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    • 专利摘要:
    PROCESS FOR WATER REMINERALIZATION, AND USE OF A MICRONIZED CALCIUM CARBONATE The present invention relates to a process for treating water and the use of calcium carbonate in such a process. In particular, the present invention is directed to a process for the remineralization of water comprising the steps of (a) supplying water supply having a carbon dioxide concentration of at least 20 mg / l, preferably in a range of 25 to 100 mg / l and more preferably in a range of 30 to 60 mg / l, (b) providing an aqueous slurry comprising micronized calcium carbonate and (c) combining the feed water from step (a) and the aqueous slurry of step (b) in order to obtain remineralized water.
    公开号:BR112014001145B1
    申请号:R112014001145-1
    申请日:2012-07-17
    公开日:2020-12-01
    发明作者:Michael Skovby；Martine Poffet
    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, the feed water used for drinking purposes was mainly surface water and groundwater. However, the treatment of sea water, brine, brackish water and contaminated effluent water is gaining increasing importance for environmental and economic reasons.
    [0003] In order to recover seawater or brackish water, for drinking uses, several processes are known, which are of considerable importance for dry areas, coastal regions and maritime islands and such processes include distillation, electrolytic processes, as well as osmotics and reverse osmotics. The water obtained by such processes is very soft and has a low pH value because of the loss of pH buffering salts and, thus, tends to be highly reactive and unless treated, this can create several corrosion difficulties during transportation in conventional pipes. In addition, untreated desalinated water cannot be used directly as a source of drinking water. To avoid the dissolution of undesirable substances in piping systems, to prevent corrosion of water services, such as pipes and valves, and to make the water pleasant, it is necessary to remineralize the water.
    [0004] Conventional processes that are mainly used for water remineration are lime dissolution by carbon dioxide and limestone bed filtration. 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] Lime process involves the treatment of lime solution with water acidified with CO , In which the following reaction is involved:

    [0006] As can be obtained from the reaction scheme above, two CO2 equivalents are required 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 basic anion hydroxide into buffered bicarbonate species. For water remineration, a saturated calcium hydroxide solution, commonly called lime water, from 0.1 to 0.2% by weight based on the total weight, is prepared from a lime milk (usually in most 5% by weight). Therefore, a saturator to produce lime water must therefore be used where large volumes of lime water are needed to reach the target level of remineralization. An additional disadvantage of this method is that the hydrated lime is corrosive and requires proper handling and specific equipment. In addition, a poorly controlled addition of hydrated lime to soft water can lead to unwanted pH changes due to the absence of lime buffering properties.
    [0007] The limestone bed filtration processes comprise the step of passing soft water through a granular limestone bed that dissolves calcium carbonate in the water flow. Contacting the limestone with water acidified with CO2 mineralizes the water according to:

    [0008] In a different way, the lime process, only one CO2 equivalent is stoichiometrically necessary to convert an equivalent of CaCO3 to Ca ”and bicarbonate for remineralization. In addition, limestone is non-corrosive and due to the buffering properties of major CaCO2 pH changes it is avoided.
    [0009] An additional advantage of using calcium carbonate instead of lime is an impression of very low carbon dioxide. In order to produce a ton of calcium carbonate, 75 kg of CO2 is emitted, as 750 kg of CO2 are emitted for the production of a ton of lime. Therefore, the use of calcium carbonate instead of lime avoids some environmental benefits.
    [00010] However, the rate of dissolution of granular calcium carbonate is slow and large filters are required for the limestone filtration process. This causes the scalable impression of these filters and large plant surfaces are required for such limestone bed filtration systems.
    [00011] Methods for remineralizing water using lime milk or lime slurry are described in US 7.374 694 and EP 0 520826. US 5,914,046 describes a method for reducing acidity in effluent discharges using a bed of pulsed limestone.
    [00012] The applicant is also aware of European Patent Application 10 172 771.7 which describes a method for the reminerilazation of fresh, desalinated water by injecting micronized calcium carbonate slurry and gaseous carbon dioxide into feed water.
    [00013] However, all of the prior art documents cited above describe processes for reminerizing the feed water not containing or containing a low concentration of carbon dioxide prior to the remineralization process.
    [00014] Still, there is also feed water having a high or sufficient concentration of carbon dioxide before the remineralization process, based on the desired level or remineralization. A high or sufficient concentration of carbon dioxide means an amount of at least 20 mg of CO2 per liter of feed water.
    [00015] A type of feed water having a high concentration of carbon dioxide is soil water that originates from water that has been filtered through limestone rocks or due to anaerobic conditions.
    [00016] Another type of feed water having a carbon dioxide concentration of at least 20 mg / 1, can, for example, be found during waste water treatment in a sewage plant. The reason for this is that a waste water treatment step consists of the desalination of waste water by the use of reverse osmosis. However, in order to prevent or reduce the formation of fouling on the membranes of the reverse osmosis mechanisms, acid, in particular sulfuric acid is added to the reverse osmosis feed water in order to decrease the pH. The addition of acid in the reverse osmosis feed leads to a conversion of the carbonate species in the feed water to free the carbon dioxide that is not removed by the membranes of the reverse osmosis mechanism and, therefore, is present in the feed water that leaves the osmosis mechanism. This excess carbon dioxide in the feed water, however, must be removed before adding lime. At present, the removal of excess carbon dioxide in the feed water is accomplished using decarbonators that consume cost, time and energy.
    [00017] In this way, considering the disadvantages of known processes for remineralization of water, it is an objective of the present invention to provide an alternative or improved process for remineralization of water having an initial carbon dioxide concentration of at least 20 mg / 1 and where remineralized water has a defined level of remineralization, for example, a calcium concentration of 30 to 40 mg / 1 as CaCO3.
    [00018] Another objective of the present invention is to provide a process for the reminerilazation of water that does not require a corrosive compound and, in this way, avoids the danger of fouling, eliminates the need for corrosion resistant equipment and provides a safe environment for people who work at the plant. It should also be desirable to provide a process that is environmentally friendly and that reduces operating costs due to omitting a time, energy and cost consuming process step.
    [00019] 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.
    [00020] 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, compared to the limestone process. It should also be desirable to provide a process that can be operated on plant surfaces smaller than the limestone bed filtration process.
