process for the remineralization of water, and, use of a solution of calcium carbonate

专利摘要:
PROCESS FOR WATER REMINERALIZATION, AND USE OF A CALCIUM CARBONATE SOLUTION. The present invention relates to a process for the treatment of water and the use of calcium carbonate in such a process. In particular, the present invention is directed to a process for remineralizing water, comprising the steps of supplying feed water, providing an aqueous solution of calcium carbonate, wherein the aqueous solution of calcium carbonate comprises calcium carbonate dissolved and reaction species thereof, and combination of feed water and aqueous calcium carbonate solution.
公开号:BR112014004926B1
申请号:R112014004926-2
申请日:2012-08-28
公开日:2020-10-20
发明作者:Martine Poffet；Michael Skovby；Michael Pohl
申请人:Omya International Ag；
IPC主号:

专利说明:

[0001] The invention relates to the field of water treatment, and, more specifically, to a process for the remineralization of water and the use of calcium carbonate in such a process.
[0002] Drinking water has become scarce. Even in countries that are rich in water, not all sources and reservoirs are suitable for the production of drinking water, and many sources today are threatened by a dramatic deterioration in water quality. Initially feed water used for drinking was mainly surface and groundwater. However, the treatment of sea water, salt water, brackish water, waste water and contaminated effluents is gaining more and more importance, for environmental and economic reasons.
[0003] In order to recover sea water or brackish water, for drinking uses, several processes are known, which are of considerable importance for dry areas, coastal regions and sea islands, and these processes include the distillation, electrolytic process, as well as osmotic or reverse osmotic. The water obtained by these processes is very soft and has a low pH value, due to the lack of pH buffer salts, and thus tends to be highly reactive and, if left untreated, this can create serious difficulties in corrosion during transport in conventional pipelines. In addition, untreated desalinated water cannot be used directly as a source of drinking water. To prevent the dissolution of undesirable substances in piping systems, to prevent corrosion of hydraulic works, such as tubes and valves and to make the water palatable, it is necessary to remineralize the water.
[0004] Conventional processes that are used mainly for the remineralization of water are the dissolution of lime by carbon dioxide and filtration in a bed of limestone. Other, less common remineralization processes include, for example, the addition of hydrated lime and sodium carbonate, the addition of calcium sulfate and sodium bicarbonate, or the addition of calcium chloride and sodium bicarbonate.
[0005] The process involves the treatment of lime solution with water acidified by CO2, where the following reaction is involved: Ca (OH) 2 + 2 CO2 - + Ca2 + + 2 HCO3
[0006] As can be collected from the reaction scheme above, two CO2 equivalents are needed to convert one Ca (OH) 2 equivalent to Ca2 + and bicarbonate for remineralization. This method is dependent on the addition of two CO2 equivalents in order to convert the alkaline hydroxide ions into the HCO3 buffering species. For the remineralization of water, a saturated solution of calcium hydroxide, commonly called lime water, from 0.1 to 0.2% by weight, based on the total weight, is prepared from a lime milk (usually maximum of 5% by weight). Therefore, a saturator to produce lime milk must be used and large volumes of lime water are required to reach the target level of remineralization. Another disadvantage of this method is that hydrated lime is corrosive and requires specific handling and appropriate equipment. In addition, a poorly controlled addition of hydrated lime to the soft water can lead to unwanted pH changes due to the lack of buffering properties of the lime.
[0007] The limestone bed filtration process comprises the step of passing the soft water through a granular bed of limestone, dissolving the calcium carbonate in the water flow. Entering the limestone contact with water acidified with CO2 mineralizes the water according to: CaCO3 + CO2 + H2O Ca2 + + 2 HCO3
[0008] Unlike the lime process, only one CO2 equivalent is stoichiometrically needed to convert one CaCCh equivalent to Ca2 + and bicarbonate for remineralization.
[0009] In addition, limestone is non-corrosive and, due to the buffering properties of CaCCh, large pH changes are prevented.
[00010] An additional advantage of using calcium carbonate over limestone is its presence of very low carbon dioxide. In order to produce one ton of calcium carbonate, 75 kg of CO2 is emitted, whereas 750 kg of CO2 is emitted for the production of one ton of lime. Therefore, the use of calcium carbonate instead of lime has some environmental advantages.
[00011] The rate of dissolution of granular calcium carbonate, however, is slow and filters are necessary for this process. This induces a considerable presence of these filters and large installation surfaces are necessary for the limestone bed filtration systems.
[00012] Methods for remineralizing water from lime milk or a lime slurry are described in US 7,374,694 and EP 0 520 826. US 5,914,046 describes a method for reducing acidity in discharges of effluents using a bed of pulsed limestone.
[00013] Thus, considering the drawbacks of known processes for remineralization of water, it is an object of the present invention to provide an alternative or improved process for remineralization of water.
[00014] Another objective of the present invention is to provide a process for the remineralization of water that does not require a corrosive compound, and thus, avoids the risk of fouling, eliminates the need for corrosion resistant equipment, and provides a safe environment for people working on the installation. It would also be desirable to provide a process that is environmentally friendly and requires low amounts of carbon dioxide when compared to current water remineralization with lime processes.
[00015] Another objective of the present invention is to provide a process for the remineralization of water, in which the amount of minerals can be adjusted to the required values.
[00016] Another objective of the present invention is to provide a process for remineralization using limestone that allows the use of smaller remineralization units, or to provide a remineralization process that allows the use of smaller volumes of the remineralization compound, for example, in comparison with the lime process. It would also be desirable to provide a process that can be operated on the surface of installations smaller than the limestone bed filtration process.
[00017] Although the Applicant knows it as a solution, unpublished European Patent Application No. 10 172771.7 describes a method for remineralizing desalinated and fresh water by injecting a micronized calcium carbonate slurry, preceding objects and other objects are solved by providing a process for water remineralization, comprising the steps of (a) providing feed water, (b) providing an aqueous solution of calcium carbonate, characterized by the fact that the solution of calcium carbonate comprises carbonate of dissolved calcium and its reaction type, and (c) combining the feed water from step (a), and the aqueous solution of calcium carbonate from step (b).
[00018] According to another aspect of the present invention, the use of an aqueous solution of calcium carbonate comprising calcium carbonate and reaction species dissolved therein for the remineralization of water is provided.
[00019] Advantageous embodiments of the present invention are defined in the corresponding subclaims.
[00020] According to one embodiment, the concentration of calcium carbonate in the solution is 0.1 to 1 g / L, preferably 0.3 to 0.8 g / L, and more preferably 0 , 5 to 0.7 g / L, based on the total weight of the solution.
[00021] According to another embodiment, the calcium carbonate used for the preparation of the aqueous solution of calcium carbonate in step b) has a weight average particle size of 0.1 to 100 pm, from 0, 5 to 50 pm, 1 to 15 pm, preferably 2 to 10 pm, more preferably 3 to 5 pm, or calcium carbonate has a weight average particle size from 1 to 50 pm, from 2 to 20 pm , preferably from 5 to 15 pm, and more preferably from 8 to 12 pm. The calcium carbonate particles can be obtained through friction based techniques, for example, grinding or grinding, either under wet or dry conditions. However, it is also possible to produce the calcium carbonate particles by any other appropriate method, for example, by precipitation, rapid expansion of supercritical solutions, spray drying, classification or fractionation of naturally occurring sand or sludge, sol-gel processes water filtration, spray reaction synthesis, flame synthesis, or liquid foam synthesis.
[00022] According to a preferred embodiment of the present invention, the aqueous solution of calcium carbonate from step b) has been prepared by one of the following steps: A) preparing an aqueous suspension of calcium carbonate in a first step, and introducing either: (i) a carbon dioxide generating compound, (ii) a carbon dioxide generating compound and an acid, or (iii) an acid in an aqueous suspension of calcium carbonate in a second step, or B ) introduce in a first step, either: (i) a carbon dioxide generating compound, (ii) a carbon dioxide generating compound and an acid, or (iii) an acid in the water to be used for the preparation of the solution calcium carbonate, and then introduce the calcium carbonate, either in dry form or as a second step suspension in water, or C) introduce a calcium carbonate suspension and either: (i) a generating compound carbon dioxide, (ii) a carbon dioxide-generating compound and an acid or (iii) an acid simultaneously.
[00023] For the purpose of the present invention, the term "carbon dioxide-generating compound" encompasses gaseous carbon dioxide, liquid carbon dioxide, solid carbon dioxide, a gas containing carbon dioxide, that is, a mixture of at least one gas and carbon dioxide, as well as compounds that release carbon dioxide during heat or chemical treatment. Preferably, the carbon dioxide-generating compound is a gaseous mixture of carbon dioxide and other gases, such as carbon dioxide that contains exhausted waste gases from industrial processes such as combustion processes or calcination processes or the like, or the compound carbon dioxide generator is carbon dioxide gas. When a gas mixture of carbon dioxide and other gases is used, then carbon dioxide is present in the range of 8 to about 99% by volume, and preferably in the range of 10 to 25% by volume, for example , 20% by volume.
