process for the preparation of an aqueous solution, use of an aqueous solution, and, process for the

专利摘要:
PROCESS FOR THE PREPARATION OF A WATER SOLUTION, USE OF A WATER SOLUTION, AND, PROCESSES FOR THE MINERALIZATION OF WATER AND FOR THE PRODUCTION OF A PRECIPITATED ALKALINE-EARTH CARBONATE. The present invention relates to a process for the preparation of an aqueous solution comprising at least an alkaline earth hydrogen carbonate and its uses. The process can be carried out in a reactor system comprising a tank (1) equipped with an agitator (2) and at least one filtration device (4) and a grinding device (18).
公开号:BR112014017679B1
申请号:R112014017679-5
申请日:2013-01-31
公开日:2020-11-17
发明作者:Patrick A. C. Gane；Matthias Buri；Samuel Rentsch；René Vinzenz Blum；Martine Poffet
申请人:Omya International Ag；
IPC主号:

专利说明:

[0001] The invention relates to the field of a process producing an aqueous solution of alkaline earth hydrogen carbonate and the use of such solutions.
[0002] Calcium carbonate is used extensively in the paper industry as a filler component in paper. It is a low-cost, high-gloss filler used to increase the gloss and opacity of the sheet. Its use has increased dramatically in recent decades due to the conversion of acid-to-alkaline papermaking in paper mills. Both natural and synthetic calcium carbonates are used in the paper industry. Natural carbonate, or limestone, is ground to a small particle size before use on paper, while synthetic calcium carbonate is manufactured by a precipitation reaction and is called precipitated calcium carbonate (PCC).
[0003] In addition to its use in the papermaking industry, precipitated calcium carbonate is also used for several other purposes, for example, as a filler or pigment in the paint manufacturing industries, and as a functional filler for the manufacture of materials plastics, plastisols, sealing compounds, printing inks, rubber, toothpaste, cosmetics, food, pharmaceuticals etc.
[0004] Precipitated calcium carbonate exists in three primary crystalline forms: calcite, aragonite and valerite, and there are many different polymorphs (crystal habits) for each of these crystalline forms. Calcite has a trigonal structure with typical crystal habits such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal, pinacoidal, colloidal (C-PCC), cubic, and prismatic (P-PCC). Aragonite is an orthorhombic structure with crystal habits typical of twin hexagonal prismatic crystals, as well as a diverse variety of thin elongated prismatic shapes, curved blade shapes, sharp pyramids, chiseled crystals, branched tree and coral or worms.
[0005] Generally, PCC is prepared by introducing CO2 into an aqueous suspension of calcium hydroxide, the so-called Ca (OH) 2 lime + CO2 CaCO3 + H2O.
[0006] There are numerous patent applications known to the person skilled in the art that describe the preparation of precipitated calcium carbonate. One of them is EP 1 966 092 Bl, where the precipitated calcium carbonate obtained is only a by-product of CO2 sequestration. Another document is WO 2010/12691, this describing the production of PCC by the addition of an alkaline earth hydroxide to water that contains alkaline earth ions.
[0007] International Patent Application WO 2006/008242 A1, for example, describes the production of high purity calcium carbonate or magnesium carbonate from a feed charge comprising a mixed metal oxide comprising Ca or Mg, wherein the feed charge is contacted with a CO2 containing gas in order to sequester the CO2 and, in another step, calcium carbonate or high purity magnesium carbonate is precipitated from the aqueous solution that resulted from contact of the feed load with CO2.
[0008] In addition to the fields mentioned above, calcium carbonate can also be used in the field of water treatment and mineralization.
[0009] Drinking water is becoming 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 water purposes was mainly surface water and groundwater. However, the treatment of sea water, brine, brackish water, waste water and contaminated effluent water are gaining more and more importance for environmental and economic reasons.
[00010] In order to recover water from 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 such processes include distillation, electrolytic processes, as well as osmotic or reverse osmotic processes. The water obtained by such processes is very soft and has a low pH value due to the lack of pH buffering salts and, thus, tends to be highly reactive and, unless treated, can create various corrosion problems during the transport in conventional pipes. In addition, untreated desalinated water cannot be used directly as a source of drinking water. In order to prevent the dissolution of undesirable substances in piping systems, to prevent corrosion of hydraulic installations such as pipes and valves and to make the water palatable, it is necessary to mineralize the water.
[00011] The conventional processes that are mainly used for the mineralization of water are the dissolution of lime by carbon dioxide and filtration in limestone bed. 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.
[00012] The lime process involves the treatment of lime solution with water acidified with CO2, in which the following reaction is involved: Ca (OH) 2 + 2 CO2 -> Ca2 + + 2 HCOf
[00013] As can be inferred from the reaction scheme above, two CO2 equivalents are needed to convert one Ca (OH) 2 equivalent into Ca2 + and bicarbonate for remineralization. This method is dependent on the addition of two CO2 equivalents in order to convert the alkaline hydroxide ions to the HCO3 buffer species. For water remineralization, a saturated calcium hydroxide solution, commonly called lime water, of 0.1 - 0.2% by weight based on the total weight, is prepared from a lime milk (usually at most 5% by weight). Thus, a saturator to produce lime water must be used and large volumes of lime water are required to achieve the target level of remineralization. Another drawback of this method is that 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 undesirable pH shifts due to the absence of lime buffering properties.
[00014] The limestone bed filtration process comprises the step of passing the soft water through a granular limestone bed by dissolving the calcium carbonate in the water flow. Contacting the limestone with water acidified with CO2 mineralizes the water according to: CaCO3 + CO2 + H2O-> Ca2 + + 2 HCOf
[00015] Unlike the lime process, only one CO2 equivalent is stoichiometrically necessary to convert one CaCO3 equivalent to Ca2 + and bicarbonate for remineralization. In addition, limestone is non-corrosive and due to the CaCO3 buffering properties, larger pH shifts are avoided.
[00016] An additional advantage of using calcium carbonate compared to limestone is that it has a very low carbon dioxide environmental footprint. In order to produce one ton of calcium carbonate, 75 kg of CO2 are emitted, while 750 kg of CO2 are emitted for the production of one ton of lime. Thus, the use of alkaline earth carbonates such as marble, dolomite or just burnt dolomite, instead of lime, has some environmental benefits.
[00017] The rate of dissolution of granular calcium carbonate, however, is slow and filters are required for this process. This induces a scalable footprint of these filters and large installation surfaces are required for limestone bed filtration systems.
[00018] Methods for remineralizing water using lime milk or a 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 pulsed limestone bed .
[00019] WO 2010/12691 describes a process for treating water containing at least calcium and / or magnesium salts through reverse osmosis type membranes. The process comprises at least one step of recovering water that is at least partially desalinated, a step of recovering a concentrate originating from the membranes and containing bicarbonates, a step of injecting CO2 or an acid into at least , partially desalinated water, and a step to remineralize at least partially desalinated water. CO2 is added to the bicarbonate solution in order to decarbonate the concentration and form calcium carbonate clusters outside the bicarbonates.
[00020] The applicant is also aware of the following unpublished European patent applications in the field of water treatment.
[00021] European Patent Application 11 175 012.1 describes a method for remineralizing fresh, desalinated water containing a certain level of carbon dioxide by injecting a micronized calcium carbonate slurry into the feed water.
[00022] European Patent Application 10 172 771.7 describes a method for remineralizing fresh, desalinated water by injection of the micronized calcium carbonate slurry.
[00023] Finally, European Patent Application 11 179 541.5 describes a method for remineralizing water by combining a solution of calcium carbonate and feed water.
[00024] In the three unpublished European patent applications for the water treatment field, no indication is made of the specific surface area (SSA) of the alkaline earth carbonates used. From the average particle size mentioned in the examples of these patent applications, it is not possible to calculate the specific surface area (SSA) of the corresponding products. No indication is given regarding the influence of the specific surface area on an efficient production of an alkaline earth hydrogen carbonate solution. Also, no indication is given with respect to a parallel particle division in situ in order to improve the process.
[00025] Thus, considering the drawbacks of known processes for mineralization or remineralization of water, it is the object of the present invention to provide an alternative and improved process for mineralization of water.
[00026] Another object of the present invention is to provide a process for mineralization of water that does not require a corrosive compound and thus avoids the danger of fouling, eliminates the need for corrosion resistant equipment, and provides a safe environment for people who work 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.
[00027] Another object of the present invention is to provide a process for the mineralization of water, in which the amount of minerals can be adjusted to the required values.
[00028] The above objects and others are resolved by providing a process for the preparation of an aqueous solution comprising at least one alkaline earth hydrogen carbonate, the process comprising the steps of: a) providing water, b) providing at least one substance comprising at least one alkaline earth carbonate and optionally at least one alkaline earth hydroxide in a lesser amount compared to alkaline earth carbonate, at least one substance being in a form dry or in an aqueous form, c) supplying CO2, d) combining either: (i) water from step a), at least one substance comprising at least one alkaline earth carbonate and the optional at least , a step b) alkaline earth hydroxide and step c) CO2, or (ii) step a) water and at least one substance comprising at least one alkaline earth carbonate and the optional one, at least one alkaline earth hydroxide from step b) in order to obtain an aqueous suspension the alkaline of at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide and subsequently combining the aqueous alkaline suspension with step c) CO2 (iii) in order to obtain a resulting suspension S having a pH between 6 and 9, the resulting suspension S containing particles, e) filtering at least a part of the resulting suspension S, passing at least a part of the resulting suspension S through a filtration in order to obtain the aqueous solution comprising at least one alkaline earth hydrogen carbonate, f) subjecting at least part or all of the particles of the resulting suspension S to a particle division step, in which step f) can occur before and / or in parallel to and / or after step e), where the particles of the resulting suspension S, which is obtained in step d), represent a total particle surface area (SSAtotai) that is at least 1,000 m2 / tonne of suspension S re result, and with the proviso that an addition of step c) CO2 does not occur before the addition of at least one substance comprising at least one alkaline earth carbonate and the optional one, at least one alkaline earth hydroxide of step b).
[00029] When the specific surface area of the substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide is known, then the total particle surface of the step d) alkaline aqueous suspension can be easily adjusted. Alternatively, the specific surface area of the substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide needs to be determined by the method which is known to the person skilled in the art and which is specified in the ISO standard 9277.
[00030] According to another aspect of the present invention, the use of an aqueous solution comprising at least one alkaline earth hydrogen carbonate is provided for the production of a precipitated alkaline earth carbonate and, in particular, for the production of precipitated calcium carbonate.
[00031] In accordance with yet another aspect of the present invention, the use of an aqueous solution comprising at least an alkaline earth hydrogen carbonate is provided for the production of precipitated hydromagnesite.
[00032] In accordance with another aspect of the present invention, the use of an aqueous solution comprising at least an alkaline earth hydrogen carbonate is provided for the mineralization of water.
[00033] In accordance with yet another aspect of the present invention, a process is provided for the mineralization of water, the process comprising the following steps: I) providing feed water, II) providing an aqueous solution comprising at least one carbonate alkaline earth hydrogen, and III) combining the step I) feed water and the aqueous solution comprising at least one step II alkaline earth hydrogen carbonate to obtain mineralized water.
[00034] Yet another aspect of the invention is a process for the production of a precipitated alkaline earth carbonate, the process comprising the following steps: IV) providing an aqueous solution comprising at least one alkaline earth hydrogen carbonate, and V ) heat the aqueous solution comprising at least one alkaline earth hydrogen carbonate of step IV) in order to obtain the precipitated alkaline earth carbonate and / or VI) add at least one alkaline earth hydroxide or alkaline earth oxide earth to the solution of step IV) to obtain the precipitated alkaline earth carbonate.
[00035] Advantageous embodiments of the present invention are defined in the corresponding subclaims.
[00036] According to an embodiment of the present invention, the particles of the resulting S suspension represent a total particle surface area (SSAtotai) which is in the range of 5 000 - 5 000 000 m2 / ton of the resulting S suspension, preferably in the range of 10 000 to 5 000 000 mV tonnes of the resulting suspension S, and more preferably in the range of 70 000 - 500 000 m2 / ton of the resulting suspension S, for example, 100 000 to 500 000 m2 / ton.
[00037] According to another embodiment, at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide of step b) is selected from the group comprising marble, limestone, chalk, half-burnt lime, burnt lime, dolomitic limestone, limestone dolomite, half-burned dolomite, burnt dolomite, and precipitated alkaline earth carbonates such as precipitated calcium carbonate, for example, of calcite mineral crystal structure, aragonitic and / or characteristic, for example, from water hardening by the addition of Ca (OH) 2. The use of marble, limestone, chalk and dolomite is preferred because they are naturally occurring minerals and the turbidity of the final quality of drinking water is guaranteed using a clear aqueous solution comprising at least one alkaline earth hydrogen carbonate that is produced using these naturally occurring minerals. Natural marble deposits are mainly containing acid insoluble silicate impurities. However, such acid-insoluble, sometimes colored silicates do not affect the final quality of the water with respect to turbidity when using the product that is prepared by the process of the invention.
[00038] In addition, suspensions or solutions prepared using naturally occurring minerals such as marble, limestone, chalk or dolomite are containing essential healthy trace elements improving the quality of drinking water.
[00039] The option, at least one alkaline earth hydroxide is preferably calcium hydroxide and / or magnesium hydroxide. Due to the very low solubility of Mg (OH) 2 in water compared to Ca (OH) 2, the reaction speed of Mg (OH) 2 with CO2 is very limited and in the presence of Ca (OH) 2 in suspension the reaction CO2 with Ca (OH) 2 is much more preferred. Surprisingly, using the process of the invention it is possible to produce a suspension of alkaline earth hydrogen carbonate rich in Mg (HCO3) 2 also in the presence of Ca (OH) 2 in the suspension.
[00040] According to another embodiment, at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide of step b) has a median particle size in weight (0/50) in the range of 0.1 pm to 1 mm, and preferably in the range of 0.7 to 100 pm.
[00041] The at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide step b) preferably has a specific surface area in the range of 0.01 to 200 m2 / g, and more preferably in the range of 1 to 100 m2 / g, for example, 1 to 15 m2 / g.
[00042] The term "specific surface area (SSA)", in the meaning of the present invention, describes the property of pigment / minerals / solids material that measures the surface area per gram of pigments. The unit is m2 / g.
[00043] The term "total particle surface area (SSAtotai)", in the meaning of the present invention, describes the total surface area per ton of suspension S.
[00044] In a preferred embodiment of the present invention, the at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide of step b) has an insoluble content hydrochloric acid (HCl) from 0.02 to 90% by weight, preferably from 0.05 to 15% by weight, based on the total weight of the dry substance. The insoluble content of HCl can be, for example, minerals such as quartz, silicate, mica and / or pyrite.
[00045] According to yet another embodiment of the present invention, the resulting suspension S, which is obtained in step d), has a solids content in the range of 0.1 to 80% by weight, preferably in the range of 3 to 50% by weight, more preferably in the range of 5 to 35% by weight, based on the total weight of the resulting suspension S.
[00046] Step water a) is preferably selected from distilled water, tap water, desalinated water, brine, treated waste water or natural water such as ground water, surface water or rainwater. It can also contain between 10 and 2000 mg NaCl per liter.
