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    • 专利摘要:
    PROCESS FOR THE PREPARATION OF PRECIPITATED CALCIUM CARBONATE, PRECIPITATED CALCIUM CARBONATE, AND USE OF A PRECIPITATED CALCIUM CARBONATEThe present invention relates to a process for the preparation of precipitated calcium carbonate comprising the steps of: a) providing and calcining material comprising calcium carbonate; b) erase the reaction product obtained from step a) with an aqueous solution of ammonium chloride; c) separating insoluble components from the calcium chloride solution obtained from step b); d) carbonate the calcium chloride solution obtained from step c); e) separating the precipitated calcium carbonate obtained from step d); the precipitated calcium carbonate obtained by this process, as well as its uses.
    公开号:BR112013009985A2
    申请号:R112013009985-2
    申请日:2011-10-20
    公开日:2021-01-26
    发明作者:Bahman Tavakkoli；Jörg Sötemann；Michael Pohl；Thomas Schmölzer
    申请人:Omya Development Ag；
    IPC主号:
    专利说明:

    “PROCESS FOR THE PREPARATION OF PRECIPITATED CALCIUM CARBONATE, PRECIPITATED CALCIUM CARBONATE AND USE OF A PRECIPITATED CALCIUM CARBONATE” The present invention relates to a process for the production - of high purity precipitated calcium carbonate, carbonate precipitated calcium of high purity obtained by this process, as well as its use.
    Calcium carbonate is one of the most commonly used additives: in the paper, ink and plastic industries.
    Although naturally occurring ground calcium carbonate (GCC) is normally used as a filler in many applications, synthetically manufactured precipitated calcium carbonate (PCC) can be tailored to its particle size and morphology, | allowing these materials to perform their additional functions. | However, commonly known PCC production processes including the steps of calcining raw calcium carbonate, extinguishing it with water, and subsequently precipitating calcium carbonate by passing carbon dioxide through the resulting calcium hydroxide suspension, require high starting materials quality, as there is no reasonable method of separating impurities from the raw material during this process.
    There are numerous approaches in the prior art to - producing calcium carbonate with certain properties, such as high purity, most of which, however, are focusing only on this property, whereas the processes do not allow to completely control other properties as well, such as shape crystalline, particle size, etc., or large amounts of tailings are often produced by such - known processes.
    In Chinese patent application No. 1757597, a process for preparing porous superfine calcium carbonate is described.
    This is achieved by preparing an aqueous solution of calcium chloride, as well as, separately, an aqueous solution of hydrogen ammonium carbonate and carbon dioxide, and reacting these solutions in a collision reaction, which is an overly complex reaction in practice, yet controlling flow and temperature, resulting in the formation of porous superfine precipitated calcium carbonate with a high specific surface area. The mother liquor - containing ammonium chloride is reused to dissolve calcium chloride in it, but ammonium chloride is not used as a reagent as such. Thus, the process according to CN 1757597 starts with a high quality starting material, in which high porosity and high fineness are particularly achieved by the specific type of collision reaction. The waste, inter alia ammonium chloride solution, is not reused as a reagent, but simply as a solvent, which will lead to an enrichment of ammonium carbonate not only in the solution, but also in the final product, until it is separated. No mention is made in this document of how to obtain precipitated calcium carbonate with a high purity and defined crystalline structure.
    Japanese patent application JP 2007-161515 is aimed at | a method for producing calcium carbonate, in which the impurity content, | in particular, the strontium content is reduced. The method comprises the following steps: (A) a dissolution step, where an aqueous solution of hydrochloric acid, nitric acid, ammonium chloride or ammonium nitrate is added to an aqueous suspension in order to dissolve calcium hydroxide; (B) a precipitation step, where aqueous ammonia is added to the solution of a calcium salt obtained in the dissolution stage, and the pH of the liquid is increased to more than 12, in order to precipitate impurities together with the precipitation of hydroxide calcium; (C) a solid-liquid separation step, where precipitated impurities and an aqueous solution of calcium salt are separated; (E) a precipitation step, where carbon dioxide gas is blown into the separated aqueous calcium salt solution, in order to precipitate calcium carbonate; and (F) a recovery step, where the precipitated calcium carbonate is recovered. Thus, the JP 2007-161515 process is somewhat complicated and not really environmentally friendly using compounds such as hydrochloric and nitric acid, and nitrates, which are not returned to the reaction cycle.
    In addition, the separation of co-precipitated metal hydroxides from calcium hydroxide is based on the different dissolving behaviors of hydroxides at high temperatures, which is not very accurate and requires a high energy consumption.
    In addition, no information is given on how to obtain specific crystalline structures of the precipitated calcium carbonate.