    [00021] The foregoing and other objectives are solved by providing a process for the remineralization of water comprising the steps of (a) providing a feed water having a carbon dioxide concentration of at least 20 mg / 1, preferably in a range of 25 to 100 mg / 1 and more preferably in a range of 30 to 60 mg / 1, (b) providing an aqueous slurry comprising micronized calcium carbonate and (c) combining the feed water of step a ) and the aqueous slurry from step b) in order to obtain remineralized water.
    [00022] According to another aspect of the present invention, the use of a micronized calcium carbonate for the remineralization of water is provided.
    [00023] Advantageous embodiments of the present invention are defined in the corresponding subclaims.
    [00024] According to an embodiment the concentration of calcium carbonate in the slurry is 0.05 to 40% by weight, from 1 to 25% by weight, from 2 to 20% by weight, preferably from 3 to 15% by weight and more preferably 5 to 10% by weight based on the total weight of the slurry or a concentration of calcium carbonate in the slurry is 10 to 40% by weight, 15 to 30% by weight or 20 to 25% by weight based on the total weight of the slurry. According to another embodiment, calcium carbonate has a particle size of 0.1 to 100 pm, 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 particle size from 1 to 50 pm, from 2 to 20 pm, preferably from 5 to 15 pm, more preferably from 8 to 12 pm. According to another embodiment, calcium carbonate has an insoluble HCl content of 0.02 to 2.5% by weight, 0.05 to 1.5% by weight or 0.1 to 0.6% by weight. weight based on the total weight of the micronized calcium carbonate. According to another embodiment, calcium carbonate is crushed calcium carbonate, modified calcium carbonate or precipitated calcium carbonate or mixtures thereof.
    [00025] According to one embodiment the slurry further comprises minerals containing magnesium, potassium or sodium, preferably magnesium carbonate, calcium magnesium carbonate, for example, dolomitic limestone, calcareous dolomite, dolomite or half-burned dolomite; magnesium oxide such as burnt dolomite, magnesium sulfate, hydrogen potassium carbonate or hydrogen sodium carbonate. According to another embodiment, the slurry is recently prepared by mixing water and calcium carbonate. According to another embodiment, the period of time between the preparation of the slurry and the injection of the slurry 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, the injected slurry meets the microbiological quality requirements specified by the national drinking water instructions.
    [00026] According to one embodiment the remineralized water obtained has a concentration of calcium as calcium carbonate of 15 to 200 mg / 1, preferably 50 to 150 mg / 1 and more preferred from 100 to 125 mg / 1 or from 15 to 100 mg / 1, preferably from 20 to 80 mg / 1 and more preferably from 40 to 60 mg / 1.
    [00027] According to another embodiment the remineralized water obtained has a magnesium concentration of 5 to 25 mg / 1, preferably from 5 to 15 mg / 1 and more preferred from 8 to 12 mg / 1. 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.
    [00028] According to another preferred embodiment, remineralized water has a Langelier Saturation index of -2 to 1, preferably from -1.9 to 0.9 and more preferably from -0.9 to 0. According to with another embodiment remineralized water has a SDI15 Slit Density index below 5, preferably below 4 and more preferred below 3. According to another embodiment remineralized water has an MFIOJ45 Membrane Dirt Index below of 4, preferably below 2.5, more preferred below 2.
    [00029] According to one embodiment, the feed water is desalinated sea water, brackish or brine water, waste or treated water or natural water, such as soil water, surface water or rain and preferably sea water desalinated water, brackish or brine water, residual or treated water or groundwater.
    [00030] According to one embodiment, remineralized water is combined with feed water. According to another embodiment, the process further comprises a particle removal step.
    [00031] According to one 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, concentration of calcium, pH, CO2 concentration, total dissolved solids and turbidity of remineralized water, (e) compare the measured parameter value with a predetermined parameter value and (f) provide the amount of injected slurry based on the difference between the measured and predetermined parameter value. According to another embodiment, the predetermined parameter value is a pH value, where the value is 5.5 to 9, preferably 7 to 8.5.
    [00032] According to one embodiment, micronized calcium carbonate is used for the remineralization of water, in which the remineralized water is selected from drinking water, recreation water such as swimming pool water, industrial water for process applications, irrigation water or water for recharging an aquifer or well.
    [00033] The term "alkalinity (TAC)" as used in the present invention is a measurement 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 / 1 as CaCO3. Alkalinity can be measured with a titrator.
    [00034] For the purposes of the present invention, the term "calcium concentration" refers to the total calcium content in the solution and is specified in mg / 1 as Ca or as CaCO3. The concentration can be measured with a titrator.
    [00035] "Conductivity" in the meaning of the present invention is used as the indicator of how much salt-free, ion-free or impurity-free the measured water is; the purer the water, the lower the conductivity. Conductivity can be measured with a conductivity meter and is specified in pS / cm.
    [00036] "Crushed calcium carbonate (GCC)" in the meaning of the present invention is a calcium carbonate obtained from natural sources including marble, chalk, limestone or dolomite. Calcite is a mineral carbonate 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 from 380 to 470 ° C and vaterite is even less stable. Crushed calcium carbonate is processed through a treatment, such as crushing, evaluating and / or wet and / or dry fractionation, for example, by a cyclone. It is known to the skilled person that the crushed calcium carbonate inherently contains a defined concentration of magnesium, as is the case for dolomitic calcite.
    [00037] 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 that indicates scale forming 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:

    [00038] where pH is the actual pH value of the aqueous liquid in CaCO3 saturation. The pHs can be estimated as follows:

    [00039] where A is the numerical value indicator of total dissolved solids (TDS) present in the aqueous liquid, B is the indicator of the numerical value of the aqueous liquid in K, C is the numerical value indicator of the calcium concentration of the liquid aqueous in mg / 1 of CaCO3 and D is the numerical heat indicator of alkalinity of the aqueous liquid in mg / 1 of CaCO3. Parameters A to D are determined using the following equations:


    [00040] where TDS are the total dissolved solids in mg / 1, T is in temperature in ° C, [Ca2] is the calcium concentration of the aqueous liquid in mg / 1 of CaCO3 and TAC is the alkalinity of the aqueous liquid in mg / 1 of CaCO3.
