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    • 专利摘要:
    The present invention relates to the use of a depolymerized carboxylated cellulose solution for preparing an aqueous suspension of Precipitated Calcium Carbonate (PCC) by extinguishing a material containing calcium oxide in water and then carbonating lime milk thus obtained, said depolymerized carboxylated cellulose solution having a solids content of between 25% and 40% by weight relative to the total weight of the solution and said depolymerized carboxylated cellulose having a molecular weight of between 10 000 g / mol and 40,000 g / mol.
    公开号:FR3038895A1
    申请号:FR1556789
    申请日:2015-07-17
    公开日:2017-01-20
    发明作者:Christian Jacquemet
    申请人:Coatex SAS；
    IPC主号:
    专利说明:

    PRODUCTION OF PRECIPITATED CALCIUM CARBONATE
    The present invention relates to the use of a depolymerized carboxylated cellulose to prepare an aqueous suspension of Precipitated Calcium Carbonate (PCC), wherein said depolymerized carboxylated cellulose is optionally used in combination with at least one extinguishing additive.
    Context of the invention
    Calcium carbonate is one of the most used additives in the paper, paint and plastic industries. Natural Calcium Carbonate (CCN) is, for example, used as a mineral filler in many applications. Precipitated Calcium Carbonate (PCC), for its part, can be made to measure in terms of morphology and particle size, which gives other properties to the materials that contain it. Scalenohedral Precipitated Calcium Carbonate (CCP-S) is particularly used as a mineral filler in combination with cellulose fibers in mass-load applications in paper.
    The methods of producing PCC include the steps of quenching a calcium oxide-containing material (commonly referred to as "quicklime") with water to produce a suspension of calcium hydroxide ( generally referred to as "lime milk"), followed by the subsequent synthesis of calcium carbonate by circulating carbon dioxide through said resultant calcium hydroxide slurry. Such methods produce PCC suspensions having a low solids content. Therefore, these methods generally include an additional concentration step to obtain a CCP slurry having a higher solids content, which is of interest in transporting the PCC slurry. Nevertheless, such additional steps of concentration are energy consuming, expensive and require the use of specific equipment (eg a centrifuge, requiring significant maintenance). Moreover, the use of such equipment can lead to the destruction of the structure of the CCP formed, as is the case of the CCP-S prepared in the form of clusters.
    The processes for preparing PCC in the presence of various additives are described in the literature.
    A number of documents are concerned with the preparation of PCC in the presence of negatively charged polymers, for example (meth) acrylic acid polymers.
    In particular, the document WO 2005/000742 A1 relates to a process for the preparation of lamellar PCC comprising the steps of providing a suspension of calcium hydroxide, carbonating said suspension, and adding a polyacrylate to the suspension before the end of the carbonation to precipitate lamellar calcium carbonate.
    Also, the unpublished patent application EP 14166751.9 filed on behalf of the present applicants concerns the use of a combination of at least one water-soluble polymer (for example a polyacrylic acid) and at least one extinguishing additive in a process for producing an aqueous suspension of precipitated calcium carbonate. Other documents describe the use of positively charged additives prepared, for example, from monomeric units having a quaternary amine.
    The unpublished patent application FR 15 51690 filed in the name of the present applicants relates to the use of a cationic polymer, optionally in the presence of an extinguishing additive, in a process for producing an aqueous suspension of calcium carbonate. precipitate. The invention described in this document makes it possible to prepare suspensions of CCP having cationic surface charges, even at alkaline pH. Finally, other documents focus on the use of additives that are at least partially bio-sourced. For example, patent application WO 2007/067146 A1 describes a process for preparing PCC in the presence of starch or carboxymethylcellulose (CMC).
    Objects of the invention
    An object of the present invention is to provide a solution for the production of CCP suspensions using an additive of bio-sourced origin, that is to say not from a fossil energy. This approach is part of a concept of green chemistry and sustainable development.
    Another object of the present invention is to provide a solution for the production of CCP suspensions having, for example, a high solids content, without resorting to an additional step of thermal or mechanical concentration.
    Another object of the present invention is to provide a solution for the production of CCP suspensions with a high dry matter content having easily manageable viscosities, that is to say a solution for increasing the solids content of the solids. CCP suspensions, while preventing the increase of the viscosity of the suspensions.
    It is also desirable that said solution does not adversely affect the kinetics of the carbonation step and / or does not alter the crystallographic structure of the PCC.
    Another object of the present invention is to provide a solution for the preparation of PCC slurries for direct use as a mineral filler in a papermaking process.
    Brief description of the invention
    The present invention relates to the use of at least one depolymerized carboxylated cellulose solution for preparing an aqueous suspension of Precipitated Calcium Carbonate (PCC) by extinguishing a material containing calcium oxide in water and then carbonating milk of lime thus obtained.
    According to one embodiment of the present invention, said depolymerized carboxylated cellulose solution has a solids content of between 25% and 40% by weight relative to the total weight of the solution.
    According to another embodiment, said depolymerized carboxylated cellulose has a molecular weight Mw of between 10 000 g / mol and 40 000 g / mol.
    The present invention further relates to the use of a combination of at least one depolymerized carboxylated cellulose solution and at least one extinguishing additive in a process for producing an aqueous suspension of precipitated calcium carbonate. .
    The present invention also relates to the use of at least one depolymerized carboxylated cellulose solution for preparing Precipitated Calcium Carbonate (PCC) in dry form by extinguishing a material containing calcium oxide in water carbonation of the milk of lime thus obtained and at least drying of the suspension of PCC.
    Detailed description of the invention Definitions
    For the purposes of the present invention, the terms given below are to be understood as having the following meanings:
    "Calcium oxide-containing material" means a mineral or synthetic material having a calcium oxide content of not less than 50% by weight, for example not less than 75% by weight, or of at least 90% by weight or at least 95% by weight relative to the total weight of the material containing calcium oxide.
    "Mineral material" means a solid substance having a defined inorganic chemical composition and a crystalline and / or amorphous characteristic structure.
    "Natural Calcium Carbonate (SCC)" means calcium carbonate obtained from natural sources such as limestone, marble or chalk and subjected to a wet and / or dry treatment such as grinding sieving and / or fractionation, for example using a cyclone or a sorter.