[00024] The acid used in the present invention is preferably an acid selected from the group consisting of sulfuric acid, hydrochloric acid, sulfurous acid, phosphoric acid, and is preferably sulfuric acid or phosphoric acid.
[00025] According to yet another embodiment, calcium carbonate has a content of HCl insoluble compounds of 0.02 to 2.5% by weight, from 0.05 to 1.5% by weight, or 0.1 to 0.6% by weight based on the total weight of calcium carbonate. According to yet another embodiment, calcium carbonate is ground calcium carbonate, modified calcium carbonate, or precipitated calcium carbonate, or mixtures thereof.
[00026] According to an embodiment, the solution of step b) further comprises minerals containing magnesium, potassium or sodium, preferably magnesium carbonate, calcium and magnesium carbonate, for example, dolomitic limestone, limestone dolomite or semi-burnt dolomite, magnesium oxide, such as burnt dolomite, magnesium sulfate, potassium hydrogen carbonate, or sodium hydrogen carbonate.
[00027] According to another embodiment, the solution from step b) is prepared immediately before use in step b). According to yet another embodiment, the time between preparing the solution from step b) and combining the feed water from step a) and the solution from step b) in step c) is less than 48 hours , less than 24 hours, less than 12 hours, less than 5 hours, less than 2 hours or less than 1 hour. In accordance with yet another embodiment, the solution in step b) satisfies microbiological quality requirements specified by the national guidelines for drinking water.
[00028] According to one embodiment, the remineralized water obtained has a concentration of calcium as calcium carbonate from 15 to 200 mg / 1, preferably from 30 to 150 mg / L, and more preferably from 100 to 125 mg / L, or 15 to 100 mg / L, preferably 20 to 80 mg / L, and more preferably 40 to 60 mg / L.
[00029] According to another embodiment, the remineralized water obtained has a magnesium concentration of 5 to 25 mg / L, preferably 5 to 15 mg / L, and more preferably 8 to 12 mg / L . According to another embodiment, remineralized water has a turbidity value of less than 5.0 NTU, less than 1.0 NTU, less than 0.5 NTU, or less than 0.3 NTU. According to yet another embodiment, remineralized water has a Langelier saturation index of -1 to 2, preferably from -0.5 to 0.5, more preferably from -0.2 to 0 ,two. According to yet another embodiment, remineralized water has an SDI15 sediment density index less than 5, preferably less than 4, and most preferred less than 3. According to yet another form of In this embodiment, remineralized water has an MFI045 membrane encrustation index less than 4, preferably less than 2.5, most preferred less than 2.
[00030] According to one embodiment, the feed water is desalinated sea water, brackish or salt water, treated waste water or natural water, such as groundwater, surface water or rainwater.
[00031] According to one embodiment, remineralized water is mixed with feed water. According to another embodiment, the process further comprises a step of removing particles.
[00032] According to an embodiment, the process further comprises the steps of (d) measuring a parameter value of remineralized water, in which the parameter is selected from the group comprising alkalinity, total hardness, conductivity, calcium concentration, pH, CO2 concentration, total dissolved solids, and remineralized water turbidity, (e) comparing the measured parameter value with a predetermined parameter value, and (f) providing the amount of calcium carbonate solution, based on the difference between the measurement and the predetermined parameter value. According to another embodiment, the predetermined parameter value is a pH value, wherein the pH value is 5.5 to 9, preferably 7 to 8.5.
[00033] According to one embodiment, micronized calcium carbonate is used for remineralization of water, in which remineralized water is selected from drinking water, recreation water, such as water for swimming pools, industrial waters for process applications, irrigation water, or water for aquifer or well recharge.
[00034] "Dissolved calcium carbonate and reaction species" in the sense of the present invention is understood to encompass the following substances and ions: calcium carbonate (CaCCb), calcium ions (Ca2 +), bicarbonate ions (HCO3), carbonate ions (CO32), carbonic acid (H2CO3), as well as dissolved CO2, depending on the amount of dissolved CO2 under equilibrium conditions.
[00035] The term "alkalinity (TAC)" as used in the present invention is a measure of a solution's ability to neutralize acids to the carbonate or bicarbonate equivalence point. The alkalinity is equal to the stoichiometric sum of the bases in the solution and is specified in mg / L of CaCCh. Alkalinity can be measured with a titrator.
[00036] For the purpose of the present invention, the term "calcium concentration" refers to the total calcium content in the solution and is specified in mg / 1, as Ca2 + or as CaCCb. The concentration can be measured with a titrator.
[00037] "Conductivity" in the sense of the present invention is used as an indicator of how, free of ions, or free of impurity, free of salt the water measured is; the purer the water, the lower the conductivity. Conductivity can be measured with a conductivity meter, specified in S / m.
[00038] "Milled calcium carbonate (GCC)" in the sense of the present invention is a calcium carbonate obtained from natural sources, including marble, chalk, limestone or dolomite. Calcite is a carbonate mineral and the most stable polymorph of calcium carbonate. The other polymorphs of calcium carbonate are the minerals aragonite and vaterite. Aragonite will change to calcite at 380 to 470 ° C, and vaterite is even less stable. Ground calcium carbonate processed through a treatment, such as milling, sieving and / or fractionation, wet and / or dry, for example, by a cyclone. It is known to the person skilled in the art that ground calcium carbonate can intrinsically contain a defined concentration of magnesium, as is the case for dolomitic limestone.
[00039] The term "Langelier saturation index (LSI)" as used in the present invention describes the tendency for an aqueous liquid to scale or corrode, with a positive LSI indicating scale formation trends and a negative LSI indicating a corrosive character. A balanced Langelier saturation index, that is, LSI = 0, therefore means that the aqueous liquid is in chemical equilibrium. The LSI is calculated as follows: LSI = pH - pHs, where pH is the actual pH value of the aqueous liquid and pHs is the pH value of the aqueous liquid in CaCO saturation. The pH values can be estimated as follows: pH = (9.3 + A + B) - (C + D), where A is the numerical value indicator of total dissolved solids (TDS) present in the aqueous liquid, B is the numerical value of the aqueous liquid temperature indicator in K, C is the numerical value of the calcium concentration in the aqueous liquid in mg / 1 of CaCCh, D and is the numerical value of the alkalinity of the aqueous liquid in mg / 1 of CaCCh. Parameters A to D are determined using the following equations: A = (Logio (TDS) -l) / 10, B = -13.12 x Logio (T + 273) + 34.55, C = logio [Ca2 +] - 0.4, D = Logio (TAC), where TDS is the total dissolved solids in mg / 1, T is the temperature in ° C, [Ca2 +] is the calcium concentration of the aqueous liquid in mg / 1 of CaCOs, and TAC is the alkalinity of the aqueous liquid in mg / L of CaCO .
[00040] The term "sediment density index (SDI)" as used in the present invention refers to the amount of particulate matter in water and correlates with the tendency to scale in nanofiltration systems or reverse osmosis. The SDI can be calculated, for example, from the clogging rate of a 0.45 pm membrane filter when water is passed through a constant applied water pressure of 208.6 kPa. The SDI, 5 value is calculated from the clogging rate of a 0.45 pm membrane filter when water is passed through a constant applied water pressure of 208.6 kPa for 15 minutes. Typically, spiral-wound reverse osmosis systems will need an SDI less than 5, and hollow fiber reverse osmosis systems will need an SDI less than 3.
[00041] The term "modified fouling index (IMF)" as used in the present invention refers to the concentration of suspended matter and is a more accurate indicator than SDI for predicting the tendency of a water to encrust nanofiltration membranes or reverse osmosis. The method that can be used to determine the MFI can be the same as for the IDE, except that the volume is recorded every 30 seconds during a 15 minute filtration period. The MFI can be obtained graphically as the slope of the straight part of the curve when t / V is plotted against V (t is the time in seconds to collect a volume of V in liters). An MFI value of <1 corresponds to a value of about SDI <3 and can be considered low enough to control colloidal and particulate scale.
[00042] In case an ultrafiltration membrane (UF) is used for MFI measurements, the index is called MFI-F, in contrast to MFIO, 45 where a 0.45 pm membrane filter is used.
[00043] For the purpose of the present invention, the term "micronized" refers to a particle size in the micrometer range, for example, a particle size of 0.1 to 100 pm. The micronized particles can be obtained by means of friction-based techniques, for example, grinding or grinding, either under wet or dry conditions. However, it is also possible to produce micronized particles by any other appropriate method, for example, by precipitation, rapid expansion of supercritical solutions, spray drying, or classification or fractionation of naturally occurring sand or sludge, sol-gel filtration processes water, spray reaction synthesis, flame synthesis, or liquid foam synthesis.