    [00041] The term "Sediment Density Index (SDI)" as used in the present invention refers to the amount of particulate material in water and correlates with the dirt tendency of reverse osmosis and nanofiltration systems. The SDI can be calculated, for example, from the buffering rate of a 0.45 pm membrane filter when water is passed through a constant applied water pressure of 208.6 kPa. The SDI15 value is calculated from the buffering rate of a 0.45 pm membrane filter when the water is passed through a constant applied water pressure of 208.6 kPa for 15 minutes. Typically, spiral-wound reverse osmosis systems will require an SDI less than 5 and hollow fiber reverse osmosis systems will need an SDI less than 3.
    [00042] The term "Modified Dirt Index (MFI)" as used in the present invention refers to a concentration of matter in suspension and is a more accurate index than SDI for predicting a water's tendency to soil membranes reverse osmosis or nano filtration. The method that can be used to determine the MFI can be the same as for the SDI except that the volume is recorded every 30 seconds over 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 an SDI value of about <3 and can be considered low enough to control colloidal and particulate dirt.
    [00043] In case an ultrafiltration (UF) membrane is used for MFI measurements, the index is called MFI-UF in contrast to MFIQ.45 where a 0.45 pm membrane filter is used.
    [00044] 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. Micronized particles can be obtained by friction-based techniques, for example, grinding or grinding under wet or dry conditions under wet or dry conditions. However, it is also possible to produce micronized particles by any suitable method, for example, by precipitation, rapid expansion of supercritical solutions, spray drying, classification or fractionation of naturally occurring sand or sludge, water filtration, sol-gel processes , spray reaction synthesis, flame synthesis or liquid foam synthesis.
    [00045] Throughout this document, the "particle size" of a calcium carbonate product is described by its particle size distribution. The dx value represents the relationship in which x% by weight of the particles have diameters less than 4. This means that the value d2o is the particle size in which 20% by weight of all particles are smaller and the value d75 is the particle size where 75% by weight of all particles are smaller. The d50 value is, in this way, the average particle size by weight, i.e. 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 specified as a weighted average particle size d50 unless otherwise indicated. To determine the weighted average particle size d50 value for particles having a d5o greater than 0.5 pm, a Sedigraph 5100 device from Micromeritics, USA can be used.
    [00046] "Precipitated calcium carbonate (PCC)" in the meaning of the present invention is a synthesized material, in general, obtained by precipitation following the reaction of carbon dioxide and lime in an aqueous environment or by the precipitation of calcium and carbonate ions and water or by the precipitation of calcium and carbonate ions, for example, CaCl2 and Na2CO3, out of solution. Precipitated calcium carbonate exists in three primary crystalline forms: calcite, aragonite and vaterite and there are many different polymorphs (crystalline forms) for each of these crystalline forms. Calcite has a trigonal structure with typical crystalline forms, such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal, pinacoidal, colloidal (C-PCC), cubic and prismatic (P-PCC). Aragonite is a rhombohedral structure with crystalline shapes typical of similar hexagonal prismatic crystals, as well as diverse classification of crystals in elongated prismatic shape, curved blade, pyramidal fencing, chisel, shape similar to tree branch and coral or worm.
    [00047] "Modified calcium carbonate" in the meaning of the present invention is a surface-reacted natural calcium carbonate which is obtained by a process where the natural calcium carbonate is reacted with one or more acids having a pKa at 25 ° C of 2.5 or less and with CO gaseous formed in situ / or coming from an external supply and, optionally, in the presence of at least one aluminum silicate and / or at least one synthetic silica and / or at least one calcium silicate and / or at least one silicate of monovalent salt, 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. Additional details on the preparation of surface-reacted natural calcium carbonate are disclosed in WO 00/39222 and US 2004/0020410 A1, the contents of these included references being included in the present patent application.
    [00048] The term "remineralization" as used in the present invention refers to the restoration of minerals in water containing no minerals at all or in sufficient quantity to obtain a water that is pleasant. A remineralization can be achieved by adding at least carbonate calcium to the water to be treated. Optionally, for example for health benefits or to ensure proper absorption of some essential minerals and trace elements, additional substances can be mixed with the calcium carbonate and then added to the water during the process According to national instructions on human health and drinking water quality, the remineralized product may comprise additional minerals containing magnesium, potassium or sodium, eg magnesium carbonate, magnesium sulfate, hydrogen potassium carbonate, sodium carbonate hydrogen or other minerals containing essential trace elements.
    [00049] For the purpose of the present invention, a "slurry" comprises insoluble solids and water and, optionally, additional additives and usually contains large amounts of solids and is therefore more viscous and, in general, of density higher than the liquid from which it is formed.
    [00050] The term "total dissolved solids (TDS)" as used in the present invention is a measurement of the combined content of all inorganic and organic substances in a liquid in molecular, ionized or microgranular suspension (colloidal sol). In general, the operational definition is that the solids should be small, although they survive filtration through a 2 micrometer-sized sieve. Total dissolved solids can be estimated with a conductivity meter and are specified in mg / 1.
    [00051] "Turbidity" in the meaning of the present invention describes the cloudiness or turbidity of a fluid caused by individual particles (suspended solids) that are, in general, invisible to the naked eye. Turbidity measurement is a key 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).
    [00052] The inventive process for remineralization of water comprises the steps of (a) providing a feed water having a carbon dioxide concentration of at least 20 mg / 1, preferably in the range of 25 to 100 mg / 1 and more preferably in a range of 30 to 60 mg / 1, (b) providing an aqueous slurry comprising micronized calcium carbonate and (c) combining the feed water from step (a) and the aqueous slurry from step (b) in order to obtain remineralized water.
    [00053] The feed water that should be used in the inventive process can be derived from several sources. The feed water preferably treated by the process of the present invention is desalinated sea water, brackish or brine water, waste or treated water or natural water, such as soil water, surface or rain water and more preferably desalinated sea water, water brine or brine, residual or treated water or groundwater.