    By "Precipitated Calcium Carbonate (PCC)" is meant a synthetic material generally obtained by precipitation following the reaction of carbon dioxide and calcium hydroxide (hydrated lime) in an aqueous medium or by precipitation of a source of calcium and a source of carbonate in the water. On the other hand, the precipitated calcium carbonate may also be the product for introducing calcium and carbonate salts, calcium chloride and sodium carbonate, for example in an aqueous medium. The PCC can be in the form of vaterite, calcite or aragonite. The PCCs are described, for example, in EP 2447213 A1, EP 2524898 A1, EP 2371766 A1.
    For purposes of the present invention, the "dry matter content" or "dry extract" of a liquid composition is a measure of the amount of material remaining after evaporation of all solvents or water.
    Throughout this paper, the "particle size" of precipitated calcium carbonate or other particulate materials is described by its particle size distribution. The dx value represents the diameter for which x% by weight of the particles have a diameter less than dx. This means that the i / 20 value is the particle size at which 20% by weight of all the particles have a diameter less than the d value and the ifes value is the particle size at which 98% by weight of all the particles have a smaller diameter. to the value d. The ifes value is also called "top cut". The dso value is referred to as the median particle size by weight, i.e. 50% by weight of the particles have a diameter smaller or larger than this particle size. For purposes of the present invention, the particle size is indicated as the median particle size by weight dso unless otherwise indicated. In order to determine the median particle size in dso weight or the particle size of the top cut dg & a Sedigraph 5100 or 5120 device from Micromeritics, USA, can be used.
    A "specific surface according to the BET (SS) method", within the meaning of the present invention, is defined as being the surface of the particles of precipitated calcium carbonate divided by the mass of the PCC particles. As used herein, the specific surface area is measured by N2 adsorption using BET isotherms (ISO 9277: 1995) and is reported in m 2 / g. For the purposes of the present invention, "stable in an aqueous suspension having a pH of 12 and a temperature of 90 ° C" means that the polymeric additive retains its physical properties and its chemical structure when it is added to an aqueous suspension having a pH of 12 and a temperature of 90 ° C. For example, the polymeric additive retains its dispersion qualities and is not depolymerized or degraded under said conditions.
    For purposes of the present invention, the term "viscosity" or "Brookfield viscosity" refers to Brookfield viscosity. Brookfield viscosity is measured using a Brookfield viscometer (RVT type) at 25 ° C. ± 1 ° C. at 100 rpm using a suitable motive and is indicated in mPa.s.
    For purposes of the present invention, the "water-soluble" materials are defined as materials which, when mixed with deionized water and filtered on a filter having a pore size of 0.2 μπι at 20 ° C to recover the liquid filtrate, lead to a mass less than or equal to 0.1 g of solid material recovered after evaporation between 95 ° C and 100 ° C of 100 g of said liquid filtrate. "Water-soluble" materials are defined as materials leading to a mass greater than 0.1 g of solid material recovered after evaporation between 95 ° C and 100 ° C of 100 g of said liquid filtrate.
    A "suspension", within the meaning of the present invention, comprises insoluble solids and water, and possibly other additives. It is likely to contain large amounts of solids and therefore to be more viscous and to have a higher density than the liquid of which it is formed.
    The term "comprising" as used in this specification and the present claims does not exclude other elements. For purposes of the present invention, the term "constituted by" is considered to be a preferred embodiment of the term "comprising". If a group is defined below as comprising at least a number of embodiments, it should also be understood that it describes a group which preferably consists of only these embodiments.
    The terms "obtainable" or "can be defined" and "obtained" or "defined" are used interchangeably. For example, this means that, unless the context dictates otherwise, the term "obtained" does not indicate that an embodiment must be achieved by the sequence of steps following the term "obtained" even if such an understanding limited is always included by the term "obtained" or "defined" as a preferred embodiment.
    Cellular depolymerized cellulose and method of preparation
    By "carboxylated cellulose" is meant a cellulose which has been chemically modified and comprises carboxylic units, for example carboxymethyl-CH 2 -COOH units. The carboxylated cellulose is, at least partially, of bio-sourced origin. It may be provided in the form of a powder or in the form of a solution, for example in the form of an aqueous solution.
    According to one embodiment of the present invention, the carboxylated cellulose is carboxymethylcellulose.
    In the context of the present invention, a carboxylated cellulose is used which has been depolymerized to exhibit optimum molecular weight for the present application. The inventors demonstrate that the use of a non-depolymerized CMC does not increase the dry matter content of lime milk while maintaining a viscosity permitting the handling of the suspension.
    In the context of the present invention, the terms "polymeric additive" and "depolymerized carboxylated cellulose" are used in an equivalent manner.
    According to one embodiment of the present invention, said depolymerized carboxylated cellulose solution is obtained according to a process described in the patent application WO 2015/063402. In particular, said depolymerized carboxylated cellulose solution may be obtained by a process comprising: 1) a depolymerization step according to which: la) a carboxylated cellulose to be depolymerized having a degree of substitution of between 0.2 and 2. ) a reactor containing water is heated to a temperature between 50 ° C and 85 ° C (inclusive), for example at a temperature between 75 ° C and 85 ° C (inclusive), le) is added in the reactor, in a progressive and simultaneous manner, the carboxylated cellulose to be depolymerized and a peroxide while maintaining the temperature according to 1b) and 1d) after the addition of all the reagents according to 1a, the temperature of the mixture according to 1b) is maintained until the total consumption of the peroxide, 2) a cooling step of the mixture at a temperature below 75 ° C, for example at a temperature below 70 ° C and 3) optionally a step neutralization of the mixture.
    According to one embodiment of the present invention, the depolymerized carboxylated cellulose has a molecular weight Mw of between 10 000 g / mol and 40 000 g / mol, for example between 13 000 g / mol and 35 000 g / mol or for example between 13,000 g / mol and 25,000 g / mol.
    The molecular weight of the depolymerized carboxylated cellulose can be determined by Steric Exclusion Chromatography (CES) or in English "Gel Permeation Chromatography" (GPC). This method is described in particular in the patent application WO 2015/063402. In addition, a specific example of measurement is given in the experimental part of this patent application. The IP polydispersity index corresponds to the molecular weight distribution of the different macromolecules within the cellulose obtained. If all the macromolecules have a neighboring molecular weight Mw, the IP index decreases and approaches the theoretical value of 1. If, on the other hand, the macromolecules have different molecular weights, the IP index increases.
    According to one embodiment of the present invention, said depolymerized carboxylated cellulose has a polydispersity index IP of between 2 and 10, for example between 3 and 5.
    In one embodiment, the depolymerized carboxylated cellulose is provided as a solution.
