WO2014131950A1 - Préparation de particules de sels à partir de carbonate de calcium précipité - Google Patents

Préparation de particules de sels à partir de carbonate de calcium précipité Download PDF

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WO2014131950A1
WO2014131950A1 PCT/FI2014/050150 FI2014050150W WO2014131950A1 WO 2014131950 A1 WO2014131950 A1 WO 2014131950A1 FI 2014050150 W FI2014050150 W FI 2014050150W WO 2014131950 A1 WO2014131950 A1 WO 2014131950A1
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salt
particles
starting material
solvent
gas
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PCT/FI2014/050150
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English (en)
Inventor
Steliana Aldea
Kari ERÄNEN
Henrik GRENMAN
Jyri-Pekka Mikkola
Dmitri MURZIN
Tapio Salmi
Johan WÄRNÅ
Mats FAGERHOLM
Mathias SNÅRE
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Nordkalk Oy Ab
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Publication of WO2014131950A1 publication Critical patent/WO2014131950A1/fr

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    • 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
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • 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
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
    • C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • the present invention concerns a process for producing precipitated salts from starting materials including ions of alkali metals, earth alkali metals or transition metals in solvent media containing a neoteric solvent, particularly by precipitating these salts from said solvent media.
  • Precipitated calcium carbonate is a highly desired material due to its wide range in the industrial application field. For example, it is used as a pigment, filler or extender in the production of paper, plastics, paints, adhesives, textiles, detergents, pharmaceuticals, cosmetics or food.
  • the various applications are strictly defined by the characteristic properties of the material prepared, such as average particle size, particle size distribution, specific surface area, morphology or chemical purity.
  • the physicochemical properties of PCC are highly influenced by different synthesis procedures, methods or synthesis conditions.
  • Inorganic calcium hydroxide is leached from carbide slag waste from industrial processes to provide a starting product for the preparation of calcium carbonate as is disclosed in CN 01891229.
  • Another particular aim of the invention is to provide a process for producing also such precipitated particles that are poorly dissolved in water.
  • the present invention introduces molten salts or analogs thereof, such as ionic liquids, low-temperature molten salts or eutectics, or the equivalents or mixtures thereof, as alternative solvents in the production of precipitated calcium carbonate (PCC).
  • PCC precipitated calcium carbonate
  • the invention also introduces said molten salts or analogs, equivalents or mixtures thereof as alternative solvents in the production of alternative precipitated salts.
  • the exemplary ionic liquids are simply such molten salts that are liquid at temperatures below 150°C (some varieties even at room temperature) that present an advantageously wide liquidus range.
  • Most ionic liquids are composed from an organic cation and an inorganic or organic polyatomic anion. The great number of possible cation-anion combinations gives this class of materials its unlimited potential and dissolution
  • the present invention relates to a process for producing precipitated product particles, which contain salts formed from the ions of a starting material, such as precipitated calcium carbonate (PCC), and optionally from the ions of a solvent salt, wherein a slurry formed through the dissolution of the starting material in a solvent system containing at least one molten solvent salt, is subjected to a precipitation, whereby final product particles are formed.
  • a starting material such as precipitated calcium carbonate (PCC)
  • PCC precipitated calcium carbonate
  • the process of the present invention for producing precipitated product salt particles is characterized by what is stated in the characterizing part of Claim 1.
  • Considerable advantages are obtained by means of the invention.
  • this alternative process is simple and more compact than existing processes, and is capable of utilizing existing equipment, such as an only slightly modified PCC reactor.
  • the product salt can be recovered as crystals with novel morphologies that can give rise to entirely new products, including surface-modified particles.
  • the invention provides the possibility to use a wide range of solvents in the precipitation and the preceding dissolution step, which solvents can be recycled in the same process, and which solvents provide an improved dissolution of also those starting materials that dissolve poorly or not at all in water.
  • molten salts capable of dissolving significant amounts of various minerals, and using processes that can reprecipitate the extracted salt, for example as nano- particles with desired properties, eliminates the high energy consuming kiln-treatment of lime, the waste production and the C0 2 emissions commonly linked to the precipitation of the exemplary product, calcium carbonate.