[00047] According to an embodiment of the present invention CO2 is selected from gaseous carbon dioxide, liquid carbon dioxide, solid carbon dioxide or a gas mixture of carbon dioxide and at least one other gas, and is preferably carbon dioxide gas. When CO2 is a gas mixture of carbon dioxide and at least another gas, then the gas mixture is a carbon dioxide containing combustible gas exhausted from industrial processes such as combustion processes or processed calcination or the like. CO2 can also be produced by reacting an alkaline and / or alkaline earth carbonate with acid. In addition, it can be produced by combustion of organics, such as ethyl alcohol, wood and the like, or by fermentation. When a gas mixture of carbon dioxide and at least another gas 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. According to a most preferred embodiment, CO2 is pure gaseous CO2 with a purity of> 99%, for example, a purity of> 99.9%.
[00048] In light of an ecological concept, it is desirable to follow, as far as possible, the Kyoto protocol on reducing combustion from petrochemical sources and reducing the CO2 derived from petrochemical products so that the CO2 used for the process has a decay of 14C to 12C of at least 500, more preferred at least 800, most preferred at least 850 to 890 decay per h and g of C in CO2.
[00049] Following the Kyoto protocol, it is also desirable that at least some or all of the electrical energy used in the process of the present invention is derived from solar energy, for example, from thermal and / or voltammetric solar panels.
[00050] In another preferred embodiment of the present invention following the Kyoto protocol, the amount of CO2 used, in moles, to produce 1 mol of at least one alkaline earth hydrogen carbonate in the aqueous solution is in the range of only 0.5 to 4 moles, preferably in the range of only 0.5 to 2.5 moles, more preferably in the range of only 0.5 to 1.0 moles, and most preferably in the range of only 0.5 to 0 moles , 65 mol.
[00051] The process according to the present invention contains a step f), in which all or a part of the resulting suspension S is subjected to a step of dividing particles from the particles that are contained in the resulting suspension S. The particle division step f) can occur before step e), parallel to step e), after step e) or before and after step e). In a preferred embodiment, the particle division step f) is a crushing and / or grinding step and is most preferably a crushing step. This step provides the benefit that the speed of the (chemical) reaction of the process of the invention is increased by continuous production of a newly prepared and thus active surface of the substance comprising at least one alkaline earth carbonate and the optional at least an alkaline earth hydroxide. In addition, this process step decreases the particle size of the substance comprising alkaline earth carbonate and the optional, at least one alkaline earth hydroxide of step b) and thus allows the continuous operation of the process.
[00052] The term "grinding" in the meaning of the present invention is used when the feed material that is subjected to this step is in the centimeter (cm) range, for example, 10 cm.
[00053] The term "crushing" in the meaning of the present invention is used when the feed material that is subjected to this step is in the range of millimeter (mm) or nanometer (nm), for example, 10 mm.
[00054] According to another preferred embodiment of the invention, the aqueous solution comprising at least an alkaline earth hydrogen carbonate which is obtained in step e) or step f) has a hardness of 5 to 130 ° dH, preferably from 10 to 60 ° dH, and most preferably from 15 to 50 ° dH.
[00055] For the purpose of the present invention, hardness refers to German hardness and is expressed in "German hardness degrees, ° dH". In this respect, hardness refers to the total amount of alkaline earth ions in the aqueous solution comprising the alkaline earth hydrogen carbonate, and is measured by complexometric titration at pH 10 using ethylene diamine tetraacetic acid (EDTA) and Eriochrome T as an equivalent point indicator.
[00056] The aqueous solution comprising at least one alkaline earth hydrogen carbonate, which is obtained in step e) or step f), preferably has a pH in the range of 6.5 to 9, preferably in the range of 6 , 7 to 7.9, and most preferably in the range of 6.9 to 7.7, at 20 ° C.
[00057] According to an embodiment of the present invention, the aqueous solution comprising at least an alkaline earth hydrogen carbonate, which is obtained in step e) or step f), has a concentration of calcium, as calcium carbonate, from 1 to 700 mg / 1, preferably from 50 to 650 mg / 1, and most preferably from 70 to 630 mg / 1. According to another embodiment, the aqueous solution comprising at least one alkaline earth hydrogen carbonate, which is obtained in step e) or step f), has a magnesium concentration, such as magnesium carbonate, from 1 to 200 mg / 1, preferably from 2 to 150 mg / 1, and most preferably from 3 to 125 mg / 1.
[00058] According to yet another embodiment of the present invention the aqueous solution comprising at least one alkaline earth hydrogen carbonate, which is obtained in step e) or step f), has a turbidity value of less than 1.0 NTU, preferably less than 0.5 NTU, and most preferably less than 0.3 NTU.
[00059] It is preferred that at least step d) be carried out at a temperature in the range of 5 to 55 ° C, and preferably in the range of 20 to 45 ° C.
[00060] According to an even more preferred embodiment of the present invention the aqueous solution obtained in step e) or step f) comprises: (x) a calcium hydrogen carbonate, preferably with a calcium concentration of 25 to 150 mg / 1, as calcium carbonate, or (xx) a magnesium hydrogen carbonate, preferably with a magnesium concentration of> 0 to 50 mg / 1, or (xxx) a mixture of calcium hydrogen carbonate and magnesium, preferably at a concentration of calcium and total magnesium of 25 to 200 mg / 1, such as calcium carbonate and magnesium carbonate.
[00061] According to a most preferred embodiment of the present invention the aqueous solution obtained in step e) or step f) optional comprises: a calcium hydrogen carbonate with a calcium concentration of 45 mg / 1, as carbonate calcium, or a mixture of calcium and magnesium hydrogen carbonate with a calcium concentration of 80 to 120 mg / 1, as calcium carbonate, and a magnesium concentration of 20 to 30 mg / 1, as calcium carbonate magnesium.
[00062] A mixture of calcium and magnesium hydrogen carbonate can be obtained when material containing half-burned dolomite and / or completely burnt dolomite is used as the substance comprising alkaline earth carbonate. In the meaning of the present invention, burnt dolomite comprises calcium oxide (CaO) and magnesium oxide (MgO), while half-burnt dolomite comprises Mg in the form of magnesium oxide (MgO) and Ca in the form of calcium carbonate (CaCO3) , but it can also include some minor amount of calcium oxide (CaO).
[00063] In a preferred embodiment of the present invention, the process is a continuous process. However, the process of the present invention can also be carried out in a semi-stacked mode. In this case, the resulting suspension S can, for example, represent a total particle surface area that is around 1,000,000 m2 / ton and is subjected to the process of the present invention. Then, the product, that is, the aqueous solution of alkaline earth hydrogen carbonate, is discharged from the process until the remaining resulting S suspension represents a total particle surface area that is around 1,000 m2 / ton, and then a new amount of at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide in a smaller amount compared to alkaline earth carbonate is introduced in the process. It is noted that the total particle surface can be determined for each point of the continuous process by determining the specific surface area (SSA) of the suspension S, as well as the dry state content of the suspension S.
[00064] Most preferably, the continuous process is controlled by the amount of aqueous solution discharged comprising at least one alkaline earth hydrogen carbonate and the measurement of the solid content of suspension S either by complexometric titration or by measuring the conductivity of the alkaline earth hydrogen carbonate solution.
[00065] In yet another embodiment of the present invention, the step filtration device e) is a membrane filter, such as a microfiltration and / or ultrafiltration membrane. In a preferred embodiment, the step filtration device e) is a tube membrane filter with a pore size between 0.02 µm and 0.5 µm, and preferably between 0.05 and 0.2 µm. Preferred are flat filters and / or tube filters. Tube filters preferably have an inner tube diameter of 0.1 to 10 mm, and more preferably 0.1 to 5 mm. In a preferred form the membranes are made of sintered material, porous porcelain or synthetic polymers, such as polyethylene, Teflon® or others.
[00066] Another object of the present invention is the use of an aqueous solution comprising at least an alkaline earth hydrogen carbonate obtained by the process of the invention for the production of a precipitated alkaline earth carbonate and / or hydromagnesite, and in particular , for the production of precipitated calcium carbonate and / or hydromagnesite. Such precipitated alkaline earth carbonates and, in particular, a precipitated calcium carbonate and hydromagnesite are usable as fillers in many industrial applications, for example, as fillers in paper, paint or plastic.
[00067] Another object of the present invention is the use of an aqueous solution comprising, at least, an alkaline earth hydrogen carbonate obtained by the process of the invention for the mineralization of water.
[00068] Another object of the present invention is a process for the mineralization of water comprising the following steps: I) providing feed water, II) providing an aqueous solution comprising at least one alkaline earth hydrogen carbonate, and III) combining the feed water of step I) and the aqueous solution comprising at least one alkaline earth hydrogen carbonate of step II) to obtain mineralized water.
[00069] According to an embodiment of the process for the mineralization of water, the aqueous solution comprising at least one alkaline earth carbonate of step II) has a hardness that is at least 3 ° dH, and preferably at least 5 ° dH greater than the hardness of the feed water of step I).
[00070] According to a preferred embodiment, the aqueous solution comprising at least one alkaline earth carbonate (step II) has a hardness of at least 15 ° dH.
[00071] According to another embodiment of the process for the mineralization of water, the mineralized water has a concentration of calcium, such as calcium carbonate, from 1 to 700 mg / 1, preferably from 50 to 650 mg / 1, and most preferably from 70 to 630 mg / 1. According to yet another embodiment of the process for the mineralization of water, the mineralized water has a concentration of magnesium, such as magnesium carbonate, from 1 to 200 mg / 1, preferably from 2 to 150 mg / 1, and more preferably from 3 to 125 mg / 1.
[00072] Yet another object of the present invention is a process for the production of a precipitated alkaline earth carbonate, the process comprising the following steps: IV) providing an aqueous solution comprising at least one alkaline earth hydrogen carbonate, and V) heat the aqueous solution comprising at least one alkaline earth carbonate of step IV) in order to obtain the precipitated alkaline earth carbonate, and / or VII) add at least one alkaline earth hydroxide or oxide alkaline earth for the solution of step IV) to obtain the precipitated alkaline earth carbonate.
[00073] By heating the aqueous solution comprising at least one alkaline earth hydrogen carbonate, the water is evaporated from the solution and after a certain time the alkaline earth carbonate begins to precipitate out of the solution.
[00074] According to a preferred embodiment of the process for the production of a precipitated alkaline earth carbonate, the precipitated alkaline earth carbonate is selected from an amorphous alkaline earth carbonate, such as calcium carbonate or amorphous magnesium carbonate, crystalline calcium carbonate in calcitic, aragonitic or vateritic, magnesite and hydromagnesite form, or is a mixture of the above mentioned.
[00075] "Conductivity", in the meaning of the present invention, is used as an inverse indicator of how 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 S / m.
[00076] "Crushed calcium carbonate (GCC)", in the meaning of the present invention, is a calcium carbonate obtained from natural sources including marble, chalk or limestone, and processed through a treatment such as crushing, sieving and / or fractionation in a wet and / or dry state, for example, by a cyclone.
[00077] "Precipitated calcium carbonate (PCC)", in the meaning of the present invention, is a synthesized material, generally obtained by precipitation following the reaction of carbon dioxide and lime in an aqueous environment or by precipitation from a source of calcium and carbonate in water or by precipitation of calcium and carbonate ions, for example, CaCb and Na2COs, from solution. Precipitated calcium carbonate exists in three primary crystalline forms: calcite, aragonite and valerite, and there are many different polymorphs (crystal habits) for each of these crystalline forms. Calcite has a trigonal structure with typical crystal habits such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal prismatic, pinacoidal, colloidal (C-PCC), cubic, and prismatic (P-PCC). Aragonite is an orthorhombic structure with crystal habits typical of twin hexagonal prismatic crystals, as well as a diverse variety of thin elongated prismatic shapes, curved blade shapes, sharp pyramids, chiseled crystals, branched tree and coral or worms.
[00078] Throughout this document, the "particle size" of a calcium carbonate product is described by its particle size distribution. The dx value represents the relative diameter at which x% by weight of the particles have smaller diameters than dx. This means that the d2o value is the particle size in which 20% by weight of all particles are smaller, and the d75 value is the particle size in which 75% by weight of all particles are smaller. The value d∞ is thus the median particle size by weight, 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 specified as the median particle size in weight d∞, unless otherwise indicated. These values were measured using a Mastersizer 2000 device from Malvem Instruments GmbH, Germany.
[00079] The term "mineralization" as used in the present invention refers to the increase of essential mineral ions in water containing no minerals at all or in insufficient quantity to obtain water that is palatable. Mineralization can be achieved by adding at least calcium carbonate to the water to be treated. Optionally, for example, for health related benefits or to ensure proper intake of some other essential mineral ions and trace elements, other substances can be mixed in the calcium carbonate and then added to the water during the remineralization process. According to national guidelines on drinking water quality and human health, the remineralized product may comprise additional minerals containing magnesium, potassium or sodium, for example, magnesium carbonate, magnesium sulfate, potassium hydrogen carbonate, hydrogen carbonate of sodium or other minerals containing essential trace elements.
[00080] Substances usable for use in the process of the invention to prepare an aqueous solution comprising at least one alkaline earth hydrogen carbonate are natural calcium and / or magnesium carbonate containing inorganic substances or salts, or synthetic calcium and / or magnesium carbonate containing inorganic substances or salts.
[00081] The naturally occurring inorganic substances that can be used are, for example, marble, limestone, chalk, dolomitic marble and / or dolomite. Synthetic substances are, for example, calcium carbonates precipitated in crystalline calcitic, aragonitic and / or vateritic form. However, naturally occurring inorganic substances are preferred because they inherently contain some essential trace elements.
[00082] "Turbidity", in the meaning of the present invention, describes the cloudiness or opacity of a fluid caused by individual particles (solids placed in suspension) that are generally invisible to the naked eye. Turbidity measurement is a key test of water quality and can be performed with a nephelometer. Turbidity units from a nephelometer calibrated as used in the present invention are specified as nephelometric turbidity units (NTU).
[00083] The process of the invention for the preparation of an aqueous solution comprising at least one alkaline earth hydrogen carbonate comprises the steps of: a) providing water, b) providing at least one substance comprising at least an alkaline earth carbonate and optionally at least one alkaline earth hydroxide in a smaller amount compared to alkaline earth carbonate, to at least one substance being in a dry form or in an aqueous form, c) supply CO2 , d) combining either: (i) water from step a), to at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide from step b) and step c) CO2, or (ii) step a) water and at least one substance comprising at least one earth carbonate and the optional at least one alkaline earth hydroxide step b) a in order to obtain an aqueous alkaline suspension of at least one substance comprising at least u m alkaline earth carbonate and the optional at least one alkaline earth hydroxide and subsequently combining the aqueous alkaline suspension with step c) CO2 in order to obtain a resulting suspension S having a pH between 6 and 9, at resulting suspension S containing particles, e) filtering at least part of the resulting suspension S by passing the resulting suspension S through a filtration device to obtain the aqueous solution comprising at least one alkali-hydrogen carbonate earthy, f) subjecting at least a part of the particles of the resulting suspension S to a particle division step, in which step f) can occur before and / or parallel to and / or after step e), in which the particles of the resulting suspension S, which is obtained in step d), represents a total particle surface area (SSAtotai) that is at least> 1,000 m2 / ton of the resulting suspension S, and with the proviso that an addition of step c CO2) does not occur before an addition of, eg at least, a substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide from step b).
[00084] The process according to the present invention is preferably carried out in a reactor system comprising at least one tank, at least one filtration device, and means for connecting the tank and at least one device filtration systems, such as tubes or pipes. In addition, the reactor system can also comprise measuring equipment, such as units for measuring pressure, temperature, pH, turbidity, and others.
