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    • 专利摘要:
    process for the production of a precipitated divalent metal ion carbonate product, aqueous suspension, dry precipitated divalent metal ion carbonate, and, uses of an aqueous suspension, and a dry precipitated divalent metal ion carbonate the present invention relates to a process for producing a precipitated divalent metal ion carbonate product that has been recovered from scrap, the precipitated divalent metal ion carbonate product having an improved transparency, the process comprising the steps of: providing a low purity divalent metal ion carbonate material, the divalent metal ion carbonate material being recovered from the refuse; calcining the carbonate material of divalent metal ions to obtain an oxide of divalent metal ions; extinguish the oxide of divalent metal ions in order to obtain an aqueous suspension of a divalent metal ion hydroxide; carbonating the aqueous suspension of divalent metal ion hydroxide with a carbon dioxide containing the compound, so as to obtain fine precipitated particles of divalent metal ion carbonate; post-treating fine precipitated divalent metal ion carbonate particles to obtain discrete precipitated divalent metal ion carbonate particles; add the discrete precipitated fine particles of divalent metal ion carbonate to an aqueous suspension of divalent metal ion hydroxide that was obtained by quenching the high purity divalent metal ion hydroxide to obtain a resulting reaction mixture ; and carbonating the resulting reaction mixture in order to obtain the precipitated divalent metal ion carbonate product having an improved transparency.
    公开号:BR112013029361B1
    申请号:R112013029361-6
    申请日:2012-05-08
    公开日:2020-10-06
    发明作者:Michael Pohl；Thomas Schmölzer
    申请人:Omya International Ag；
    IPC主号:
    专利说明:

    TECHNICAL FIELD OF THE INVENTION
    [01] The present invention relates to a process for the production of precipitated calcium carbonate (PCC) from waste lime, the mineral pigments of the precipitated calcium carbonate (PCC) species obtained by this process and the use of these pigments of minerals. BACKGROUND OF THE INVENTION
    [02] Calcium carbonate is used extensively in the paper industry as a filler component in paper. Low-cost, high-transparency filler used to increase the transparency and opacity of the sheet. Its use has increased dramatically in recent decades due to the conversion of acid into alkaline paper production in paper mills. Both natural and synthetic calcium carbonates are used in the paper industry. Natural carbonate, such as limestone, marble or chalk, is ground to a small particle size for use on paper, while synthetic calcium carbonate is manufactured by a precipitation reaction and is therefore called carbonate. precipitated calcium (PCC).
    [03] Usually, the PCC is prepared by introducing CO2 in an aqueous suspension of calcium hydroxide, the so-called Ca (OH) 2 + lime milk - CO2 -► CaCO3 + H2O
    [04] This process has demonstrated the ability to produce PCCs with superior opacification characteristics. PCC is typically superior in opacification and leaf transparency compared to ground calcium carbonate (so called GCC). The scaleneedric precipitated calcium carbonate conformed with an aggregate structure such as rosette, has been observed to communicate high leaf opacity. The carbonation process has also shown flexibility in producing various conformations and particle sizes for various applications such as a paper filler and paper coatings.
    [05] 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 industries, and as a functional filler for the manufacture of plastic materials, plastisols , sealing compounds, printing inks, rubber, toothpaste, cosmetics, etc. TECHNICAL PROBLEMS
    [06] Currently, with an ecological concept, it focuses on unused recovery material derived from a process or material used in the recovery of products or processes and on the reuse of recovered materials.
    [07] For example, in the chemical recovery system in Kraft pulp mills, large amounts of calcium carbonate with low chemical purity are discharged as solid scrap materials and therefore should be readily available as a source of materials inexpensive raw materials for the manufacture of calcium carbonate fillers and / or coating pigments.
    [08] Due to a crude particle size, the presence of bleaching impurities and the low gloss of this “pulp milling scrap calcium carbonate”, the use of such a material is, however, prohibitive or limited to very low quantities , if the gloss of the final calcium carbonate product can be maintained at a sufficiently high level and the performance of the application can reach the level of products that are manufactured from high quality raw materials, such as calcium carbonate fillers or pigments of coating produced from chalk, limestone or marble.
    [09] Consequently, a method to increase the brightness of calcium carbonate products containing calcium carbonate recovered from refuse and, in particular, pulp milling refuse, and to convert the recovered material into calcium carbonate mineral fillers and / or coating pigments that can be used for typical applications, should be highly desirable.
    [10] The prior art processes are based on processing the calcium carbonate material recovered from pulp mill waste. For example, the Brazilian patent application PI 0903782-9 describes a process where the recovered calcium carbonate material that forms the causticity process of the cellulose industry is treated with phosphoric acid in order to improve and purify said calcium carbonate material .
    [11] JP 6073690 A discloses the preparation of a precipitated calcium carbonate having a specific surface area of at least 6 m2 / g. Waste carbon dioxide and waste lime produced in paper-making factories can be used in the preparation of this PCC. In one example, the lime containing trivalent metal oxide impurities was reacted at 50 ° C for 1 hour, and the reaction product was passed through a screen to obtain the lime milk. Subsequently, the lime milk was subjected to wet crushing and was diluted to prepare lime milk having a concentration of 8% by weight. Afterwards, it was subjected to carbonation and again passed through a screen in order to obtain the precipitated calcium carbonate.
    [12] WO 96/32354 A1 relates to a method for treating material containing solid contained in, or produced from, waste paper or an effluent from a plant for treating paper or waste paper, material containing solid including organic material and inorganic particulate material. The solid-containing material treated by the method can include calcium carbonate, which is calcined to form calcium oxide, and the calcium oxide being converted to calcium hydroxide when the calcium oxide is formed in an aqueous suspension. Lime milk is then converted to precipitated calcium carbonate by introducing carbon dioxide. This precipitated calcium carbonate is then used for the preparation of paper coating compositions. Examples of material comprising precipitated calcium carbonate, as well as other minerals, such as kaolin clays, showed an ISO luminescence of 70.6 or 75.5%.
    [13] WO 97/11030 A1 relates to a method for making high purity calcium carbonate, by combining a source of impure calcium oxide or calcium hydroxide with water, to form an aqueous suspension. The solids within the suspension are allowed to settle so that a saturated, clear solution of calcium hydroxide is formed. This solution is then further reacted with carbon dioxide to obtain the precipitated high purity calcium carbonate. However, nowhere is it mentioned in this document that lime milk, as formed, is used in another carbonation step, without the need to remove any impurities contained in lime milk.
    [14] US 2010/0000444 A1 also describes a method for producing a composition comprising carbonates, wherein the method comprises using scrap sources of metal oxides, such as calcium oxide or calcium hydroxide. An aqueous solution of divalent cations derived from the source of scrap metal oxides is placed in contact with carbon dioxide and subjected to precipitation conditions in order to provide compositions containing carbonates, such as calcium carbonate. The resulting product can be used in construction, such as cement. No information is given regarding the ISO luminescence, the specific surface area or the particle diameter of the resulting calcium carbonate.
    [15] EP 0 946 417 Bl and EP 0 815 175 BI also describe methods for recovering calcium from waste material or contaminated natural calcium material, which basically comprises the steps of providing the calcium compound in a soluble form in acid, such as calcium oxide and calcium carbonate, by preparing an aqueous suspension of the calcium compound material and carbonating the aqueous suspension of the calcium compound material to obtain precipitated calcium carbonate. EP 0 815 175 BI recycled calcium carbonate has been tested for its performance on paper.
    [16] EP 0.604.095 BI and EP 1.052.227 BI are also known, presenting methods for the recovery of by-products from an industrial process in order to provide mixed aggregate materials.
    [17] Finally, EP 2,070,578 Al refers to the segregation of carbon dioxide by reaction with alkaline solid waste containing accessible calcium oxide and / or calcium hydroxide. Since the focus of this invention was the separation of carbon dioxide, this document is silent on the properties of the resulting precipitated calcium carbonate.
    [18] Although there are numerous prior art documents describing the recycling of calcium carbonate, calcium oxide or calcium hydroxide in order to obtain calcium carbonate having a good shine, the need for the production of calcium carbonate still remains high quality with improved gloss that can be used in industries such as the production of paper, ink, plastics and others.
    [19] In particular, there is no provision for further processing of precipitated calcium carbonate obtained at various stages of the refuse, and in particular the pulp milling refuse, to produce fine particles that can be used as seeds for deposition of high quality precipitated calcium carbonate mineral material onto the low quality substrate obtained from the waste resources. OBJECTIVE OF THE INVENTION
    [20] Consequently, it is an object of the present invention to provide a new process for the production of a divalent metal ion carbonate product precipitated from a divalent metal ion carbonate that has been recovered from the refuse, the ion carbonate product. of precipitated divalent metal having a comparable or even improved gloss compared to other precipitated divalent metal ion carbonate products which are obtained from scrap resources and are produced by prior art processes.