    Thus, there is a continuing need for processes that provide high-purity PCCs with defined structures, and that allow for the control of several desired PCC properties, where the starting material may be a low quality material that would otherwise be deposited because of its low quality, which is especially advantageous from an environmental point of view and in relation to increasing demands for | sustainable processes.
    Equally, it is an objective of the present invention, on the one hand, to produce as little waste as possible and, on the other hand, to reuse as much waste as possible, which can be recycled or fed in other applications.
    It has surprisingly been observed that, by the process of the present invention, low quality carbonates can be transformed into very pure precipitated calcium carbonates with an excellent gloss and defined structure.
    Thus, according to the process of the present invention, it is possible to separate essentially all impurities from the starting material, regardless of the quality or types of raw material.
    In this way, the exposed objective is solved by a process for the preparation of precipitated calcium carbonate comprising the steps of:
    a) providing and calcining material comprising calcium carbonate; b) erase the reaction product obtained from step a) with an aqueous solution of ammonium chloride; c) separate insoluble components from the calcium chloride solution obtained in step b); d) carbonate the calcium chloride solution obtained from step c); e) separating the precipitated calcium carbonate obtained from step d).
    The process according to the present invention provides a high purity precipitated calcium carbonate, in which mineral impurities present in the feed material are easily separated, and in which essentially no by-products or undesirable residues are produced.
    i The fundamental chemical reactions of the presented process can be summarized as follows, where "Imp" means the amount of undesirable impurities basically coloring: | CaCO (Imp) —A—> cao (Imp) + COL t CaOflmp) + 2 NHCI ——> CaCh + 2 NHi + HO + Impt CaCh + 2 NH; + CO + HO CaCO; zY + 2 NILCI In step a), a feed material is provided, which comprises calcium carbonate, and is calcined. Calcination is a heat treatment process applied to materials containing calcium carbonate in order to perform a thermal decomposition resulting in the formation of calcium oxide and carbon dioxide gas.
    It is a special advantage of the present invention that, for this purpose, also materials comprising low quality calcium carbonate can be used, which are normally not suitable for the production of high quality fillers and pigments and are therefore deposited as waste material .
    Materials comprising calcium carbonate that can be used as feed materials in the present process can be any materials comprising calcium carbonate such as those selected from the group comprising precipitated calcium carbonates; To minerals containing natural calcium carbonate such as marble, limestone and chalk, and mixed alkaline earth carbonate minerals comprising 5 - calcium carbonate such as dolomite, or rich fractions of calcium carbonate from other sources, any of which may comprise impurities varied, for example, those that can be burned in carbon dioxide, for example, graphite or other organic impurities, OR, especially, impurities that are insoluble in an alkaline ammonia environment, such as silicates, iron oxides, or iron hydroxides .
    Generally, in the context of the present invention, the term "impurity" refers to any component other than calcium carbonate.
    For efficiency, it is preferable that the feed material has a minimum calcium carbonate content of at least 15% by weight, more preferably at least 50% by weight, | especially at least 75% by weight, and above all preferably at least 90% by weight, for example, 98% by weight based on the total weight of the feed material.
    Calcium carbonate decomposes at about 1,000ºC in calcium oxide (commonly known as quicklime). The calcination step can be carried out under conditions and using equipment well known to those skilled in the art. Generally, calcination can be carried out in furnaces or reactors (sometimes referred to as calcining furnaces) of various designs, including vat furnaces, rotary calcination furnaces, multiple sill furnaces and fluidized bed reactors.
    The end of the calcination reaction can be determined, for example, by monitoring the change in density, the residual carbonate content, for example, by X-ray diffraction, or by extinguishing the reactivity by common methods.
    Subsequently, unlike usual PCC production processes using only water to extinguish calcium oxide resulting in the formation of insoluble calcium hydroxide according to the process of the present invention, step b) is performed by combining calcium oxide obtained from step a) with an aqueous solution of ammonium chloride, resulting in the formation of highly soluble calcium chloride, whereas unwanted impurities initially contained in the calcium carbonate feed material remain insoluble or are at least less soluble than calcium chloride in the ammonia medium resulting alkaline, allowing a separation.
    The ammonium chloride used in the process of the present invention can be any commercially available product.
    The concentration of the ammonium chloride solution is essentially not critical. However, for the sake of efficiency, it is preferred to be somewhat high, for example, 200 g ammonium chloride per liter of water.
    With respect to the amount of calcium oxide, the molar ratio of ammonium chloride to calcium oxide is preferably 1: 1 to 8: 1, more preferably 1.5: 1 to 4: 1, for example, 2: 1 to 3: 1.
    The progress of the reaction can be observed by measuring the conductivity of the reaction mixture, which initially decreases rapidly and reaches an essentially constant level as soon as the reaction is completed. Likewise, it can be monitored by controlling temperature and turbidity.