[00044] Throughout this document, the "particle size" of a calcium carbonate product is described by its particle size distribution. The dx value represents the diameter at which x% by weight of the particles have diameters less than dx. This means that the d2o value is the particle size in which 20% by weight of all particles are smaller, and the d S value is the particle size in which 75% by weight of all particles are smaller. The dso value is thus the weight average particle size, that is, 50% by weight of all grains are larger or smaller than this particle size. For the purpose of the present invention, the particle size is determined as the weighted average particle size, unless otherwise indicated. For determining the weighted average particle size dso value for particles having a dso greater than 0.5 pm, a Sedigraph 5100 device from Micromeritics, USA can be used.
[00045] "Precipitated calcium carbonate (PCC)" in the sense of the present invention is a synthesized material, in general, obtained by precipitation following the reaction of carbon dioxide and lime in an aqueous medium or by precipitation from a calcium source and carbonate in water or by precipitation of calcium and carbonate ions, for example, CaCE and Na2CÜ3, out of the solution. Precipitated calcium carbonate exists in three main crystalline forms: calcite, aragonite and vaterite, and there are many different polymorphs (crystalline habits) for each of these crystalline forms. Calcite has a trigonal structure with typical crystalline habits such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal prismatic, colloidal pinacoidal (C-PCC), cubic and prismatic (P-PCC). Aragonite is an orthorhombic structure with crystalline habits typical of twin hexagonal prismatic crystals, as well as a diverse variety of thin elongated prismatic shapes, with curved blades, steep pyramid, chisel-shaped crystals, branched tree, and coral or wormlike types.
[00046] "Modified calcium carbonate" in the sense of the present invention is a surface-reacted natural calcium carbonate that is obtained by a process in which the natural calcium carbonate is reacted with another acid with a pKa, at 25 ° C , 2.5 or less and with CO2 gas formed in situ / or from an external source, and optionally in the presence of at least one aluminum silicate and / or at least one synthetic silica and / or at least at least one calcium silicate and / or at least one monovalent salt silicate, such as sodium silicate and / or potassium silicate and / or lithium silicate, and / or at least one aluminum hydroxide and / or at least one sodium and / or potassium silicate. More details on the preparation of surface reacted natural calcium carbonate are disclosed in WO 00/39222 and US 2004/0020410 A1, the content of such references hereinafter being included in the present patent application.
[00047] For the purpose of the present invention, a "slurry" comprises solids that are insoluble in water and water and optionally other additives and generally contains large amounts of solids and is therefore more viscous and generally of greater density than liquid from which it is formed.
[00048] The term "remineralization" as used in the present invention refers to the recovery of minerals in water containing no minerals at all, or in an insufficient amount, in order to obtain a water that is palatable. Remineralization can be achieved by adding at least calcium carbonate to the water to be treated. Optionally, for example, the health benefits of ensuring adequate intake of some essential minerals and trace elements, additional substances can be mixed in or with calcium carbonate and then added to the water during the remineralization process. According to national guidelines on human health and drinking water quality, the remineralized product may contain additional minerals containing magnesium, potassium or sodium, for example, magnesium carbonate, magnesium sulphate, potassium hydrogen carbonate, hydrogen carbonate sodium or other minerals that contain essential trace elements.
[00049] For the purpose of the present invention, a calcium carbonate solution means a clear solution of calcium carbonate in a solvent, where all or almost all of the CaCCb has been dissolved in the solvent to form a visually transparent solution . The solvent is preferably water.
[00050] The term "total dissolved solids (TDS)" as used in the present invention is a measure of the total content of all inorganic and organic substances contained in a liquid, in suspended molecular, ionized or micro granular form (colloidal sol) . In general, the operational definition is that the solids must be small enough to survive filtration through a sieve with an opening size of two micrometers. Total dissolved solids can be estimated with a conductivity meter and are specified in mg / L.
[00051] "Turbidity" in the sense of the present invention describes the opacity or turbidity of a liquid caused by individual particles (of suspended solids), which are generally invisible to the naked eye. Turbidity measurement is an important test of water quality and can be performed with a nephelometer. The turbidity units of a nephelometer calibrated as used in the present invention are specified as Nephelometric Turbidity Units (NTU). The process of the invention for remineralization of water comprises the steps of (a) supplying feed water, (b) providing an aqueous solution of calcium carbonate, wherein the aqueous solution of calcium carbonate comprises dissolved calcium carbonate and reaction species, and (c) the combination of the feed water from step a) and the aqueous solution of calcium carbonate from step b).
[00052] The feed water to be used in the process of the invention can be derived from several sources. The feed water preferably treated by the process of the present invention is desalinated sea water, brackish or salt water, treated waste water or natural water, such as groundwater, surface water or rainwater.
[00053] According to an embodiment of the present invention, the feed water cannot be pre-treated. Pre-treatment may be necessary, for example, if the feed water is derived from surface water, groundwater or rainwater. For example, to achieve drinking water guidelines, water needs to be treated through the use of chemical or physical techniques in order to remove pollutants, such as unwanted minerals and organic products. For example, ozonation can be used as a first pre-treatment step, followed by coagulation, flocculation, or decantation as a second treatment step. For example, iron (III) salts, such as FeCISCU or FeCb, or aluminum salts, such as AICI3, AUCSO4 s or polyaluminium can be used as flocculating agents. Flocculated materials can be removed from the feed water, for example, using sand filters or multilayer filters. Other water purification processes that can be used to pre-treat the feed water are described, for example, in EP 1 975 310, EP 1 982 759, EP 1 974 807, or EP 1 974 806.
[00054] According to another exemplary embodiment of the present invention, seawater or brackish water is firstly pumped out of the sea by abstraction in the open sea or underground abstraction, such as wells, and then subjected to physical pre-treatments such as sifting, sedimentation or sand removal processes. Depending on the quality of the water required, additional treatment steps, such as coagulation and flocculation, may be necessary in order to reduce the potential for fouling in the membranes. Seawater or pre-treated brackish water can then be distilled, for example, using instant multi-stage vaporization, multiple-effect distillation, or membrane filtration, such as ultrafiltration or reverse osmosis, to remove remaining particles and dissolved substances .
[00055] The aqueous solution of calcium carbonate from step b) was preferably prepared by one of the following steps: A) prepare an aqueous suspension of calcium carbonate in a first step, and introduce either: (i) a compound that generates carbon dioxide, (ii) a carbon dioxide-generating compound and an acid, or (iii) an acid in an aqueous calcium carbonate suspension in a second step, or B) introducing in a first step, either: (i ) a carbon dioxide generating compound, (ii) a carbon dioxide generating compound and an acid, or (iii) an acid in the water to be used for the preparation of the calcium carbonate solution, and then introducing calcium carbonate, either in dry form or as a second stage suspension in water, or C) introducing a calcium carbonate suspension and either: (i) a carbon dioxide-generating compound, (ii) a generating compound of carbon dioxide and an acid, or (iii) an acid simultaneously.
[00056] The carbon dioxide generating compound used is selected from gaseous carbon dioxide, liquid carbon dioxide, solid carbon dioxide and a gas containing carbon dioxide, and preferably carbon dioxide generating compound is a mixture carbon dioxide gas and other gases such as carbon dioxide containing waste gases exhausted from industrial processes, such as combustion processes or calcination processes or equivalent, or the carbon dioxide-generating compound is carbon dioxide gas. When a gas mixture of carbon dioxide and other gases is used, then carbon dioxide is present in the range of 8 to about 99% by volume, and preferably in the range of 10 to 25% by volume, for example. example, 20% by volume.
[00057] Carbon dioxide gas can be obtained from a storage tank, in which it is kept in the liquid phase. Depending on the rate of carbon dioxide consumption and the environment, isolated tanks both cryogenic and conventional can be used. The conversion of liquid carbon dioxide to carbon dioxide gas can be done using a heated air vaporizer, or an electric or vapor-based vaporization system. If necessary, the pressure of the carbon dioxide gas can be reduced before the injection step, for example, using a pressure reducing valve.
[00058] Carbon dioxide gas can be injected into a stream of feed water at a controlled rate, forming a dispersion of carbon dioxide bubbles in the stream and allowing the bubbles to dissolve therein. For example, the dissolution of carbon dioxide in the feed water can be facilitated by providing the feed water stream at a flow rate of 40 to 60 mg / 1 according to the starting CO2 concentration in the permeate / distillate, the value final target pH (excess CO2) and final target calcium concentration (CaCO3 added).
[00059] According to an exemplary embodiment, carbon dioxide is introduced into the water used for the preparation of the calcium carbonate solution in a turbulent region of the water, where turbulence can be created, for example, by a restriction in the pipe. For example, carbon dioxide can be introduced into the choke of a Venturi placed in the pipeline. The narrowing of the cross-sectional area of the pipe in the venturi strangulation creates a turbulent flow of energy sufficient to break carbon dioxide into relatively small bubbles and therefore facilitate its dissolution. According to one embodiment, carbon dioxide is introduced under pressure into the water stream. According to another embodiment of the present invention, the dissolution of carbon dioxide in the water used for the preparation of the calcium carbonate solution is facilitated by a static mixer.