    [21] It is another object of the present invention to provide the various precipitated divalent metal ion carbonate products obtained by the process of the invention.
    [22] Another object of the present invention is also to provide the use of the various precipitated divalent metal ion carbonate products.
    [23] Yet another object of the present invention is also to provide a process for producing the divalent metal ion carbonate product precipitated from a divalent metal ion carbonate that has been recovered from the scrap that is more economical compared to processes described in the prior art.
    [24] These and other objects and advantages will be better understood by virtue of the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS:
    [25] In the drawings: Figure 1 is a SEM photomicrograph of a scrap calcium carbonate when discharged from a chemical recovery process of a kraft pulp mill. Figure 2 is a SEM photomicrograph of a PCC shaped into a scalenohedral having a rosette-like aggregate structure and being produced according to the carbonation process of the prior art described in Example 1; Figure 3 is a micrograph photo of a PCC shaped into a scalenohedral having a rosette-like aggregate structure and being produced according to this invention by the process described in Example 2; Figure 4 is a SEM photomicrograph of a scalenehedral shaped PCC used for coating, being produced according to this invention by the process described in Example 5; Figure 5 is a diagram showing the process path of the process according to a prior art process that is known to the applicant; and Figure 6 is a diagram showing the process path according to the present invention. DETAILED DESCRIPTION OF THE INVENTION
    [26] All parts, percentages and ratios contained herein are expressed in dry matter weight, unless otherwise specified. All documents cited herein are incorporated by reference.
    [27] The present invention aims to solve the objects outlined above by providing a process for the production of a divalent metal ion carbonate product precipitated from a divalent metal ion carbonate that has been recovered from refuse, the product of precipitated divalent metal ion carbonate having a comparable or even improved gloss compared to other precipitated divalent metal ion carbonate products obtained from scrap resources, produced by prior art processes, and as described in the present invention and as defined in the claims.
    [28] In view of the foregoing, the inventors of the invention surprisingly observed that the luster of the divalent metal ion carbonate mineral fillers and / or the coating pigments that were recovered from the scrap resources, can be substantially improved by a process that understand the steps of: (a) providing a low-purity divalent metal ion carbonate material, the divalent metal ion carbonate material being recovered from the refuse; (b) calcining the divalent metal ion carbonate material of step (a) so as to obtain an oxide of divalent metal ions; (c) extinguishing the oxide of divalent metal ions obtained in step (b) in order to obtain an aqueous suspension of a divalent metal ion hydroxide; (d) carbonating the aqueous suspension of the divalent metal ion hydroxide obtained in step (c) with a compound containing carbon dioxide in order to obtain fine particles of precipitated divalent metal ion carbonate; (e) post-treating the precipitated divalent metal ion carbonate fine particles obtained in step (d) to obtain discrete precipitated divalent metal ion carbonate particles; (f) mixing the fine carbonate particles of discrete precipitated divalent metal ions obtained in step (e) with an aqueous suspension of divalent metal ion hydroxide which have been obtained by calcining the high purity divalent metal ion oxide in order to obtain a resulting reaction mixture; and (g) carbonating the reaction mixture resulting from step (f) in order to obtain the precipitated divalent metal ion carbonate product having an improved gloss compared to the precipitated divalent metal ion carbonate particles obtained in step ( d).
    [29] In addition, the inventors also surprisingly observed that, by the process according to the present invention, the amount of low-purity divalent metal ion carbonate in the precipitated final product, can almost be doubled without impairing the good gloss of the product resulting end. It can be said that the gloss of the final product is improved even though it contains almost twice as much low-purity divalent metal ion carbonate as the comparable product known from the prior art.
    [30] For the purposes of the present invention, the term "refuse" is defined as inorganic materials remaining from a production process or as material being derived from the recycling of a product containing such inorganic materials, such as, for example, inorganic materials that have been derived from paper recycling. Some components of the refuse have economic value and can be recycled once properly recovered. In the present invention, the component having economic value is a material of divalent metal ion carbonate, such as, for example, the materials calcium carbonate, magnesium carbonate, beryllium carbonate, strontium carbonate or barium carbonate, and in particularly the material calcium carbonate, or naturally occurring, ground (or natural) calcium carbonate (GCC), and / or precipitated calcium carbonate (PCC), which is also known as synthetic calcium carbonate. The refuse can be each refuse containing an essential amount of the divalent metal ion carbonate material and especially the calcium carbonate material, and is, for example, refuse derived from a pulp and / or the papermaking industry .
    [31] A "slurry", in the meaning of the present invention, is a suspension (comprising essentially insoluble solids and water and, optionally, other additives) and usually has a higher density than the liquid without solids from which it is formed .
    [32] A "specific surface area" (SSA) or "specific surface area BET", in the meaning of the present invention, refers to the specific surface area through the method provided in the section of examples provided hereinafter.
    [33] “Ground calcium carbonate” (GCC), in the meaning of the present invention, is a calcium carbonate obtained from natural sources such as marble, chalk or limestone, and processed through a treatment such as grinding, screening and / or fragmentation under wet and / or dry conditions, for example by a cyclone.
    [34] “Precipitated calcium carbonate” (PCC), in the meaning of the present invention, is a synthesized material, generally obtained by precipitation following a reaction of carbon dioxide and calcium hydroxide (hydrated lime) in an aqueous environment or by precipitation of a source of calcium and carbonate in water. In addition, the precipitated calcium carbonate can also be the product of introducing calcium and carbonate salts, calcium chloride and sodium carbonate, for example, in an aqueous environment.
    [35] The term "brightness", as used in the context of the present invention, is a measure of the percentage of diffused light reflected from a paper surface or a powdered tablet produced from a pigment. A brighter sheet or pigment reflects more diffused light. As used herein, the brightness of the paper or pigment can be measured at a light wavelength of 457 nm (R457) and is specified as a percentage.
    [36] "The low-purity divalent metal ion carbonate material", in the meaning of the present invention, is a divalent metal ion carbonate, such as calcium carbonate or magnesium carbonate, having an ISO R457 gloss of less than about 90%, measured according to ISO 2469.
    [37] “The high-purity divalent metal ion carbonate material”, in the meaning of the present invention, is a divalent metal ion carbonate, such as calcium carbonate or magnesium carbonate, having an ISO R457 shine of at least least 94%, measured according to ISO 2469.
    [38] “The PCC / CaCO Composite product, Refuse” in the meaning of the present invention, is defined as the precipitated calcium carbonate product that is obtained after the second carbonation step [step (g)] of the invention process . Both expressions are used synonymously.
    [39] "Post-treatment" in the meaning of the present invention is defined as a step to produce the desired discrete precipitated precipitated metal ion carbonate particles. Post-treatment is, in particular, a mechanical de-agglomeration of clusters or agglomerates in grinding media or the like, or is a recrystallization in a heat curing step or the like, or is a recrystallization in a natural quenching step by heat or the like, or is subjected to high-pressure mechanical dehydration, followed by redispersion of the filter cake.
    [40] Figure 5 illustrates a process flow diagram for producing a calcium carbonate product from a pulp milling scrap carbonate according to a prior art process known to the inventors. In a first step, carbonate scrap calcium 10 from pulp grinder is placed in contact with water to form an aqueous suspension 12 of calcium carbonate, followed by wet grinding 14 of calcium carbonate. The "scrap calcium carbonate" thus processed has a gloss of 67.2%, measured according to ISO 2469, and a specific BET surface area (SSA) of 14.9 m2 / g. In parallel, lime burned in high purity (CaO) 18 for the production of precipitated calcium carbonate is hydrated with water to obtain a paste resulting from calcium hydroxide (the so-called “lime milk”) 20. The paste of calcium hydroxide 20 is then combined 16 with the “scrap calcium carbonate” obtained by wet grinding 14, and then the combined mixture 16 of the “scrap calcium carbonate” and the calcium hydroxide paste is subjected to a carbonation step 17 with the use of a compound containing carbon dioxide, such as carbon dioxide or a gas containing carbon dioxide. The final product obtained after this carbonation step is a calcium carbonate product 22 containing up to 15% by weight of the "scrap calcium carbonate", referred to as the dry weight of the calcium carbonate product. The final product of calcium carbonate has a gloss of 83.8%, measured according to ISO 2469, a specific BET surface area (SSA) of 13.9 m2 / g, and a medium weight particle diameter of 1.7 pm according to Sedigraph 5100.