    According to one embodiment of the present invention, the depolymerized carboxylated cellulose solution has a solids content greater than 25% by weight, for example between 25% and 40% by weight relative to the total weight of the solution; or a solids content greater than 30% by weight, for example between 30% and 40% by weight relative to the total weight of the solution or for example between 31% and 35% by weight.
    According to one embodiment of the present invention, said depolymerized carboxylated cellulose is partially or completely neutralized by means of one or more neutralizing agent (s) chosen from the group consisting of sodium hydroxides, calcium hydroxides magnesium hydroxides, potassium hydroxides and amines.
    Material containing calcium oxide
    The aqueous suspension of PCC is prepared by extinguishing a material containing CaO calcium oxide. Thus, in the process for producing an aqueous suspension of precipitated calcium carbonate, a calcium oxide-containing material is provided.
    Said material containing calcium oxide can be obtained by calcining a material containing calcium carbonate. Calcination is a heat treatment process applied to the calcium carbonate containing material to cause thermal decomposition leading to the formation of calcium oxide and gaseous carbon dioxide. The calcium carbonate-containing materials that can be used in such a calcination process are those selected from the group consisting of precipitated calcium carbonates, natural calcium carbonate-containing minerals such as marble, limestone and chalk, and minerals containing a mixture of alkaline earth carbonates including calcium carbonate such as dolomite or calcium carbonate rich fractions from other sources. It is also possible to subject a residual material containing calcium carbonate to a calcination process to obtain a material containing calcium oxide.
    Calcium carbonate decomposes at about 1000 ° C into calcium oxide (commonly known as quicklime). The calcination step can be performed under conditions and using equipment well known to those skilled in the art. In general, calcination may be carried out in furnaces or reactors (sometimes referred to as furnaces) of various designs, including shaft furnaces, rotary kilns, multi-furnace furnaces and fluidized bed reactors.
    The end of the calcination reaction can be determined, for example, by monitoring the change in density, the residual carbonate content, for example by X-ray diffraction, or the extinction reactivity by common methods.
    According to one embodiment of the present invention, the material containing calcium oxide is obtained by calcining a material containing calcium carbonate, for example selected from the group consisting of precipitated calcium carbonate, natural minerals containing calcium carbonate such as marble, limestone and chalk; minerals containing a mixture of alkaline earth carbonates including calcium carbonate such as dolomite or mixtures thereof.
    For reasons of efficiency, it is preferred that the calcium oxide-containing material has a minimum calcium oxide content of at least 75% by weight, preferably at least 90% by weight, and most preferably all of 95% by weight relative to the total weight of the material containing calcium oxide. According to one embodiment, the material containing calcium oxide consists of calcium oxide.
    The material containing calcium oxide may consist of a single type of material containing calcium oxide. Alternatively, the calcium oxide-containing material may consist of a mixture of at least two types of calcium oxide-containing materials.
    The material containing calcium oxide can be used in the process of the invention in its original form, that is to say in the form of raw material, for example more or less large pieces. Alternatively, the calcium oxide-containing material can be milled before use. According to one embodiment of the present invention, the material containing calcium carbonate is in the form of particles having a median particle size by weight dso ranging from 0.1 μm to 1000 μm and, for example, from 1 μm to 500 μm. .
    Use of depolymerized carboxylated cellulose
    The present invention relates to the use of a depolymerized carboxylated cellulose to prepare a Precipitated Calcium Carbonate (PCC).
    More specifically, the present invention relates to the use of a depolymerized carboxylated cellulose solution for preparing a Precipitated Calcium Carbonate (PCC) in dry form or in the form of an aqueous solution or aqueous suspension.
    The processes for producing an aqueous suspension of PCC generally include the steps of (i) preparing a lime milk by mixing water and the calcium oxide containing material, and optionally the at least one additive of quenching, and (ii) carbonating the lime milk obtained in step (i) to form an aqueous suspension of precipitated calcium carbonate.
    The term "carbonate" is intended to circulate carbon dioxide in the suspension of calcium hydroxide Ca (OH) 2, so as to form precipitated CaCCL calcium carbonate.
    According to the present invention, at least one depolymerized carboxylated cellulose solution is used to prepare an aqueous suspension of Precipitated Calcium Carbonate (PCC) by extinguishing a material containing calcium oxide in water and then carbonating the milk. lime thus obtained, said depolymerized carboxylated cellulose solution having a solids content of between 25% and 40% by weight relative to the total weight of the solution and a molecular weight Mw of between 10 000 g / mol and 40 000 g / mol .
    Etaye extinction
    In the first step of the CCP production process, that is, the "quench step" (named step i) above, a lime milk is prepared by mixing water, the material containing calcium oxide, the depolymerized carboxylated cellulose and optionally the at least one extinguishing additive.
    The reaction of the calcium oxide-containing material with water leads to the formation of a milky suspension of calcium hydroxide, better known as milk of lime. Said reaction is highly exothermic and is also referred to in the art as "lime quenching".
    According to one embodiment, said depolymerized carboxylated cellulose solution is present in the extinguishing water of the calcium oxide-containing material.
    According to one embodiment of the present invention, the temperature of the water, which is used in the quenching step, that is to say the temperature of the water which is used for extinguishing the material containing calcium oxide, is adjusted to be in the range of 0 ° C to 100 ° C, for example 1 ° C to 70 ° C or 2 ° C to 50 ° C or ° C to 50 ° C or 35 ° C to 45 ° C. It will be apparent to those skilled in the art that the initial temperature of the water is not necessarily the same as the temperature of the mixture prepared in the quenching step because of the highly exothermic nature of the quenching reaction and or the mixture of substances having different temperatures. According to one embodiment of the present invention, the step of quenching the process comprises the steps of: a1) mixing the depolymerized carboxylated cellulose solution with water, optionally the at least one extinguishing additive and a2 ) add the material containing calcium oxide to the mixture of step a1). According to one embodiment, step a1) is carried out at a temperature of between 0 ° C. and 99 ° C., for example between 1 ° C. and 70 ° C. or between 2 ° C. and 50 ° C. or between 30 ° C. and 50 ° C or between 35 ° C and 45 ° C.
    According to another embodiment of the present invention, the step of quenching the process comprises the steps of: bl) mixing the calcium oxide-containing material, the depolymerized carboxylated cellulose solution, and optionally the at least one an extinction additive and b2) add water to the mixture of step b1).