[00085] The tank is equipped with a stirrer with at least one inlet for water, carbon dioxide and the substance comprising at least one alkaline earth carbonate and the optional one, at least one alkaline earth hydroxide. Connected to the tank, there is also a filtration device where at least part of the resulting suspension S having a pH between 6 and 9 and which is prepared in the tank is passed through in order to obtain the aqueous solution comprising at least one alkaline earth hydrogen carbonate.
[00086] In addition, the reactor system contains a dividing device (particle size reduction device), which is mounted in an arrangement in parallel or in series with respect to the filtration device or is introduced into the tank. The tank is connected to the grinding and / or grinding device, where at least part of the particles contained in the resulting suspension S are subjected to a reduction in particle size. The grinding and / or grinding device can be arranged in such a way that only a part of the resulting suspension S, which is contained in the tank, passes through the grinding and / or grinding device before circulating back to the tank (“arrangement parallel ”), or can be arranged in line (in series) with the filtration device, so that any resulting suspension S that passes through the grinding and / or grinding device will subsequently be filtered in the filtration device. The filtration device can also be placed in line before the grinding and / or grinding device ("in line or in series"). If the grinding and / or grinding device is introduced into the tank, some or all of the resulting suspension S passes through the grinding and / or grinding device.
[00087] Preferably, at least a part of the solution leaving the filtration device is collected in order to obtain the aqueous solution comprising at least one alkaline earth hydrogen carbonate. However, if the observed turbidity value of the aqueous solution comprising at least one alkaline earth hydrogen carbonate so that it exits the filtration device is found to be above 1.0 NTU, then the aqueous solution comprising, at least one alkaline earth hydrogen carbonate is recirculated in the reactor.
[00088] The water that can be used in the process of the invention can be derived from several sources. The water preferably treated by the process of the present invention is desalinated sea water, brackish or brine water, treated waste water or natural water such as groundwater, surface water or rainwater.
[00089] According to another exemplary embodiment of the present invention, sea water or brackish water is first pumped out of the sea through open sea entrances or subsurface entrances such as wells, and then undergoes physical pretreatments such as sieving processes. , sedimentation or sand removal. 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 scale on the membranes. Pre-treated seawater or brackish water can then be distilled, for example, using instant multistage distillation, multiple effect distillation, or membrane filtration such as ultrafiltration or reverse osmosis, to remove the remaining particulates and dissolved substances.
[00090] A flow control valve or other means can be used to control the flow rate of carbon dioxide in the stream. 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.
[00091] The carbon dioxide dose is preferably controlled by the pH of the aqueous alkaline earth hydrogen carbonate solution produced.
[00092] The aqueous alkaline suspension formed in the reactor system has a solids content in the range of 0.1 to 80% by weight, preferably in the range of 3 to 50% by weight, more preferably in the range of 5 to 35% by weight. weight, based on the total weight of the resulting suspension S.
[00093] The substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide that is dosed in the tank can be in a dry form or in an aqueous form. Preferably, the substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide has a median particle size by weight (ZZO) in the range of 0.1 pm to 1 mm, and preferably in the range of 0.7 pm to 100 pm. According to an embodiment of the present invention, the substance comprising at least one alkaline earth carbonate is preferably a ground calcium carbonate (GCC) such as marble, limestone or chalk; or a dolomite.
[00094] According to another embodiment of the present invention, the substance comprising at least one alkaline earth carbonate and the optional, at least one alkaline earth hydroxide has an insoluble HCl content of 0.02 to 90 % by weight, preferably from 0.05 to 7% by weight, based on the total weight of the dry substance. The content of insoluble HCl can be, for example, minerals such as quartz, silicate, mica and / or pyrite.
[00095] According to yet another embodiment of the present invention, the aqueous suspension of at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide in an amount lower compared to alkaline earth carbonate, and recently prepared by mixing water and substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide in a smaller amount compared to alkaline carbonate - earthy. Preparation at the aqueous suspension site may be preferred because premixing the aqueous suspensions may require the addition of other 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 aqueous suspension and the injection of the aqueous suspension is short enough to prevent bacterial growth in the aqueous suspension. According to an exemplary embodiment, the time between the preparation of the aqueous suspension and the injection of the aqueous suspension 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 aqueous suspension meets the microbiological quality requirements specified by the national guidelines for drinking water.
[00096] The aqueous suspension of at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide in a lesser amount compared to alkaline earth carbonate can be prepared, for example, using a mixer as a mechanical stirrer for diluted slurry, or a specific powder-liquid mixing device for more concentrated slurry. Depending on the concentration of the prepared aqueous suspension, the mixing time can range from 0.5 to 30 min, from 1 to 20 min, from 2 to 10 min, or from 3 to 5 min. According to an embodiment of the present invention, the aqueous suspension is prepared using a mixing machine, wherein the mixing machine allows simultaneous mixing and dosing of the aqueous suspension.
[00097] The water used to prepare the aqueous suspension can be, for example, distilled water, feed water or industrial water. According to a preferred embodiment of the present invention, the water used to prepare the aqueous suspension is feed water, for example, permeate or distillate obtained from a desalination process.
[00098] According to one embodiment, the aqueous solution comprising at least one alkaline earth hydrogen carbonate is injected directly into a stream of feed water. For example, a clear solution comprising alkaline earth hydrogen carbonate can be injected into the feed water stream at a controlled rate by measuring continuous conductivity.
[00099] According to an embodiment, the value of the predetermined parameter is a pH value, where the pH value is 6.5 to 9, preferably 7 to 8.
[000100] Figures 1 and 2 are intended to illustrate the process according to the present invention.
[000101] Figure 1 exemplifies an embodiment of the present invention, in which the filtering device and the grinding device are arranged in a series or in line arrangement. The process according to the present invention is preferably carried out in a reactor system comprising a tank (1) that is equipped with an agitator (2), at least one inlet (not shown) for water, carbon dioxide and at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide as well as a pH measuring device (not shown). At least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide in a lesser amount compared to alkaline earth carbonate can be introduced into the tank in a dry state or aqueous. At least one filtration device (4) is connected to the reactor which has an outlet for the aqueous solution comprising at least one alkaline earth hydrogen carbonate. When more than one filtration device is present, then they can be either arranged in parallel, or one in line (in series), or one parallel and one in line mode. The filtration device (4) is preferably a membrane filter. A grinding device (18) is arranged following the filtration device (4) and is also connected to the tank (1). The at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide (6) in a lesser amount compared to alkaline earth carbonate, water (14) and CO2 is introduced into the tank (1) via at least one inlet (not shown) and is agitated with an agitator (2) in order to obtain the resulting suspension S having a pH between 6 and 9. Then, the suspension S resultant is fed (8) to the filtration device (4), where the coarse particles, that is, all particles having a size of at least 0.2 pm, which are contained in the suspension are retained in the filtration device ( 4). At least part of the suspension exiting the filtration device (4) is fed into the grinding device (18), and then it is recirculated back to the tank (1). At least a part of the clear aqueous solution comprising at least one alkaline earth hydrogen carbonate is discharged (10) from the filtration device (4).
[000102] In this embodiment, CO2 (20) is preferably fed into the reactor system before the grinding device (18), but after the filtering device (4). The crushing step provides the benefit that the speed of the (chemical) reaction of the process of the invention is increased by continuous production of a surface of the newly prepared and thus active substance comprising at least one alkaline earth carbonate and the optional, at least least an alkaline earth hydroxide. In addition, this process step reduces the particle size of the substance comprising alkaline earth carbonate and the optional, at least one alkaline earth hydroxide of step c) and thus allows the continuous operation of the process. The flow rate of the suspension S through the filtration device (4) is at least 1 m / s, and is preferably in the range of 1.5 to 10 m / s, and most preferably in the range of 3 to 6 m / s. The flow rate of the suspension S through the grinding device is 0.01 to 6 m / s, and preferably 0.1 to 0.5 m / s.
[000103] Optionally, other treatments (16) can be carried out, such as, for example, a mechanical treatment or the addition of biocides or other additives in order to change the pH of the solution (for example, adding a base such as NaOH), the conductivity of the solution, or the hardness of the solution. As another option, the clear aqueous solution comprising at least one alkaline earth hydrogen carbonate discharged from the filtration device can be diluted with more water (14). The coarse particles contained in the suspension and which are retained in the filtration device can optionally be recirculated to the reactor in order to be available for further conversion.
[000104] Figure 2 exemplifies another embodiment of the present invention. The process of this embodiment differs from that of Figure 1, in that the grinding device (18) is not arranged following the filtration device, but rather parallel to the filtration device. The grinding device (18) is connected to the tank (1), such that the content of the grinding device (18) can be recirculated to the tank (1). A part of the resulting suspension S having a pH value between 6 and 9 is fed (8) to the filtration device, while another part of the resulting suspension S, having a pH between 6 and 9, is fed to the filtration device. crushing (18). In this embodiment, CO2 (22) is preferably fed into the reactor system before the grinding device (18). The resulting crushed aqueous suspension S is then circulated (24) from the crushing device (18) back to the tank (1). This grinding step provides the benefit that the speed of the (chemical) reaction of the process of the invention is increased by the continuous production of a newly prepared and thus active surface of the substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide. In addition, this step in the process decreases the particle size of the substance comprising the alkaline earth carbonate and the optional at least one alkaline earth metal hydroxide from step c), and therefore allows continuous operation of the process. The flow rate of the suspension S through the filtration device (4) is at least 1 m / s, and is preferably in the range of 1.5 to 10 m / s, and more preferably in the range of 3 to 6 m /s. The flow rate of the suspension S through the grinding device is 0.01 to 6 m / s, and preferably 0.1 to 0.5 m / s.
[000105] Figure 3 exemplifies another embodiment of the present invention. The process of this embodiment differs from that of Figures 1 and 2, in which the grinding device (18) consists of grinding beads (3) which are arranged in the tank (1). Connected to the reactor is at least one filtration device (4) that has an outlet for the aqueous solution comprising at least one alkaline earth hydrogen carbonate. When more than one filtration device is present, then they can be arranged either in parallel, or in line (in series), or in a parallel and in line mode. The filtration device (4) is preferably a membrane filter. The filtration device (4) is connected to the tank (1) in such a way that a recirculation of a part of the suspension from the filtration device (4) to the tank (1) is possible, if necessary. At least one substance comprising at least one alkaline earth carbonate and optionally at least one alkaline earth hydroxide (6) in a smaller amount, compared to alkaline earth carbonate, water (14) and the CO2 is introduced into the tank (1) through at least one inlet (not shown) and is agitated with an agitator (2) in order to obtain the resulting suspension S having a pH of between 6 and 9. In this embodiment some or all of the particles of the resulting suspension S are crushed by the crushing beads (3) that are contained in the tank. Then, the resulting suspension S is fed (8) to the filtration device (4), in which the coarse particles, that is, all particles having a size of at least 0.2 pm, which are contained in the suspension, are retained in the filtration device (4), and a clear aqueous solution comprising at least alkaline earth hydrogen carbonate is obtained. At least part of the clear aqueous solution, comprising at least one alkaline earth hydrogen carbonate, is discharged (10) from the filtration device (4).
[000106] Optionally, other treatments (16) can be carried out, such as, for example, a mechanical treatment or the addition of biocides or other additives in order to change the pH of the solution (for example, adding a base such as NaOH), the conductivity of the solution, or the hardness of the solution. As another option, the clear aqueous solution comprising at least one alkaline earth hydrogen carbonate discharged from the filtration device can be diluted with more water (14). The coarse particles contained in the suspension and which are retained in the filtration device can optionally be recirculated (12) to the reactor in order to be available for another conversion.
[000107] According to one embodiment the flow rate of the feed water is 20,000 to 500,000 m3 per day.
[000108] The process of the invention can be used to produce drinking water, water for recreational use, such as pool water, industrial water for process applications, irrigation water, or water for the production of purified alkaline earth carbonates.
[000109] According to one embodiment, the alkaline earth hydrogen carbonate solution obtained by the process of the invention has a calcium concentration of 1 to 700 mg / 1, as CaCO3, preferably 50 to 650 mg / 1, as CaCCh, and most preferred from 70 to 630 mg / 1, as CaCO3. In case the slurry comprises another magnesium salt such as magnesium hydrogen carbonate, or magnesium sulfate, the alkaline earth hydrogen carbonate solution obtained by the process of the invention may have a concentration of magnesium, such as magnesium carbonate, from 1 to 200 mg / 1, preferably from 2 to 150 mg / 1, and most preferably from 3 to 125 mg / 1.
[000110] According to an embodiment of the present invention, the alkaline earth hydrogen carbonate solution has a turbidity of less than 1.0 NTU, preferred less than 0.3 NTU. Examples Specific surface area (SSA) of a material
[000111] The specific surface area (SSA) was measured using a Malvern Mastersizer 2000 (based on the Fraunhofer equation). Particle size distribution (mass% of particles with a diameter <X) and median diameter by weight (d5o) of a particulate material
[000112] Grain weight median diameter and the mass distribution of grain diameter of a particulate material were determined using a Malvern Mastersizer 2000 (based on the Fraunhofer equation). pH of an aqueous suspension
[000113] The pH was measured using a Mettler-Toledo pH meter. Calibration of the pH electrode was performed using standard pH values of 4.01, 7.00 and 9.21. Solids content of an aqueous suspension
[000114] The suspended solids content (also known as “dry weight”) was determined using an HR73 Moisture Analyzer from Mettler-Toledo, Switzerland, with the following settings: temperature of 120 ° C, automatic shutdown 3 , standard drying, 5 to 20 g of suspension. Turbidity
[000115] Turbidity was measured with a Hach Lange 2100AN IS laboratory turbidity meter and calibration was performed using StabCal turbidity standards (formazine standards) of <0.1, 20, 200, 1000, 4000 and 7500 NTU. Determination of hardness (German hardness; expressed as “° dH”)
[000116] Hardness refers to the total amount of alkaline earth ions in the aqueous solution comprising alkaline earth hydrogen carbonate, and is measured by complexometric titration using ethylene-diamine-tetra-acetic acid (EDTA; trade name Titriplex III ) and Eriochrome T as an equivalent point indicator.
[000117] EDTA (chelating agent) forms with the ions Ca2 + and Mg2 + complexes of soluble and stable chelates. 2 ml of a 25% ammonia solution, an ammonia / ammonium acetate buffer (pH 10) and Black T Eriochrome indicator were added to 100 ml of a water sample to be tested. The indicator and the buffer are generally available as so-called "indicator buffer tablet". The indicator, when masked with a yellow dye, forms a red complex with ions Ca2 + and Mg24-. At the end of the titration, which is when all the ions are bound by the chelating agent, the remaining Black T Eriochrome indicator is in its free form which shows a green color. When the indicator is not masked, then the color changes from magenta to blue. The total hardness can be calculated from the amount of EDTA that was used.
[000118] The table below shows a conversion for units other than water hardness. Conversion to units other than water hardness [1]