    [41] In contrast, Figure 6 illustrates a process flow diagram for producing a divalent metal ion carbonate product from a divalent metal ion carbonate that has been recovered from the refuse according to the process of the invention.
    [42] Firstly, a low-purity divalent metal ion carbonate material 10 (hereinafter referred to as "scrap carbonate material" 10) is provided which has been recovered from the scrap. The low-purity divalent metal ion carbonate material 10 is a material having the formula M2 + COs2 '(i.e., MCO3), where M2 + is a divalent metal ion selected from the group comprising Be2 +, Mg2 +, Ca2 +, Sr2 + and Ba2 +, and is preferably Mg2 + and Ca2 +, and most preferably Ca2 +.
    [43] In a first step, the scrap carbonate material 10 is subjected to a calcination step 24 in order to obtain the corresponding divalent metal ion oxide. In this regard, the waste carbonate material 10 is introduced into an oven or furnace with an optional supply for oxygen-containing gas, and the oven or furnace is heated to a temperature sufficient to convert the waste carbonate material 10 into the oxide. corresponding divalent metal ion. For calcination of calcium carbonate (CaCCb) the typical temperatures are in the range of 900 to 1300 ° C, and for magnesium carbonate (MgCCh) the typical temperatures are in the range of 800 to 1200 ° C . The divalent metal ion oxide is a material having the formula M2 + O2 (i.e., MO), where M2 + is a divalent metal ion selected from the group comprising Be2 +, Mg2 +, Ca2 +, Sr2 + and Ba2 +, and is preferably Mg2 + and Ca2 +, and the most preferable is Ca2 +.
    [44] The corresponding divalent metal ion oxide obtained is then subjected to an extinction step 26. In this regard, the divalent metal ion oxide is added to the water in a stirred reactor. Before adding the oxide of divalent metal ions, however, the water temperature is adjusted in a range of 30 to 90 ° C, preferably 70 ° C, and additives, such as the citric acid sodium salt, can optionally be added . Then, the aqueous suspension of the divalent metal ion oxide is hydrated under continuous agitation in order to obtain a corresponding aqueous suspension of the divalent metal ion hydroxide, in the case of the hydroxide being calcium hydroxide, this suspension being the so-called “Lime milk”. Divalent metal ion hydroxide is a material that has the formula M2 + (OH) 2 [ie, M (0H) 2], where M2 + is a divalent metal ion selected from the group comprising Be2 +, Mg2 +, Ca2 +, Sr2 + and Ba2 +, and is preferably Mg2 + and Ca2 +, and the most preferable is Ca2 +. The aqueous suspension resulting from the divalent metal ion hydroxide preferably has a solids content in the range of 5 to 30% by weight, based on the dry weight of the divalent metal ion hydroxide.
    [45] The aqueous suspension of the divalent metal ion hydroxide, which can optionally be sieved, is then subjected to a carbonation step 28 with a compound containing carbon dioxide. The carbon dioxide-containing compound used in the present invention is selected from gaseous carbon dioxide, liquid carbon dioxide, solid carbon dioxide and a gas containing carbon dioxide, and preferably the carbon dioxide-containing compound is a gas mixture of carbon dioxide. carbon and other gases such as flue gases containing carbon dioxide exhausted from industrial processes like combustion processes or calcination processes or the like. When a gas mixture of carbon dioxide and other gases is used, then carbon dioxide is present in the range of 8 to about 99% by volume, and preferably in the range of 10 to 25% by volume, for example 20% in volume. Before the introduction of the compound containing carbon dioxide, the temperature of the aqueous suspension of the divalent metal ion hydroxide is adjusted in a range of 10 to 70 ° C, and more preferable in the range of 10 to 30 ° C, for example 20 ° Ç. In addition, additives such as sucrose, sugar alcohols or citric acid can optionally be added to the reaction mixture. Then, the carbon dioxide-containing compound is introduced into the aqueous suspension of the divalent metal ion hydroxide at an index of 0.05 to 2 kg CCk / h per kg of dry Ca (OH) 2 and, preferably, between 0, 2 to 0.8 kg of CCb / h per kg of dry Ca (OH) 2, under simultaneous stirring of the reaction mixture. The end of the carbonation reaction is reached when the electrical conductivity of the reaction mixture has gone through a minimum level and pH of the aqueous suspension of the divalent metal ion hydroxide, which is usually in the pH range 10 to 13, has dropped to a value of 6 to 8, indicating that substantially all of the divalent metal ion hydroxide has been converted to the corresponding divalent metal ion carbonate.
    [46] The resulting suspension of the precipitated divalent metal ion carbonate particles, which consist of groups or agglomerates of fine particles, is then further processed or treated in a post-treatment step 30 to obtain a suspension of fine carbonate particles. of discrete precipitated divalent metal ions. Any kind of post-treatment for de-agglomeration known to the person skilled in the art, such as, for example, mechanical de-agglomeration in membrane mills or the like or recrystallization (Ostwald enhancement) in a heat curing or similar step or dehydration high pressure mechanics followed by redispersion of the filter cake, can be applied to produce the desired discrete precipitated precipitated metal ion carbonate particles.
    [47] By discrete particles, particles are denoted as being neither clusters nor aggregated particles nor agglomerated particles.
    [48] Fine carbonate particles of discrete precipitated divalent metal ions have the formula M2 + COs2 (ie, MCO3), where M2 + is a divalent metal ion selected from the group comprising Be2 +, Mg2 +, Ca2 +, Sr2 + and Ba2 + , and is preferably Mg2 + and Ca2 +, and most preferable is Ca2 +. In the case when fine particles of discrete precipitated divalent metal ion carbonate are discrete precipitated calcium carbonate particles, said particles have a brightness of about 70%, measured according to ISO 2469, and a specific surface area ( SSA) BET of about 30 m2 / g.
    [49] The fine particles of discrete precipitated divalent metal ion carbonate in the meaning of the present invention have a particle size of> 10 to 500 nm, preferably in the range of 50 to 200 nm, and a specific surface area of 5 to> 15 m2 / g, preferably in the range of 20 to 50 m2 / g.
    [50] In another step, the suspension obtained from fine particles of discrete precipitated divalent metal ions is mixed with an aqueous suspension of divalent metal ion hydroxide which was obtained by extinction 18 of the metal ion oxide high purity divalents 16 in order to obtain a resulting reaction mixture. Any oxide of high purity divalent metal ions can be used. Preferably high-purity divalent metal ion oxide is used in dry form, for example dry CaO or dry MgO. The solids content of the discrete precipitated divalent metal ion carbonate particles in the suspension usually depends on the process selected for post-treatment (for example, by mechanical de-agglomeration or recrystallization in a heat curing step) of the fine ions carbonate. precipitated divalent metals obtained after carbonation step 28, but is in a range of 5 to 60% by weight and, preferably, in a range of 10 to 40% by weight, based on the total weight of the suspension.
    [51] In a next step, the reaction mixture resulting from the aqueous suspension of divalent metal ion hydroxide and the precipitated divalent metal ion carbonate is subjected to another carbonation step 34 with a compound containing carbon dioxide. The carbon dioxide-containing compound used in the present invention is selected from gaseous carbon dioxide, liquid carbon dioxide, solid carbon dioxide, and a gas containing carbon dioxide, and preferably the carbon dioxide-containing compound is a gas mixture of dioxide carbon and other gases such as combustion gases containing carbon dioxide exhausted from industrial processes such as combustion processes or calcination processes, or the like. When a gas mixture of carbon dioxide and other gases is used, then carbon dioxide is present in the range of 8 to about 99% by volume, and preferably in the range of 10 to 25% by volume, for example 20% in volume. Before the introduction of the compound containing carbon dioxide, the temperature of the reaction mixture resulting from the aqueous suspension of divalent metal ion hydroxide with the fine or ultrafine carbonate of precipitated divalent metal ions is adjusted in a range of 10 to 70 ° C , and more preferable in the range of 15 to 60 ° C, for example 50 ° C. In addition, additives such as sucrose, sugar alcohols or citric acid can optionally be added to the reaction mixture. Then, the compound containing carbon dioxide is introduced into the reaction mixture resulting from the aqueous suspension of divalent metal ion hydroxide and the fine or ultrafine carbonate of discrete precipitated divalent metal ions in a ratio of 0.05 to 2 kg CCh / h per kg of dry Ca (OH) 2, and preferably between 0.2 to 0.8 kg of CCb / h per kg of dry Ca (OH) 2, with simultaneous stirring of the reaction mixture. The end of the carbonation reaction is reached when the electrical conductivity of the reaction mixture has followed through a minimum pH level and the aqueous suspension of the divalent metal ion hydroxide, which is usually in the pH range 10 to 13, has fallen at a value of 6 to 8, indicating that substantially all of the divalent metal ion hydroxide has been converted to the corresponding divalent metal ion carbonate 36. The precipitated divalent metal ion carbonate 36 has the formula M2 + COa2 (i.e., MCO3), where M2 + is a divalent metal ion selected from the group comprising Be2 +, Mg2 +, Ca2 +, Sr2 + and Ba2 +, and is preferably Mg2 + e Ca2 +, and the most preferable is Ca2 +.