[00060] A flow control valve or other means can be used to control the flow of carbon dioxide in the water used to prepare the calcium carbonate solution. For example, a CO2 metering block and an in-line CO2 metering device can be used to control the CO2 flow rate. According to an exemplary embodiment of the invention, CO2 is injected using a combined unit comprising a CO2 metering unit, a static mixer and an in-line CO2 measurement device.
[00061] Carbon dioxide acidifies the feed water, forming carbonic acid. The amount of carbon dioxide that is injected into the feed water will depend on the amount of carbon dioxide that is already present in the feed water. The amount of carbon dioxide that is already present in the feed water, in turn, will depend, for example, on the treatment upstream of the feed water. Feed water, for example, which has been desalted by rapid evaporation will contain a different volume of carbon dioxide, and thus a different pH, than the feed water which has been desalinated by reverse osmosis. Feedwater, for example, that has been desalinated by reverse osmosis can have a pH of about 5.3 and a CO2 amount of about 1.5 mg / 1.
[00062] The remineralization of the feed water is induced by injecting the calcium carbonate solution that comprises the dissolved calcium carbonate and their reaction to the feed water.
[00063] The calcium carbonate solution, which is injected into the feed water comprises dissolved calcium carbonate. According to one embodiment, the concentration of calcium carbonate in the solution is 15 to 200 mg / L, preferably 30 to 150 mg / L, and more preferably 100 to 125 mg / L, or 15 at 100 mg / L, preferably from 20 to 80 mg / L, and more preferably from 40 to 60 mg / L.
[00064] The calcium carbonate used for the preparation of the aqueous solution of calcium carbonate of step b) has a weighted average particle size in the micrometer range. According to one embodiment, micronized calcium has a weight average particle size of 0.1 to 100 pm, 0.5 to 50 pm, from 1 to 15 pm, preferably from 2 to 10 pm, more preferably from 3 to 5 pm, or calcium carbonate has a weight average particle size of 1 to 50 pm, from 2 to 20 pm, preferably from 5 to 15 pm, and more preferably from 8 to 12 pm .
[00065] Examples of suitable calcium carbonates are ground calcium carbonate, modified calcium carbonate or precipitated calcium carbonate, or a mixture thereof. A ground natural calcium carbonate (CGC) can be derived from, for example, one or more of marble, limestone, chalk, and / or dolomite. A precipitated calcium carbonate (PCC) may have, for example, one or more of the crystalline mineral forms aragonitic, vateritic and / or calcitic. Aragonite is commonly used in the acicular form, while vaterite belongs to the hexagonal crystal system. Calcite can form scalenohedral, prismatic, spherical and rhombohedral shapes. A modified calcium carbonate can have a natural calcium carbonate ground or precipitated with a modification of the internal and / or surface structure, for example, the calcium carbonate can be treated or coated with a hydrophobizing surface treatment agent, such as such as, for example, an aliphatic carboxylic acid or a siloxane. Calcium carbonate can be treated or coated to become cationic or anionic, for example, a polyacrylate or polymac.
[00066] According to an embodiment of the present invention, calcium carbonate is a ground calcium carbonate (GCC). According to a preferred embodiment, calcium carbonate is a ground calcium carbonate with a particle size of 3 to 5 pm.
[00067] According to another embodiment of the present invention, calcium carbonate comprises a content of HCl insoluble compounds from 0.02 to 2.5% by weight, from 0.05 to 1.5% by weight , or 0.1 to 0.6% by weight, based on the total weight of calcium carbonate. Preferably, the content of HCl insoluble compounds in calcium carbonate does not exceed 0.6% by weight, based on the total weight of calcium carbonate. The content of HCl insoluble compounds can be, for example, minerals, such as quartz, silicate or mica.
[00068] In addition to calcium carbonate, the calcium carbonate solution may contain other micronized minerals. According to one embodiment, the calcium carbonate solution may comprise micronized magnesium carbonate, calcium and magnesium carbonate, for example, dolomitic limestone, limestone dolomite or semi-burnt dolomite, magnesium oxide, such as burnt dolomite, magnesium sulfate, potassium hydrogen carbonate, sodium hydrogen carbonate or other mineral salts that contain essential trace elements.
[00069] In accordance with an embodiment of the present invention, the calcium carbonate solution is prepared before being combined with the feed water. On-site preparation of the calcium carbonate solution may be preferred. The reason is that, when the calcium carbonate solution is not prepared on the spot and / or freshly prepared the addition of other agents, such as stabilizers, biocides in the calcium carbonate solution may be necessary for reasons of stabilization. However, such agents can be the unwanted compounds in remineralized water, for example, for toxic reasons or can inhibit the formation of freely available Ca2 + ions. According to a preferred embodiment of the present invention, the time between the preparation of the calcium carbonate solution and the injection of the calcium carbonate solution is short enough to prevent bacterial growth in the calcium carbonate solution. According to an exemplary embodiment, the time between the preparation of the calcium carbonate solution and the injection of the calcium carbonate solution is less than 48 hours, less than 24 hours, less than 12 hours, less than 5 hours, less than 2 hours or less than 1 hour. According to another embodiment of the present invention, the injected solution satisfies the microbiological quality requirements specified by the international drinking water guidelines.
[00070] The calcium carbonate solution can be prepared, for example, using a mixer such as a mechanical stirrer for solutions, or a specific powder-liquid mixing device for the most concentrated calcium carbonate solutions, or a reactor of closed circuit. According to an embodiment of the present invention, the calcium carbonate solution is prepared using a mixing machine, in which the mixing machine allows simultaneous mixing and dosing of the calcium carbonate solution.
[00071] The water used to prepare the solution can, for example, be distilled water, feed water or industrial water. According to a preferred embodiment of the invention, the water used to prepare the feed water solution is, for example, permeate or distillate obtained from a desalination process. According to an exemplary embodiment, the water used to prepare the calcium carbonate solution is acidified carbon dioxide. Without being bound by any theory, it is believed that such CO2 pretreatment of the water used to prepare the calcium carbonate solution increases the dissolution of calcium carbonate in the water, and thus decreases the reaction time.
[00072] According to one embodiment, the calcium carbonate solution comprising dissolved calcium carbonate is injected directly into a stream of feed water. For example, the calcium carbonate solution can be injected into the feed water stream at a controlled rate by means of a pump that communicates with a storage container for the solution. Preferably, the calcium carbonate solution can be injected into the feed water stream at a rate of 1 to 200 1 / m3 of feed water, depending on the concentration of the solution and the final concentration in the remineralization water. According to another embodiment, the calcium carbonate solution comprising dissolved calcium carbonate is mixed with the feed water of a reaction chamber, for example, using a mixer such as a mechanical mixer. According to yet another embodiment, the calcium carbonate solution is injected into a tank that receives the entire flow of feed water.
[00073] According to an embodiment of the present invention, only a part of the feed water is remineralized by injection of the calcium carbonate solution, and subsequently, the remineralized water is mixed with untreated feed water. Optionally, only a portion of the feed water is remineralized at a high calcium carbonate concentration compared to the final target value, and subsequently the remineralized water is mixed with untreated feed water.
[00074] According to another embodiment, the concentrated calcium carbonate solution or a part of the concentrated calcium carbonate solution is separated by filtration, for example, by ultrafiltration, to further reduce the level of water turbidity remineralization.
[00075] For the purpose of the present invention, the term "concentrated calcium carbonate solution" is to be understood as a calcium carbonate solution that contains the largest possible amount of calcium carbonate dissolved in the respective solvent. This greatest possible amount of dissolved calcium carbonate can be determined by methods known to those skilled in the art, such as conductivity measurement, or titration hardness measurement.
[00076] The quality of remineralized water can, for example, be assessed by the Langelier saturation index (LSI). According to one embodiment, remineralized water has a Langelier saturation index of -1 to 2, preferably from -0.5 to 0.5, more preferably from -0.2 to 0.2. According to another embodiment, remineralized water has an SDI15 sediment density index less than 5, preferably less than 4, and most preferred less than 3. According to yet another embodiment , remineralized water has an MFIo membrane encrustation index, 45 less than 4, preferably less than 2.5, most preferred less than 2. The assessment can be done, for example, by measuring the pH of untreated feed water continuously. Depending on the remineralization system, the pH of the treated pH can be measured, for example, in a stream of treated water, in the reaction chamber, where the calcium carbonate solution and the feed water are mixed, or in a tank storage for remineralized water. According to an embodiment of the present invention, the pH is measured 30 min, 20 min, 10 min, 5 min or 2 minutes after the remineralization step. The pH value measurement can be done at room temperature, that is, about 20 ° C.
[00077] According to an exemplary embodiment of the invention, the amount of injected calcium carbonate solution is controlled by detecting the pH value of the treated feed water. Alternatively or in addition, the amount of injected calcium carbonate solution is controlled by detecting parameters such as alkalinity, total hardness, conductivity, calcium concentration, CO2 concentration, total dissolved solids, or turbidity. According to an embodiment, the process of the present invention further comprises the steps of (d) measuring a parameter value of remineralized water, in which the parameter is selected from the group comprising alkalinity, total hardness, conductivity, calcium concentration, pH, CO2 concentration, total dissolved solids, or remineralized water turbidity, (e) compare the measured parameter value with a predetermined parameter value, and (f) provide the amount of injected calcium carbonate solution , based on the difference between the measurement and the predetermined parameter value.