[000119] The carbon dioxide used in the examples is commercially available as "Kohlendioxid 3.0" from PanGas, Dagmarsellen, Switzerland. The purity was> 99.9% by volume. Examples The prior art examples were prepared in the following manner
[000120] Examples from the prior art show different slurries with varying concentrations of calcium carbonate that were prepared from different carbonate rocks and dosed into feed water in a batch mode.
[000121] The feed water was obtained from a process of desalination by reverse osmosis and was acidified with about 50 mg / 1 of CO2. The slurries were prepared by mixing an appropriate amount of calcium carbonate with 100 ml of feed water at room temperature using a magnetic stirrer, with stirring between 1000 and 1500 rpm and a mixing time between 3 and 5 min.
[000122] Remineralization was carried out by adding the slurry in small quantities to about one liter of the acidified feed water, in which the slurry and the feed water were mixed using a magnetic stirrer, with agitation between 1000 and 1500 rpm and a mixing time of 2 minutes. After each addition of slurry, a sample was taken from the treated feed water to control alkalinity, turbidity, conductivity, pH, temperature. A final calcium concentration of 125 mg / 1 as CaCO3 was chosen as a target for the remineralization of feed water. 125 mg of CaCO3 / l represents a concentration of 0.0125% by weight. For each sample, the turbidity of the remineralized water was measured directly after mixing and after a minimum laying period of 60 minutes. The turbidity measured in the settled samples was carried out in order to observe the impact of sedimentation in the remineralization process.
[000123] Turbidity was measured with a Hach Lange 2100AN IS laboratory turbidity meter and calibration was performed using StabCal turbidity standards (formazin standards) of <0.1, 20, 200, 1000, 4000 and 7500 NTU.
[000124] Total alkalinity was measured with a Mettler-Toledo T70 titrator using the related LabX Light titration software. A DGilll-SG pH electrode was used for this titration according to the corresponding Mettler-Toledo method M415 in the application brochure 37 (water analysis). Calibration of the pH electrode was performed using Mettler-Toledo standards of pH values 4.01, 7.00 and 9.21. Example 1 - Slurry A
[000125] Two slurries having a calcium carbonate concentration of 0.5 and 5% by weight, based on the total slurry weight, were prepared from micronized calcium carbonate derived from marble (Salses, France) having an average particle size of 3.5 pm and an insoluble HCl content of 0.2% by weight, based on the total weight of calcium carbonate.
[000126] The results compiled in table 1 show similar turbidity values for both remineralization processes with CaCOa slurries of 0.5% by weight and 5% by weight. After a period of laying, the samples showed turbidity values less than 0.5 NTU. Example 2 - Slurry B
[000127] Three slurries having a calcium carbonate concentration of 0.5, 1 and 10% by weight, based on the total slurry weight, were prepared from micronized calcium carbonate derived from marble (Bathurst, Australia ) having an average particle size of 2.8 µm and an insoluble HCl content of 1.5% by weight, based on the total weight of calcium carbonate.
[000128] The results compiled in table 1 show similar turbidity values for all three remineralization processes. However, the turbidity values measured for the seated samples taken after two minutes of remineralization are higher than those of example 1, which may be due to the difference in the insoluble HCl content of marble calcium carbonate. Example 3 - C slurry
[000129] A slurry having a calcium carbonate concentration of 5% by weight, based on the total weight of the slurry, was prepared from lime-derived micronized calcium carbonate (Orgon, France) having an average particle size 3 pm, a specific surface area (SSA) of 2.6 m2 / g, and an insoluble HCl content of 0.1% by weight, based on the total weight of calcium carbonate.
[000130] The results compiled in Table 1 show that the turbidity value measured for the seated sample is much lower compared to the values in Example 1 and 2, which may be due to the different geological structures of the carbonate rocks.
Table 1
[000131] The results compiled in table 1 show a strong turbidity of the fresh samples and for most samples even after laying.
[000132] Example 4 - Different particle sizes
[000133] Three slurries having a calcium carbonate concentration of 5% by weight, based on the total slurry weight, were prepared from micronized calcium carbonate derived from marble, having a particle size of 3.5 , 9, and 20 pm, respectively, and an insoluble HCl content of 0.2% by weight, based on the total weight of calcium carbonate.
[000134] The results compiled in Table 2 show that, after a laying period, the turbidity of remineralized water with a larger particle size, ie 20 pm, has a lower turbidity value compared to a turbidity of remineralized water with a smaller particle size, ie 3.5 pm which is logical due to the fact that coarse particles settle much faster compared to fine particles.
[000135]
Table 2
[000136] The results compiled in table 2 show a strong turbidity for fresh samples. After a laying period, water that has been remineralized with a larger particle size, ie, 20 pm, shows a lower turbidity value compared to water that has been remineralized with a smaller particle size, that is, 3.5 pm , which is considered to be logical due to the fact that the coarse particles settle much faster than the fine ones, but the turbidity of the sample will increase immediately if the sample is agitated.
[000137] Calcium carbonate based on marble having a median diameter by weight (W50) of 3.5 pm represents approximately a total particle surface of 2.61 m2 / g corresponding to 326.3 m2 / ton of suspension at 0 , 0125% by weight of solids.
[000138] Calcium carbonate based on marble having a median diameter by weight (W50) of 9 pm represents approximately a total particle surface of 1.75 m2 / g corresponding to 218.8 m2 / ton of suspension at 0.0125 % by weight of solids.
[000139] Calcium carbonate based on marble having a median diameter by weight (í / 50) of 20 µm represents approximately a total particle surface of 0.94 m2 / g corresponding to 117.5 m2 / ton of suspension at 0 , 0125% by weight of solids.
[000140] It can be derived from the above information that the rate of dissolution of calcium carbonate is reduced by the specific reduced surface of the calcium carbonate particles that are present in the suspension. Examples related to the invention
[000141] A general process flow diagram of the process according to the present invention is shown in figures 1 to 3.
[000142] The feed water used in the examples of the invention was obtained from an ion exchange equipment from Christ, Aesch, Switzerland Typ Elite IBTH, the feed water having the following water specification after the ion exchanger: Sodium 169 mg / 1 Calcium 2 mg / 1 Magnesium <1 mg / 1 ° dH 0.3
[000143] The following different process routes were used to exemplify the process according to the present invention:
[000144] Process A The suspension of the reactor passes in a mill with crushing beads in the mill Example 5 - Microdol A extra (Dolomite)
[000145] In the present example, Microdol A extra, a dolomite obtained from Norwegian Talc, Knarrevik, was used as the at least one alkaline earth carbonate. The reaction and operating conditions are given in tables 3 and 4.
[000146] Process A, 25 ° C (tank temperature)