    According to yet another embodiment of the present invention, in the process extinction step, the calcium oxide-containing material, the depolymerized carboxylated cellulose, optionally the at least one extinguishing additive and the water are mixed simultaneously.
    According to yet another embodiment of the present invention, the at least one extinguishing additive is added before or after the quenching step of the process.
    The depolymerized carboxylated cellulose solution may be added to the quenching step in whole or in parts, for example in two, three, four, five or more parts. The quenching step of the process can be carried out at room temperature, ie at a temperature of 20 ° C ± 2 ° C or at an initial temperature of between 30 ° C and 50 ° C or between ° C and 45 ° C. The reaction being exothermic, the temperature generally reaches a temperature between 85 ° C and 99 ° C during step i), preferably a temperature between 90 ° C and 95 ° C. According to a preferred embodiment, step i) of the process is carried out by mixing or stirring, for example with mechanical stirring. Equipment suitable for mixing or stirring the process is known to those skilled in the art.
    The progress of the quenching reaction can be observed by measuring the temperature and / or the conductivity of the reaction mixture.
    The inventors have surprisingly found that the addition of a specific depolymerized carboxylated cellulose as defined above and optionally a quenching additive as defined above, before or during the quenching step of a production process. of CCP, may allow the preparation not only of a lime milk having a low dry matter content but also of a lime milk having a high dry matter content. Indeed, it is interesting to note that, according to one aspect of the invention, by carbonating said highly concentrated lime milk, it is possible to obtain an aqueous suspension of PCC which also has a high dry matter content. Accordingly, the process of the present invention does not require an additional concentration step to obtain a CCP slurry having a high solids content.
    According to one embodiment of the present invention, the lime milk of the quenching step has a solids content of at least 15% by weight, for example ranging from 15% to 45% by weight or for example from 20% to 40% by weight or for example from 25% to 37% by weight relative to the total weight of the milk of lime.
    According to one embodiment of the present invention, the lime milk of the quenching step has a Brookfield viscosity ranging from 1 mPa.s to 1000 mPa.s at 25 ° C, for example from 5 mPa.s to 800 mPa.s at 25 ° C or for example from 10 mPa.s to 500 mPa.s at 25 ° C, as measured at 100 rpm.
    In the context of the present invention, additional water may be introduced during the quenching reaction to control and / or maintain and / or reach the dry matter content or Brookfield viscosity of the milk of the invention. desired lime. The quench step of the process can be performed as a batch, semi-continuous or continuous process.
    In the quenching step, the calcium oxide-containing material and the water may be mixed in a weight ratio of from 1: 1 to 1: 12, for example from 1: 2 to 1:12, for example from 1: 2.5 to 1: 6.
    According to one embodiment, said depolymerized carboxylated cellulose solution is used in combination with at least one extinguishing additive.
    In this case, the at least one extinguishing additive may be chosen from the group consisting of organic acids, organic acid salts, sugar alcohols, monosaccharides, disaccharides, polysaccharides, gluconates and phosphonates. lignosulfonates and mixtures thereof.
    According to one embodiment, the at least one extinguishing additive is selected from the group consisting of sodium citrate, potassium citrate, calcium citrate, magnesium citrate, monosaccharides, disaccharides, polysaccharides, sucrose, sugar alcohols, meritol, citric acid, sorbitol, sodium salt of diethylenetriamine pentaacetic acid, gluconates, phosphonates, sodium tartrate, sodium lignosulfonate, calcium lignosulfonate and their mixtures. Carbonation step
    In this step of the CCP production process, that is to say the carbonation step (named step ii) above), the lime milk obtained at the end of the quenching step is carbonated. to form an aqueous suspension of precipitated calcium carbonate.
    Carbonation is carried out by means and under conditions well known to those skilled in the art. The introduction of carbon dioxide into the milk of lime rapidly increases the concentration of carbonate ions (CO32) and the calcium carbonate is formed. In particular, the carbonation reaction can be easily controlled taking into account the reactions involved in the carbonation process. The carbon dioxide dissolves, according to its partial pressure, to form carbonate ions via the formation of carbonic acid (H2CO3) and unstable hydrogen carbonate ions (HCO3) in alkaline solution. During the continuous dissolution of the carbon dioxide, the hydroxide ions are consumed and the concentration of carbonate ions increases until the concentration of dissolved calcium carbonate is greater than the solubility product and the solid calcium carbonate precipitates.
    According to one embodiment of the present invention, the carbonation is carried out by incorporating pure carbon dioxide gas or technical gases containing at least 10% by volume of carbon dioxide in the milk of lime.
    The progress of the carbonation reaction can be easily observed by measuring the conductivity and / or the pH. In this respect, the pH of the milk of lime before the addition of carbon dioxide will be greater than 10, generally between 11 and 12.5 and will decrease continuously until a pH of about 7 is reached. then be stopped. The conductivity decreases slowly during the carbonation reaction and then decreases rapidly to low values when the precipitation is complete. The progression of carbonation can be monitored by measuring the pH and / or the conductivity of the reaction mixture.
    According to one embodiment of the process for producing PCC, the temperature of the lime milk obtained at the end of the quenching step, which is used in the carbonation step, is adjusted to be included in the range from 20 ° C to 60 ° C and, for example, from 30 ° C to 50 ° C. It will be apparent to those skilled in the art that the initial temperature of the lime milk is not necessarily the same as the temperature of the mixture prepared in the carbonation step because of the exothermic nature of the carbonation reaction and / or mixture of substances having different temperatures.
    According to one embodiment of the process for producing PCC, the carbonation step is carried out at a temperature of between 5 ° C. and 95 ° C., for example 30 ° C. to 70 ° C. and, for example, 40 ° C. C at 60 ° C. The carbonation stage of the process can be carried out as a batch, semi-continuous or continuous process. According to one embodiment, the process for producing PCC involving the quenching and carbonation steps of the process is carried out as a batch, semi-continuous or continuous process.
    According to one embodiment of the present invention, the process for producing PCC does not comprise a step of concentrating the aqueous suspension of precipitated calcium carbonate obtained in the quenching and carbonation stages of the process.
    Thus, the present invention relates to the use of depolymerized carboxylated cellulose in a process for the preparation of PCC, more precisely in the step of preparing a milk of lime which must be carbonated thereafter.