    In step c), the impurities are separated as insoluble components in the alkaline calcium chloride solution formed in step b), which can be achieved by sieving or settling and decanting and / or filtration.
    It may be especially preferable to carry out microfiltration (particle separation> 0.6 pm) or even nanofiltration (particle separation> 0.01 pm) subsequent to any of these separation steps, especially after sedimentation and decantation, in order to separate impurities colloidal dyes and unwanted crystal seeds, and obtain products of an even greater shine.
    The techniques mentioned can be performed using any equipment known for such purposes.
    Insoluble components can be flocculated before recovering them, by adding high molecular flocculants known in the art for such purposes, in which cationic, anionic and / or nonionic flocculants, preferably polyacrylic acid based copolymers can be used.
    However, it is preferred to use flocculants | anions that provide a flocculation of impurities such as hydroxide | iron preferably in a matter of seconds.
    The flocculants can be added in an amount of 1 to 50 ppm, preferably 2 to 40 ppm, more preferably 3 to 25 ppm, and most of all preferably 5 to 15 ppm, based on dry CaO. i After separation, a clear and practically colorless concentrate of easily soluble calcium chloride is obtained.
    Impurities that can be separated in step c), for example, are impurities that are insoluble, or poorly soluble, in an alkaline ammonia environment, such as silicates, iron oxides, iron hydroxides, magnesium chloride, etc., and even fons of manganese or strontium can be enriched in the tailings.
    It is an additional advantage of the process of the present invention that these impurities, which are separated from the reaction cycle as tailings, can be used in other applications, for example, as a base material for fertilizers or soil conditioners, since they contain high amounts of ammonium chloride compounds.
    Other applications could - be catalysts, for example, in floor tile applications, or in any other use, where, for example, finely dispersed iron (oxide) is advantageously used as a catalyst.
    In step d), the carbonation of the calcium chloride solution obtained from step c) results in precipitation of pure calcium carbonate.
    Carbonation can be carried out by feeding pure carbon dioxide gas or technical gases containing at least 10% by volume of carbon dioxide in the alkaline solution of calcium chloride. In this regard, it is possible to use any technical fuel gas, as long as it does not contain any components that cause unwanted side reactions, or that introduce new impurities in the process of the present invention, such as heavy metals or sulfur components. Carbonation is carried out by means and under conditions well known to those skilled in the art. The introduction of carbon dioxide in the alkaline solution of calcium chloride rapidly increases the concentration of carbonate ion (CO3 ”) and calcium carbonate is formed.
    In particular, the carbonation reaction can be easily controlled by considering the reactions involved in the carbonation process.
    Carbon dioxide dissolves according to its partial pressure, which forms carbonate ions via the formation of carbonic acid (H2CO;), and hydrogen ions | carbonate (HCO;) which are unstable in the alkaline solution Through 'continued dissolution of carbon dioxide, hydroxide ions are consumed and the concentration of carbonate ions increases until the concentration of dissolved calcium carbonate exceeds the solubility product and calcium carbonate solid precipitate.
    Occasionally, there may be supersaturation that slows down precipitation, which is attributed to a decrease in the concentration of carbonate ion, while the concentration of hydrogen carbonate ion increases and - subsequently, calcium hydrogen carbonate (CaHCO; 3 ”) cations are formed which are more soluble than calcium carbonate.
    Consequently, the precipitated calcium carbonate yield may not be 100% of the theoretical value. The yield could be increased to 100% by an excess of ammonia, leading to a greater
    | carbonate anion concentration. However, it is preferred that the process according to the present invention is conducted as a closed process, in which any of the reagents can be recycled to the process, for example, unreacted calcium chloride and / or ammonium chloride can be - directly returned to step b) of the process.
    In a special embodiment, seed crystals can be added to the calcium chloride solution obtained from step c) prior to precipitation to ensure that the precipitation products crystallize in a certain shape and particle size range.
    The seed crystals can be added in an amount of 0.1 to 10% by weight, preferably in an amount of 0.1 to 8% by weight, more preferably in an amount of 0.2 to 5% by weight, above all preferably in an amount of 0.5 to 2% in | weight, for example, 1% by weight, based on the weight of CaO.
    It is especially preferred that the mother liquor obtained after precipitation is completely recycled, which, as mentioned, can advantageously be achieved by a closed system that reduces emissions almost completely.
    The progress of the carbonation reaction can be easily - observed by measuring conductivity density, turbidity and / or pH.
    In this regard, the pH of the calcium chloride solution before adding carbon dioxide will be more than 10 and will decrease constantly until a pH of about 7 is reached. At this point, the reaction can be stopped.
    Conductivity decreases slowly during the carbonation reaction and decreases rapidly to low levels when precipitation is completed.