  • molten salts also known as ionic liquids, as solvents provides a means for dissolving minerals that are hardly water soluble and to dissolve them at low temperatures, even at room temperature.
  • the preferred ionic or mixed ionic molecular solvent present many characteristics that are interesting for a wide variety of industrial fields, such as frequent low vapor pressures (they do not produce VOC's, no loss by evaporation), non-flammable (though other examples exist), can be recycled, and are considered "supersolvents" for many classes of organic/inorganic compounds (some can dissolve cellulose or sulfidic and other ore metals) and many common gases (e.g. S0 2 and C0 2 ).
  • gaseous C0 2 can be employed in the recovery/preparation of the recycled ionic liquids.
  • Figure 1 shows the dissolution rate of CaC0 3 in (a) 25 wt. % hydroxyethyl ammonium formate aqueous solution (dissolution conditions: 25°C, 1020 rpm, 24h, under 2 bar N 2 or C0 2 ) and (b) 85 wt. % hydroxyethyl ammonium lactate aqueous solution (dissolution conditions: 50°C, 1020 rpm, 24h, under 2 bar N 2 or C0 2 ).
  • Figure 2 shows SEM images of particles recovered from (a) CaC0 3 /l-ethylimidazolium hydrosulphate and (b) CaC0 3 /l -methyl pyrazolium tetrafluorob orate.
  • Figure 3 shows SEM images of particles recovered from CaCCVCholine chloride - oxalic acid deep eutectic system, treated at rt (a), 50°C (b) and 70°C (c). Inlets in the images represent a higher magnification of the same material.
  • the present invention concerns a process for producing precipitated mineral salts, particularly calcium salts (e.g. calcium carbonate), from a slurry formed through the dissolution of a starting material in a solvent system in a reaction zone, using molten salts (particularly ionic liquids) as solvents of said system.
  • precipitated mineral salts particularly calcium salts (e.g. calcium carbonate)
  • molten salts particularly ionic liquids
  • solvent salts are capable of actively taking part in the reaction in the process, if that is desired and the process conditions are selected to favor such a reaction.
  • the precipitated mineral product salts can be formed from the ions of the starting material and optionally from the ions of the solvent salt(s).
  • the solvent salts that have not taken actively part in the precipitation reaction are preferably recirculated and reused.
  • One embodiment of the invention relates to a process for producing such precipitated salts from starting materials containing alkali metals, earth alkali metals or transition metals, wherein a slurry containing the metals is formed in a dissolution step using a molten salt as a so-called enabling solvent of the slurry, followed by precipitation of product particles containing at least one product salt, either as pure particles or as particles having a chemically or structurally modified surface.
  • the "chemical modification” is intended to mean that one type of metal salt is attached to the surface of another, while the term “structurally modified” is intended to include surfaces modified by coating, by partial dissolution of the particle raw material or by reprecipitation of the particles. These types of modifications can be used to give particle surfaces with, for example, high porosity.
  • suitable metals of the salts of the starting material are alkali metals and earth alkali metals, as well as their co-salts and mixtures, particularly selected from the group of sodium, calcium, magnesium, manganese and cadmium.
  • these are selected from earth alkali metal ions, more preferably from calcium and magnesium ions, most suitably being calcium ions.
  • the starting material is obtained from or is a source material selected from limestone (particularly crystalline limestone), recycled calcium carbonate or waste material rich in calcium minerals, preferably from limestone, most suitably from a mineral material rich in calcium carbonate.
  • the salt of the starting material is a naturally occurring compound.
  • the salt of the starting material has a solubility in water in the range of 0.001 - 0.100 g/100 ml H 2 0, preferably 0.010 - 0.075 g/100 ml H 2 0, particularly preferably 0.012 - 0.05 g/100 ml H 2 0, and as such can be described as hardly soluble in water.
  • the salt of the starting material is insoluble in water
  • the starting material is a naturally occurring compound that is, in a preferred embodiment hardly soluble in water. In a particularly preferred embodiment the starting material is insoluble in water.
  • slurry is intended to include suspensions, dispersions, solutions, liquids and mixtures, which are at least partially in liquid form and which contain one or more solvents.