    [52] In one embodiment of the present invention, at least part of the precipitated divalent metal ion carbonate product obtained in step (g) can be subjected to at least one other carbonation step, in which at least part of the product of precipitated divalent metal ion carbonate obtained in step (g) is first mixed with an aqueous suspension of divalent metal ion hydroxide which was obtained by extinguishing high purity divalent metal ion oxide to obtain a resulting reaction mixture, and then the resulting reaction mixture is subjected to carbonation. Thus, it is possible to adjust the brightness of the final product depending on the additional application of the product. In other words, subjecting the precipitated divalent metal ion carbonate product obtained in step (g) to at least one other carbonation step, wherein at least part of the precipitated divalent metal ion carbonate product obtained in step (g) ) is first mixed with an aqueous suspension of divalent metal ion hydroxide which was obtained by quenching the high-purity divalent metal ion oxide to obtain a resulting reaction mixture and then the resulting reaction mixture is subjected to carbonation being possible obtain final products having a higher brightness than the precipitated divalent metal ion carbonate product obtained in step (g).
    [53] It is also possible to repeat carbonation step (d) at least once before continuing with post-treatment step (e).
    [54] In a preferred embodiment according to the invention, the precipitated divalent metal ion carbonate particles obtained in step (g) of the process of the invention have an ISO R457 gloss in the range of 88 to 94%, measured according to ISO 2469.
    [55] In another preferred embodiment according to the invention, the precipitated divalent metal ion carbonate particles obtained in step (g) have a specific surface area (SSA) in the range of 3 to 30 m2 / g, preferably in range from 5 to 20 m2 / g, measured according to the BET method using ISO 9277.
    [56] Furthermore, it is preferable that the precipitated divalent metal ion carbonate particles obtained in step (g) have an average dso particle diameter in the range of 0.5 to 7 pm, preferably in the range of 0.8 to 5 pm, more preferable in the range 1 to 3 pm, measured using a Sedigraph®, sold by the company MICROMERITICS.
    [57] In another embodiment of the present invention, the low-purity divalent metal ion carbonate material from step (a) is preferably a calcium carbonate material and the precipitated divalent metal ion carbonate product from step (g) ) is precipitated calcium carbonate. In this case, the final product obtained is a calcium carbonate product 36 containing up to 50% by weight of the "scrap calcium carbonate", based on the dry weight of the final calcium carbonate product. The final calcium carbonate product 36 has an ISO R457 gloss of 90.0%, measured according to ISO 2469, a specific BET surface area (SSA) of 17.0 m2 / g, and an average particle diameter of dso of about 1.5 pm.
    [58] It is observed that the weight percentage of the “scrap calcium carbonate” that the final product contains is dependent on the brightness of the final product and the purity of the “scrap calcium carbonate”. In the present case where a very low purity “scrap calcium carbonate” has been used, only up to 25% by weight of the said “scrap calcium carbonate” can be contained in the calcium carbonate product 36 for minimum gloss specified 90% R457 according to ISO 2469.
    [59] Without wishing to be bound by any theory, it is believed that in this other stage 34 of carbonation the fine particles of discrete precipitated divalent metal ions carbonate are acting as seed material for the precipitation of product 36 of carbonate ions of precipitated divalent metals which is formed by reacting the compound containing carbon dioxide and the high purity divalent hydroxide in this other carbonation step. The precipitated divalent metal ion carbonate derived from the high purity divalent metal ion hydroxide is growing as a "shell" around the precipitated divalent metal ion carbonate particles ("core") that are of low purity and low shine. In this way, the present inventors obtained a precipitated divalent metal ion carbonate product having an improved gloss compared to the precipitated divalent metal ion carbonate particles obtained in step 28 of the first carbonation, and compared to the carbonate products precipitated calcium compounds that are obtained from the calcium compound containing scrap materials in the prior art processes.
    [60] If necessary, the aqueous suspension comprising the precipitated divalent metal ion carbonate product from step (g) [or comprising the divalent metal ion carbonate product precipitated from at least one other carbonation step after step (g) )] can be subjected to other post-treatment steps 38 comprising, among other things, separating, filtering, concentrating and drying, in order to obtain precipitated dry calcium carbonate. It is observed that, in particular, the concentration step is very useful because, in this way, an aqueous suspension can be obtained with a solid content of the final precipitated divalent metal ion carbonate product in a range of 40 to 80% in weight, based on the total weight of the aqueous suspension, which is preferably used in other applications such as paper or cardboard coating applications.
    [61] The present invention is also directed to an aqueous suspension comprising the precipitated divalent metal ion carbonate obtained by the process according to the invention, as well as the dry precipitated divalent metal ion carbonate obtained by the process according to the invention. . In the present invention, the term "dry" preferably refers to a final product of precipitated divalent metal ion carbonate having a water content of less than 10% by weight, more preferably less than 5% by weight, and further more preferable less than 2% by weight.
    [62] Furthermore, the present invention is directed to the use of divalent metal ion carbonate precipitated in aqueous or dry suspension according to the invention in coating formulations or as fillers in the paper, plastic and ink industries.
    [63] In addition, the present invention is also directed to the use of dry precipitated divalent metal ion carbonate according to the invention in the field of paints, rubber, plastics, building materials, and paints. EXAMPLES
    [64] The following examples are intended to illustrate certain embodiments of the invention and are understood to be non-limiting to the invention in any form.
    [65] For the purposes of the present invention, the value of the parameter <Ao (%) is obtained by measurements of the particle size for which respectively 50% by mass of the particles have a diameter of less than or equal to this value.
    [66] The term w / w refers to the mass fraction of a material and is defined as the fraction of the material with mmat mass for the mass of the total mtot mixture. MEASUREMENT METHODS: Suspension pH measurement
    [67] The pH of a suspension was measured at 25 ° C using a Mettler Toledo Seven Easye pH meter and a Mettler Toledo InLab®Expert Pro pH electrode.
    [68] A three-point calibration (according to the method below) of the instrument was first performed using commercially available buffer solutions (from Aldrich) having pH values of 4, 7 and 10 at 20 ° C.
    [69] The reported pH values are endpoint values detected by the instrument (the endpoint being the point at which the measured signal differs by less than 0.1 mV from the average over the last (previous) 6 seconds). BET Specific Surface Area
    [70] The specific surface area of BET (also known as SSA) was determined in accordance with ISO 9277 using a Tristar II 3020 sold by the company MICROMERITICS®. Particle Size Distribution (% by mass of particles with a diameter <X um) and average particle diameter (<Ao) by weight of particulate material [rZso (um)] SEDIGRAPH®5100
    [71] The average particle diameter by weight and the mass distribution of the particle diameter of a particulate material were determined using the sedimentation method, that is, an analysis of the sedimentation behavior in a gravimetric field. The measurement is made with a Sedigraph® 5100 sold by the company MICROMERITICS®.
    [72] The method and instrument are known to the skilled person and are commonly used to determine the particle size of fillers and pigments. Samples were prepared by adding an amount of the product corresponding to 4 g of dry PCC to 60 ml of a 0.1% by weight aqueous solution of IS ^ P ^ O ; The samples were dispersed for 3 minutes using a high speed stirrer (Polytron PT 3000/3100 at 15,000 rpm). Then she underwent ultrasound using an ultrasonic bath for 15 minutes and thereafter added to the Sedigraph mixing chamber. Viscosity Measurement
    [73] Brookfield® viscosity was measured after 1 minute of stirring using a Brookfield® model RVT viscometer at a temperature of 20 ° C and a rotation speed of 100 rpm (revolutions per minute) with the appropriate disc spindle 2 , 3 or 4. Solids by weight (% by weight) of a suspended material
    [74] The solids by weight (also called the solids content of a material) were determined by dividing the weight of the solid material by the total weight of the aqueous suspension.