Table 3
[000147] The total mineral surface of the particles in the suspension of this experiment represents 427 500 m2 / ton of suspension.
[000148] Process at 40 ° C (tank temperature
Table 4
[000149] The total mineral surface of the particles in the suspension of this experiment represents 167,428 m2 / ton of suspension.
[000150] The ratio of CaCCh in moles produced to CO2 in moles used in this example is 1: 0.54. Example 6 - Marble
[000151] In the present example, a marble sold under the trade name "Omyacarb 10 AV" from the company Omya International, Switzerland, was used as the alkaline earth carbonate. The insoluble HCl content was 0.7% by weight. The reaction and operating conditions are given in table 5.
[000152] Process A, 27 ° C (tank temperature)

Table 5
[000153] The total mineral surface of the particles in the suspension of this experiment represents 421,500 m2 / ton of suspension.
[000154] The ratio of CaCCh in moles produced to CO2 in moles used in this example is 1: 0.45 Use of aqueous solution comprising hydrogen calcium carbonate for the production of precipitated calcium carbonate
[000155] 2 liters of clear permeate obtained according to process B in this example were heated for 2 h at 70 ° C, and the resulting precipitate was collected by filtration using a membrane filter having a pore size of 0.2 pm.
[000156] XRD analysis of the resulting precipitate shows the following: Aragonitic precipitated calcium carbonate (PCC) 85.8% by weight Magnesium-rich precipitated calcium carbonate 14.2% by weight Silica / Silicates <0.1% by weight
[000157] Thus, the XRD result shows that very light precipitated calcium carbonate can be prepared from raw material contaminated with silicate. Example 7, Marble / silicate mixture, Austria
[000158] In the present example, a marble / silicate mixture (Omyacarb 10 AV ”from Omya International, Switzerland, mixtures with 7% mica from Aspanger Kaolin, Austria) was used as the starting material. The insoluble HCL content was 7.5% by weight (mainly mica). The reaction and operating conditions are given in table 6.
[000159] Process A, 24 ° C (tank temperature)