    [00054] According to an embodiment of the present invention, the feed water can be pre-treated. A pretreatment may be necessary, for example, if the feed water is derived from surface water, soil water or rain water. For example, to achieve drinking water standards, water needs to be treated through the use of chemical and physical techniques in order to remove pollutants, such as unwanted organic and minerals. 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 FeCISCh or FeCfí or aluminum salts such as A1C13, A12 (SO4) 3OU polyalumin can be used as flocculating agents. Flocculated materials can be removed from the feed water, for example, using sand filters or multilayer filters.
    [00055] Additional 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.
    [00056] According to another exemplary embodiment of the present invention, sea water or brackish eagle is first pumped from the sea through open ocean inlets or subsurface entrances, such as wells and then it undergoes physical pretreatments, such as sieves, sedimentation and 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 potential dirt on the membranes. Pre-treated seawater or brackish water can then be distilled, for example, using multi-stage scintillation, multi-effect distillation or membrane filtration, such as ultrafiltration or reverse osmosis, for the removal of particulates and substances remaining dissolved.
    [00057] Feed water remineralization is induced by combining feed water having a carbon dioxide concentration of at least 20 mg / 1, preferably in a range of 25 to 100 mg / 1 and more preferably in a range 30 to 60 mg / 1 with the aqueous slurry comprising micronized calcium carbonate. The combination of the feed water and the aqueous slurry can be achieved by common methods known to the person skilled in the art and, for example, by injecting the aqueous slurry comprising micronized calcium carbonate into the feed water.
    [00058] The aqueous slurry which combined with the feed water comprises micronized calcium carbonate. According to one embodiment, the concentration of calcium carbonate in the slurry is 0.05 to 40% by weight, from 1 to 25% by weight, from 2 to 20% by weight, from 3 to 15% by weight or 5 to 10% by weight based on the total weight of the slurry. According to another embodiment, the concentration of calcium carbonate in the slurry is 10 to 40% by weight, 15 to 30% by weight or 20 to 25% by weight based on the total weight of the slurry.
    [00059] Micronized calcium carbonate has a particle size in the micrometer range. According to one embodiment, micronized calcium has a particle size of 0.1 to 100 pm, 0.5 to 50 pm, 1 to 15 pm, 2 to 10 pm or 3 to 5 pm or calcium carbonate has a particle size of 1 to 50 pm, 2 to 20 pm, preferably 5 to 15 pm, more preferably 8 to 12 pm.
    [00060] Examples of suitable calcium carbonates are crushed calcium carbonate, modified calcium carbonate or precipitated calcium carbonate or a mixture thereof. A crushed natural calcium carbonate (GCC) can characterize, for example, one or more of marble, limestone, chalk and / or dolomite. A precipitated calcium carbonate (PCC) can characterize, for example, one or more of the mineralogical crystalline forms. Aragonite is commonly in acircular form, a cyst that vaterite belongs to the hexagonal crystalline system. Calcite can form scalenohedral, prismatic, spherical and rhombohedral shapes. A modified calcium carbonate can characterize a natural crushed or precipitated calcium carbonate with a modification of surface and / or internal structure, for example, calcium carbonate can be treated or coated with a hydrophobizing surface treatment agent, such as, for example, an aliphatic carboxylic acid or a siloxane. Calcium carbonate can be treated or coated to make it cationic or anionic with, for example, a polyacrylate or polymac.
    [00061] According to an embodiment of the present invention, micronized calcium carbonate is a crushed calcium carbonate (GCC). According to a preferred embodiment, the micronized calcium carbonate is a crushed calcium carbonate having a particle size of 3 to 5 pm or 8 to 12 pm.
    [00062] According to another embodiment of the present invention, micronized calcium carbonate comprises an insoluble HCl content of 0.02 to 2.5% by weight, 0.05 to 1.5% by weight or 0 , 1 to 0.6% by weight based on the total weight of the micronized calcium carbonate. Preferably, the insoluble HCl content of the micronized calcium carbonate does not exceed 0.6% by weight based on the total weight of the micronized calcium carbonate. The content of insoluble HCI can be, for example, minerals, such as quartz, silicate or mica.
    [00063] In addition to micronized calcium carbonate, the slurry may comprise additional micronized minerals. According to one embodiment, the slurry may comprise micronized magnesium carbonate, magnesium calcium carbonate, for example, dolomitic limestone, calcareous dolomite, dolomite or half-burned dolomite; magnesium oxide such as burnt dolomite, magnesium sulfate, hydrogen potassium carbonate, hydrogen soda or other minerals containing essential trace elements.
    [00064] According to an embodiment of the present invention, the slurry is recently prepared by mixing water and micronized calcium carbonate. On-site slurry preparation may be preferred, as premixed slurries may require the addition of additional agents, such as stabilizers or biocides, which may be unwanted compounds in remineralized water. According to a preferred embodiment of the present invention, the time between the preparation of the slurry and the injection of the slurry is short enough to prevent bacterial growth in the slurry. According to an exemplary embodiment, the period of time between the preparation of the slurry and the injection of the slurry 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 another embodiment of the present invention, the injected slurry meets the requirements for microbiological quality specified by national drinking water instructions.
    [00065] The slurry can be prepared, for example, using a mixer, such as a mechanical stirrer for the dilution of slurry or a powder-liquid mixing device for more concentrated slurry. Depending on the concentration of the prepared slurry, the mixing time can be from 0.5 to 30 minutes, from 1 to 20 minutes, from 2 to 10 minutes or from 3 to 5 minutes. According to an embodiment of the present invention, the slurry is prepared by using a mixing machine, in which the mixing machine allows simultaneous mixing and dosing of the slurry.
    [00066] The water used for the preparation of the slurry can be, for example, distilled water, feed water or industrial water.
    [00067] According to one embodiment, the slurry comprising micronized calcium carbonate is injected directly into a stream of the feed water. For example, the slurry 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 slurry. Preferably, the slurry can be injected into the feed water stream at a rate of 1 to 10 liters per cubic meter of feed water depending on the concentration of slurry. According to another embodiment, the slurry comprising micronized calcium carbonate is mixed with the feed water in a reaction chamber, for example, using a mixer, such as a mechanical stirrer. According to another embodiment, the slurry is injected into a tank that receives the entire flow of feed water.