    The precipitated calcium carbonate obtained from step d) can be separated from the mother liquor by any conventional separation means such as filtration, for example, by means of drum filters, filter press, etc. After separation, the precipitated calcium carbonate may still contain some water, as well as dissolved ions from ammonium chloride and calcium chloride.
    Residual ammonium chloride and calcium chloride, or their respective ions, should advantageously be removed from the precipitated calcium carbonate because of their corrosive potential, odor and possible negative effects in applications such as, for example, paper, ink or plastic.
    The removal of easily soluble ammonium chloride and calcium chloride, however, is easily done simply by washing the precipitate with water, preferably water heated to the boiling point, and optionally with stirring, and subsequent separation of the precipitated calcium carbonate from the aqueous phase. by suitable separation methods known to those skilled in the art, such as filtration, in which the washing step can be repeated until the desired level of purity is reached.
    After washing, the precipitated calcium carbonate can be concentrated to obtain a paste, which can be used, for example, in paper applications, or dried, for example, in an oven at 100ºC without | - decomposition or change of the product and crystalline form, the dry product | being especially suitable, for example, in plastic applications.
    The precipitated calcium carbonate can be further processed, for example, it can be de-agglomerated or subjected to a dry milling step. Otherwise, it can also be milled wet in the form of a paste.
    As mentioned earlier, the process according to the present invention is preferably a closed process, which can be carried out in batch or continuously.
    Thus, any of the reagents can be recycled to the process.
    In an advantageous embodiment, even the carbon dioxide produced in step a) can be recycled to the closed reaction cycle in step I). Also, exhausted ammonia can be recycled to the process, in which any of the gaseous components are advantageously taken through - conventional gas purifiers for purification purposes, when they are recycled.
    The precipitated calcium carbonate obtained by the process of the present invention preferably contains less than 0.5% by weight of impurities (i.e., components other than calcium carbonate), more preferably less than 0.3% by weight, especially less than 0 , 1% by weight, and above all preferably less than 0.05% by weight of impurities.
    The precipitated calcium carbonate may have aragonitic, calcitic or vateritic crystalline structure, or mixtures thereof.
    It is a further advantage of the present invention that the crystalline structure and morphology of the precipitated calcium carbonate can be controlled, for example, by the addition of seed crystals or other structure-modifying chemical compounds.
    The purity of the desired mineral phase can be greater than 90% by weight, and even greater than 95% by weight, especially if corresponding seed crystals are used.
    Thus, especially aragonitic PCC can be obtained in very high purity using corresponding seed crystals, such as, for example, ultrafine ground aragonitic calcium carbonate products.
    Without seed crystals, the formation of vateritic structures will be favored, recrystallizing in the absence of any stabilizing agent in the calcitic structures.
    The high purity of the precipitated calcium carbonate obtained by the process of the present invention leads to excellent optical properties, | | | | especially high brightness and low yellow index, measured using an Elrepho spectrometer available from Datacolor calibrated with a standard barium sulfate according to standard procedures. Thus, the products obtained by the process of the present invention - may have a TAPPI (R457) gloss of at least 88, preferably at least 90, more preferably at least 92, for example, from 95 to 99, such as 97.
    The luminous reflectance factor R, of the precipitated calcium carbonate obtained by the process of the present invention preferably has a value of at least 90, preferably at least 92, more preferably at least 95, for example, from 96 to 99, such as 98. The yellow index (calculated using the formula I = 100 * (Rx-R,) / R,) of the precipitated calcium carbonate obtained by the process of this | the invention preferably has a value of 0.5 to 6, more preferably | 0.7 to 3, above all preferably 1 to 2. | 15 In addition, a small particle size can be | achieved by the process of the present invention. Thus, the precipitated calcium carbonate obtained by the process of the present invention can have a weighted median diameter ds of not more than 20 µm, preferably not more than | 10 µm, more preferably not more than 5 µm, above all preferably not more than 2 µm, for example, not more than 1 µm.
    For determining the weighted median particle size a Sedigraph 5100 device from Micromeritics, USA was used. The measurement was made in an aqueous solution of Na, P2O; 0.1% by weight. The samples were dispersed using a high - speed shaker and ultrasound.
    The possibility of obtaining a small particle size like this according to the invention is attributed to the high purity of the material. It can additionally be controlled by applying a high partial pressure of | carbon dioxide during calcium carbonate precipitation, as well as by high mechanical shear during the precipitation step or afterwards by high agitation rates. | Thus, it is still possible to obtain structured particles with a median particle diameter weighted in the nanometer range.
    In this regard, it is also possible to obtain precipitated calcium carbonate with a very narrow particle size distribution, which can be further improved by the use of certain crystallization blocking additives such as oil or sugar-based chemicals, or judicious de-agglomeration. by means of grinding, ultrasound and the like.
