / or after a first stirring step, it can be carried out under reflux conditions.
  • the salt slag be a slag from a second melting process of aluminum, with special preference for slags coming from a rotary kiln of fixed axis, and especially when they have an equal size or less than 1 mm.
  • the process of the present invention can also be applied to salt slags from other processes related to aluminum, these other alternatives being included within the scope of the invention.
  • the ratio between the amount of saline slag and the volume of acidic or basic aqueous solution with which it is contacted in step a) may be between 10 g / liter and 100 g / liter. It is considered appropriate to contact, for example, 2 g of saline slag with 0.2 liters of aqueous, acidic or basic solution, as in the Examples of the present application.
  • the most important are the pH of the activation solution, the concentration of the chemical agents, the time and the contact temperature.
  • the pH of the extraction solution is less than 2 or greater than 10, although it depends on the concentration of the acid or base. Specifically, the concentration of acids and bases used in this work varied between 0 and 2 mol / liter, obtaining that a greater amount of extracted aluminum is obtained when concentrations of 2 mol / liter are used.
  • concentrations of the acidic or alkaline aqueous solution concentrations of 2 mol / liter or less are preferred.
  • the acids can be organic or mineral origin, such as nitric (HN0 3 ), sulfuric (H 2 S0 4 ) or hydrochloric (HCI) acids.
  • HN0 3 nitric
  • sulfuric H 2 S0 4
  • HCI hydrochloric
  • sodium hydroxide stands out, but others, such as sodium bicarbonate (NaHC0 3 ), can also be used, which results in alkaline pH closer to neutrality. , about 8.
  • the extraction temperature it may be between room temperature and reflux temperature, but the latter is preferable since the amount of aluminum extracted is greater.
  • the salt slag is removed from the solution with which the aluminum has been extracted in the form of Al 3+ cations.
  • any separation technique such as filtration, centrifugation, supernatant decantation can be used after resting the salt slag mixture and dissolution and the like.
  • the use of filtration is preferred.
  • the extracted aluminum is used in step c) of the process of the invention for the synthesis of anionic clays. Said synthesis is carried out according to this invention, using directly and hotly the solution in which the aluminum has been extracted, without any conditioning step, this new method being the main object of the invention, as explained above.
  • the temperature range in step c) in which this process could be used without additional heating of the solution containing the extracted Al 3+ would be between 40 and 60 e C.
  • the solution containing Al 3+ is reacts with a solution of a divalent metal that also contains a precipitating agent and an anion intended to compensate for the laminar charge. In the case of using a lower extraction temperature, the amount of aluminum extracted will be much lower.
  • the amount of anionic clay that can be synthesized will also be smaller or it will be necessary to increase the volume of the equipment since the volume of the solutions to maintain the yields will also be greater. In this second case, the volume of water to be managed will increase. It should also be noted that an additional heating step of the solution containing Al 3+ , up to at least 40-60 e C, will be necessary, since the reaction for obtaining the anionic clay must be hot. Therefore, the temperature of the solution containing the divalent metal, the precipitating agent and the anion should also be at least 40-60 e C when Al 3+ is added and must be maintained at least at that temperature during the time of reaction between Al 3+ and the other reagents that give rise to anionic clay.