    [00068] According to an embodiment of the present invention, only a part of the feed water is remineralized by the injection of the slurry and, subsequently, the remineralized water is combined with the untreated feed water. Optionally, only a portion of the feed water is remineralized to a high calcium carbonate concentration compared to the final target values and subsequently, the remineralized water is combined with untreated feed water.
    [00069] According to another embodiment, the treated water or part of the treated water is filtered, for example, by ultrafiltration, to further reduce the turbidity level of the remineralized water.
    [00070] According to an embodiment of the present invention, the slurry is injected in such an amount that complete dissolution of the calcium carbonate is achieved.
    [00071] The amount of calcium carbonate injected into the feed water is selected in such a way this way to give the water of desired quality. For example, the quality of remineralized water can be assessed by the Langelier Saturation Index (LSI). According to one embodiment, remineralized water has a Langelier Saturation index of -2 to 1, preferably from -1.9 to 0.9 and more preferably from - 0.9 to 0. According to another form embodiment, remineralized water has an SDI15 Slit Density index below 5, preferably below 4 and more preferred below 3. According to another embodiment remineralized water has a MFI0I45 Membrane Dirt index below 4 , preferably below 2.5, more preferred below 2. The assessment can be made, for example, by measuring the pH of the continuously treated feed water. Depending on the remineralization system, the pH of the treated pH can be measured, for example, in a stream in a stream of treated water, in a reaction chamber, in which the slurry and the feed water are mixed, or in a storage tank for remineralized water. According to an embodiment of the present invention, the pH is measured 30 minutes, 20 minutes, 10 minutes, 5 minutes or 2 minutes after the remineralization step. The measurement of the pH value can be done at room temperature, ie around 20 ° C.
    [00072] According to an exemplary embodiment of the invention, the amount of the injected slurry is controlled by detecting the pH value of the treated feed water. Alternatively or additionally, the amount of injected slurry is controlled by detecting parameters such as alkalinity, total hardness, conductivity, CCF concentration, pH, calcium 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, concentration of calcium, pH, CO2 concentration, total dissolved solids, or turbidity of remineralized water, (e) compare the measured parameter value with a predetermined parameter value and (f) provide the amount of injected slurry based on the difference between the measured and predetermined parameter value.
    [00073] According to one embodiment, the predetermined parameter value is a pH value, where the value is 5.5 to 9, preferably 7 to 8.5.
    [00074] Fig. 1 shows a schematic of a mechanism that can be used for operating the inventive method. Feed water flows from a reservoir (1) in a pipeline (2). An inlet (4) is located downstream of the pipeline (2) through which the slurry comprising micronized calcium carbonate is injected into a stream of feed water from a storage tank (6) into the slurry. The slurry is prepared on site using a suitable mixer (8) by mixing water which is obtained from the reservoir (1) by means of a tube (10) and micronized calcium carbonate obtained from a storage container ( 12). The pH of remineralized water can be measured downstream of the slurry entry (10) at a sample point (14). According to one embodiment the flow rate of the feed water is 20,000 and 500,000 m3 per day.
    [00075] The inventive process can be used to produce drinking water, recreation water such as water for swimming pools, industrial water for process applications, irrigation water or water for recharging aquifer or well.
    [00076] According to one embodiment, the carbon dioxide and calcium carbonate concentrations in remineralized water meet the required values for drinking water quality, which are presented by national procedural standards. According to one embodiment, remineralized water obtained by the inventive process has a calcium concentration of 15 to 200 mg / 1 as CaCO3, preferably 50 to 150 mg / 1 as CaCO3 and more preferred from 100 to 125 mg / 1 as CaCO3 or from 15 to 100 mg / 1, preferably from 20 to 80 mg / 1 and more preferably from 40 to 60 mg / 1. In case the slurry comprises an additional magnesium salt such as magnesium carbonate, or magnesium sulfate, the remineralized water obtained by the inventive process can have a magnesium concentration from 5 to 25 mg / 1, preferably from 5 to 15 mg / 1 and more preferred from 8 to 12 mg / 1.
    [00077] 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.
    [00078] According to an exemplary embodiment of the present invention remineralized water has an LSI of -0.9 to +0.0, the calcium concentration of 15 to 200 mg / 1, the magnesium concentration of 5 to 25 mg / 1, an alkalinity between 20 and 100 mg / 1 as CaCO3, a pH between 7 and 8.5 and a turbidity less than 1.0 NTU.
    [00079] According to an embodiment of the present invention a step of particle removal carried out after mineralization, for example, to reduce the level of turbidity of remineralized water. It is also possible to carry out a particle removal step before the injection of the slurry, for example, to reduce the turbidity level of the feed water or part of the feed water. According to an embodiment, the sedimentation step is carried out. For example, feed water and / or remineralized water can be transported in a clarifier or storage tank to further reduce the level of water turbidity. According to another embodiment, the particles can be removed by decanting. Alternatively, at least a part of the feed water and / or remineralized water can be filtered, for example, by ultra filtration, still to reduce the level of water turbidity.
    [00080] The invention will now be described in detail in the following examples. Examples Measurement methods: CO2 measurement
    [00081] The concentration of carbon dioxide contained in the samples of feed water used was determined using a titrimetric method. The principle of this method consists in the fact that CO2 reacts with sodium carbonate or sodium hydroxide to form sodium bicarbonate (NaHCO3). The completion of the reaction is indicated potentiometrically or by the development of the pink color characteristic of the phenolphthalein indicator at the pH equivalence of 8.3
    [00082] Feed water titration was conducted at 25 ° C using a Mettler Toledo M 416.
    [00083] A three-point calibration (according to the segment method) of the instrument was first done using commercially available buffer solutions (from Mettler Toledo) having pH values of 4.01, 7.00 and 9, 21.
    [00084] Then the pH of the sample of 100 ml of the feed water was measured according to the amount of titrator used until the pH 8 end point was reached. In the present measurement, the titrator was a 0.01 mol / 1 sodium hydroxide solution.
    [00085] From the amount of the titrator that it was necessary to reach the pH 8.3 end point and using the following equation (I), the CO can be easily calculated.

    [00086] A = ml of titrator, N = normal NaOH and b = ml of sample.