    Without wishing to be bound by any theory, it can be thought that the affinity of the PCC particles formed in the process described above with the cellulose fibers or fibrils of the paper sheet is improved by the use of said cellulose. carboxylated depolymerized during the process of producing PCC. Indeed, when the depolymerized carboxylated cellulose is present during the step of extinguishing the calcium oxide-containing material to form the PCC, it can be thought that it is incorporated within the PCC particles and plays, thus, a binding role between these PCC particles and the fibrous mat of the cellulose used to form the paper sheet.
    According to one embodiment of the present invention, the use of depolymerized carboxylated cellulose in the process of preparing PCC provides the aqueous suspensions of PCC produced Zeta potential less than 0 mV, but higher than the Zeta potential of a prepared PCC in the presence of negatively charged polymers, for example polymers of (meth) acrylic acid, especially those described in application WO 2005/000742 A1, which remains an advantage for the application of mass load.
    According to another embodiment, the aqueous suspensions of CCP obtained using the depolymerized carboxylated cellulose are characterized in that they have a Zeta potential of less than 0 mV, for example between 0 mV and -40 mV, for example between 0 mV and - 30 mV.
    According to one embodiment, the use of depolymerized carboxylated cellulose during the process of preparation of the PCC confers on the aqueous suspensions of PCC produced a Mütek filler of less than 0 peg / g.
    According to another embodiment, the aqueous suspensions of CCP obtained using the depolymerized carboxylated cellulose are characterized in that they have a Mütek filler of less than 0 peq / g, for example between 0 peq and -1 peq / g or between 0 and - 0.8 peq / g.
    According to one embodiment of the present invention, the depolymerized carboxylated cellulose is added during the first step of the CCP production process, i.e., the depolymerized carboxylated cellulose is added before or during step d 'extinction. The milk of lime, known to those skilled in the art, obtained by extinguishing a material containing calcium oxide with water generally has a pH of between 11 and 12.5 measured at a temperature of 25 ° C. C according to the concentration of the material containing calcium oxide in the milk of lime. Since the quenching reaction is exothermic, the temperature of the milk of lime can reach a temperature above 80 ° C, for example between 80 ° C and 99 ° C. According to one embodiment, the depolymerized carboxylated cellulose used in the context of the present invention is chosen so as to be stable in an aqueous suspension having a pH of 12 and a temperature of 90 ° C. For the purposes of the present invention, "stable in an aqueous suspension having a pH of 12 and a temperature of 90 ° C" means that the polymeric additive retains its physical properties and its chemical structure when it is added to an aqueous suspension having a pH of 12 and a temperature of 90 ° C. For example, the polymeric additive retains its dispersion qualities and is not degraded under said conditions.
    According to one embodiment of the present invention, the depolymerized carboxylated cellulose is added in an amount ranging from 0.01% by weight to 2% by weight, for example from 0.02% by weight to 1% by weight, and for example, from 0.05% by weight to 0.5% by weight relative to the total weight of the material containing calcium oxide.
    Extinguishing additive
    In the first step of the CCP production process (or quenching step), at least one extinguishing additive may be used in addition to the depolymerized carboxylated cellulose. Thus, according to one embodiment, said depolymerized carboxylated cellulose solution is used in combination with at least one extinguishing additive.
    The at least one extinguishing additive may be chosen from the group consisting of organic acids, organic acid salts, sugar alcohols, monosaccharides, disaccharides, polysaccharides, gluconates, phosphonates, lignosulfonates and their mixtures.
    According to one embodiment of the present invention, the at least one extinguishing additive is chosen from the group consisting of sodium citrate, potassium citrate, calcium citrate, magnesium citrate, monosaccharides and disaccharides. polysaccharides, sucrose, sugar alcohols, meritol, citric acid, sorbitol, sodium salt of diethylenetriamine pentaacetic acid, gluconates, phosphonates, sodium tartrate, sodium lignosulfonate, calcium lignosulfonate and mixtures thereof. According to a preferred embodiment, the at least one extinguishing additive is sodium citrate and / or sucrose.
    According to one embodiment of the present invention, the at least one extinguishing additive used consists of a single type of extinguishing additive. Alternatively, the at least one extinguishing additive used may consist of a mixture of at least two types of extinguishing additives.
    The at least one extinguishing additive may be added in an amount of from 0.01% by weight to 2% by weight, based on the total amount of calcium oxide-containing material, for example in an amount ranging from From 0.05% to 1% by weight, for example from 0.06% to 0.8% by weight or, for example, from 0.07% to 0.5% by weight. The addition of an extinguishing additive may be useful for controlling the size of the PCC particles and their crystalline morphology without affecting the viscosity of the aqueous suspension.
    As mentioned previously, the inventors have surprisingly found that the addition of a depolymerized carboxylated cellulose as defined previously, optionally combined with the addition of a quenching additive before or during the quenching step of a process for producing PCC can enable the preparation of a PCC slurry having a high solids content. It is also believed that omitting a concentration step improves the quality of the PCC particles produced since particle surface damage, which may occur during the concentration step, is avoided. It is also believed that said PCC slurry can be further concentrated to a solids content of 52% by weight with acceptable viscosities, for example Brookfield viscosities less than or equal to 1000 mPa.s at 25 ° C and at 100 rpm. Additional steps of the process
    The process for producing precipitated calcium carbonate may include additional steps.
    Lime milk can be sieved to remove oversized particles. A suitable sieve may comprise, for example, a sieve having a size of from 100 μm to 700 μm, for example about 100 μm or about 300 μm. According to one embodiment of the present invention, the lime milk is sieved after the quenching step and before the carbonation step, for example using a sieve having a size ranging from 100 μm to 300 μm. pm. The process for producing precipitated calcium carbonate may further comprise an additional step of separating the precipitated calcium carbonate from the aqueous suspension obtained at the end of the carbonation step.
    For purposes of the present invention, the term "separation" means that the CCP is removed or isolated from the aqueous suspension obtained at the carbonation stage of the process. Any conventional separation means known to those skilled in the art can be used, for example a mechanical and / or thermal means. Examples of mechanical separation processes are filtration, for example by means of a drum filter or a filter press, nanofiltration or centrifugation. An example of a thermal separation process is a concentration process by applying heat, for example in an evaporator.
    The CCP obtained can be converted, for example deagglomerated or subjected to a dry grinding step. It can also be milled wet in the form of suspension. If the PCC is subjected to dehydration, dispersion and / or milling steps, these steps can be accomplished by methods known in the art. Wet milling can be carried out in the absence or in the presence of a grinding aid agent. Dispersants may also be included to prepare dispersions where appropriate.