  • this reaction consists in adding dropwise, and preferably under stirring, the solution containing Al 3+ on a solution containing the divalent metal cation (Me 2+ ) together with the agent precipitant and the anion.
  • the precipitating agent is preferably sodium hydroxide, although others may be used, including ammonium hydroxide and triethanolamine;
  • the anion is preferably carbonate (C0 3 2+ ), although they may be others, such as those that are usually involved in the composition of materials called anionic clays, double lamellar hydroxides, mixed metal hydroxides or hydrotalcite-type compounds, such as they can be: N0 3 " , OH “ , CI " , Br, ⁇ , S0 4 2” , Si0 3 2 " , Cr0 4 2” , B0 3 2 " , MnO 4" , HGa0 3 2 " , HVC 2” , CI0 3 " CI0 4 " I0 3 " S 2 0 3 2” , W
  • the divalent metal cation it is preferred that it be selected from the group of Co 2+ , Ni 2+ , Mg 2+ or Zn 2+ , although it can also be Cu 2+ , Mn 2+ , Ba 2+ , Fe 2+ , Ca 2+ or other divalent metal cations.
  • the solution containing the divalent metal, together with the precipitating agent and the anion, is preferably prepared once the concentration of aluminum in the extraction solution is known, by choosing the concentration of the salt of the metal cation in order to obtain solid with the desired Me 2 7AI 3+ ratios. Preference is given to the range of ratios used in the Examples of the present invention, that is, Me 2 7AI 3+ molar ratios between 2: 1 and 4: 1, both values included.
  • the reaction time between the solutions may vary, although it is considered appropriate that it is comprised between at least until the solution has been added with the solution. aluminum and up to a maximum of 6 hours, preferably between 1 and 6, as in the examples of the present application.
  • the reaction is carried out under stirring, it being recommended that the stirring speed be in the range between 100 and 700 rpm.
  • the method of the invention include further steps in which the clay is separated from the supernatant and subjected to heat treatment.
  • the separation of the anionic clay from the supernatant can be carried out by filtration, centrifugation or decantation with filtration being preferred.
  • the subsequent heat treatment preferably consists in subjecting it to a temperature between 50 and 400 e C, preferably in the range of 200 e C to 400 e C, for a time between 0.1 and 100 hours, the most usual between 0.5 and 48 hours.
  • the present invention also relates to the anionic clays obtained by the method of the present invention.
  • Said clays respond to the formula [Me (ll) 1 - x Me (lll) x (OH) 2 (A n " ) x / n] -mH 2 0, where
  • M (ll) is a divalent cation (Me 2+ )
  • M (lll) is Al 3+
  • A is a charge anion n
  • x is a rational number between 0.2 and 4, determines the charge density in each layer and the anion exchange capacity
  • n represents the negative electronic charge of the interlaminar anion and is an integer which can vary between -1 and -8
  • m represents the water molecules present as hydration water or as water present in the interlaminar region and is a rational number between 0 and 10, where A, x, n and m are in such a way that the formula meets the rule of neutrality of its total load.
  • anionic clays that comprise Al 3+ cations and divalent metal cations, and anions and water in the interlaminar space.
  • its specific surface area varies between 19 and 281 m 2 / g and its total pore volume is between 0.045 and 0.685 cm 3 / g. This degree of porosity makes them suitable for use in catalytic and adsorption processes.
  • Example 1 Obtaining anionic clays of Ni
  • a salt slag from a rotary kiln with a fixed axis and of a size smaller than 1 mm was used for the extraction of aluminum by chemical agents.
  • the amount of aluminum extracted was analyzed by ICP-radial and is between 3 and 1609 mg A
  • Ni anionic clays were prepared from aqueous solutions of Ni (N0 3 ) 2 -6H 2 0 (PA, Panreac) and Na 2 C0 3 (Sigma-Aldrich) in order to obtain solids with molar ratios Ni 2 7AI 3 + between 2: 1 and 4: 1 (see Table 2).