    [75] The weight of the solid material was determined by weighing the solid material obtained by evaporating the aqueous phase of the suspension and drying the material obtained to a constant weight. Measurement of brightness and yellowness index
    [76] The pigment brightness and the yellowness index of the particles obtained were measured using an ELREPHO 450x from the company Datacolor according to ISO 2469 and DIN 6167, respectively.
    [77] The samples were dried in an oven at 105 ° C to a residual moisture content of <0.5% by weight, and the resulting powder was treated to de-agglomerate the dust particles. Of the 12 g of the powder, a tablet was pressed by applying bar pressure 4 for 15 seconds. The resulting powder tablet with a diameter of 45 mm was then subjected to measurement.
    [78] In the present measurement, the yellowness index was measured by measuring the reflectance of the precipitated calcium carbonate product obtained, the lighting fixture used being the D 65 and the standard observer function being 10 °.
    [79] The Yellowness Index according to DIN 6167 is calculated as follows:
    where X, Y and Z are the CIE Tristimulus values and the coefficients depend on the illuminant and the observer's function as indicated in the Table below:
    measurement of PPS roughness
    [80] Parker Print-Surf's roughness was determined according to ISO 8791-4; 2007 and is specified in pm. The roughness of the PPS is obtained by measuring the air flow over the surface of a sheet of paper, that is, in the xy plane. The measurement is made with a defined measuring device, with defined pressure of the measurement facility for the paper surface and with a rubber plate defined on the opposite side of the paper, the resulting values are calculated from the pressure differences and describe the width of the gap that allows air to pass between the measuring installation and the paper surface. A. PRODUCTION OF PRECIPITATED CALCIUM CARBONATE FROM PULP MILLING WASTE EXAMPLE 1 - COMPARATIVE EXAMPLE
    [81] This example describes a prior art process for the production of a calcium carbonate product, starting from the calcium carbonate obtained from the pulp milling waste in which the calcium carbonate obtained from the pulp milling waste is wet milled and then used in a carbonation reaction together with a high purity calcium hydroxide slurry.
    [82] The low purity refuse CaCCb discharged from a chemical recovery process for the grinding of brown paper pulp was obtained from Klabin Papers S.A., Telemaco Borba mill (Brazil). 845 kg of the referred refuse CaCCh that contained 75.9% w / w of dry matter were added to 300 liters of tap water at 20 ° C supplied in a 700 liter agitated vessel, equipped with a dissolution plate. Prior to the addition of the scrap CaCCb, 20.7 kg of an appropriate dispersing agent well known to the person skilled in the art were added to the water as dispersing aids. The refuse CaCCb was converted to a refuse CaCCb slurry by introducing the wet cake under vigorous stirring. The waste CaCOs slurry had a solid content of 56.2% by weight.
    [83] The paste obtained from the refuse CaCCb was then wet milled in two passes over a 50 liter vertical bead mill filled with 96 kg of zirconium oxide milling beads containing 1.0 mm diameter ceria (passage 1 ) and 0.45 mm in diameter (passage 2), respectively. To obtain a final target accuracy of about 83% of particles having an average particle size by weight of <1 pm (measured using a Sedigraph 5100), a total specific milling energy of 156 kWh / DMT (DMT = Dry metric ton) was required. Prior to wet grinding, another 12.4 kg of an appropriate dispersing agent well known to the person skilled in the art were added to the mill feed.
    [84] 200 kg of high purity lime CaO graded from PCC (Kalkwerk LEUBE, Golling / Austria) were added to 1700 liters of tap water at 50 ° C in a stirred muffling reactor. Before muffling, 0.66 kg of a 30% w / w aqueous solution of sodium citrate was added to the muffled water. The lime was smothered for 30 minutes with continuous stirring and the paste resulting from calcium hydroxide ("lime milk") was adjusted to a solids content of 13.7% by diluting the lime milk with water at 60 ° C and was then sieved over a 200 µm screen to remove gravel.
    [85] Carbonation was conducted in a 2000 liter muffled cylindrical stainless steel reactor equipped with a gasification stirrer, a stainless steel carbonation tube to direct a stream of carbon dioxide / air and gas to the impeller and the probes to monitor the pH and conductivity of the suspension. 71 liters of the aforementioned wet grinding CaCCb slurry containing 55.9% w / w dry CaCOí dry matter were added to the carbonator and mixed with 1679 liters of the 13.7% w / w aqueous suspension of hydroxide calcium obtained in the smothering step as described above. The temperature of the reaction mixture was adjusted to 50 ° C. A 20% volume CO2 gas in air was then bubbled upward through the reaction mixture in a standard volumetric flow of 200 m3 / h (standard volume flow as defined in DIN 1343, at a temperature of 0 ° C (273 , 15 K), 101.325 kPa, and 0% relative humidity) under vigorous agitation. During carbonation, the temperature of the reaction mixture was not controlled and was allowed to rise due to the heat generated in the exothermic precipitation reaction. The carbonation was maintained until the conductivity suddenly dropped and passed through a minimum, indicating that the carbonation was substantially complete. The introduction of the gas containing CO2 continued for another 10 minutes before the introduction of the gas was interrupted. The carbonation time, calculated from the beginning of the gas introduction to the minimum conductivity time, was 97 minutes. The reaction mixture was then sieved over a 45 pm sieve and the sieved product was recovered as a CaCCE slurry. Based on the total CaCCh dry matter in the PCC / Refug CaCOs composite product obtained, the portion of the CaCO , low purity pulp milling waste was 15.6% w / w. The ISO R457 transparency of the PCC / Refuse CaCOs composite product obtained was 83.8%.
    [86] The physical properties of the product obtained in the process described in Example 1 are given in Table 1 below. Example 2 - Example of the Invention
    [87] This example refers to the process of the invention for the production of a calcium carbonate product, starting from calcium carbonate obtained from pulp mill waste, in which the calcium carbonate obtained from pulp mill waste is calcined to obtain a muffled pulp milling lime (CaO), and the resulting lime milk is subsequently carbonated and processed to obtain a precipitated calcium carbonate (PCC) from particular pulp milling refuse, featuring discrete particles ultrafine. The resulting material is then subjected to a carbonation reaction together with a high-purity calcium hydroxide slurry (so-called “lime milk”).
    [88] The low purity refuse CaCCb of Example 1, which is typically discharged from the Klabin Papers Kraft pulp mill chemical recovery process, Telemaco Borba Mill, was calcined at a temperature in the range of 900 at 1300 ° C in a rotary kiln and pre-crushed in a hammer mill to obtain a low purity pulp mill refuse CaO. 200 kg of this refuse CaO (quicklime) was added to 1800 liters of tap water at 70 ° C in a stirred muffling reactor. The quicklime was smothered for 30 minutes with continuous stirring and the resulting slurry was recovered as an aqueous suspension of calcium hydroxide ("waste lime milk"). 1800 liters of said lime waste milk were added to the carbonator and the temperature of the lime waste milk was adjusted to 20 ° C; Before carbonation, 1.3 liters of a 70% w / w aqueous solution of a sugar alcohol (Sorbitol 80%, Brenntag CEE GmbH) were added.
    [89] Carbonation was carried out in the same manner as described in Example 1. The carbonation time, calculated from the beginning of the gas introduction to the minimum conductivity time, was 54 minutes. The reaction mixture was then sieved on a 45 pm screen and mechanically dehydrated on a settling centrifuge (KHD Humboldt Wedag AG, Type SC 01). The filter cake discharged from the centrifuge was then redispersed with water and converted (prepared) into a slurry containing 30.4% w / w dry matter of “PCC Pulp Grinding Refuse”. During the preparation of the paste, a suitable amount of an appropriate dispersing agent well known to the person skilled in the art was added. This “PCC Pulp Grinding Pulp” paste containing 30.4% w / w solids was then passed through a vertical medium mill equipped with 0.4 to 0.7 mm zirconium oxide grinding beads containing for de-agglomeration. The specific energy input during processing in the medium mill was 74 kWh / DMT CaCOs (DMT = dry metric ton). The slurry discharged from the medium mill containing 29.7% w / w of dry matter of CaCCb was recovered as a slurry of “Processed Pulp Mill PCC” to be used as seed material for the carbonation described below. The structure of the material determined in SEM micrograph was of discrete ultrafine precipitated calcium carbonate particles (PCC) with primary particle sizes (determined from SEM) of about 50 to 200 nm.