    The process for producing precipitated calcium carbonate may further comprise an additional step of drying the precipitated calcium carbonate, for example separated precipitated calcium carbonate obtained at the end of the separation step described above.
    The term "drying" refers to a process in which at least a portion of the water is removed from a material to be dried, so that a constant weight of the "dry" material obtained at 120 ° C is achieved. In addition, a "dry" material may be further defined by its total moisture content which, unless otherwise indicated, is less than or equal to 1.0% by weight, preferably less than or equal to 0.5% by weight. weight, more preferably less than or equal to 0.2% by weight and most preferably between 0.03% by weight and 0.07% by weight relative to the total weight of the dry material.
    In general, the drying step may be carried out using any suitable drying equipment and may, for example, include thermal drying and / or drying under reduced pressure using equipment such as an evaporator, flash dryer, oven, spray dryer and / or drying in a vacuum chamber. The drying step results in a dry precipitated calcium carbonate having a low total moisture content which is less than or equal to 1.0% by weight based on the total weight of the dry precipitated calcium carbonate.
    The precipitated calcium carbonate obtained by the process of the invention may be post-treated, for example during and / or after a drying step, by an additional component. According to one embodiment, the precipitated calcium carbonate is treated with a fatty acid, for example stearic acid, a silane or phosphoric esters of fatty acid.
    According to one embodiment of the process for producing PCC, the precipitated calcium carbonate obtained has a median particle size by weight dso ranging from 0.1 .mu.m to 100 .mu.m, for example from 0.25 .mu.m to 50 .mu.m, for example from 0.degree. , 3 pm to 5 pm and, for example, from 0.4 pm to 3.0 pm.
    The precipitated calcium carbonate may have a crystalline aragonite, calcite or vaterite structure or mixtures of these structures. Another advantage of the present invention is that the crystalline structure and morphology of precipitated calcium carbonate can be controlled, for example by adding seed crystals or other structural modifying chemicals. According to a preferred embodiment, the precipitated calcium carbonate obtained by the process of the invention has a scalenohedral crystalline structure in clusters.
    The BET specific surface area of the precipitated calcium carbonate obtained by the process according to the present invention can range from 1 m 2 / g to 100 m 2 / g, for example from 2 m 2 / g to 70 m 2 / g, for example 3 m 2 / g at 50 m 2 / g, for example from 4 m 2 / g to 30 m 2 / g, measured using nitrogen and the BET method according to ISO 9277. The BET specific surface area of the precipitated calcium carbonate obtained by the process of the present invention can be controlled using additives, for example surfactants, which involve shearing during the precipitation step or subsequently high mechanical shear rates leading not only to a small particle size but also to a high BET surface area.
    According to one embodiment of the present invention, the suspension of precipitated calcium carbonate obtained has a solids content of at least 10% by weight, for example ranging from 20% to 50% by weight, for example 25% by weight. 45% by weight or for example from 30% to 40% by weight relative to the total weight of the suspension.
    According to one embodiment of the present invention, the PCC slurry has a Brookfield viscosity less than or equal to 1000 mPa.s at 25 ° C, for example less than or equal to 800 mPa.s at 25 ° C or for example lower or 600 mPa.s at 25 ° C as measured at 100 rpm.
    Another aspect of the present invention relates to the use of a combination of at least one water-soluble polymer and an extinguishing additive in a process for producing an aqueous suspension of precipitated calcium carbonate, wherein: the depolymerized carboxylated cellulose solution has a solids content of between 25% and 40% by weight relative to the total weight of the solution and a molecular weight of between 10 000 g / mol and 40 000 g / mol and the additive of quenching is selected from the group consisting of organic acids, organic acid salts, sugar alcohols, monosaccharides, disaccharides, polysaccharides, gluconates, phosphonates, lignosulfonates and mixtures thereof.
    EXAMPLES 1. Measurement methods
    The measurement methods implemented in the examples are described below. Brookfield Viscosity
    The Brookfield viscosity of the aqueous suspensions was measured after one hour of production and after one minute of stirring at 25 ° C. ± 1 ° C. at 100 rpm using an RVT type Brookfield viscometer fitted with a suitable disk rotor. , for example a mobile 2 to 5.
    PH measurement
    The pH of a slurry or solution was measured at 25 ° C using a Mettler Toledo Seven Easy pH meter and a Mettler Toledo InLab® Expert Pro pH electrode. A three-point calibration (according to the segmentation method) of the instrument was performed initially using commercially available buffer solutions (from Sigma-Aldrich Corp., USA) having a pH of 4.7. and 10 to 20 ° C. The reported pH values are the terminal values detected by the instrument (the measurement is complete when the measured signal differs by less than 0.1 mV from the average over the last 6 seconds).
    Particle size distribution
    The particle size distribution of the prepared PCC particles was measured using a Sedigraph 5100 from Micromeritics, USA. The method and the instrument are known to those skilled in the art and are commonly used to determine the grain size of mineral fillers and pigments. The measurement was carried out in an aqueous solution comprising 0.1% by weight of NaiPiCb. The samples were dispersed using a high speed stirrer and ultrasound. For the measurement of the dispersed samples, no other dispersing agent was added.
    Dry matter content of an aqueous suspension
    The dry matter content of the suspension (also called "dry weight") was determined using a MJ33 Moisture Analyzer from Mettler-Toledo, Switzerland, with the following settings: drying temperature 160 ° C, stop automatic if the mass does not vary by more than 1 mg over a period of 30 seconds, standard drying from 5 g to 20 g of suspension.
    Specific Surface (SS)
    The specific surface area was measured using the BET method according to ISO 9277 using nitrogen, followed by conditioning the sample by heating at 250 ° C for a period of 30 minutes. Prior to these measurements, the sample is filtered through a Buchner funnel, rinsed with deionized water and dried overnight at a temperature of between 90 ° C and 100 ° C in an oven. Then, the dry filter cake is thoroughly ground in a mortar and the resulting powder is placed in a moisture analysis scale at 130 ° C until a constant weight is obtained.
    Specific duration of carbonation
    The control of the conductivity, which decreases slowly during the carbonation reaction and then decreases rapidly to a minimum value indicating that the reaction is complete, was used to determine the time required to allow complete precipitation. The specific carbonation time (min / kg of Ca (OH) 2) was determined by the following formula:
    Specific duration Carbonation =
    in which :
    Tf (min) is the time required to complete the carbonation of the lime milk, as determined by monitoring the conductivity, M (g) is the weight of the lime milk introduced into the carbonation reactor and TMSLdc (%) is the content in dry matter by weight of milk of lime.