  • the solution with extracted aluminum was added dropwise and under stirring at 500 rpm, to the solution resulting from dissolving nickel nitrate and sodium carbonate.
  • the temperature and reaction time were 60 e C and 1 h.
  • AI_2 1 2: 1 6495 mg / liter 12990 mg / liter 0.8 mol / liter 0.19 mol / liter
  • AI_4 1 4: 1 6564 mg / liter 26256 mg / liter 0.8 mol / liter 0.19 mol / liter
  • the suspensions were filtered to separate the solid from the solution.
  • the textural properties of the solids obtained were determined by adsorption of N 2 (Air Liquide, 99.999%) at -196 e C in a commercial static volumetric equipment (ASAP 2010 of the Micromeritics commercial house).
  • the solids were previously degassed for 24 h and at a pressure below 0.1 Pa.
  • the amount of solid used in the experiment was 0.2 g.
  • the adsorption of N 2 provides a series of quantitative properties such as surface area and pore volume.
  • the surface area can be calculated by applying the BET equation [48]: plp ° 1
  • the surface area of the slag can be calculated using the equation: S being the surface area, V m the monolayer volume, to the area occupied by a molecule of N 2 adsorbed on the clay surface (16.2 ⁇ 2 / molec), N A Avogadro's number (6.023-10 23 molec / mol) and V the volume occupied by one mole of N 2 at 25 e C and 1 atmosphere (22,386 cm 3 / mol).
  • Total pore volumes (Vp To tai) are estimated from the volumes of N 2 adsorbed at a relative pressure value of 0.99 [48], assuming that the density of nitrogen in the pores is equal to that of nitrogen liquid at -196 e C (0.81 g / cm 3 ) [48].
  • Fig. 2 The X-ray diffraction results included in Fig. 2 confirm the obtaining of Ni anionic clays. Therefore, the method presented in this invention makes it possible to obtain anionic clays from aluminum extracted from residues from the aluminum industry. In the case of the textural results included in Table 3, the method presented in this invention also allows to obtain solids with high values of specific surface area and pore volume, solids that will be suitable for application as adsorbents and as catalysts.
  • the anionic clays of Co were prepared from aqueous solutions of Co (N0 3 ) 2 -6H 2 0 (99%, Sigma-Aldrich) and Na 2 C0 3 (Sigma-Aldrich) in order to obtain solids with Co molar ratios 2 7AI 3+ between 2: 1 and 4: 1 (see Table 4).
  • the solution with extracted aluminum is added dropwise and under stirring, to the solution resulting from dissolve nickel nitrate and sodium carbonate.
  • the temperature and reaction time were 60 e C and 1 h.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Le procédé selon la présente invention permet d'utiliser directement l'aluminium extrait à l'aide de solutions acides ou basiques de scories salines issues de processus de recyclage de l'aluminium dans la synthèse d'argiles anioniques, avec un nombre réduit d'étapes, par addition goutte à goutte, à chaud, de la solution ayant servi à extraire l'aluminium à une solution contenant le cation métallique divalent, l'anion interlamellaire et un agent précipitant, les argiles anioniques se formant à partir de celles-ci. Le procédé permet entre autres d'obtenir des argiles anioniques d'aluminium et de Co2+,Mg2+, Ni2+ ou Zn2+, avec du carbonate en tant qu'anion interlamellaire. Les matières obtenues présentent une surface spécifique pouvant atteindre 290 m2/g et un volume de pores pouvant atteindre 0,700 cm3/g.
PCT/ES2017/070835 2016-12-22 2017-12-20 Procédé de fabrication d'argiles anioniques d'aluminium et leurs dérivés à partir de scories salines issues des processus de recyclage de l'aluminium Ceased WO2018115560A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ESP201631655 2016-12-22
ES201631655A ES2673587B2 (es) 2016-12-22 2016-12-22 Procedimiento de fabricación de arcillas aniónicas de aluminio y sus derivados a partir de escorias salinas procedentes de los procesos de reciclaje del aluminio