    [90] 200 kg of CaC of high purity virgin lime from PCC (Kalkwerk LEU BE, Golling / Austria) were added to 1700 liters of tap water at 50 ° C in a stirred muffling reactor. Before muffling, 0.66 kg of a 30% w / w aqueous solution of sodium citrate was added to the muffling water. The lime was smothered for 30 minutes with continuous stirring and the resulting paste of calcium hydroxide ("lime milk" was adjusted to 13.3% solids content by diluting the lime milk with water at 60 ° C, and was then sieved over a 200 pm sieve to remove cuttings.
    [91] Carbonation was conducted in a 2000 liter muffled cylindrical stainless steel reactor equipped with a gas stirrer, a stainless steel carbonation tube to direct a stream of carbon dioxide / air gas to the impeller and probes to monitor the pH and conductivity of the suspension. 250 liters of the “Processed Pulp Mill Refuse PCC” paste containing 29.7% w / w solids and obtained in the process described above, were added to the carbonator and mixed with 1550 liters of the 13.3% w aqueous suspension / p of calcium hydroxide obtained in the smothering step as described above. The temperature of the reaction mixture was adjusted to 50 ° C. A 20% by volume CO2 gas in air was then bubbled up through the reaction mixture in a standard volumetric flow of 200 m3h (standard volume flow as defined in DIN 1343, at a temperature of 0 ° C (273, 15 K), 101.325 kPa, and 0% relative humidity) under vigorous agitation. During carbonation, the temperature of the reaction mixture was not controlled and was allowed to rise due to the heat generated in the exothermic precipitation reaction. The carbonation was maintained until the electrical conductivity suddenly dropped and passed through a minimum, indicating that the carbonation was substantially complete. The introduction of the CO2-containing gas continued for another 10 minutes before the introduction of the gas was interrupted. The carbonation time, calculated from the beginning of the gas introduction until the moment of minimum conductivity, was 86 minutes. The reaction mixture was then sieved through a 45 pm sieve and the sieved product was recovered as a CaCO Slurry. Based on the CaCO Dry matter, total in the PCC / Refug CaCO3 composite product obtained, the portion of the refuse CaCO3 from the original low-purity pulp grinder was 23.5% w / w. The transparency of the ISO R457 of the composite product PCC / Refugo obtained was 90.0%.
    [92] The physical properties of the product obtained by the process according to the invention as described above, are listed in Table 1. EXAMPLE 3 - COMPARATIVE EXAMPLE
    [93] This example relates to a prior art process for the production of a calcium carbonate product, starting with calcium carbonate obtained from the pulp press refuse, in which the calcium carbonate obtained from the press refuse of pulp is calcined to obtain a pulp press lime (CaO). The pulp press lime is then mixed with high-purity PCC graded lime, smothered and the resulting lime milk mixture is then used in a carbonation reaction.
    [94] The low purity refuse CaCO3 of Example 1, which is typically discharged from the chemical recovery process of Klabin Papers' Kraft paper pulp grinder, Telemaco Borba Mill, was calcined in a rotary kiln at a temperature in the range of 900 to 1300 ° C, and pre-compressed over a hammer mill to obtain a low purity pulp mill refuse CaO. 30 kg of this refuse CaO was mixed with 170 kg of a high purity CaC lime of PCC grade (Lhoist Belocal, Arcos MG / Brazil) and this lime mixture was added to 1700 liters of tap water at 60 ° C in a stirred choking reactor. Before muffling, 0.80 kg of a 30% w / w aqueous solution of sodium citrate was added to the muffling water. The lime was smothered for 30 minutes with continuous stirring and the resulting paste of calcium hydroxide ("lime milk") was adjusted to a solids content of 13.6% by diluting the lime milk with 60 ° water. C, and was then sieved through a 200 u sieve to remove coarse sand. 1800 liters of said lime milk were added to the carbonator, and the temperature of the lime milk was adjusted to 50 ° C.
    [95] Carbonation was carried out in a 2000 liter muffled cylindrical stainless steel reactor equipped with a gasification stirrer. A stainless steel carbonation tube to direct a stream of carbon dioxide / air gas to the impeller, and probes to monitor the pH and conductivity of the suspension. A 20% vol. CO2 gas in air was then bubbled up through the reaction mixture in a standard volumetric flow of 200 m3 / h (standard volume flow as defined in DIN 1343, at a temperature of 0 ° C ( 273.15 K) 101.325 kPa, and 0% relative humidity) under vigorous agitation. During carbonation, the temperature of the reaction mixture was not controlled and was allowed to rise due to the heat generated in the exothermic precipitation reaction. The carbonation was maintained until the electrical conductivity suddenly dropped and passed through a minimum, indicating that the carbonation was substantially complete. The introduction of the gas containing CO2 continued for another 10 minutes before the introduction of the gas was interrupted. The carbonation time, calculated from the beginning of the gas introduction until the moment of minimum conductivity, was 84 minutes. The reaction mixture was then sieved through a 45 pm sieve and the sieved product was recovered as a CaCO 2 slurry. Based on the total CaCCb dry matter in the PCC / CaCCh composite product obtained, the scrap CaCCb portion of the original low-purity pulp grinder was 150% w / w. The transparency of ISO R457 of the composite product PCC / obtained was 90.6%.
    [96] The physical properties of the product obtained by the process described in Example 3, are listed in Table 1. B. Use of Precipitated Calcium Carbonate Obtained in Coating Tests
    [97] The following examples demonstrate the use of the precipitated divalent metal ion carbonate product obtained according to the inventive process as a pigment in pre-coating formulations.
    [98] First of all, the aqueous suspension of the precipitated divalent metal ion carbonate product having a solid content in the range of 10 to 30% by weight, based on the total weight of the aqueous suspension, is concentrated to have a content final solid in the range of 40 to 80% by weight, preferably in the range of 50 to 75% by weight, and more preferable in the range of 60 to 75% by weight. Concentration can be achieved by any method known to the skilled person, such as thermal concentration, partial dehydration, and others. However, an alternative means of obtaining the precipitated divalent metal ion carbonate product from the suspension, having a solids content in the range of 40 to 80% by weight, based on the total weight of the aqueous suspension, is to dehydrate the carbonate product. of precipitated divalent metal ions from aqueous suspension having a solids content in the range of 10 to 30% by weight, using a press filter or similar medium, and redispersing the dehydrated residue obtained from the divalent metal ion carbonate product precipitated in an amount of liquid sufficient to produce an aqueous suspension of the precipitated divalent metal ion carbonate product having a solid content in the range of 40 to 80% by weight.
    [99] This is described below in Examples 4 and 5 for the products obtained in Examples 2 and 3, respectively. Example 4 - Comparative Example
    [100] The PCC / PCC CaCCh composite product obtained in the prior art process described in Example 3, was mechanically dehydrated in a filter press and the discharged filter cake was redispersed in the presence of an adequate amount of a dispersion well known to the person skilled in the art, in a high shear mixture to obtain a high solids paste that can be used as a coating pigment. The product, after conversion, was recovered as a slurry containing 72.8% dry matter of the PCC / Refug CaCCh composite product (i.e., a high solids slurry).
    [101] The physical properties of the product obtained in the process described in Example 4 are listed in Table 1. Example 5 - Example of the Invention
    [102] The PCC / PCC CaCCh composite product obtained in the process of the invention described in Example 2, was mechanically dehydrated in a filter press and the discharged filter cake was redispersed in a high-shear mixer to obtain a high solids content that can be used as a coating pigment. During the conversion of the filter cake to the paste (reduction in the paste), an appropriate amount of an appropriate dispersing agent well known to the person skilled in the art was added. The product after conversion (reduction) was recovered as a slurry containing 66.8% dry matter of the residual PCC / CaCCh composite product.
    [103] The physical properties of the product obtained in the process described in Example 5 are listed in Table 1 and the SEM micrograph is disclosed in Fig. 4.
    [104] In pilot coating tests, the residual PCC / CaCCh composite coating pigments obtained in Examples 4 (prior art) and 5 (invention) were evaluated in pre-coating formulations of Liquid Packaging Card (LPB) and compared to the prior art coating pigments typically used for this application.
    [105] Using the products obtained in Example 4 (prior art) and Example 5 (invention), described above, the first and second pre-coating formulations were prepared (tests M8 and M9). In addition, a first and a second pre-coating formulations containing no residual PCCs were also prepared for comparison (Test No. 1).
    [106] In tests No. 2 (invention) and No. 3 (prior art), all early pre-coating formulations also contained a latex, a synthetic thickener, and a crosslinker in addition to the specific residual PCC. The second pre-coating formulation also contained a latex, carboxymethyl cellulose (CMC), a crosslinker, and calcium stearate (Ca-stearate) in addition to the specific residual PCC.