Table 6
[000160] The total mineral surface of the particles in the suspension of this experiment represents 153 500 m2 / ton of suspension.
[000161] The ratio of CaCCh in moles produced to CO2 in moles used in this example is 1: 1.66.
[000162] This example clearly demonstrates that the present invention can also be carried out with highly impure starting products (in this case the impurity is mica). This is a cost efficient alternative for processes where only pure starting products can be used and need to be shipped to the far-away production site. Use of aqueous solution comprising calcium hydrosene carbonate for the production of precipitated calcium carbonate
[000163] 2 liters of clear permeate obtained according to process B in this example were heated for 2 h at 70 ° C, and the resulting precipitate was collected by filtration using a membrane filter having a pore size of 0.2 µm.
[000164] XRD analysis of the resulting precipitate shows the following: PCC Aragonitic 97.3% by weight Calcitic PCC rich in magnesium 2.7% by weight Silica / Silicates <0.1% by weight
[000165] Thus, the XRD result shows that very light precipitated calcium carbonate is obtained from a starting product that contains an insoluble content (impurities) of 7.5% by weight. Example 8, Half-burned Dolomite
[000166] Process A = pass the mill with crushing beats in the mill, T = 20 ° C
[000167] Dolomite from Germany crushed and partially burned, with an average particle size of 7.5 pm and a specific surface area (SSA) of 0.90 m2 / g, from Dolomitwerk Jettenberg, Schõndorfer GmbH, Obeijettenberg, was dispersed in feed water (Christ ion exchange equipment) at a solids content of 2% by weight. The resulting suspension has a conductivity of 1 104 pS / cm.
[000168] The suspension was pumped in a circulation mode at a rate of 2200 1 / h and a temperature of 20 ° C of the reactor passing 3 membrane modules of 0.2 m2 each (Microdyn-Modul MD 063 TP 2N) and was pumped back to the reactor. The membrane modules were arranged in a series line.
[000169] Every 15 minutes, the samples were taken from the suspension and the conductivity, the German hardness, as well as the pH of the samples were determined. Table 7 lists the results obtained.
Table 7
[000170] Table 7 shows a pH below 9.5 and stable conditions with respect to conductivity after 3 to 3.5 hours.
[000171] Table 8 lists the results of ion chromatography (882 Compact IC Plus, Metrohm) of the samples taken after 15, 90, 120, 195 and 285 minutes.
Table 8 [1] In this respect, the ppm unit is used for 1 mg / 1 CaCOa. [2] In this respect the ppm unit is used in the meaning of 1 mg / 1 MgCCh
[000172] Table 8 also shows the stable conditions regarding the magnesium content after 3 to 3.5 hours.
[000173] Table 9 lists the reaction conditions used, as well as pH, hardness, <7io, ÍZ50, O dw and specific surface area (SSA) of samples taken after 15, 90, 120, 195 and 285 minutes. Sampling location was the tank, and the pH value of the permeate was determined by titration.
Table 9
[000174] In the beginning the total particle surface in the suspension of this experiment represents 15 912 mV ton of suspension, and the average diameter (í / 5 °) was determined to be 7.5 pm. After 195 minutes the average diameter (í / 50) was determined to be 0.74 pm, and the total particle surface in the suspension represented 126,000 m2 / ton of suspension. Use of aqueous solution comprising calcium hydrogen carbonate for the production of precipitated calcium carbonate
[000175] 2 liters of clear permeate sampled after 285 minutes were heated for 2 h at 70 ° C and the resulting precipitate (P) was collected by filtration using a 0.2 pm pore size membrane filter and analyzed by XRD. The filtrate was evaporated and dried and the residue (R) was analyzed by XRD.
[000176] The XRD analysis of the resulting precipitate, as well as the residue obtained, shows the following:
Example 9, PCC Langenau
[000177] In this experiment precipitated calcium carbonate (PCC) was used.
[000178] The PCC was produced by adding a 0.1% solution by weight of portlandite to the tap water of 25 ° dH to increase the pH of the water from pH 6.4 to pH 7.8. The precipitated CaCCh thus obtained was used for this experiment.
[000179] Process A, 20 ° C (tank temperature)