    The specific BET surface area of the precipitated calcium carbonate obtained by the process of the present invention can be controlled by the use of additives, for example, active surface agents, shear during the precipitation step or thereafter at high rates of mechanical shear not only leading to to a small particle size, but also a high specific BET surface area.
    The specific BET surface area of the precipitated calcium carbonate obtained by the process according to the present invention can be from 1 to 100 m / G, preferably from 5 to 70 m "/ g, more preferably from 10 to 50 m" / g , especially from 15 to 30 m / g, for example, from 18 to 20 m / g, - measured using nitrogen and the BET method according to ISO 9277.
    Because of the above-described properties of the precipitated calcium carbonate obtained by the process according to the present invention, which can be easily controlled in the desired manner, it is an additional aspect of the present invention to use these precipitated calcium carbonates in applications such as paint applications or plastic, as well as in paper applications.
    The precipitated calcium carbonate obtained by the process according to the present invention can advantageously be used as fillers and / or pigments in plastic, such as in breathable films, inks and papers.
    The figures described below, and the following examples and experiments, serve to illustrate the present invention and should not be restricted in any way. Description of the Figures Figure 1 shows a main flow chart of a configuration for the process of the present invention.
    EXAMPLES In the following examples, the process according to the present invention is exemplified, and product properties of the precipitated calcium carbonates obtained by this process are described:
    1. Basic configuration for carrying out the present invention In figure 1, a schematic illustration of an advantageous embodiment of how the process of the present invention can be conducted in principle is given by a flow chart, also comprising optional steps such as ammonia recycling for the process , including purification and washing in order to purify exhaust gases and precipitated calcium carbonate product. | For the following examples, qualities of low chalk and | limestone from different mines was chosen as feed material, which is normally not suitable for preparing common PCC qualities. Among these materials, a residual material from a sieving step of a marble feed stone (so called "Riesel") was selected. While chalk and limestone feed materials were ground to obtain a suitable feed size of 1 to 8 mm for the process of the present invention, the Riesel material was sieved at 1 mm to remove clay minerals.
    2. Preparation and characterization of products obtained by the process of the present invention
    In order to determine the purity of the product obtained by the process and thus the efficiency of the process of the present invention, the precipitated calcium carbonate was prepared as follows and its chemical composition, as well as that of the feed material and the tailings, was determined and —sumarized following table.
    2.1. Preparation of high-purity PCC from different materials and characterization with respect to brightness and yellow index
    2.1.1. Preparation For the following laboratory experiments, several different feed materials were used in the process of the present invention and subsequently analyzed for their optical properties: | Feed material Sample No. 1: Riesel 1-4 mm Gummern (Austria) Sample No. 2: Chalk Harmignies (Belgium) Sample No. 3: Ordinary chalk Omey (France) Sample No. 4: Chalk Mjelnik (Poland) Sample No 5: Riesel 1-4 mm Gummern (Austria) Sample No. 6: Fe-rich marble Gummern (Austria) Sample No. 7: Burgberg Limestone (Germany) Sample No. 8: Vollmer Limestone (Germany) a) 5,000 g of respective feeding material were calcined in a laboratory oven at a temperature of 1,000ºC for 2 hours. b) 400 g of the burnt limestone obtained from the calcination step - were fed in an 8 L reactor, which was previously fed with 800 g of ammonium chloride dissolved in 4 L of water. The reaction mixture was removed under stirring at room temperature for 30 minutes, while the temperature of the solution decreased. c) Subsequently, insoluble components were separated from the resulting solution of calcium chloride by sieving at 100 µm. The separate tailings were analyzed, as mentioned below. d) The obtained calcium chloride solution was fed into a precipitation reactor, in which pure carbon dioxide gas was fed - from a storage tank under stirring at an initial temperature of 40ºC. When the reaction was completed, which was determined by pH control, the precipitated calcium carbonate was filtered off, the filtrate was washed with water, filtered again, and finally dried in a drying cabinet at 105ºC.
    2.12. Characterization The sample No. | it was compared to precipitated calcium carbonate produced by a prior art process, meaning that the burnt lime was extinguished in water instead of an ammonium chloride solution, resulting in the formation of calcium hydroxide. | The results are summarized in table 1 below, in which the | brightness of the feed material was measured to a particle size of dso = 5 µm, while the final products are measured as received. Table 1
    EEE Tappi Sample 1 / 65.8 712.2 65.4 PCC feed material 91.7 95.6 94.8 91.6 4.3 (prior technology) 91.7 Sample 1 | 96-98 96-98.8 96-98.7 96-98.1 0.6-1.5 product - final invention Looking at these results, it is evident that the precipitated calcium carbonate produced according to the process of the present invention from a low quality natural calcium carbonate material it has excellent gloss, which is even better than the precipitated calcium carbonate produced according to a prior art process.