    Load measurement - Mütek
    The load measurement was carried out using a Mütek PCD 03 device equipped with a Mütek PCD titrator. 0.5 g to 1 g of dry PCC is weighed into the plastic measuring cell and diluted with 20 mL of deionized water. Move the displacement piston to the "on" position. As the piston oscillates in the cell, wait for the flow current between the two electrodes to stabilize.
    The sign of the measured value displayed on the screen indicates whether the sample load is positive (cationic) or negative (anionic). An oppositely charged polyelectrolyte having a known charge density is added to the sample as a titrant (either 0.001 N sodium polyoxyethylene sulphate or 0.001 N pDADMAC). The titrant loads neutralize the existing charges in the sample. The titration is interrupted as soon as the zero point of charge (0 mV) is reached.
    The consumption of the titrant in mL is used as a basis for subsequent calculations. The amount of specific charge q [eq / g of suspension] is calculated according to the following formula: q = (V * c) / m V: volume of titrant consumed [L] c: concentration of the titrant [eq / L] or [eq / L] m: mass of the weighed suspension [g] q: specific loading quantity [eq / g of suspension] or [eq / g of suspension]
    Zeta potential
    To measure the Zeta potential, a few drops of PCC suspension are dispersed in a sufficient amount of serum obtained by mechanical filtration of said suspension to obtain a slightly hazy colloidal suspension.
    This suspension is introduced into the measuring cell of the Malvem Zetasizer Nano-ZS device which directly displays the Zeta potential value of the CCP suspension in mV. 2. Preparation of a depolymerized CMC
    The process for preparing the depolymerized CMC according to the invention comprises three steps: a depolymerization step, a cooling step and a neutralization step.
    Etaye depolymerization
    In a one-liter reactor, 800 g of bi-permutated water and 0.017 g of FeSO 4 .7H 2 O catalyst are introduced. The reactor is heated to 80 ° C ± 2 ° C. Then, a solution of hydrogen peroxide at 35% by weight at 189 mg / min and CMC (Sigma-Aldrich reference 419281, Mw = 250,000 g / mol, DS = 1.2) was injected for 2 hrs. 25 g aliquots every 15 minutes (continuous process). The reaction is allowed to continue for 2.5 hours after the end of the injections. It is verified that all of the hydrogen peroxide has been consumed.
    Etaye cooling
    The reactor is cooled to 70 ° C. The pH as measured in the reactor is 4.4.
    Etaye neutralization
    A solution of 10% NaOH is introduced so as to reach a pH of 7.4. Characterization of the depolymerized CMC thus obtained:
    Molecular weight determination method (Mw) and IP index of depolymerized CMC
    The molecular weight of the CMC is determined by Steric Exclusion Chromatography (CES) or in English "Gel Permeation Chromatography" (GPC).
    Such a technique implements in this case a WATERS ™ brand liquid chromatography apparatus equipped with a detector. This detector is a WATERS ™ refractometric concentration detector.
    This liquid chromatography apparatus is provided with a steric exclusion column appropriately chosen by those skilled in the art in order to separate the different molecular weights of the CMCs studied. The liquid elution phase is an aqueous phase adjusted to pH 9.00 with 1N sodium hydroxide containing 0.05M NaHCO 3, 0.1M NaNO 3, 0.02M trietanolamine and 0.03% NaN 3.
    In a detailed manner, according to a first step, the solution of CMC in the solvent for solubilization of the CES, which corresponds to the liquid phase of elution of the CES to which 0.04% is added, is diluted to 0.9% of the dry solution of CMC. of dimethylformamide which acts as a flow marker or internal standard. Then, it is filtered at 0.2 μm. 100 μl are then injected into the chromatography apparatus (eluent: an aqueous phase adjusted to pH 9.00 with 1N sodium hydroxide containing 0.05M NaHCCE, 0.1M NaNCE, 0.02M trietanolamine and 0.03 % NaN3). The liquid chromatography apparatus contains an isocratic pump (WATERS ™ 515) with a flow rate of 0.8 mL / min. The chromatography apparatus also comprises an oven which itself comprises in series the following column system: a precolumn GUARD COLUMN type ULTRAHYDROGEL WATERS ™ 6 cm long and 40 mm internal diameter and a linear column type ULTRAHYDROGEL WATERS ™ 30 cm long and 7.8 mm inside diameter. The detection system consists of a RI WATERS ™ 410 type refractometric detector. The oven is heated to a temperature of 60 ° C and the refractometer is heated to a temperature of 45 ° C. The chromatography apparatus is calibrated with powdered polyacrylate standards of various molecular weights certified for the supplier: POLYMER STANDARD SERVICE or AMERICAN POLYMER STANDARDS CORPORATION. 3. Preparation of Precipitated Calcium Carbonate (PCC)
    A milk of lime was prepared by mixing, with mechanical stirring, water and various polymeric additives, optionally in the presence of an extinguishing additive (for example dry sodium citrate, NaCl), at an initial temperature of between 40.degree. ° C and 41 ° C (the amounts of polymeric additives and possibly extinguishing additives are shown in Table 1 below). Then, calcium oxide (raw lime from Golling, Austria) was added with stirring. The resulting mixture was stirred for 25 minutes and then sieved through a 200 μm sieve.
    The resulting lime milk was transferred to a stainless steel reactor in which the lime milk was cooled to 50 ° C. Then, the lime milk was carbonated by introducing an air / CO 2 mixture (26% by volume of CO2 and a flow rate of 23 L / min). During the carbonation step, the reaction mixture was stirred at a speed of 1400 rpm. The kinetics of the reaction were monitored by in-line pH and conductivity measurements.
    Polymeric additives cited as examples: PI = depolymerized CMC prepared according to 2 (according to the invention), P2 = non-depolymerized CMC - Blanose ® Ashland 12M8P (degree of substitution 1,2 and molecular weight 395,000 g / mol) (outside the invention) and P3 = sodium polyacrylate (excluding the invention) - Mw = 4270 g / mol, PDI = 2.3 (Mw and PDI determined according to the unpublished patent application EP 14166751.9)
    Table 1 Characteristics of milk milks (INV: according to the INVention - HINV: Excluding INVENTED)
    The characteristics of milk milks and aqueous suspensions of prepared PCCs are described in Table 2 below.