[00078] According to an embodiment, the value of the predetermined parameter is a pH value, wherein the pH value is 5.5 to 9, preferably 7 to 8.5.
[00079] Fig. 1 shows a schematic of an apparatus that can be used to operate the method of the invention. In this embodiment, the feed water flows from a reservoir (1) into a pipe (2). Another tube (12) is arranged between the reservoir (1) and a storage tank (9). The tube (12) has a gas inlet (5) through which carbon dioxide from a carbon dioxide source (4) can be injected into the feed water to prepare CO2-acidified water, in a first step . A mixer (8) is connected to the tube (12) downstream of the reservoir (1). In the mixer (8), the calcium carbonate solution is prepared on the spot by mixing water, which is obtained from the reservoir (1) through the tube (12) and the calcium carbonate obtained from a storage container (7). A storage tank (9) can be connected to the tube (12). When present, it is supplied after the mixer (8), in order to preserve the calcium carbonate solution before its introduction into the feed water stream. An inlet (10) is located downstream of the reservoir (1) in the pipeline (2) through which the calcium carbonate solution comprising dissolved calcium carbonate from the mixer (8) is injected into the feed water stream, through of the storage tank (9), when present. The pH of remineralized water can be measured downstream of the slurry inlet (10) at a sample point (11). According to one embodiment, the flow of the feed water is between 20000 and 500000 m3 per day.
[00080] Fig. 2 shows another embodiment of the present invention. In this embodiment, the aqueous suspension of calcium carbonate is prepared in a first step by introducing the calcium carbonate obtained from a storage container (7) into the feed water, which is obtained from the reservoir (1 ) and flows through the tube (12). In a second step, the carbon dioxide from a carbon dioxide source (4) is combined with the pipe water (12) that already contains the calcium carbonate suspension in the mixer (8). Then, the water containing the calcium carbonate suspension and the carbon dioxide are mixed in order to obtain the solution of the calcium carbonate which comprises dissolved calcium carbonate. Through the inlet (10) located in the pipeline (2) downstream of the reservoir (1), the calcium carbonate solution comprising dissolved calcium carbonate from the mixer (8) is then injected into the feed water stream. The pH of remineralized water can be measured downstream of the slurry inlet (10) at a sample point (11). According to one embodiment, the flow of the feed water is between 20000 and 500000 m3 per day.
[00081] Note that the storage tank (9) is an optional feature for carrying out the process of the present invention. In other words, the storage tank (9) does not have to be present in embodiments of the present invention. In this case, the calcium carbonate solution is injected directly from the mixer (8) into the water supply pipe (2) through the inlet (10).
[00082] The process of the invention can be used to produce drinking water, recreation water, such as swimming pool water, industrial water for process applications, irrigation water, or water for aquifer or well recharge.
[00083] According to one embodiment, the concentrations of carbon dioxide and calcium carbonate in remineralized water meet the necessary values for the quality of drinking water, which are established by national guidelines. According to an embodiment, the remineralized water obtained by the process of the invention has a calcium concentration of 15 to 200 mg / L of CaCCh, preferably from 30 to 150 mg / L, and more preferably from 40 to 60 mg / L, or preferably from 50 to 150 mg / L as CaCCh, and more preferably from 100 to 125 mg / L as CaCCU If the solution further comprises a magnesium salt such as magnesium carbonate, or magnesium sulfate, the remineralized water obtained by the process of the invention may have a magnesium concentration of 5 to 25 mg / L, preferably 5 to 15 mg / L, and more preferably 8 to 12 mg / L.
[00084] According to an embodiment of the present invention, remineralized water has a turbidity of less than 5.0 NTU, less than 1.0 NTU, less than 0.5 NTU, or less than 0, 3 NTU.
[00085] According to an exemplary embodiment of the present invention, remineralized water has an LSI of -0.2 to 0.2, a calcium concentration of 15 to 200 mg / L, a magnesium concentration of 5 to 25 mg / L, an alkalinity between 100 and 200 mg / L as CaCCE, a pH value between 7 and 8.5, and a turbidity less than 0.5 NTU.
[00086] According to an embodiment of the present invention, a particle removal step is performed after mineralization, for example, to reduce the level of turbidity of the remineralized water. According to an embodiment of a sedimentation step, it is carried out. For example, feed water and / or remineralized water can be channeled to a storage tank or clarifier to further reduce the level of water turbidity. According to another embodiment, the particles can be removed by decanting. Alternatively, at least part of the feed water and / or remineralized water can be filtered, for example, by ultrafiltration, to further reduce the level of water turbidity. Examples Measurement methods: Specific surface area BET
[00087] The specific surface area BET (also known as SSA) was determined according to the ISO 9277 standard using a Tristar II 3020 sold by the company MICROMERITICS ™. Particle size distribution (mass% of particles with a diameter <X nm) and weight average particle diameter (dso) of particulate material (dso (um) Sedigraph ™ 5100
[00088] The weight average particle diameter and the particle diameter mass distribution of a particulate material were determined using the sedimentation method, that is, the analysis of the sedimentation behavior in a gravimetric field. The measurement is made with a Sedigraph 5100 ™ sold by MICROMERITICS ™.
[00089] The method and the instrument are known to those skilled in the art and are normally used to determine the size of particles in fillers and pigments. The samples were prepared by adding an amount of product corresponding to 4 g of dry PCC to 60 ml of a 0.1% aqueous solution of Na4P2Ü7 by weight. The samples were dispersed for 3 minutes using a high speed stirrer (Polytron PT 3000/3100 at 15000 rpm). Then, it was submitted to ultrasound, using an ultrasonic bath for 15 minutes and then added to the Sedigraph mixing chamber. Weight of solids (% by weight) of a suspended material
[00090] The weight of solids (also called the solids content of a material) was determined by dividing the weight of the solid material with the total weight of the aqueous suspension.
[00091] The weight of the solid material was determined by weighing the solid material obtained by evaporating the aqueous phase of the suspension and drying the material obtained to a constant weight.
[00092] The following examples show the preparation of the various solutions of calcium carbonate in various concentrations, which were prepared from a range of calcium carbonate products according to their physical and chemical properties, for example, rocks carbonate, average particle size, content of insoluble compounds, and so on.
[00093] Table 1 below summarizes the different calcium carbonate products used during remineralization tests.
Table 1 [11It should be noted that all of the calcium carbonates listed above are commercially available from Omya, Switzerland. A. Laboratory examples:
[00094] Three samples were evaluated for this study, sample A is a limestone calcium carbonate from France and samples B and C are a marble calcium carbonate supplied from the same facility in Australia, but with different weights of average particle size.
[00095] Table 2 summarizes the different products used during the remineralization tests carried out on a laboratory scale.
Table 2
[00096] The water used for these remineralization tests was water that was obtained by reverse osmosis (RO), and which has the following average quality:

[00097] The carbon dioxide used is commercially available as “Kohlendioxid 3.0” from PanGas AG, Dagmersellen, Switzerland. Purity is> 99.9% by Vol .. A.l Maximum concentration of calcium carbonate dissolved in the solution; Preparation of a calcium carbonate solution
[00098] The maximum concentration of calcium carbonate dissolved in RO water (reverse osmosis) was investigated by mixing CaCOs with RO water that was pre-dosed with carbon dioxide (CO2). Under conditions acidified by CO2, it is expected to dissolve up to 1 g of CaCOs. All laboratory tests were performed by batching of 1L of RO water with pre-dosing of CO2 of 1.5 L / min for 30 seconds through a glass nozzle placed in the RO water sample.
Table 3
[00099] The maximum alkalinity from the four supernatants was 466.8 mg / L as CaCOs. This maximum alkalinity was obtained in the supernatant prepared by the addition of 1.0 g / L of CaCOs in RO water acidified by CO2. However, some precipitate can still be seen at the bottom of the flask.
[000100] The calcium carbonate samples of marble B and C are produced from a single production site, but have different weight average particle size. Both products were also tested to determine the maximum concentration of CaCOs dissolved in RO water acidified by CO2.
[000101] This test was carried out under the same conditions as for the previous tests. The initial CaCOs concentrations used were 0.5 and 0.7 g / L for both samples B and C. The supernatants obtained after 24 hours of sedimentation were collected and analyzed.
[000102] Table 4 shows the different results obtained for the preparation of the various CaCOs solutions concentrated in CO2 acidified water using samples B and C, in two different CaCOs concentrations in the RO.