  • the source or starting material in the form of a powder or granules, can be mixed with the solvent to form batches of said slurry.
  • the solvent can be continuously conveyed through the solid raw material, thus providing a continuous stream of the formed slurry.
  • the process can be operated batchwise or continuously.
  • the concentration of metals or metal ions in the formed slurry is 0.05 to 10 %, preferably 0.1 to 5 %, more preferably 0.5 to 2%, and most suitably 0.5 to 1%, calculated from the total weight of the slurry. These concentrations are very high, since for example, even the smallest concentration of 0.05 % by weight is (for calcium) about 70 times higher than its solubility in water.
  • additional co-solvent can be separately fed into the reaction zone.
  • the solvent used to form the slurry in the process is generally a solvent media or solvent system containing one or more neoteric solvents.
  • this solvent system includes the above described molten salts or analogs thereof, such as ionic liquids, low-temperature molten salts or eutectics, or the equivalents or mixtures thereof.
  • At least one of the solvents of this system is a so-called "enabling solvent", which is intended to mean the solvent that is capable of reacting with the source or starting material, and thereby functionalizes the solvent system.
  • said solvent system can be formed from one or more solvents.
  • the enabling solvent is formed of one or more of said molten salts.
  • Additional co-solvents can be selected from any common solvents, particularly being polar organic solvents or water.
  • the above described molten salt is preferably an ionic liquid.
  • "Ionic liquids” are molten salts that are liquid at temperatures that are suitable for the dissolution of mineral salts, preferably below 150°C (some varieties even at or below room temperature), and that present a wide liquidus range. These ionic liquids include zwitterionic solvents, "self- associated” distillable ionic media and deep eutectic solvents.
  • the molten salts are preferably formed by a combination of an organic cation and a polyatomic anion, the latter being inorganic or organic, preferably inorganic.
  • the cation is typically selected from organic hydrocarbons having 1 to 15 carbon atoms and containing at least one heteroatom that is easily protonated, such as nitrogen, sulphur or phosphorous.
  • suitable cations for use as components in the ionic liquid are organic ammonium ions, optionally containing further heteroatoms, such as the
  • aromatic ammonium ions such as ions based on pyridines, pyrimidines, pyrazines, pyridazines, pyrazoles, imidazoles and their polyaromatic varieties, as well as their non-aromatic variants, such as ions based on piperidine and pyrrolidine.
  • aromatic variants are, however, more preferred.
  • Suitable anions for use as components in the molten salts are the inorganic ions of halogens, nitrates, phosphates, borates, sulfides and silicates, but also organic anions, such as carboxylates can be used., e.g. formate, lactate or acetate.
  • Preferred anions are borates and carboxylates, the latter most suitably being formate or lactate.
  • ionic liquids for use in the present process are N-methyl- bis-(2-hydroxyethyl) ammonium formate (MDEAF), bis-(2-hydroxy ethyl) ammonium formate (DHEAF), hydroxyethyl ammonium formate (HEAF) and 2- hydroxyethylammonium lactate (HEAL).
  • MDEAF N-methyl- bis-(2-hydroxyethyl) ammonium formate
  • DHEAF bis-(2-hydroxy ethyl) ammonium formate
  • HEAF hydroxyethyl ammonium formate
  • HEAL 2- hydroxyethylammonium lactate
  • the molten salt is mixed with water or another polar solvent, i.e. forming a type of solvent system.
  • the water used can be conventional process water, optionally deionized by conventional means.
  • the water content is preferably maintained below 50% of the total amount of solvent, particularly below 40%, in order to keep the water content sufficiently low to avoid a
  • the dissolution step to form said slurry is preferably carried out by dissolving the starting material in said solvent system at room temperature or a slightly elevated temperature using moderate stirring.
  • the dissolution step (and any other steps of the process of the invention at least up to the precipitation or reprecipitation of the product) is carried out at a temperature below 150 °C, preferably between 10 and 100 °C. If possible, a temperature close to room temperature is maintained. However, any temperature, where the solvent is in a molten state while not destroying the starting material can be used, such as between 50 and 100 °C.