    [00087] Is formula (I) described in chapter 4500-CO Carbon dioxide on pages 4-28 to 4-34 of "Standard Methods for the Examination of Water & Wastewater, 21st edition, 2005, prepared and published by the American Public Health Association, American Water Works Association, Water Environment Federation, publication American Public Health Association office 800 I Street, NW, Washington, DC 20001-3710, Centennial Edition. " From this it can be derived that the CO2 levels given in the present invention refer to the content of free CO2 in the water. Surface area specified by BET
    [00088] The specific surface area by BET (also referred to as SSA) was determined according to ISO 9277 using a Tristar II 3020 sold by the company MICROMERITICS1M Particle size distribution (mass% of particles with a diameter <X one ) and weighted average particle diameter (dsn) of the particulate material (d ^ p (jum)) Sedigraph ™ 5100
    [00089] The weighted average particle diameter and the particle diameter mass distribution of the particulate material were determined using the sedimentation method, ie an analysis of the sedimentation behavior in a gravimetric field. The measurement is made with a Sedigraph ™ 5100 sold by MICROMERITICS ™
    [00090] The method and instrument are known to the person skilled in the art and are commonly used to determine the particle size of fillers and pigments. The samples were prepared by adding the amount of the product corresponding to 4 g of dry PCC to 60 ml of a 0.1% by weight aqueous solution of Na4P2O7. The samples were dispersed for 3 minutes using a high speed stirrer (Polytron PT 3000/3100 at 15,000 rpm). This was then subjected to ultrasound using an ultrasonic bath for 15 minutes and therefore added to the Sedigraph mixing chamber. Solids by weight (% by weight) of a suspended material
    [00091] The solids by weight (also called solids content of a material) were determined by dividing the solid material by weight by the total weight of the aqueous suspension.
    [00092] 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 at a constant weight.
    [00093] The micronized products used to prepare the slurries of the present invention consist of several micronized carbonate rocks:
    [00094] A marble calcium carbonate with an insoluble HCl content of 1.5% by weight from Bathurst, Australia, with d50 = 2.8 pm (sample A),
    [00095] A marble calcium carbonate with an insoluble HCl content of 0.1% by weight from Salses, France, with two different particle sizes d50 = 5.5 pm (sample D) and d5o = 3.5 um (sample E),
    [00096] A limestone calcium carbonate with an insoluble HCl content of 0.7% by weight from Superior, Arizona (sample F: d50 = 3.5 pm),
    [00097] A marble calcium carbonate with an insoluble HCl content of 1.0% by weight from Lucerne Valley, California (sample J: d5o = 2.0 pm)
    [00098] A limestone calcium carbonate with an insoluble HCl content of 0.1% by weight from Orgon, France (sample K: d50 ~ 3.0 pm)
    [00099] Table 1 summarizes the different products used during remineralization tests

    [000100] Membrane Dirt Index (MFI) and Langelier Saturation Index (LSI) during remineralization of RO water:
    [000101] Permeate produced by desalination processes is corrosive to concrete and metal because of its low pH and LSI value. If the permeate is not stabilized, it leaches calcium from unprotected concrete in storage tanks, reservoirs and corrodes the ductile iron pipe coated with mortar cement commonly used for water distribution. In most advanced water and wastewater treatment facilities, the permeate is stabilized by the addition of chemicals, such as lime.
    [000102] However, dosing of chemicals by post-treatment can result in high turbidity (> 0.2 NTU) and high particulate levels (high Modified Dirt index, for example, in the range of units 2 - 15) in final treated water therefore increased the potential for dirt in the injection reservoirs.
    [000103] For indirect drinking use, injection of barrier reservoirs to control seawater intrusion is specified that the permeate to water turbidity must be <0.2 NTU units and the Modified Dirt Index (MFI) must be <2.0 units.
    [000104] The feed water used by the remineralization tests of the present examples was obtained from the reverse osmosis desalination process of two different sewage plants (Plant 1 and Plant 2) and has the following parameters:

    [000105] RO permeate remineralization tests were performed using 2-liter cubic jars with the help of increasing RO water hardness, for example, 0.8 mg / L as CaCO3, up to the target around 50 mg / L as CaCO3.
    [000106] The different types of micronized calcium carbonate (samples A, D, E, F, J and K) were tested by MFI and LSI analyzes. The solid content of the CaCO3 slurries was 3.5% by weight, based on the weight of the micronized calcium carbonate. An appropriate dosage of CaCO3 slurries was added to achieve the desired water quality. Completed stabilized water must meet the following quality requirements:


    [000107] After adding the CaCO3 slurry, the samples were allowed to mix for 4 hours and samples collected at 10, 20, 30, 60, 120 and 240 minutes. Turbidity, pH, total alkalinity and calcium hardness were measured at the individual sampling times. The equilibrium time was determined when the turbidity stabilizes. After the equilibrium time was reached, LSI was calculated and MFI measured.
    [000108] Table 2 shows the different results obtained for the reminerylation of two different RO waters after the addition of approximately 50 mg / L as CaCO3 using 3.5% by weight of the CaCO3 slurries, based on the weight of the micronized calcium carbonate .

    [000109] As can be seen from Table 2, the use of micronized calcium carbonate products for RO water reminerization is found in the requirements of water quality by pH, total alkalinity, calcium hardness and MFI for all the tests performed. The micronized calcium carbonate products have a turbidity level between 0.5 and 1.7 NTU and LSI values between -1.85 and -0.88. Based on the turbidity measurements with respect to time, the equilibrium time required for the dissolution of the calcium carbonate products was approximately 120 minutes.
    权利要求:
    Claims (16)
    [0001]
    1. Process for the remineralization of water, characterized by the fact that it comprises the steps of: a) supplying a feed water having a carbon dioxide concentration of 20 to 60 mg / l, b) providing an aqueous slurry comprising carbonate of micronized calcium, where the calcium carbonate has a particle size of 0.1 to 5 gm, and an insoluble HCl content of 0.02 to 2.5% by weight, based on the total weight of the micronized calcium carbonate, and c) combining the feed water from step a) and the aqueous slurry from step b) in order to obtain remineralized water, in which the concentration of calcium carbonate in the slurry is 2 to 40% by weight, based on total weight of the slurry.