Table 4
[000103] As can be deduced from Table 4, the maximum alkalinity of the four supernatants was obtained by adding 0.7 g / L of CaCCh in CO2-acidified RO water, reaching 529.0 and 516, 4 mg / L as CaCOs for the supernatants prepared from sample B and sample C, respectively. The alkalinity of the supernatant prepared from sample C, with an initial concentration of 0.5 g / L was lower than expected. The reason for this is not clear, but it is probably due to an inaccurate dosage.
[000104] However, it fits with the lowest values also observed for conductivity and turbidity. However, some precipitate can also be seen at the bottom of the flask. A.2 Change in pH during remineralization with calcium carbonate:
[000105] Some remineralization tests were carried out by dosing the concentrated CaCCb solutions of CaCCb marble (samples B and C) to the RO water. By diluting the concentrated CaCOs solution in the RO water, suitable properties for the treated water can be achieved.
[000106] The volume of concentrated CaCOs solution added to the RO water was calculated according to its alkalinity, aiming to increase the alkalinity of 45 mg / L as CaCOs. This dose corresponds to a dilution factor of 8 to 12 with respect to the initial alkalinity of the CaCOs solutions. The RO water used for these remineralization tests had a pH value of 5.32, and the alkalinity was 6.32 mg / L of CaCOs.
[000107] After 2 minutes of mixing, sampling was performed and the conductivity and turbidity were measured, giving values between 107 to 118 pS / cm and 0.4 to 0.6 NTU, respectively. After 10 minutes, the final pH and alkalinity were also measured providing pH values of 6.3 to 6.4, and 50 to 53 mg / L as CaCOi for the final alkalinity, respectively.
[000108] Table 5 shows the different results obtained for remineralization of RO water by dosing a CaCO Solution, concentrated from samples B and C to RO water (addition of 45 mg / L of CaCOs).
Table 5 [1] measured 10 minutes after adding the CaCO3 solution to the RO water. [2] measured 2 minutes after adding the CaCO3 solution to the RO water.
[000109] From pH 5.32 of RO water the addition of CaCO3 solutions induced a rapid change in pH up to 6.3 to 6.4, and within a few minutes, the pH reaches an equilibrium state. The final pH is less than the target values between 7.0 and 8.5. It is suspected that CO2 was overdosed during this test.
[000110] As a conclusion for concentrated CaCO3 solutions in CO2-saturated RO water, the maximum values for alkalinity were in rounded numbers 470 mg / L as CaCO3 for the limestone sample A, and between 520 and 530 mg / L as CaCO3 for marble samples B and C. Remineralization with concentrated CaCO3 solutions showed a rapid increase in pH, and the stabilized pH was obtained within a few minutes. The final pH shows values between 6.3 and 6.4 for the remineralization of RO water up to 50 mg / L alkalinity, as CaCO3, starting with RO water with a pH of 5.5, and an alkalinity of 6 mg / L as CaCO3. B. examples on a pilot scale: B.1 Pilot remineralization unit 1;
[000111] After initial remineralization tests on a laboratory scale, the pilot test aimed to study the performance of processes on a larger scale. Different types of calcium carbonate were also tested in this pilot unit. The water used was deionized water instead of reverse osmosis water. The carbon dioxide used is commercially available as “Kohlendioxid 3.0” from PanGas AG, Dagmersellen, Switzerland. Purity is> 99.9% by Vol ..
[000112] The pilot unit consists of a 100 L mixing vessel, where CaCOs in powder form and deionized water were mixed at the beginning of each test. The resulting CaCOs solution was then pumped through the tubular reactor at a pressure of up to 2 bar. CO2 was administered at the beginning of the tubular reactor, at a defined flow rate, and remineralized water then flowed through the tubular reactor to allow CaCOs to completely dissolve in the water. Samples of the concentrated CaCOs solutions were taken at the end of the tube, and pH, conductivity and turbidity were measured.
[000113] The deionized water used for these tests had the following average quality:
B.1.1 Maximum concentration of calcium carbonate dissolved in the solution (Sample A):
[000114] The maximum concentration of calcium carbonate dissolved in deionized water, was also tested in a pilot unit in a continuous mode. The pilot tests were carried out under acidic conditions by measuring carbon dioxide (CO2) for a suspension of calcium carbonate in water. According to previous laboratory tests, maximum alkalinity was obtained by initial concentration between 500 and 700 mg / L of calcium carbonate in deionized water under conditions acidified by CO2. For all pilot tests, a solution having an initial concentration of calcium carbonate was mixed with deionized water and was pumped through a tubular reactor at an average flow rate of 15 L / h under a pressure of about 2 bar.
[000115] Lime calcium carbonate (Sample A) was used for the initial pilot test with initial concentrations of 0.5, 0.6, 0.7 g / L of CaCCh in CO2 acidified water. The residence time in the tubular reactor was about 45 minutes and, when a steady state was reached, the resulting concentrated calcium carbonate solutions were collected at the outlet of the tubular reactor and analyzed for pH, turbidity, conductivity and alkalinity.
[000116] Table 6 shows the different results obtained for the preparation of the concentrated solution of CaCCh in water acidified by CO2 using sample A in different initial concentrations of CO3 in deionized water.
Table 6
[000117] As can be seen from Table 6, the maximum alkalinity (within the dose range used) when using sample A was obtained by adding 0.7 g / L of CaCCb to the CO2-acidified feed water and reached 458 mg / L as CaCCb, for which the turbidity was 3.03 NTU. B.1.2 Different types of calcium carbonate:
[000118] Lime calcium carbonate (sample A) from France was compared with other calcium carbonate products for the preparation of a concentrated calcium carbonate solution. From two different production facilities, two marble calcium carbonates with different weight average particle sizes were tested, ie sample D and sample E were produced at the same facility in Austria, but have a weight average particle size 3.3 and 8.0 pm, respectively. Similarly, sample F and sample G were produced at the same facility in France, and have a weight average particle size of 4.4 and 10.8 pm, respectively. The main difference between the two production sites is the quality of the starting material, with a high content of insoluble compounds of 2.0% for the first unit (samples D and E) and a content of insoluble compounds low of 0.2 % for the second installation (samples F and G). The last product tested, sample H, was a precipitated calcium carbonate (PCC) product from Austria, which is very pure and fine.
[000119] Table 7 summarizes the different calcium carbonate products used during the remineralization tests carried out on a pilot scale.
Table 7
[000120] The pilot tests were carried out with a starting concentration for each calcium carbonate product of 0.5 g / L of CaCO , in water acidified by CO2. The residence time in the tubular reactor was the same as in the previous pilot tests, that is, about 45 minutes with a flow rate of 15 L / h. When a steady state was reached, the resulting concentrated calcium carbonate solutions were collected at the outlet of the tubular reactor and analyzed for pH, turbidity, conductivity and alkalinity.
[000121] Table 8 shows the different results obtained for the preparation of CaCCL solutions concentrated in water acidified by CO2 with different calcium carbonates for a defined CaCO3 concentration in deionized water.
Table 8
[000122] As can be seen from Table 8, when sampled at the outlet of the tubular reactor, concentrated calcium carbonate solution with maximum alkalinity was obtained when using precipitated calcium carbonate (PCC) product (sample A) . However, the measured turbidity for the concentrated calcium carbonate solution is not the minimum value obtained for this series of tests. In comparison with all marble products (samples D, E, F, G), limestone calcium carbonate (sample A) had low turbidity values. When comparing the two products of different particle sizes, for example, as samples D and E, or as samples F and G, it was surprisingly found that the larger the average particle size, the lower turbidity can be achieved. However, as expected, the smaller the average particle size, the greater the final conductivity and alkalinity. B.1.3 Dilution to achieve remineralization concentration:
[000123] To satisfy the target water qualities, the concentrated calcium carbonate solution was dissolved with deionized water. Dilution factors were defined according to the initial alkalinity of the concentrated calcium carbonate in order to decrease the alkalinity below 45 mg / L as CaCOs. The final pH was adjusted to 7.8 with a 5% by weight NaOH solution, and the final turbidity was measured.
[000124] Table 9 shows the different results for remineralized water obtained by dosing a concentrated solution of sample A CaCOs for deionized water (addition of 45 mg / L of CaCOs).
Table 9
[000125] As can be deduced from Table 9, the lowest level of turbidity for these remineralization tests using a calcium carbonate concentrate was 0.39 NTU (rounded to 0.4 NTU). The other tests gave higher levels of turbidity between 0.8 and 1.0 (rounded values of 0.97 and 1.03) NTU.
[000126] Following a respective WHO guidance, there is very likely, in the future, the demand to also adjust the content of magnesium compounds soluble in final drinking water to around 10 mg / L of Mg.
[000127] An attempt was made to adjust the Mg content in the solution by mixing a magnesium salt with the calcium carbonate sample A before introducing the solution into the tubular reactor. MgSCU was selected as the soluble Mg salt, however, it is mentioned that the final sulfate level in the water must still remain in the permitted range (<200 ppm), especially when treated water is used for agricultural applications. Dilution factors were also defined according to the initial alkalinity of the concentrated calcium carbonate in order to decrease the alkalinity below 45 mg / L as CaCO ,. The final pH was adjusted to 7.8 with a 5% by weight NaOH solution, and the final turbidity was measured.