  • the pressure is particularly 0.1 to 25 bar, preferably 0.5 to 10 bar, whereby an elevated pressure can be obtained for example using a N 2 or C0 2 purge.
  • the dissolution rate is generally 5 to 25 g/L/h (typically about 15g/L/h). However, this rate depends on, among others, the particle size, the mixing, and the temperature.
  • a chemical or physical treatment of the formed slurry is carried out after said dissolution step.
  • the possible treatments include a temperature change, a pressure change, a change in the pH of the liquid, a centrifugation and an acid-gas treatment, using e.g. C0 2 , S0 2 , NO x -gases and halogen-containing gases, typically C0 2 -containing gases.
  • the aim of this step is to guide the balance of the chemical equation of the formation of the final product salt particles towards the formation of the particular desired salt, or to simply facilitate the following precipitation, or to speed up the reactions.
  • the equilibrium of the formation of the product salt particles can be guided towards the reprecipitation of particles of the mineral salt of the starting material (here represented by calcium carbonate), or towards the precipitation of salts containing ions of the solvent salt(s) (the solvent ions here represented by the terms caf and an , but they are not necessarily monovalent):
  • the possible optional acid-gas treatments include the conventional carbonation reaction, in which C0 2 gas is introduced into the slurry, dissolves and reacts to form carbonate.
  • a further solvent can be utilized after the carbonation to facilitate the following precipitation of the carbonate.
  • This solvent can be any cost-effective solvent providing the necessary precipitation, for example, a polar solvent, particularly ethanol.
  • Further possible functions of the acid-gas treatments include the function of the gas, such as C0 2 , to change the pH of the slurry, and its function in guiding the balance of the chemical reaction towards the recovery of the product salt, or in the recovery of the solvent salts used in the process (for recirculation).
  • the gas such as C0 2
  • a gas source is supplied to the reaction zone.
  • This gas source may comprise a gas or a liquid containing or capable of releasing the acidic gas.
  • the gas can be pure or it can be a gas mixture enriched with the acidic gas.
  • C0 2 -containing gases examples include air enriched with carbon dioxide, carbon dioxide in gaseous form, optionally containing inert gas components, and flue gas. By using excess pressure, the carbon dioxide can be provided in liquid form, optionally even at supercritical conditions.
  • the used acid-gas source contains at least 5 % by volume, preferably at least 10 % by volume, in particular about 15 to 100 % by volume of acidic gas.
  • the acid-gas treatment is operated using gaseous C0 2 in pure form.
  • the step of precipitation or reprecipitation of the product salt is carried out in a manner that yields salt particles in either pure form or in a form having a chemically or structurally modified surface.
  • Said step is preferably carried out by changing the pH of the slurry to a value that is > 7.
  • the pH value can be elevated further to > 10.
  • the identity of the precipitated salt depends on the identities of the components of the starting material and the components of the solvent system, and on the equilibrium of their dissolution and precipitation reactions.
  • the process of the invention typically involves the dissolution of a salt, for example being a calcium salt, such as calcium carbonate, utilizing an ionic liquid, and the reprecipitation of the calcium salt, according to the exemplary material, as pure calcium carbonate or calcium carbonate having a chemically or structurally modified surface.
  • a salt for example being a calcium salt, such as calcium carbonate, utilizing an ionic liquid
  • the reprecipitation of the calcium salt according to the exemplary material, as pure calcium carbonate or calcium carbonate having a chemically or structurally modified surface.
  • product particles including a mixture of two or more salts is produced, e.g. in the form of a core of one salt with a modified surface formed using the other salt (i.e. the above mentioned structural modification).
  • the components of both salts are then selected from the same list of metals or metal ions, the carbonate ion and the ions of the enabling solvent.
  • the process steps are optimized as regards the temperature, pressure and residence time, based on the desired contents of the product particles.
  • the overall “residence time” is here meant to include the dissolution step and the precipitation step.
  • the optional surface modification of the resulting product particles can, for example, take place via a chemical reaction between the dissolved ions of the starting material and the ions of the molten solvent, or via an adsorption of the ions of the molten solvent onto the surface of the salt particles forming the core of the product particles.
  • the first mentioned surface modification is a chemical modification
  • the second one is a structural modification.