    [0002]
    Process according to claim 1, characterized in that the concentration of calcium carbonate in the slurry is from 2 to 20% by weight, preferably from 3 to 15% by weight and more preferably from 5 to 10% by weight weight based on the total weight of the slurry or a concentration of calcium carbonate in the slurry is 10 to 40% by weight, 15 to 30% by weight or 20 to 25% by weight, based on the total weight of the slurry fluid paste.
    [0003]
    Process according to claim 1 or 2, characterized in that the calcium carbonate is a crushed calcium carbonate, modified calcium carbonate or precipitated calcium carbonate or mixtures thereof.
    [0004]
    Process according to any one of the preceding claims, characterized by the fact that the slurry still comprises minerals containing magnesium, potassium or sodium, preferably magnesium carbonate, magnesium calcium carbonate, for example, dolomitic limestone, calcareous dolomite, dolomite or half-burned dolomite, magnesium oxide, such as burnt dolomite, magnesium sulfate, hydrogen potassium carbonate or hydrogen sodium carbonate.
    [0005]
    5. Process according to claim 4, characterized by the fact that the period of time between the preparation of the slurry and the injection of the slurry 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.
    [0006]
    Process according to any one of the preceding claims, characterized in that the remineralized water obtained has a concentration of calcium as calcium carbonate of 15 to 200 mg / l, preferably 50 to 150 mg / l and more preferred of 100 at 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.
    [0007]
    Process according to any one of claims 4 to 6, characterized in that the remineralized water obtained has a magnesium concentration of 5 to 25 mg / l, preferably from 5 to 15 mg / l and more preferred from 8 to 12 mg / l.
    [0008]
    8. Process according to any of the preceding claims, characterized by the fact that remineralized water has a turbidity value of less than 1.0 NTU, less than 0.5 NTU or less than 0.3 NTU.
    [0009]
    9. Process according to any of the preceding claims, characterized by the fact that remineralized water has a Langelier Saturation Index from -2 to 1, preferably from -1.9 to 0.9 and more preferably from -0, 9 to 0.
    [0010]
    10. Process according to any one of the preceding claims, characterized by the fact that remineralized water has a SDI15 Slit Density Index below 5, preferably below 4 and most preferred below 3.
    [0011]
    11. Process according to any of the preceding claims, characterized by the fact that remineralized water has a MFI Membrane Dirt Index 0.45 below 4, preferably below 2.5, more preferably below 2.
    [0012]
    12. Process according to any one of the preceding claims, characterized by the fact that the feed water is desalinated sea water, brackish or brine water, treated waste water or natural water, such as ground water, surface water or rain and preferably desalinated sea water, brackish or brine water, treated waste water or subsoil water.
    [0013]
    13. Process according to any of the preceding claims, characterized by the fact that remineralized water is combined with feed water.
    [0014]
    14. Process according to any of the preceding claims, characterized by the fact that the process still comprises a particle removal step.
    [0015]
    15. Process according to any one of the preceding claims, characterized by the fact that the process still comprises the steps of: d) measuring a parameter value of remineralized water, in which the parameter is selected from the group comprising alkalinity, conductivity, concentration of calcium, pH, total dissolved solids and turbidity of remineralized water, e) comparing the measured parameter value with a predetermined parameter value and f) providing the amount of injected slurry based on the difference between the measured and predetermined parameter value.
    [0016]
    Process according to claim 15, characterized in that the predetermined parameter value is a pH value, wherein the value is 5.5 to 9, preferably 7 to 8.5.
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    同族专利:
    公开号 | 公开日
    CN103702947A|2014-04-02|
    MA35354B1|2014-08-01|
    CA2840529A1|2013-01-31|
    CO6852087A2|2014-01-30|
    CA2840529C|2017-05-02|
    US9598295B2|2017-03-21|
    RS53994B1|2015-10-30|
    BR112014001145A2|2017-02-21|
    DK2548848T3|2015-06-29|
    WO2013014026A1|2013-01-31|
    TWI551550B|2016-10-01|
    IL230106A|2017-02-28|
    SI2548848T1|2015-06-30|
    EP2548848B1|2015-03-25|
    CN106006912A|2016-10-12|
    MX370547B|2019-12-17|
    AU2012289016B2|2015-11-05|
    PL2548848T3|2015-08-31|
    ME02142B|2015-10-20|
    PT2548848E|2015-06-22|
    CL2014000143A1|2014-08-22|
    MX2014000367A|2014-03-31|
    CY1116320T1|2017-02-08|
    US20150037463A1|2015-02-05|
    EP2548848A1|2013-01-23|
    AU2012289016A1|2014-02-27|
    CN103702947B|2016-06-08|
    RU2014106702A|2015-08-27|
    MY162579A|2017-06-30|
    KR20140022473A|2014-02-24|
    HRP20150634T1|2015-07-31|
    ES2537376T3|2015-06-08|
    EP2739575A1|2014-06-11|
    JP2014520670A|2014-08-25|
    AR087217A1|2014-02-26|
    TW201307213A|2013-02-16|
    JO3222B1|2018-03-08|
    NZ621402A|2015-05-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3833463A|1972-10-26|1974-09-03|Owens Illinois Inc|Method of decolorizing waste process liquid discharged by a paper mill|
    JPS6058294A|1983-09-07|1985-04-04|Mitsubishi Heavy Ind Ltd|Apparatus for preparing drinking water from prepared water in seawater desalting apparatus|
    SU1412232A1|1986-03-06|1990-09-15|Предприятие П/Я М-5371|Method of preparing drinkable water|
    JP2568299B2|1990-07-23|1996-12-25|呉羽化学工業株式会社|Method and apparatus for improving the Langerian index of tap water|
    GB9113971D0|1991-06-28|1991-08-14|Boc Group Plc|Treatment of water|
    JPH0615477A|1992-07-02|1994-01-25|Tanaka Kikinzoku Kogyo Kk|Ag brazer|