[000128] Table 10 shows the different results for remineralized water obtained by dosing a concentrated solution of CaCCh from sample A and magnesium sulfate in deionized water (addition of 45 mg / L of CaCO3).
Table 10
[000129] Some samples of remineralized water were sent to a water quality control laboratory in order to assess all the properties of drinking water. For example, remineralized water obtained using only calcium carbonate and which showed the lowest level of turbidity was obtained from Tests No. 12 and No. 15. Remineralized water obtained by using a mixture of calcium carbonate and magnesium sulfate and which showed the lowest level of turbidity was obtained from Test n ° 17. These three samples were sent to Carintian Institut for Food Analysis and Quality Control in Austria for analysis, and as water samples were approved by the institute for complying with strict Austrian guidelines for drinking water quality and WHO guidelines for soluble magnesium.
[000130] Table 11 shows the quality of drinking water for remineralized water obtained by dosing a concentrated solution of sample A CaCOs for deionized water (addition of 45 mg / L of CaCOs).
Table 11 B.2 Pilot remineralization unit 2:
[000131] After the initial pilot remineralization tests, a new series of pilot scale tests were carried out in another remineralization unit capable of working in a pressure range of 2 to 7 bar, an RO water flow between 300 and 400 L / h, and a CO2 dosage between 1.1 and 5.5 L / min. The carbon dioxide used is commercially available as “Kohlendioxid 3.0” from PanGas AG, Dagmersellen, Switzerland. Purity is> 99.9% by Vol.
[000132] The pilot unit consists of a 60 L mixing vessel, where CaCOs in powder form and RO water were introduced at the defined times (that is, more than once).
[000133] The resulting CaCOs solution was then pumped through a mixer, where the CO2 was dosed at a defined flow, and the concentrated CaCOs solution was passed through a tube to allow the complete dissolution of the CaCOs in the water. The residence time in the tubular reactor was about 45 minutes and, when a steady state was reached, the resulting concentrated calcium carbonate solutions were collected at the outlet of the tubular reactor and analyzed for pH, turbidity, conductivity and alkalinity. B.2.1 Different working pressures:
[000134] Different working pressures were tested in the pilot remineralization unit described above, in order to study the effect of pressure on the dissolution of calcium carbonate in RO water under acidic conditions, with carbon dioxide (CO2). According to the results of the first pilot test, an initial concentration of 500 mg / L of calcium carbonate in RO water was prepared, and the resulting solution was dosed with an excess of CO2. The pilot tests carried out at different working pressures had a flow rate of 3001 / h, and the pressure varied between 2 and 7 bar. The calcium carbonate used for these pilot tests was a limestone from France (Sample A).
[000135] Table 12 shows the different results obtained for the preparation of the concentrated CaCOs solution in CO2 acidified water using a sample with a concentration of 0.5 g / L of CaCOs in the RO water with different pressures and for a flow rate CO2 of 3.3 L / min.
Table 12
[000136] These pilot tests showed that in these conditions, the test of a higher pressure does not improve the dissolution of CaCO3 resulting in a higher level of turbidity for higher tested pressures. One of the consequences of using a higher pressure is to increase the temperature of the CaCO3 solution which is due to the pumps. Therefore, remineralized water coming out of the pilot unit is hotter, which can have an impact on the CO2 solubility in the water. In other words, the higher the water temperature, the less CO2 will dissolve in the water. As a consequence of the reaction scheme below: CaCO3 + CO2 + H2O Ca2 + + 2 HCO3
[000137] There is less CaCO3 dissolved in the solution, 0 which in turn leads to a higher level of turbidity, due to the amount of undissolved CaCO B.2.2 Different CO2 flows:
[000138] It is highly suspected that the dosage of CO2 will have a significant impact on the rate of dissolution of CaCO3 in RO water. Therefore, different CO2 flows were tested for the preparation of the concentrated CaCO3 solution. All tests were performed using the same protocol described for the previous tests for a defined pressure, but with different CO2 flow rates.
[000139] Table 13 shows the different results obtained for the preparation of the concentrated solution of CaCO3 in water acidified by CO2 using a sample with a concentration of 0.5 g / L of CaCO3 in the RO water, at a pressure of 5, 5 bar, using different CO2 flow rates.
Table 13
[000140] It can be seen from the results presented in Table 13, that under the conditions tested, the solubility of CaCCb in RO water can be improved when the CO2 flow is increased. This can be achieved by increasing the conductivity and decreasing the turbidity at the outlet of the reaction tube, when increasing the CO2 flow. B.2.3 Residence time:
[000141] The residence time allocated for the dissolution of CaCCb to occur was also studied. In this regard, pilot tests were performed using a single or two tubes connected one after the other. This configuration made it possible to double the residence time of approximately 45 minutes for a tube of about 90 minutes for two connected tubes, and, therefore, to study the impact of the residence time on the resulting turbidity and conductivity.
[000142] Table 14 shows the different results obtained for the preparation of the concentrated CaCO solution in water acidified by CO2 using a sample with a concentration of 0.5 g / L of CaCCh in RO water, with a defined CO2 flow and pressure for different residence times.
Table 14
[000143] The two sets of tests presented in Table 14 clearly show that residence time has a direct effect on the dissolution of CaCOs in RO water for both conditions tested, ie Tests n 0 28 and 0 29, and the Tests n 0 30 and n °. 31. It can clearly be seen that the longer the residence time, the lower the turbidity, respectively, and the greater the conductivity. C. Additional examples: Marble / Limestone
[000144] The following examples show the preparation of concentrated solutions of calcium hydrogen carbonate in reverse osmosis (RO) water by dosing CO2 in a calcium carbonate suspension, and filtering the resulting suspension through a ultrafiltration membrane to remove the rest of the insoluble compounds.
[000145] Two calcium carbonate products were selected according to their physical and chemical properties, for example, carbonate rocks, average particle size, content of insoluble compounds, and specific surface area and were compared with each other in with respect to the final turbidity and conductivity of the filtered and concentrated calcium hydrogen carbonate solutions.
[000146] The following Table 15 summarizes the different calcium carbonate products used during the pilot tests for the preparation of calcium hydrogen carbonate solutions.
Table 15 [1] It should be noted that all of the above-mentioned calcium carbonates are commercially available from Omya, Switzerland.
[000147] The RO water used for these tests has the following average quality:
C.l. Pilot scale examples:
[000148] A series of pilot scale tests were carried out on a reactor system under the following working conditions:
[000149] Pressure: ~ 2.5 bar, and flow rate: 300 L / h and CO2 dosage: 3.3 L / min.
[000150] The carbon dioxide used is commercially available as "Kohlendioxid 3.0" from PanGas AG, Dagmersellen, Switzerland. Purity is> 99.9% by Vol ..
[000151] The reactor system consisted of a 60 L mixing tank in which the powdered CaCCh and RO water were introduced at the defined times (that is, more than once), in order to have a initial calcium carbonate concentration of 500 to 1000 mg / L (0.05 to 1% by weight). The suspension of starting CaCOs was then pumped through a mixer, where CO2 was dosed at a defined flow rate to allow the dissolution of calcium carbonate in RO water according to the following reaction: CaCOs (s) + CO2 (aq ) + H2O Ca (HCChh (aq)
[000152] The resulting suspension was passed through a tube for the complete dissolution of CaCOs in the water. The residence time in the tube was about 40 minutes and, when a steady state was reached, the resulting suspension was collected at the outlet of the tube and analyzed for conductivity and turbidity.
[000153] The resulting suspension was then pumped through an ultrafiltration membrane, type Inge Dizzer P 2514-0.5, to remove insoluble material. Two modes of cross-flow filtration, with no outlet, were tested: the first mode consists of 2/3 of the flow to be recirculated and 1/3 of the flow through the membrane, and the last so that it consists of having the flow total going through the ultrafiltration membrane.
[000154] The filtered calcium hydrogen carbonate solutions were analyzed for conductivity and turbidity as well, and compared to the initial feed calcium carbonate solutions and the resulting suspensions were filtered which were recirculated back to the tank. C.l.l Tests with very pure calcium carbonate
[000155] CaCCh feed (or starter) solutions were prepared with sample A, at different initial concentrations of calcium carbonate in reverse osmosis water, but also with stoichiometric excess of CO2 and different residence time.
[000156] Table 16 shows the working conditions in the cross flow mode for the preparation of the solution of calcium hydrogen carbonate (sample A) in RO water.
Table 16
[000157] Table 17 shows the different results obtained for the CaCOs feed suspensions (sample A) and the resulting unfiltered suspensions and the filtered calcium hydrogen carbonate solutions.
Table 17
[000158] The residence time used for preparing the CaCO feed suspension it did not affect the conductivity and turbidity of the filtered calcium hydrogen carbonate solution (Tests 1 and 2). This means that the reduction of residence time can also be used for the preparation of the calcium hydrogen carbonate solution, when ultrafiltration is used for the final removal of the insoluble part. The resulting unfiltered suspension that was recirculated to the tank showed a significantly lower turbidity level than the CaCCh feed suspension, and kept decreasing as the recirculation proceeded.