  • the precipitated product particles can be withdrawn from the reaction mixture, i.e. the slurry, using any conventional means, such as filtration, seeding or using centrifugation, and optionally recrystallized to obtain a product with a higher purity.
  • the product particles withdrawn from the reaction zone have a particle size depending on the precipitation parameters, generally between 0.02 to ⁇ .
  • smaller particles e.g. nano-particles, such as nano-carbonate (generally referring to nano-sized calcium carbonate) can be obtained, particularly having a particle size of 20 - 500 nm.
  • nano-particles such as nano-carbonate (generally referring to nano-sized calcium carbonate)
  • these particles are typically in the form of calcite, aragonite or vaterite.
  • the invention is implemented in a reactor comprising at least one reaction zone, such as one or more reactor(s), as well as means for recycling the solvent system, and optional means for recycling the crystallization solvent.
  • the reactor(s) allow for operating at pressurized conditions.
  • reaction zones can be used, operated either in sequence or in parallel.
  • Example 1 The solubility of CaCO ⁇ in various ionic liquids and water content Various materials suitable for use as ionic liquids were tested for their capability of dissolving CaC0 3 (see Table 1).
  • CaC0 3 (0.06 - 0.1 g) was dissolved in the ionic liquid or ionic liquid aqueous solution (3g) at room temperature or 50°C. The mixture was strongly stirred for 3 days by means of a magnetic stirrer. The remaining undissolved CaC0 3 was removed from the mixture by means of centrifugation (6000 rpm for 30 min) and/or filtration. Quantitatively, the solubility of calcium carbonate was determined by inductively coupled plasma optical emission spectrometry (ICP-OES) measurements. Table 1 - Compounds used as ionic liquids, as well as their aqueous mixtures, and the solubility therein of CaC0 3 in the previous reported conditions.
  • ICP-OES inductively coupled plasma optical emission spectrometry
  • Hydroxyl ammonium ionic liquids (°C) (g CaC0 3 /kg solvent(IL+H 2 0))
  • a certain water content in the ionic liquid is preferred.
  • the optimal content varies depending on the ionic liquid. However, generally, already a content of about 5% provides an improved dissolving capability, while a content closing up on 100% will reduce the advantages obtained with the help of the ionic liquid.
  • Example 2 Preparation of ionic liquids, and the use of these ionic liquids in the dissolution and reprecipitation of CaCO ⁇ using minimum residence times
  • an ionic liquid of interest (here exemplified using formate and lactate ionic liquids) was prepared by a neutralization reaction of a hydroxyl amine with a carboxylic acid as shown in the following scheme.
  • the synthesis proceeded as follows: approx. 1.5 mol hydroxyl amine was transferred to a 500 ml round-bottom flask.
  • the recipient equipped with a reflux condenser, was placed in a water bath at a constant temperature of 0 °C.
  • the acid in this case 1.5 mol of L-(+)-lactic acid, was added to the amine under slight N 2 pressure during a time period of lh, while stirring.
  • the stirring and the N 2 supply continued for 6 h at 0°C followed by 12 h at 25°C. However, such reaction/ stirring times are not necessary.
  • the reactions will have proceeded much before the stirring at said temperatures was stopped.
  • the water was removed from the thus formed ionic liquid by evaporation under vacuum ( ⁇ 5 mbar, 50-70°C) for 3 h.
  • the CaC0 3 dissolution experiments were performed in a semibatch reactor under slight N 2 or C0 2 pressure (generally 2 bar), at 25°C or 50°C. Two ionic liquids were used: hydroxyethyl ammonium formate and hydroxyethyl ammonium lactate.
  • formate IL 2 g of CaC0 3 were put in contact with 150 g of formate IL aqueous solution (25 wt.% IL). The mixture was stirred for 24 hours at 1020 rpm, while maintaining the other conditions. 2 ml samples were taken at different dissolution time in order to determine the evolution of solubility values in function of time.