[000180] The total mineral surface of the particles in the suspension of this experiment represents 71 400 m2 / ton of suspension.
[000181] The ratio of CaCCb in moles produced to CO2 in moles used in this example is 1: 3.38. Example 10, Mixture of dolomite / limestone Pilot plant experience
[000182] In the present example, one part of extra Microdol A, a dolomite, as described in example 5, was mixed with two parts of limestone from the Avignon region, France, and was used as the mixture of alkaline earth carbonates.
[000183] The purpose of the experiment in example 10 was to produce a solution of alkaline earth hydrogen carbonate with a pH of 6.5 to 6.7 on a pilot scale.
[000184] The alkaline earth carbonate mixture has an IZI0 of 0.43 pm, a dso of 2.43 pm and a d ^ of 6.63 pm at the beginning of the experiment.
[000185] The mixture was fed as 50% by weight of suspension in water.
[000186] The reaction and operating conditions are given below.
[000187] Process A = pass the mill with crushing knocks on the mill, tank temperature T = 18.5 ° C
[000188] Feed tank volume: 1.0 m3
[000189] Feed water: deionized water obtained from an ion exchange equipment from Christ, Aesch, Switzerland, (<1 mg / 1 alkaline earth carbonate).
[000190] 8.0 m2 cross-flow polyethylene membrane module, internal diameter 5.5 mm, 3 m long, 174 tubes in parallel, (Seprodyn SE 150 TP 1L / DF filter module, Microdyn). Pore diameter 1.0 pm.
[000191] Suspension feed flow S for the cross flow membrane unit: 36 m3 / h, speed across the membranes: 3 m / s.
[000192] Pressure at the inlet of the cross flow membrane: 1 bar (0.1 mPa)
[000193] Pressure at the crossflow membrane outlet: 0.3 bar (0.03 mPa)
[000194] Pressure at the solution outlet: 0.05 bar (0.005 mPa)
[000195] Suspension feed flow S to the dividing device: 0.40 m3 / h
[000196] Pressure at the mill inlet: 0.7 to 0.8 bar (0.07 to 0.08 mPa)
[000197] CO2 dose: 1.0 liter / min at a pressure of 1.5 to 1.6 bar. (0.15 to 0.16 mPa)
[000198] Feed solids of suspension S: 15% by weight Results measured at 44 hours of continuous flow:

[000199] The specific particle surface of suspension S obtained according to the process of the invention and taken after 44 hours was 408000 m2 / tonne of suspension S.
[000200] A first quality tap water comprising 45 mg / 1 of alkaline earth carbonate (sum of CaCO3 / MgCO3) was produced by diluting the permeate of this experiment with feed water. The capacity resulting from this experiment corresponds to approximately 6.7 m3 / h at a concentration of 45 mg / 1 of alkaline earth carbonate.
[000201] A second tap water quality comprising 100 mg / 1 of alkaline earth carbonate 1 (CaCO3) and 10 - 15 mg / 1 of alkaline earth carbonate 2 (MgCO3) was produced by diluting the permeate of this experiment with water feed. The capacity resulting from this experiment corresponds to approximately 2.7 m3 / h at a concentration of 100 mg / 1 CaCO3 and 10 - 15 mg / 1 MgCO3. Example 11 - Other pilot scale experiments
[000202] These examples present other experiments for the preparation of aqueous solutions of calcium hydrogen carbonate on a pilot scale. The solution obtained from calcium hydrogen carbonate is then used for the remineralization of soft water, which can be, for example, natural soft water from groundwater or surface water sources, reverse osmosis desalinated water or distillation, rain water. The experiments were carried out using different calcium carbonate products as raw material for the preparation of calcium carbonate suspension, then slurries, and the resulting solutions of calcium hydrogen carbonate obtained after the carbon dioxide dosage.
[000203] The following table 10 summarizes the properties of the calcium carbonate used during the pilot remineralization experiments with an initial slurry volume of 1200 L. Table 10

[000204] The following table 11 summarizes the properties of the calcium carbonate product slurries that were used for the present experiments. Table 11

[000205] The calcium carbonate suspensions mentioned in table 11 (or "slurries") were prepared by mixing the micronized calcium carbonate powder and reverse osmosis water (RO water). RO water was produced on site using a reverse osmosis unit and is of medium quality as described in the following table 12. Table 12

[000206] The tank was completely filled with the respective calcium carbonate suspension. Then, the calcium carbonate suspension was pumped from the tank towards the mill, and from there to the membrane filtration device for filtration. The mill was used as a dosing point for the carbon dioxide that is required for the dissolution of calcium carbonate in water. The dissolved hydrogen carbonate obtained then passed through the membrane, while the undissolved calcium carbonate was fed back into the tank. Among the different water parameters, conductivity was used as a basis for measuring the amount of dissolved hydrogen carbonate obtained by this process.
[000207] The conditions for the measurement of carbon dioxide and calcium carbonate can be derived from table 13. Table 13

[000208] The following table 14 summarizes the results obtained at the end of the first and second days of testing (6-7 hours per day) of slip 2 (with a slip having a solids content of 2% by weight of sample A) and slurry 2 (with a solids content of 2% by weight of sample A). Table 14

[000209] The results shown in table 15 were performed using a slurry 1: ~ 10 weight percent sample A. The test was performed using the same CO2 dosing ratio of 0.3 L of CO2 concentrate / L and the results showed the values obtained at the end of a complete test day. Tabelal5
Impact of reason in excess of CO2
[000210] In addition to the surface area of the solids present in the suspension, it is expected that the stoichiometric ratio of carbon dioxide compared to calcium carbonate, that is, measured as CO2 flow rate / concentrate flow rate, also impacts the dissolution of calcium carbonate in the area. Thus, the final concentration of dissolved hydrogen carbonate, measured as final conductivity, must increase proportionally to the stoichiometric excess CO2 dosed in the slurry. The results presented in table 16 were performed using two slurries both made from sample A (/ / 50 = 13.7 pm, SSA = 1.3 m2 / g) with slurry 1 starting with a higher solid content (slurry 1: ~ 10% by weight) and slurry 2 leaving with a lower solid content (slurry 2: ~ 2% by weight. Carbon dioxide and concentrated flow rates were adjusted to achieve the target stoichiometric ratio CO2 / CaCCh 1-, 2.5- and 5-times, respectively, the CO2 flow rate ratio of 0.12.0.3 and 0.6 L of CO2 / L concentrate.