    [107] The compositions of the first and second pre-coating formulations are listed in Table 2. Coating Concept
    [108] Pilot coating tests were conducted at 400 m / min for the purpose of assessing the impact of different coating formulations on the properties of a doubly pre-coated packaging card.
    [109] A measured size press was used to coat a base carton having a weight of 298 g / m2, a gloss of 76.5%, and a PPS roughness of 5.8 pm with a first precoat having a coating weight of 4 g / m2. The rod used was grooved and had a diameter of 12 mm.
    [110] In a next step, the second pre-coating was applied over the first pre-coating using a jet application with a 0.38 mm thick curved blade. The applied coating weight was 10 g / m2.
    [111] By using a curved blade as well as the measured size press, good coverage and a smooth surface are obtained for good printability. The curved blade operates as a lubricating dosage unit and also promotes contour coating by compressing the surface below the coating that is applied to obtain a smooth surface whereas the measured size press applies a typical contour coating to the enhanced coverage .
    [112] The formulations, methods and conditions used, as well as results, are listed in Table 2.
    [113] From Table 1 it is clear that the precipitated calcium carbonate product obtained by the process according to the present invention shows a comparable gloss (compared to Example 1) or even a better gloss (compared to Example 3) than a precipitated calcium carbonate obtained by prior art processes. Table 1: Physical Properties of precipitated calcium carbonates obtained according to the method of the prior art and according to the present invention
    Table 2: Data and results of pilot coating tests comprising formulations containing calcium carbonate products obtained according to the methods of the prior art (Ml, M9) and according to the present invention (M8)
    [1] Natural calcium carbonate coating pigment, available from Omya AG, Oftringen, Switzerland [2] Quantity in parts per hundred per dry mass; refers to the total amount of dry matter pigment (s) dry matter in the formulation which is defined to be 100 parts. [3] Styronal 517, latex binder, available from BASF AG, Ludwigshafen, Germany [4] Sterocoll FS, synthetic thickener, available from BASF AG, Ludwigshafen, Petition [5] Cartabond MZI, crosslinker, available from Clariant AG, Muttenz, Switzerland [6] Dry matter content in the coating formulation, based on the total dry weight of the coating formulation. [7] Wet ground natural calcium carbonate coating pigment, available from Omya AG, Oftringen, Switzerland [8] Brazilian kaolin coating pigment, available from Imerys SA [9] Finnfix 30, methyl cellulose carboxy thickener, available from CP Kelco, Aanekoski, Finland [10] Calsan 50, dispersion of calcium stearate, available from BASF AG, Ludwigshafen, Germany
    [114] As can be seen in tests No. 2 (invention) and No. 3 (prior art), the inventive product obtained in Example 5 achieved a similar PPS gloss and roughness of the card after a second pre-coating compared to prior art product obtained in Example 4, despite a much higher portion of CaCO , low purity Pulp Mill residual, namely 23.5% vs. 15%.
    [115] Compared to pre-coating liquid packaging card (LPB) formulations that contain state-of-the-art “virgin” GCC pigments (Milled Calcium Carbonate) that do not contain any low-purity scrap material, gloss it was maintained at a similar level and the PPS roughness was further improved (see control test No. 1 compared to test No. 2 according to the invention).
    [116] In summary, the inventors of the present invention were able to produce a divalent metal ion carbonate product precipitated from a divalent metal ion carbonate that was recovered from scrap material, the ion carbonate product. precipitated divalent metal having a comparable or even improved gloss compared to the precipitated divalent metal ion carbonate product obtained by the prior art processes.
    [117] In addition, the inventors were able to show that the inventive precipitated divalent metal ion carbonate products, and particularly in a precipitated calcium carbonate product, can be used as coating pigments in pre-coating formulations for packaging cards, cards having similar PPS brightness and roughness compared to a card that has been treated with a pre-coating formulation containing a precipitated divalent metal ion carbonate product that was obtained by a prior art process and that contained a lower portion of low purity Pulp Mill Residual CaCOa.
    [118] Compared to LPB pre-coating formulations that contain state-of-the-art “virgin” GCC pigments (Milled Calcium Carbonate) that do not contain any low-purity scrap material, the gloss has been maintained at a similar level and the PPS roughness has been further improved.
    [119] Last and not least, the present invention contributes to the protection of the environment as it prevents cost-inefficient storage and disposal of the divalent metal ion carbonate waste from the pulp and paper manufacturing industries. In addition, the present invention also has the advantage that it reduces the costs of these industries since the inefficient storage and disposal of said divalent metal ion carbonate residues are no longer necessary.
    [120] It is mentioned that the foregoing description and examples were presented merely to illustrate the invention and are not intended to be limiting. Since modifications of the described embodiments that incorporate the spirit and substance of the invention may occur to persons skilled in the art, the invention must be interpreted broadly to include all variants that fall within the scope of the following claims and their equivalents.
    权利要求:
    Claims (26)
    [0001]
    1. Process for the production of a precipitated divalent metal ion carbonate product from a divalent metal ion carbonate that has been recovered from scrap, the precipitated divalent metal ion carbonate product having an improved luster, the process characterized by the fact that it comprises the following steps: (a) providing a low-purity divalent metal ion carbonate material having an ISO R457 gloss of less than about 90%, measured according to ISO 2469, the material of carbonate of divalent metal ions being recovered from the refuse; (b) calcining the divalent metal ion carbonate material of step (a) so as to obtain an oxide of divalent metal ions; (c) extinguishing the oxide of divalent metal ions obtained in step (b) in order to obtain an aqueous suspension of a divalent metal ion hydroxide; (d) carbonate the aqueous suspension of the divalent metal ion hydroxide obtained in step (c) with a compound containing carbon dioxide in order to obtain precipitated divalent metal ion carbonate particles consisting of groups or agglomerates of fine particles, the fine particles having a particle size of> 10 to 500 nm and a specific surface area of 5 to 50 m2 / g; (e) post-treating the precipitated divalent metal ion carbonate particles consisting of groups or agglomerates of fine particles obtained in step (d) to obtain discrete precipitated precipitated divalent metal ion carbonate particles having a particle size of> 10 to 500 nm and a specific surface area of 5 to 50 m2 / g; (f) mixing the fine particles of discrete precipitated divalent metal ion ions obtained in step (e) with an aqueous suspension of divalent metal ions hydroxide that has been obtained by calcining the divalent metal ion oxide of high purity having an ISO R457 brightness of at least about 94%, measured according to ISO 2469, in order to obtain a resulting reaction mixture; and (g) carbonating the reaction mixture resulting from step (f) in order to obtain the precipitated divalent metal ion carbonate product having an improved gloss compared to the precipitated divalent metal ion carbonate particles obtained in step ( d).
    [0002]
    2. Process according to claim 1, characterized by the fact that at least part of the precipitated divalent metal ion carbonate product obtained in step (g) is subjected to at least one other carbonation step, where at least part of the precipitated divalent metal ion carbonate product obtained in step (g) is first mixed with an aqueous divalent metal ion hydroxide suspension which was obtained by quenching high-purity divalent metal ion oxide to obtain a mixture of resulting reaction and then the resulting reaction mixture is subjected to carbonation.
    [0003]
    3. Process according to claim 1 or 2, characterized by the fact that the divalent low-purity metal ion carbonate material of step (a) is a material having the formula M2 + CO32, where M2 + is a metal ion divalent selected from the group comprising Be2 +, Mg2 +, Ca2 +, Sr2 + and Ba2 +, and is preferably Mg2 + and Ca2 +, and is most preferably Ca2 +.
    [0004]
    Process according to any one of claims 1 to 3, characterized by the fact that the post-treatment of step (e) is carried out by mechanical de-agglomeration or by recrystallization of precipitated divalent metal ion carbonate particles consisting of groups or agglomerates of fine particles obtained in step (d).
    [0005]
    Process according to any one of claims 1 to 4, characterized in that the discrete fine precipitated divalent metal carbonate particles obtained in step (e) have a particle size of> 10 to 500 nm, preferably in the range of 50 to 200 nm, and a specific surface area of 5 to> 50 m2 / g, preferably in the range of 20 to 50 m2 / g.
    [0006]
    Process according to any one of claims 1 to 5, characterized in that the precipitated divalent metal ion carbonate particles obtained in step (g) have an ISO R457 gloss in the range of 88 to 94%, as measured according to ISO 2469.
    [0007]
    Process according to any one of claims 1 to 6, characterized in that the precipitated divalent metal ion carbonate particles obtained in step (g) have a specific surface area in the range of 3 to 30 m2 / g, preferably in the range of 5 to 20 m2 / g, as measured according to the BET method using ISO 9277.