  • lactate ionic liquid 7g of CaC0 3 were mixed with 150 g aqueous solution of lactate ionic liquid (85 wt. % IL). Dissolution experiments were performed in a semibatch reactor under slight N 2 or C0 2 pressure. The mixture was stirred for 24 hours at 1020 rpm while maintaining a temperature of 50°C. The dissolution step is followed by removal of undissolved particles (e.g. by filtration or centrifugation or both).
  • the reprecipitation step was performed by precipitating the product particles from a C0 2 - saturated aqueous solution of a hydroxy ethyl ammonium IL treated with CaC0 3 .
  • the reprecipitation procedure is based on a step of C0 2 absorption followed by a pH adjustment to a value close to 10 by means of addition of a basic solution.
  • the dissolution of the calcium carbonate was carried out as described in Example 2. Parameters such as: type of ionic liquid used (here formates and lactates), water content, presence of N 2 or C0 2 gas, dissolution temperature or stirring rate were used to influence the CaC0 3 dissolution time (see Figure 1).
  • the type of the ionic liquid used has an important role in CaC0 3 dissolution rate as well as Ca recovery as CaC0 3 and/or other product salts. They can show a reasonable capacity to solubilize calcium carbonate (from approx 10 to 50 times higher than water in normal conditions - see Table 1) and can act also as surface modifiers. This would be the case of, for example, 1 -methyl pyrazolium tetrafluorob orate and 1-ethylimidazolium hydrosulphate ionic liquids. According to a general procedure, 0.015g CaC0 3 were placed in contact with approx. 3 g of ionic liquid. The mixture was strongly stirred for 3 days at room temperature by means of a magnetic stirrer.
  • the remaining undissolved CaC0 3 was washed with pure ethanol and removed from the mixture by means of centrifugation (6000 rpm for 30 min) and/or filtration. Quantitatively, the solubility of calcium carbonate was determined by inductively coupled plasma optical emission spectrometry (ICP-OES) measurements.
  • ICP-OES inductively coupled plasma optical emission spectrometry
  • phase composition consists of calcium carbonate and calcium borate and respectively, calcium carbonate and calcium sulphate salts.
  • ChCl+OA deep eutectic solvents
  • Solubility of CaC0 3 in deep eutectic solvent is prominent in the case of ChCl+OA system (solubility 0.75 g CaC0 3 /kg IL).
  • ChCl+OA IL ChCl+OA IL and it is transformed in calcium oxalate form. Fact that makes from this IL a good agent for calcium carbonate dissolution and surface functionalization.

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Abstract

L'invention concerne un procédé de production de sels précipités à partir de matériaux de départ comprenant des métaux alcalins, des métaux alcalino-terreux ou des métaux de transition, en particulier à partir de sels de calcium. Ce procédé consiste à former une suspension contenant le métal lors d'une étape de dissolution du matériau de départ dans un solvant au moins partiellement formé à partir d'un sel de solvant fondu, puis à mettre en oeuvre une étape de précipitation qui produit des particules contenant également au moins un sel métallique.
PCT/FI2014/050150 2013-02-28 2014-02-28 Préparation de particules de sels à partir de carbonate de calcium précipité WO2014131950A1 (fr)

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CN104495902A (zh) * 2014-12-12 2015-04-08 安徽雪城超细碳酸钙有限公司 一种轮胎专用纳米碳酸钙的生产方法
CN111689509A (zh) * 2020-07-10 2020-09-22 沈阳鑫博工业技术股份有限公司 一种利用电石渣制备微粉碳酸钙的装置及方法
CN113104875A (zh) * 2021-03-31 2021-07-13 陕西金禹科技发展有限公司 一种电石渣制备超细或纳米碳酸钙的工艺及其处理系统
CN114772625A (zh) * 2022-04-12 2022-07-22 四川大学 电石渣中钙离子的溶出方法及其在矿化封存co2联产轻质碳酸钙中的应用
US11685850B2 (en) 2017-12-22 2023-06-27 Oy Granula Ab Ltd Use of aqueous solution of organic ammonium carboxylate in preventing dusting of fine material and combination of an aqueous solution of organic ammonium carboxylate and fine material

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CN112010337A (zh) * 2020-08-31 2020-12-01 西南科技大学 含杂质石灰质原料碳化制备的大尺寸文石晶须及其方法

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