[000211] The result of this set of experiments shows that the conductivity is increased proportionally to the stoichiometric target ratio CO2 / CaCO.3 measured as L CO2 / L concentrate.

权利要求:
Claims (23)
[0001]
1. Process for the preparation of an aqueous solution comprising at least one alkaline earth hydrogen carbonate, the process comprising the steps of: a) providing water, b) providing at least one substance comprising at least one alkaline earth carbonate and optionally at least one alkaline earth hydroxide in a smaller amount compared to alkaline earth carbonate, to at least one substance being in a dry form or in an aqueous form, c) supply CO2, d) combining either: (i) the water from step a), at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide from step b) and the Step c) CO2, or (ii) step a) water and at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide step b) in order to obtain an aqueous alkaline suspension of at least one substance comprising at least s, an alkaline earth carbonate and the optional, at least an alkaline earth hydroxide and subsequently combining the aqueous alkaline suspension with step c) CO2 (iii) in order to obtain a resulting suspension S having a pH between 6 and 9, the resulting suspension S containing particles, e) filtering at least a part of the resulting suspension S by passing at least a part of the resulting suspension S through a filtration device in order to obtain the aqueous solution comprising, at least less, an alkaline earth hydrogen carbonate, in which the aqueous solution obtained after filtration has a turbidity value of less than 1 NTU and has a concentration of calcium, such as calcium carbonate, from 50 to 650 mg / 1, f) subjecting at least part or all of the particles of the resulting suspension S to a particle division step, in which step f) occurs before and / or in parallel to and / or after step e), and the crushed particles from step f) are recirculated back to step d), where the The particles of the resulting S suspension, which are obtained in step d), represent a total particle surface area (SSAtotai) that is at least 1,000 m2 / ton of the resulting S suspension, and in which the resulting S suspension which is obtained in step d) has a solids content in the range of 1 to 35% by weight, based on the total weight of the resulting suspension S, with the proviso that an addition of the CO2 from step c) does not occur before the addition of at least a substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide of step b), wherein the at least one substance comprising at least one alkaline earth carbonate and the optional, at least one alkaline earth hydroxide from step b) has a median particle size by weight (dso) in the range of 0.1 pm to 1 mm and where step f) of particle division is a step of grinding and / or grinding, and characterized by the fact that the at least one substance comprising at least an alkaline earth carbonate and the optional, at least one alkaline earth hydroxide from step b) is selected from the group comprising marble, limestone, chalk, half-burnt lime, burnt lime, dolomitic limestone, calcareous dolomite, half-dolomite burnt, burnt dolomite and precipitated calcium carbonate.
[0002]
2. Process according to claim 1, characterized in that the particles of the resulting S suspension represent a total particle surface area (SSAtotai) that is in the range of 5,000 - 5,000,000 m2 / ton of the resulting S suspension, preferably in the range of 10,000 - 5,000,000 m2 / ton of the resulting S suspension, and more preferably in the range of 70,000 - 500,000 m2 / ton of the resulting S suspension.
[0003]
Process according to claim 1 or 2, characterized in that the at least one substance comprising at least one alkaline earth carbonate and the optional at least one alkaline earth hydroxide of step b) has a weight median particle size (µ / 50) in the range of 0.7 pm to 100 pm.
[0004]
Process according to any one of claims 1 to 3, characterized in that the at least one substance comprising at least one alkaline earth carbonate and the optional at least one step alkaline earth hydroxide b) has a specific surface area (SSA) in the range of 0.01 to 200 m2 / g, and preferably in the range of 1 to 100 m2 / g.
[0005]
Process according to any one of claims 1 to 4, characterized in that the at least one substance comprising at least one alkaline earth carbonate and the optional at least one step alkaline earth hydroxide b) has an insoluble hydrochloric acid (HCl) content of 0.02 to 90% by weight, preferably 0.05 to 15% by weight, based on the total weight of the dry substance.
[0006]
Process according to any one of claims 1 to 5, characterized in that the resulting suspension S, which is obtained in step d), has a solids content in the range of 3 to 50% by weight, more preferably in the range from 5 to 35% by weight, based on the total weight of the resulting suspension S.
[0007]
Process according to any one of claims 1 to 6, characterized in that the water of step a) is selected from distilled water, tap water, desalinated water, brine, treated waste water or natural water such as groundwater, surface water or rainwater.
[0008]
Process according to any one of claims 1 to 7, characterized in that the CO2 of step c) is selected from carbon dioxide gas, liquid carbon dioxide, solid carbon dioxide or a gas mixture of carbon dioxide and at least one other gas, and is preferably carbon dioxide gas.
[0009]
Process according to any one of claims 1 to 8, characterized in that the amount of CO2 used, in moles, to produce 1 mol of at least one alkaline earth hydrogen carbonate in the aqueous solution is in the range from 0.5 to 4 moles, preferably in the range of 0.5 to 2.5 moles, more preferably in the range of 0.5 to 1.0 mol, and most preferably in the range of 0.5 to 0.65 mol .
[0010]
Process according to any one of claims 1 to 9, characterized in that the particle division step f) is a crushing step.
[0011]
Process according to any one of claims 1 to 10, characterized in that the aqueous solution comprising at least one alkaline earth hydrogen carbonate, which is obtained in step e) has a hardness of 5 to 130 ° dH, preferably from 10 to 60 ° dH, most preferably from 15 to 50 ° dH.
[0012]
Process according to any one of claims 1 to all, characterized in that the aqueous solution comprising at least one alkaline earth hydrogen carbonate, and which is obtained in step e) has a pH in the range of 6, 5 to 9, preferably in the range of 6.7 to 7.9, and most preferably in the range of 6.9 to 7.7, at 20 ° C.
[0013]
Process according to any one of claims 1 to 12, characterized in that the aqueous solution comprising at least one alkaline earth hydrogen carbonate, which is obtained in step e) has a concentration of calcium, as calcium carbonate, from 70 to 630 mg / 1.
[0014]
Process according to any one of claims 1 to 13, characterized in that the aqueous solution comprising at least one alkaline earth hydrogen carbonate, which is obtained in step e) has a magnesium concentration, such as carbonate magnesium, from 1 to 200 mg / 1, preferably from 2 to 150 mg / 1, and most preferably from 3 to 125 mg / 1.
[0015]
Process according to any one of claims 1 to 14, characterized in that the aqueous solution comprising at least one alkaline earth hydrogen carbonate, which is obtained in step e) has a turbidity value less than 0.5 NTU, and preferably less than 0.3 NTU.
[0016]
Process according to any one of claims 1 to 15, characterized by the fact that at least step d) is carried out at a temperature that is in the range of 5 to 55 ° C, and preferably in the range of 20 to 45 ° C.
[0017]
17. Process according to any one of claims 1 to 16, characterized by the fact that it is a continuous process.
[0018]
Process according to any one of claims 1 to 17, characterized in that the step filtration device e) is a membrane filter, and preferably a tube membrane filter with a pore size between 0.02 pm and 0.2 pm.
[0019]
19. Use of an aqueous solution comprising at least one alkaline earth hydrogen carbonate obtained by the process as defined in any one of claims 1 to 18, characterized in that it is for the production of a precipitated alkaline earth carbonate and / or hydromagnesite, and in particular for the production of precipitated calcium carbonate and / or hydromagnesite.
[0020]
20. Use of an aqueous solution comprising at least one alkaline earth hydrogen carbonate obtained by the process as defined in any one of claims 1 to 18, characterized in that it is for the mineralization of water.
[0021]
21. Process for the mineralization of water, characterized by the fact that it comprises the following steps: I) supplying drinking water, II) providing an aqueous solution comprising at least one alkaline earth hydrogen carbonate obtained by the process as defined in any one of claims 1 to 18, and III) combining the step I) feed water and the aqueous solution comprising at least one step II) alkaline earth hydrogen carbonate to obtain mineralized water.
[0022]
22. Process according to claim 21, characterized in that the aqueous solution comprising at least one alkaline earth hydrogen carbonate of step II) has a hardness that is at least 3 ° dH, and preferably, at least 5 ° dH greater than the hardness of the step I feed water).
[0023]
Process according to claim 21 or 22, characterized in that the aqueous solution comprising at least one alkaline earth carbonate (step II) has a hardness of at least 15 dH.

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CA2844656C|2017-04-18|Remineralization of desalinated and of fresh water by dosing of a calcium carbonate solution in soft water

同族专利:

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EA201491464A1|2014-11-28|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-06-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-17| 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 31/01/2013, 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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EP12153898.7A|EP2623466B8|2012-02-03|2012-02-03|Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate|

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EP12153898.7|2012-02-03|

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US201261597193P| true| 2012-02-10|2012-02-10|

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PCT/EP2013/051884|WO2013113807A1|2012-02-03|2013-01-31|Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate and its use|

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