    These results were confirmed by additional tests with samples 2 to 8, which were processed as previously described and compared with the precipitated calcium carbonate obtained in the manner summarized in Table 2 below. —Table2 Briltoragi | R | R [| R | Index | Sample supply no. —2 [97.5 98.6 98.5 97.5 12 (final product) dso = 4.8 um (feed) Sample no. 3 | 96.7 97.8 14 (final product) dso = 2.2 um 70.7 794 77.6 70.4 1.7 feeding: Sample no. - 497.8 86.5 98.4 97.7 (final product) dso = 4.8 one feed. Sample no. 5 98.2 97.9 96.3 2 (final product) dso = 6 a feed. Sample no. 6 | 95.7 9077 97.3 95.6 22 (final product) dso = 14 a feed. Sample no. 7 | 945 95.5 95.4 94.4 12 (final product) dso = 12.4 a feed Sample no. —8 / 97.8 98.5 98.4 97.7 (final product dso = 2 um
    2.1.3. Chemical Analysis The elementary analysis of the dry product, as well as the feed material and the tailings from sample 3, was performed using X-ray fluorescence (XRF ARL-9400, from Thermo-ARL). To determine the loss on ignition and the specific surface area (measured using nitrogen and the BET method according to ISO 9277), standard laboratory methods were used (cf. table 3).
    Table 3 Materia! from | Product Feed refuse (% by weight) (% by weight) hi (% by weight) 1.05 0.47 <0.04 EE MB Br 0] 4.34 o nu tea 24.56 Lo CE o A ah Ro Bag aa | sr oa o [565 ag ia ea ur aa
    3.090 From the table presented, it can be seen that the product obtained by the process according to the invention has a high chemical purity with respect to its content of calcium carbonate (CaO + loss on ignition) from 99 to 100% by weight. Particularly, comparing the contents of SiO ,, AIO3, FesOs, MEgO, PO; of the raw material, the product and the tailings, it can be seen that the separation of the corresponding impurities can be achieved almost completely. Also, the amount of heavy metals like Y, Sr, Mn and Cr | - can be significantly reduced in the product.
    2.2. Preparation and characterization of high purity PCC using seed crystals
    2.2.1. Preparation In 7 technically-scaled experiments, the method of the present invention was evaluated with respect to different feed materials and process parameters, as mentioned in the following table. Feed material Samples No. 9 - 13: Wash-Riesel 1 -4 mm (marble)
    Gummern (Austria)! Samples No. 14 - 15: Ordinary chalk Omey (France) | a) 2 t of the respective samples were calcined in a rotary calcination oven 1 at a temperature of 1,000ºC for 2 hours, to obtain - feeding material comparable to the erasing process. | b) 180 kg of the burnt lime obtained from the calcination step were | fed into an erasure reactor (volume: 2.3 m ”; diameter: 1.2 m; | height: 2 m), which was previously fed with 360 kg of ammonium chloride and 1,800 kg of water.
    The reaction mixture was removed with stirring at | a temperature of 40ºC for half an hour.
    The reaction was completed when the | Burnt lime was dissolved in a clear solution. | c) Subsequently, 15 ppm (based on CaO) of an anionic flocculant (Superfloc A-130 from Kemira) was added to the resulting reaction mixture in order to improve the separation of insoluble components from the resulting solution.
    The separation was finally carried out by settling and decanting the clear solution. d) 600 L of the resulting calcium chloride solution were fed to an Ultramill (volume: 700 L), and a defined amount of aragonitic seed crystals, given in the following table, was added to it.
    Subsequently, the calcium chloride solution was heated to the corresponding starting temperature, and a technical gas containing 20% by volume of carbon dioxide, was fed from a storage tank under a defined stirring power as mentioned in the following table and a flow of 100 m * / h.
    When the reaction was completed, - which was determined by a final pH of 7, the calcium carbonate paste | precipitate was separated by filtration on a Metso vacuum drum filter, the filter cake was washed with water and finally concentrated by centrifuge in a final paste.
    The content of solids in the precipitated calcium carbonate paste is related to recovery, whereas the content of solids in the filter cake indicates the fineness of the final product.
    The presented procedure produced PCCs with a BET surface between about 4 and about 12 and with excellent optical properties, as - mentioned in the following table. R457 Tappi brightness and yellow index were determined by Datacolor measurements as mentioned earlier.
    A comparison indicates that better results with regard to fineness and brightness could be achieved with 2% by weight of aragonitic seeds, low temperature of onset of precipitation and high power of the agitator.