    Table 2 Characteristics of milk milks and aqueous suspensions of CCP (INV: according to the INVention - HINV: Excluding INVENTED)
    The results reported in Table 2 show that the use of an extinguishing additive alone leads to a lime fluid having a high Brookfield viscosity (test 1) and that it is not possible to increase the dry matter of the milk of lime (% by weight) while preventing the increase of the viscosity of the suspension (comparison of the test 1 and the test 2).
    On the other hand, the sample 3 according to the invention confirms that the viscosities of the milk of lime and of the suspension of CCP obtained are compatible with the intended use of the PCC thus obtained, that is to say suspensions of CCP having a Brookfield viscosity less than or equal to 1500 mPa.s at 25 ° C, for example less than or equal to 1000 mPa.s at 25 ° C or less than or equal to 600 mPa.s at 25 ° C, at 100 rpm min.
    In addition, the carbonation kinetics and the crystallographic structure of the PCC prepared (results not provided) are similar to those obtained with a method involving the use of an anionic polymer (polymer P3 out of the invention, for comparison only).
    权利要求:
    Claims (10)
    [1" id="c-fr-0001]
    1. Use of at least one depolymerized carboxylated cellulose solution for preparing an aqueous suspension of Precipitated Calcium Carbonate (PCC) by extinguishing a material containing calcium oxide in water and then carbonating the milk of lime thus obtained, said depolymerized carboxylated cellulose solution having a solids content of between 25% and 40% by weight relative to the total weight of the solution and a molecular weight Mw of between 10 000 g / mol and 40 000 g / mol.
    [2" id="c-fr-0002]
    2. Use according to claim 1, wherein said depolymerized carboxylated cellulose has an IP polydispersity index of between 2 and 10.
    [3" id="c-fr-0003]
    3. Use according to one of the preceding claims, wherein said depolymerized carboxylated cellulose is partially or completely neutralized by means of one or more neutralizing agent (s) chosen from the group consisting of sodium hydroxides, calcium hydroxides, magnesium hydroxides, potassium hydroxides and amines.
    [4" id="c-fr-0004]
    Use according to any one of the preceding claims, wherein said depolymerized carboxylated cellulose solution is present in the extinguishing water of the calcium oxide-containing material.
    [5" id="c-fr-0005]
    Use according to any one of the preceding claims, wherein said calcium oxide-containing material and water are mixed in a weight ratio of from 1: 1 to 1:12.
    [6" id="c-fr-0006]
    Use according to any one of the preceding claims, wherein said depolymerized carboxylated cellulose solution is used in combination with at least one extinguishing additive.
    [7" id="c-fr-0007]
    7. Use according to the preceding claim, wherein the at least one extinguishing additive is selected from the group consisting of sodium citrate, potassium citrate, calcium citrate, magnesium citrate, monosaccharides, disaccharides polysaccharides, sucrose, sugar alcohols, meritol, citric acid, sorbitol, sodium salt of diethylenetriamine pentaacetic acid, gluconates, phosphonates, sodium tartrate, sodium lignosulfonate, calcium lignosulfonate and mixtures thereof.
    [8" id="c-fr-0008]
    8. Use according to any one of the preceding claims, wherein the lime milk has a Brookfield viscosity of from 1 mPa.s to 1000 mPa.s at 25 ° C at 100 rpm.
    [9" id="c-fr-0009]
    9. Use according to any one of the preceding claims, wherein the PCC slurry has a Brookfield viscosity of 1000 mPas or less at 25 ° C at 100 rpm.
    [10" id="c-fr-0010]
    10. Use according to any one of the preceding claims, wherein the suspension of precipitated calcium carbonate obtained has a solids content of at least 10% by weight relative to the total weight of the suspension.
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    同族专利:
    公开号 | 公开日
    US20180170765A1|2018-06-21|
    EP3325409B1|2020-10-07|
    RU2018105879A3|2019-11-28|
    FR3038895B1|2017-07-07|
    CN107787304B|2020-12-29|
    IL256473D0|2018-02-28|
    BR112017025674A2|2018-08-07|
    WO2017013323A1|2017-01-26|
    EP3325409A1|2018-05-30|
    RU2018105879A|2019-08-19|
    JP2018520079A|2018-07-26|
    CN107787304A|2018-03-09|
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    US20130312925A1|2012-05-28|2013-11-28|Nordkalk Oy Ab|Manufacture and use of a composite structure containing precipitated carbonate|
    EP2868716A1|2013-11-04|2015-05-06|Omya International AG|Process for producing a high solids pigment suspension comprising carboxymethylcellulose-based dispersant|
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    PL2939980T3|2014-04-30|2018-08-31|Omya International Ag|Production of precipitated calcium carbonate|
    EP3118161B1|2015-07-17|2018-05-16|Omya International AG|High solids pcc with depolymerized carboxylated cellulose|EP3118161B1|2015-07-17|2018-05-16|Omya International AG|High solids pcc with depolymerized carboxylated cellulose|
    WO2021214333A1|2020-04-23|2021-10-28|S.A. Lhoist Recherche Et Developpement|Calcium and/or magnesium additive for membrane fouling control and system and process for membrane fouling control using the additive|
    WO2021214334A1|2020-04-23|2021-10-28|S.A. Lhoist Recherche Et Developpement|System and process for membrane fouling control, a membrane fouling control additive, an upgrade kit and an upgrade method|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1556789A|FR3038895B1|2015-07-17|2015-07-17|PRODUCTION OF PRECIPITED CALCIUM CARBONATE|FR1556789A| FR3038895B1|2015-07-17|2015-07-17|PRODUCTION OF PRECIPITED CALCIUM CARBONATE|
    CN201680037399.8A| CN107787304B|2015-07-17|2016-06-30|Preparation of precipitated calcium carbonate|
    RU2018105879A| RU2018105879A3|2015-07-17|2016-06-30|
    PCT/FR2016/051624| WO2017013323A1|2015-07-17|2016-06-30|Production of precipitated calcium carbonate|
    JP2017560947A| JP2018520079A|2015-07-17|2016-06-30|Production of precipitated calcium carbonate|
    EP16742350.8A| EP3325409B1|2015-07-17|2016-06-30|Production of precipitated calcium carbonate|
    BR112017025674-6A| BR112017025674A2|2015-07-17|2016-06-30|use of at least one depolymerized carboxylated cellulose solution|
    US15/579,772| US20180170765A1|2015-07-17|2016-06-30|Production of precipitated calcium carbonate|
    IL256473A| IL256473D0|2015-07-17|2017-12-21|Production of precipitated calcium carbonate|
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