Publications (1)

Publication Number Publication Date
WO2018115560A1 true WO2018115560A1 (fr) 2018-06-28

Family

ID=62573026

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/ES2017/070835 Ceased WO2018115560A1 (fr) 2016-12-22 2017-12-20 Procédé de fabrication d'argiles anioniques d'aluminium et leurs dérivés à partir de scories salines issues des processus de recyclage de l'aluminium

Country Status (2)

Country Link
ES (1) ES2673587B2 (fr)
WO (1) WO2018115560A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2803955B2 (es) * 2019-07-26 2021-12-21 Univ Navarra Publica Hexaaluminatos con propiedades texturales mejoradas, preparación de los mismos a partir de escorias salinas procedentes de los procesos de reciclaje del aluminio y su uso
ES2919251B2 (es) * 2021-01-22 2023-04-20 Univ Navarra Publica Arcillas pilareadas con propiedades texturales mejoradas, preparación de las mismas a partir de escorias salinas procedentes de los procesos de reciclaje del aluminio y su uso

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4454244A (en) * 1983-03-28 1984-06-12 Ashland Oil, Inc. New compositions
US20050261381A1 (en) * 2004-05-20 2005-11-24 Eastman Kodak Company Nanoparticulate anionic clays

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4454244A (en) * 1983-03-28 1984-06-12 Ashland Oil, Inc. New compositions
US20050261381A1 (en) * 2004-05-20 2005-11-24 Eastman Kodak Company Nanoparticulate anionic clays

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GALINDO R ET AL.: "Hydrotalcite-like compounds: A way to recover a hazardous waste in the aluminium tertiary industry", APPLIED CLAY SCIENCE, vol. 95, 21 May 2014 (2014-05-21), AMSTERDAM, NL, pages 41 - 49, XP028850501, ISSN: 0169-1317 *
GALINDO R ET AL.: "Synthesis and characterization of hydrotalcites produced by an aluminium hazardous waste: A comparison between the use of ammonia and the use of triethanolamine", APPLIED CLAY SCIENCE, vol. 115, 1 August 2015 (2015-08-01), AMSTERDAM, NL, pages 115 - 123, XP029261445, ISSN: 0169-1317 *

Also Published As

Publication number Publication date
ES2673587A1 (es) 2018-06-22
ES2673587B2 (es) 2018-10-03

Similar Documents

Publication Publication Date Title
Gil et al. Management and valorization of aluminum saline slags: Current status and future trends
He et al. Hazard-free treatment of electrolytic manganese residue and recovery of manganese using low temperature roasting-water washing process
Tsakiridis et al. Aluminium recovery during black dross hydrothermal treatment
Tsakiridis Aluminium salt slag characterization and utilization–A review
Sadik et al. Review on the elaboration and characterization of ceramics refractories based on magnesite and dolomite
ElDeeb et al. Solid state and phase transformation mechanism of kaolin sintered with limestone for alumina extraction
Chatterjee Uses of metals and metallic minerals
NO314034B1 (no) Fremgangsmåte for fremstilling av en sintret blanding av materiale som hovedsakelig består av kalsiumaluminater
Taha et al. Manufacturing of ceramic products using calamine hydrometallurgical processing wastes
Kelmers et al. Chemistry of the direct acid leach, calsinter, and pressure digestion-acid leach methods for the recovery of alumina from fly ash
Benkhelif et al. Synthesis of pure magnesium aluminate spinel (MgAl2O4) from waste aluminum dross
Abi et al. Production of forsterite from serpentine–Effects of magnesium chloride hexahydrate addition
ES2630116T3 (es) Materia prima con alto contenido en alúmina y procedimiento para su fabricación
ES2673587B2 (es) Procedimiento de fabricación de arcillas aniónicas de aluminio y sus derivados a partir de escorias salinas procedentes de los procesos de reciclaje del aluminio
CN121335873A (zh) 用于生产碳酸盐结合的压实制品的方法
Chafia et al. Synthesis of high purity magnesia MgO from Algerian dolomite ore
Lukita et al. Utilization of hazardous waste of black dross aluminum: processing and application-a review.
ES2803955B2 (es) Hexaaluminatos con propiedades texturales mejoradas, preparación de los mismos a partir de escorias salinas procedentes de los procesos de reciclaje del aluminio y su uso
Oliveira et al. Novel mullite-based ceramics manufactured from inorganic wastes: I. Densification behaviour
Liu et al. Tailoring Aluminosilicate Reactivity in Red Mud via Sodium-Activated Carbothermic Reduction for Hydrothermal Extraction Applications
KR20170140900A (ko) 슬래그로부터 유용금속 및 비정질실리카 회수방법
Mustafa et al. Preparation of high purity magnesium oxide from sea bittern residual from NaCl production in Al-Basrah saltern, south IRAQ
KR101179189B1 (ko) 로터리 킬른을 이용한 ｃ12ａ7계 광물의 제조방법
ES2978735B2 (es) Método de obtención de un precursor sólido para filtros cerámicos a partir de escorias de aluminio procedentes de los procesos de reciclaje y productos obtenidos
Ju et al. Extraction of valuable metals from acidic wastewater and blast furnace slag by a collaborative utilization process

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17885361

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17885361

Country of ref document: EP

Kind code of ref document: A1