[000159] The increase in the initial concentration of the CaCO feed suspension presented a higher level of conductivity for the filtered calcium hydrogen carbonate solution; even with less excess CO2 (test 3). The extreme high turbidity level of the CaCCb feed suspension for this test, 200-240 NTU, did not affect the resulting final turbidity after ultrafiltration eg <0.8 NTU. C.1.2 Tests with calcium carbonate containing high content of insoluble compound
[000160] CaCOs feed suspensions were prepared with sample B, at different initial concentrations of calcium carbonate in reverse osmosis water, with a residence time of 40 minutes, with 6-and 3-fold stoichiometric excess of CO2 and both cross-flow and endless end as filtering modes.
[000161] Table 18 shows the working conditions for preparing the solution of calcium hydrogen carbonate in RO water using sample B.
Table 18
[000162] Table 19 shows the different results obtained for the CaCOs feed suspensions prepared with sample B and the resulting suspensions, as well as the filtered calcium hydrogen carbonate solutions.
Table 19
[000163] When comparing tests 2 and 4, the high content of insoluble compounds in sample B, obviously, has only one impact on the turbidity of the CaCOs feed suspension, that is, a turbidity of 27 to 32 NTU for the suspension of CaCOs feed prepared with sample A and a turbidity of 52 to 61 NTU for the suspension of CaCOs feed prepared with sample B. However, the final conductivity and turbidity of the filtered calcium hydrogen carbonate solutions are similar, with a maximum turbidity level from 0.7 to 0.8 NTU and conductivity from 695 to 705 pS / cm for both as filtered calcium hydrogen carbonate solutions.
[000164] When comparing tests 3 and 5, it is evident that the high content of insoluble compounds in sample B does not have an impact on any of the turbidity and conductivity of both CaCO feed suspensions, that is, with a turbidity level around 200 to 240 NTU and a conductivity level from 870 to 890 pS / cm. This is because the undissolved CaCCh present in both feed suspensions is so large that it probably induces almost all turbidity, and the insoluble part from the raw material has no impact on turbidity under these conditions.
[000165] The filtered calcium hydrogen carbonate solutions also showed similar levels of final conductivity and turbidity, with a maximum turbidity level of 0.7 to 0.8 NTU and a conductivity of 870 to 880 pS / cm. These results confirm that the insoluble content of the raw material will not affect the final quality of the calcium hydrogen carbonate solution, when ultrafiltration is used.
[000166] Finally, the endless end filtering mode did not show significant changes during the test period for test 5 and provided similar results in comparison to the tests performed using the cross flow filtration mode.

权利要求:
Claims (17)
[0001]
1. Process for the remineralization of water, characterized by the fact that it comprises the steps of: a) supply of feed water, b) supply of an aqueous solution of calcium carbonate, in which the aqueous solution of calcium carbonate comprises carbonate of dissolved calcium and its reaction species, in which the concentration of calcium carbonate in the solution is 0.1 to 1 g / L, based on the total weight of the solution, and c) the combination of the feed water from step a) and the aqueous solution of calcium carbonate from step b), in which the aqueous solution from step b) was prepared by one of the following steps: d) prepare an aqueous suspension of calcium carbonate in a first step, and introduce: or (i ) a carbon dioxide generating compound, (ii) a carbon dioxide generating compound and an acid, or (iii) an acid in an aqueous calcium carbonate suspension in a second step, or e) introducing in a first step : or (i) a carbon dioxide-generating compound, (ii) a carbon dioxide-generating compound and an acid, or (iii) an acid in the water to be used to prepare the calcium carbonate solution, and then introduce the calcium carbonate, either in the dry form or as a a second step suspension in water, or f) introducing a calcium carbonate suspension and either: (i) a carbon dioxide-generating compound, (ii) a carbon dioxide-generating compound and an acid, or (iii) an acid simultaneously, in which the calcium carbonate used for the preparation of the aqueous solution of step b) has an average particle size by weight of 0.1 to 100 gm.
[0002]
2. Process according to claim 1, characterized by the fact that the concentration of calcium carbonate in the solution is 0.3 to 0.8 g / L, preferably 0.5 to 0.7 g / L, with based on the total weight of the solution.
[0003]
Process according to claim 1 or 2, characterized by the fact that the calcium carbonate used for the preparation of the aqueous solution of calcium carbonate of step b) has an average particle size in weight dso of 0.5 to 50 pm, from 1 to 15 pm, preferably from 2 to 10 pm, more preferably from 3 to 5 pm, or calcium carbonate has an average particle size by weight of 1 to 50 pm, from 2 to 20 pm, preferably from 5 to 15 pm, and more preferably from 8 to 12 pm.
[0004]
Process according to any one of claims 1 to 3, characterized in that the calcium carbonate is a ground calcium carbonate, precipitated calcium carbonate, or mixtures thereof.
[0005]
Process according to any one of claims 1 to 4, characterized in that the remineralized water obtained has a concentration of calcium as calcium carbonate of 15 to 200 mg / L, preferably 30 to 150 mg / L, and more preferably from 100 to 125 mg / L, or from 15 to 100 mg / L, preferably from 20 to 80 mg / L, and more preferably from 40 to 60 mg / L.
[0006]
Process according to any one of claims 1 to 5, characterized in that the solution of step b) additionally comprises minerals containing magnesium, potassium or sodium, preferably magnesium carbonate, calcium and magnesium carbonate, for example example, dolomitic limestone, limestone dolomite or semi-burnt dolomite, magnesium oxide, such as burnt dolomite, magnesium sulfate, potassium hydrogen carbonate, or sodium hydrogen carbonate.
[0007]
Process according to claim 6, characterized in that the remineralized water obtained has a magnesium concentration of 5 to 25 mg / L, preferably 5 to 15 mg / L, and more preferably 8 to 12 mg / L L.
[0008]
Process according to any one of claims 1 to 7, characterized in that the remineralized water has a turbidity value of less than 5.0 NTU, less than 1.0 NTU, less than 0.5 NTU , or less than 0.3 NTU.
[0009]
Process according to any one of claims 1 to 8, characterized by the fact that remineralized water has a Langelier saturation index of -1 to 2, preferably from -0.5 to 0.5, more preferably from - 0.2 to 0.2.
[0010]
Process according to any one of claims 1 to 9, characterized in that the remineralized water has an SDLs sediment density index less than 5, preferably less than 4, and more preferably less than 3.
[0011]
Process according to any one of claims 1 to 10, characterized by the fact that remineralized water has an MFI0.45 membrane encrustation index less than 4, preferably less than 2.5, most preferably less than that 2.
[0012]
Process according to any one of claims 1 all, characterized in that the feed water is desalinated sea water, brackish or salty water, treated waste water or natural water, such as groundwater, surface water or rain.
[0013]
Process according to any one of claims 1 to 12, characterized in that the remineralized water is mixed with feed water.
[0014]
Process according to any of claims 1 to 13, characterized in that the process additionally comprises a particle removal step.
[0015]
15. Process according to any one of claims 1 to 14, characterized by the fact that the process additionally comprises the steps of: d) measuring a parameter value of remineralized water, in which the parameter is selected from the group comprising alkalinity, total hardness, conductivity, calcium concentration, pH, CO2 concentration, total dissolved solids, and remineralized water turbidity, e) compare the measured parameter value with a predetermined parameter value, and f) provide the amount of injected calcium carbonate solution, based on the difference between the measured and predetermined parameter value.
[0016]
16. Process according to claim 15, characterized by the fact that the predetermined parameter value is a pH value, wherein the pH value is 5.5 to 9, preferably 7 to 8.5.
[0017]
17. Use of a calcium carbonate solution, characterized by the fact that it is for the remineralization of water, in which the solution was prepared by one of the following steps: A) prepare an aqueous suspension of calcium carbonate in a first step, and introduce: either (i) a carbon dioxide-generating compound, (ii) a carbon dioxide-generating compound and an acid, or (iii) an acid in an aqueous calcium carbonate suspension in a second step, or B) introduce in a first step: either (i) a carbon dioxide generating compound, (ii) a carbon dioxide generating compound and an acid, or (iii) an acid in the water to be used for the preparation of the carbonate solution of calcium, and then introduce carbonate

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-04-14| B09A| Decision: intention to grant|

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2020-10-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/08/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP11179541.5|2011-08-31|

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EP11179541.5A|EP2565165B1|2011-08-31|2011-08-31|Remineralization of desalinated and of fresh water by dosing of a calcium carbonate solution in soft water|

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US201161531691P| true| 2011-09-07|2011-09-07|

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US61/531691|2011-09-07|

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PCT/EP2012/066673|WO2013030185A1|2011-08-31|2012-08-28|Remineralization of desalinated and of fresh water by dosing of a calcium carbonate solution in soft water|

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