    JPH0658294A|1992-08-04|1994-03-01|Hitachi Ltd|Electric fan|
    JP2890158B2|1992-10-07|1999-05-10|ミネベア株式会社|Composite ball bearing with integrated motor parts for OA equipment|
    US5993737A|1995-04-24|1999-11-30|Implico B.V.|Stabilization of water|
    US5914046A|1996-10-22|1999-06-22|The United States Of America As Represented By The Secretary Of The Interior|Process and apparatus for carbon dioxide pretreatment and accelerated limestone dissolution for treatment of acidified water|
    DE19741910A1|1997-09-25|1999-04-29|Henkel Ecolab Gmbh & Co Ohg|Methods for cleaning and disinfecting medical instruments|
    FR2787802B1|1998-12-24|2001-02-02|Pluss Stauffer Ag|NOVEL FILLER OR PIGMENT OR MINERAL TREATED FOR PAPER, ESPECIALLY PIGMENT CONTAINING NATURAL CACO3, METHOD FOR MANUFACTURING SAME, COMPOSITIONS CONTAINING THEM, AND APPLICATIONS THEREOF|
    CN1091430C|1999-04-09|2002-09-25|童继伟|Method for producing purified and mineralizd water|
    FR2810506B1|2000-06-21|2002-09-27|Gervais Danone Sa|PROCESS FOR PRODUCING CALCIUM-RICH WATER AND WATER OBTAINED BY THIS PROCESS|
    FR2823499B1|2001-04-12|2004-02-27|Vivendi Water Systems|PROCESS FOR THE REMINERALIZATION OF RAW WATER|
    JP2003251371A|2001-12-27|2003-09-09|Ube Material Industries Ltd|Neutralization treatment method for acidic river water|
    JP2003231371A|2002-02-12|2003-08-19|Mitsubishi Heavy Ind Ltd|Printing plate material, method for regenerating and reusing the same, and printing press|
    DK1982759T3|2007-03-21|2012-01-02|Omya Development Ag|Surface treated calcium carbonate and its use for wastewater treatment|
    SI1974806T1|2007-03-21|2012-01-31|Omya Development Ag|Process for the purification of water|
    SI1975310T1|2007-03-21|2012-06-29|Omya Development Ag|Process for the control of pitch|
    PL1974807T3|2007-03-21|2010-08-31|Omya Int Ag|Process for the removal of endocrine disrupting compounds|
    PL2108260T3|2008-04-11|2013-09-30|Omya Int Ag|Composition having biocide activity for aqueous preparations|
    US9345241B2|2008-04-11|2016-05-24|Omya International Ag|Composition having biocide activity for aqueous preparations|
    CL2009000754A1|2008-04-11|2010-05-07|Omya Int Ag|Process for the bacterial stabilization of an aqueous preparation comprising at least one mineral and at least one strain of bacteria that is resistant to, tolerant to and / or degrades biocides that release aldehyde and / or that contain aldehyde groups; composition with biocidal activity, in aqueous preparations and its use to prepare an aqueous preparation.|
    US20110155665A1|2008-06-11|2011-06-30|The Regents Of The University Of California|Method and System for High Recovery Water Desalting|
    FR2934584B1|2008-07-31|2010-09-17|Otv Sa|PROCESS FOR TREATING WATER BY REVERSE OSMOSIS INCLUDING DECARBONATION OF A CONCENTRATE AND REMINERALIZATION OF A FILTRAT|
    DK2418177T3|2010-08-13|2015-03-09|Omya Int Ag|Micronized CaCO3 opslæmningsindsprøjtningssystem to remineralisation of desalinated water and fresh water|
    JP6058294B2|2012-06-18|2017-01-11|住友ゴム工業株式会社|Pneumatic tires for motorcycles|KR101589773B1|2008-05-01|2016-01-28|우베 마테리알즈 가부시키가이샤|Slime remover, method for removing slime, and kit for preparing aqueous slime remover|
    ES2601883T3|2011-08-31|2017-02-16|Omya International Ag|Remineralization of desalinated and fresh water by dosing a solution of calcium carbonate in soft water|
    LT2623466T|2012-02-03|2017-09-25|Omya International Ag|Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate and its use|
    HUE030141T2|2012-02-03|2017-04-28|Omya Int Ag|Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate and its use|
    EP2805924B1|2013-05-24|2018-02-21|Omya International AG|Multiple batch system for the preparation of a solution of calcium hydrogen carbonate suitable for the remineralization of desalinated water and of naturally soft water|
    WO2016106328A1|2014-12-22|2016-06-30|University Of Georgia Research Foundation, Inc.|Nanoparticles for lipid homeostasis|
    ES2838023T3|2015-01-29|2021-07-01|Omya Int Ag|Process for making an alkaline earth hydrogen carbonate solution|
    EP3181521A1|2015-12-16|2017-06-21|Nestec S.A.|Purified and re-mineralized water|
    EP3202720A1|2016-02-05|2017-08-09|Omya International AG|Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate|
    EP3202719A1|2016-02-05|2017-08-09|Omya International AG|Installation for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate|
    CN106304932B|2016-08-23|2018-07-27|河海大学|A kind of soil Irrigation and fertilization system using wave energy|
    TWI684572B|2016-11-14|2020-02-11|吳昇鴻|Method and device for making alkaline water from natural water|
    EP3428128A1|2017-07-12|2019-01-16|Omya International AG|Method for increasing the magnesium ion concentration in feed water|
    EP3428129A1|2017-07-12|2019-01-16|Omya International AG|Method for increasing the magnesium ion concentration in feed water|
    BE1024584B1|2017-07-28|2018-04-11|Flamingo Holding Sa|DOMESTIC METHOD AND APPARATUS FOR THE PRODUCTION OF MINERAL WATER FROM CITY WATER|
    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-03-24| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-08-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-03| B09X| Republication of the decision to grant [chapter 9.1.3 patent gazette]|
    2020-12-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/07/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11175012.1A|EP2548848B1|2011-07-22|2011-07-22|Micronized CaCO3 slurry injection system for the remineralization of desalinated and fresh water|
    EP11175012.1|2011-07-22|
    US201161513035P| true| 2011-07-29|2011-07-29|
    US61/513035|2011-07-29|
    PCT/EP2012/063973|WO2013014026A1|2011-07-22|2012-07-17|Micronized caco3 slurry injection system for the remineralization of desalinated and fresh water|
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