    It can be concluded that very low concentrations of seed crystals increase the resulting size of the precipitated crystals, while very high concentrations reduce the viscosity and disturb the gas transport in the reactor. Also, greater stirring power and lower starting temperatures promote the formation of a larger amount of particles and finer particles.
    Table4 [Experimentno. | 9 | 10 [nm [1 [13 [1 [15 | Riesel Material Riesel | Chalk Chalk feeding Crystals 1 2 2 5 5 seeds (% by weight (based on CaO Temperature of | 55 55 40 53 55 55 55 starting (ºC Agitator (% o | 75 175 75 50 70 75 70 power) LE | | Solid content | 7.1 8.1 8.9 6.0 12.4 9.3 9.2 | CaCO paste; (before filtration (% by weight. Solid content 57.0 53.0 52 , 4 47,0 72,0 50,2 CaCO filter cake; (% by weight | m "/ g Datacolor 92,3 / 3,6 | 95,5 / 1,7 | 96,4 / 1,1 | 93.3 / 3.0 | 95.9 / 1.2 | 92.9 / 3.1 | 81.2 / 9.5 R457 / Index
    The brightness (R457) of sample 15 was somewhat pure. This, however, was attributed to an incomplete flocculation of impurities in this | sample. The brightness of this sample could be significantly improved by adding a little more flocculant. In this case, however, the sample —15 was used for the following experiments, in order to verify the efficiency of a subsequent microfiltration, which also provided good results.
    2.3. Preparation of high-purity PCC from different materials and characterization with respect to the best filtration In order to evaluate the influence of an improved filtration step after the burning of the burnt lime, samples from the above mentioned experiments 13 and 15 were filtered again by using one | microfiltration unit with 0.2 µm PP membranes from Microdyn-Nadir. | Subsequently, the filtrate was precipitated in a laboratory unit as previously mentioned with respect to example 1.
    By separating residual organic molecules and colloidal iron hydroxide impurities, an increase in additional brightness and a reduction in the index could be seen (see table 5).
    Applying the microfiltration step, high-purity aragonitic products could also be obtained. Purity was controlled by X-ray diffraction using a Bruker D8 XRD in combination with Rietveld's Topas software (cf. table 5).
    Table 5 | lTeikas7 [R ——— Index - ——JAragonite (o) = [Sampling. 15 [975979 them
    权利要求:
    Claims (22)
    [1]
    1. Process for the preparation of precipitated calcium carbonate comprising the steps of: a) providing and calcining material comprising calcium carbonate; b) erase the reaction product obtained from step a) with an aqueous solution of ammonium chloride; c) separating insoluble components from the calcium chloride solution obtained from step b); d) carbonate the calcium chloride solution obtained from step c); e) separating the precipitated calcium carbonate obtained from step d), characterized by the fact that seed crystals are added to the calcium chloride solution obtained from step c) before step d.
    [2]
    Process according to claim 1, characterized in that the calcium carbonate comprising material from step a) is selected from the group comprising precipitated calcium carbonate; natural calcium carbonate minerals such as marble, limestone and chalk, and mixed alkaline earth carbonate minerals comprising carbonate — total calcium like dolomite.
    [3]
    3. Process according to the claim | or 2, characterized by the fact that the raw calcium carbonate material from step a) has a minimum calcium carbonate content of at least 15% by weight, more preferably at least 50% by weight, especially - at least 75% by weight, and above all preferably at least 90% by weight, for example, 98% by weight based on the total weight of the feed material.
    [4]
    Process according to any one of claims 1 to 3, characterized in that the molar ratio of ammonium chloride to calcium oxide is 1: 1 to 8: 1, more preferably 1.5: 1 to 4 : 1, for example, from 2: 1 to 3: 1.
    [5]
    Process according to any one of claims 1 to 4, characterized in that, in step c), the separation of insoluble components is carried out by sieving, sedimentation and decanting and / or filtration.
    [6]
    Process according to any one of claims 1 to 5, characterized in that, in step c), insoluble components can be flocculated before their removal, by the addition of high molecular weight flocculants, in which cationic flocculants , anionic and / or non-ionic flocculants, preferably polyacrylic acid based copolymers can be used.
    [7]
    Process according to claim 6, characterized in that, in step c), the flocculant is added in an amount of 1 to 50 ppm, preferably from 2 to 40 ppm, more preferably from 3 to 25 ppm, and above all preferably from 5 to 15 ppm, based on dry CaO.
    [8]
    Process according to any one of claims 1 to 7, characterized in that, in step d), carbonation is carried out by feeding pure carbon dioxide gas or technical gases containing at least 10% by volume of carbon dioxide in the alkaline calcium chloride solution.
    [9]
    Process according to any one of claims 1 to 8, characterized in that, after step e), the calcium carbonate obtained from step d) is separated from the mother liquor by filtration.
    [10]
    Process according to any one of claims 1 to 9, characterized in that, after step e), the precipitated calcium carbonate is washed with water.
    [11]
    Process according to any one of claims 1 to 10, characterized in that, after step e), the precipitated calcium carbonate is concentrated or dried.
    [12]
    Process according to any one of claims 1 to 11, characterized in that it is conducted as a closed process, in which the reagents are recycled.
    [13]
    Process according to any one of claims 1 to 12, characterized in that it is carried out in batch or as a continuous process.
    [14]
    Process according to any one of claims 1 to 13, characterized in that the precipitated calcium carbonate contains less than 0.5% by weight of impurities, more preferably less than 0.3% by weight, especially less than 0.1% by weight, and above all preferably less than 0.05% by weight of impurities.
    [15]
    Process according to any one of claims 1 to 14, characterized in that the precipitated calcium carbonate has aragonitic, calcitic or vateritic crystalline structure, or mixtures thereof.
    [16]
    Process according to any one of claims 1 to 15, characterized in that the precipitated calcium carbonate has a TAPPI gloss of at least 88, preferably at least 90, more preferably at least 92, for example, from 95 to 99, such as 97.
    [17]
    Process according to any one of claims 1 to 16, characterized in that the precipitated calcium carbonate has a light reflectance factor R of at least 90, preferably at least 92, more preferably at least 95, for example , from 96 to 99, such as59.
    [18]
    Process according to any one of claims 1 to 17, characterized in that the precipitated calcium carbonate has a yellow index of 0.5 to 6, more preferably 0.7 to 3, above all preferably of 1 to 2.
    [19]
    19. Process according to any one of claims 1 to 18, characterized in that the precipitated calcium carbonate has a weighted median diameter dso of not more than 20 µm, preferably not: more than 10 µm, more preferably not more 5 µm, above all preferably not more than 2 µm, for example, not more than 1 µm.
    [20]
    20. Precipitated calcium carbonate, characterized by the fact that it is obtained by the process as defined in any one of claims 1 to 19.
    [21]
    21. Use of a precipitated calcium carbonate as defined in claim 20, obtained by a process as defined in any one of claims 1 to 19, characterized by the fact that it is in ink, plastic or paper applications.
    [22]
    22. Use according to claim 21, characterized in that the precipitated calcium carbonate is used as a filler and / or pigment.
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    同族专利:
    公开号 | 公开日
    TWI545085B|2016-08-11|
    JP2013540687A|2013-11-07|
    US20150183654A1|2015-07-02|
    SI2447213T1|2015-07-31|
    EP2447213A1|2012-05-02|
    CN103189315A|2013-07-03|
    CA2814435A1|2012-05-03|
    CO6680730A2|2013-05-31|
    MX346118B|2017-03-08|
    JP5961617B2|2016-08-02|
    US8992875B2|2015-03-31|
    CL2013001130A1|2013-10-18|
    RS54078B1|2015-10-30|
    CA2814435C|2017-04-04|
    WO2012055750A4|2012-07-26|
    TW201228937A|2012-07-16|
    AR083549A1|2013-03-06|
    RU2013124040A|2014-12-10|
    ES2540248T3|2015-07-09|
    RU2602140C2|2016-11-10|
    JO3218B1|2018-03-08|
    UY33682A|2012-05-31|
    WO2012055750A1|2012-05-03|
    PL2447213T3|2015-10-30|
    KR101759765B1|2017-07-19|
    DK2447213T3|2015-07-27|
    HRP20150757T1|2015-08-14|
    US9725330B2|2017-08-08|
    EP2632855A1|2013-09-04|
    PT2447213E|2015-08-20|
    KR20130126621A|2013-11-20|
    US20130336859A1|2013-12-19|
    MX2013004545A|2013-07-03|
    EP2447213B1|2015-04-29|
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    法律状态:
    2017-10-31| B15G| Petition not considered as such [chapter 15.7 patent gazette]|
    2018-01-09| B12F| Other appeals [chapter 12.6 patent gazette]|
    2021-02-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-02| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2021-03-09| B25D| Requested change of name of applicant approved|Owner name: OMYA INTERNATIONAL AG (CH) |
    2021-06-01| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|
    2021-12-14| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    EP10188840.2|2010-10-26|
    EP20100188840|EP2447213B1|2010-10-26|2010-10-26|Production of high purity precipitated calcium carbonate|
    US40920210P| true| 2010-11-02|2010-11-02|
    US61/409202|2010-11-02|
    PCT/EP2011/068319|WO2012055750A1|2010-10-26|2011-10-20|Production of high purity precipitated calcium carbonate|
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