    [0008]
    Process according to any one of claims 1 to 7, characterized in that the precipitated divalent metal ion carbonate particles obtained in step (g) have a weighted average particle diameter dso in the range of 0.5 to 7 pm, preferably in the range of 0.8 to 5 pm, and more preferably in the range of 1 to 3 pm.
    [0009]
    Process according to any one of claims 1 to 8, characterized in that the low-purity divalent metal ion carbonate material of step (a) is a calcium carbonate material and the carbonate product of precipitated divalent metal ion from step (g) is precipitated calcium carbonate.
    [0010]
    Process according to claim 9, characterized in that the precipitated carbonate is precipitated scalenehedral calcium carbonate.
    [0011]
    Process according to any one of claims 1 to 10, characterized in that the precipitated divalent metal ion carbonate is concentrated to form a precipitated divalent metal ion carbonate slurry with a solids content of about 50% or higher.
    [0012]
    Process according to any one of claims 1 to 11, characterized in that the precipitated divalent metal ion carbonate is dried to form dry precipitated divalent metal ion carbonate.
    [0013]
    13. Aqueous suspension, characterized by the fact that it comprises a precipitated divalent metal ion carbonate obtained by a process for the production of a divalent metal ion carbonate product precipitated from a divalent metal ion carbonate that has been recovered from scrap, the precipitated divalent metal ion carbonate product having an improved gloss, the process comprising the following steps: (a) providing a low purity divalent metal ion carbonate material having an ISO R457 gloss of less than about 90%, measured according to ISO 2469, the divalent metal ion carbonate material being recovered from the refuse; (b) calcining the divalent metal ion carbonate material of step (a) so as to obtain an oxide of divalent metal ions; (c) extinguishing the oxide of divalent metal ions obtained in step (b) in order to obtain an aqueous suspension of a divalent metal ion hydroxide; (d) carbonate the aqueous suspension of the divalent metal ion hydroxide obtained in step (c) with a compound containing carbon dioxide in order to obtain precipitated divalent metal ion carbonate particles consisting of groups or agglomerates of fine particles, the fine particles having a particle size of> 10 to 500 nm and a specific surface area of 5 to 50 m2 / g; (e) post-treating the precipitated divalent metal ions carbonate particles consisting of groups or agglomerates of fine particles obtained in step (d) to obtain discrete precipitated precipitated divalent metal ion carbonate particles having a particle size of> 10 to 500 nm and a specific surface area of 5 to 50 m2 / g; (f) mixing the fine carbonate particles of discrete precipitated divalent metal ions obtained in step (e) with an aqueous suspension of divalent metal ion hydroxide that has been obtained by calcination of the high purity divalent metal ion oxide having an ISO R457 brightness of at least about 94%, measured according to ISO 2469, in order to obtain a resulting reaction mixture; and (g) carbonating the reaction mixture resulting from step (f) in order to obtain the precipitated divalent metal ion carbonate product having an improved gloss compared to the precipitated divalent metal ion carbonate particles obtained in step ( d).
    [0014]
    14. Dry precipitated divalent metal ion carbonate, characterized by the fact that it is obtained by the process for the production of a precipitated divalent metal ion carbonate product from a divalent metal ion carbonate that has been recovered from scrap, the precipitated divalent metal ion carbonate product having an improved gloss, the process comprising the following steps: (a) providing a low-purity divalent metal ion carbonate material having an ISO R457 gloss of less than about 90% , measured according to ISO 2469, the divalent metal ion carbonate material being recovered from the refuse; (b) calcining the divalent metal ion carbonate material of step (a) so as to obtain an oxide of divalent metal ions; (c) extinguishing the oxide of divalent metal ions obtained in step (b) in order to obtain an aqueous suspension of a divalent metal ion hydroxide; (d) carbonate the aqueous suspension of the divalent metal ion hydroxide obtained in step (c) with a compound containing carbon dioxide in order to obtain precipitated divalent metal ion carbonate particles consisting of groups or agglomerates of fine particles, the fine particles having a particle size of> 10 to 500 nm and a specific surface area of 5 to 50 m2 / g; (e) post-treating the precipitated divalent metal ion carbonate particles consisting of groups or agglomerates of fine particles obtained in step (d) to obtain discrete precipitated precipitated divalent metal ion carbonate particles having a particle size of> 10 to 500 nm and a specific surface area of 5 to 50 m2 / g; (f) mixing the fine carbonate particles of discrete precipitated divalent metal ions obtained in step (e) with an aqueous suspension of divalent metal ion hydroxide that has been obtained by calcination of the high purity divalent metal ion oxide having an ISO R457 brightness of at least about 94%, measured according to ISO 2469, in order to obtain a resulting reaction mixture; and (g) carbonating the reaction mixture resulting from step (f) in order to obtain the precipitated divalent metal ion carbonate product having an improved gloss compared to the precipitated divalent metal ion carbonate particles obtained in step ( d), and (h) drying the precipitated divalent metal ion carbonate to form the dry precipitated divalent metal ion carbonate.
    [0015]
    15. Aqueous suspension or dry precipitated divalent metal ion carbonate according to claim 13 or 14, characterized by the fact that at least part of the precipitated divalent metal ion carbonate product obtained in step (g) is subjected to at least another carbonation step, where at least part of the precipitated divalent metal ion carbonate product obtained in step (g) is first mixed with an aqueous divalent metal ion hydroxide suspension that was obtained by extinguishing ion oxide from high-purity divalent metal to obtain a resulting reaction mixture and then the resulting reaction mixture is subjected to carbonation.
    [0016]
    16. Aqueous suspension or dry precipitated divalent metal ion carbonate according to any one of claims 13 to 15, characterized by the fact that the low-purity divalent metal ion carbonate material of step (a) is a material having the formula M2 + CO32, where M2 + is a divalent metal ion selected from the group comprising Be2 +, Mg2 +, Ca2 +, Sr2 + and Ba2 +, and is preferably Mg2 + and Ca2 +, and is most preferably Ca2 +.
    [0017]
    17. Aqueous suspension or dry precipitated divalent metal ion carbonate according to any one of claims 13 to 16, characterized by the fact that the post-treatment of step (e) is carried out by mechanical de-agglomeration or by the recrystallization of the carbonate particles precipitated divalent metal ion consisting of groups or agglomerates of fine particles obtained in step (d).
    [0018]
    18. Aqueous dry precipitated divalent metal ion carbonate or carbonate according to any one of claims 13 to 17, characterized by the fact that the discrete fine precipitated divalent metal ion carbonate particles obtained in step (e) have a size of particle of> 10 to 500 nm, preferably in the range of 50 to 200 nm, and a specific surface area of 5 to> 50 m2 / g, preferably in the range of 20 to 50 m2 / g.
    [0019]
    19. Aqueous suspension or dry precipitated divalent metal ion carbonate according to any of claims 13 to 18, characterized in that the precipitated divalent metal ion carbonate particles obtained in step (g) have an ISO R457 gloss in the range of 88 to 94%, as measured according to ISO 2469.
    [0020]
    20. Aqueous suspension or dry precipitated divalent metal ion carbonate according to any of claims 13 to 19, characterized in that the precipitated divalent metal ion carbonate particles obtained in step (g) have an area of specific surface in the range of 3 to 30 m2 / g, preferably in the range of 5 to 20 m2 / g, as measured according to the BET method using ISO 9277.
    [0021]
    21. Aqueous suspension or dry precipitated divalent metal ion carbonate according to any one of claims 13 to 20, characterized in that the precipitated divalent metal ion carbonate particles obtained in step (g) have a particle diameter weighted average dso in the range of 0.5 to 7 pm, preferably in the range of 0.8 to 5 pm, and more preferably in the range of 1 to 3 pm.
    [0022]
    22. Aqueous suspension or dry precipitated divalent metal ion carbonate according to any one of claims 13 to 21, characterized in that the low-purity divalent metal ion carbonate material from step (a) is a material of calcium carbonate and the precipitated divalent metal ion carbonate product of step (g) is precipitated calcium carbonate.
    [0023]
    23. Aqueous suspension or dry precipitated divalent metal ion carbonate according to claim 22, characterized in that the precipitated carbonate is scalenehedral precipitated calcium carbonate.
    [0024]
    24. Aqueous suspension or dry precipitated divalent metal ion carbonate according to any of claims 13 to 23, characterized in that the precipitated divalent metal ion carbonate is concentrated to form a slurry of carbonate ion carbonate. precipitated divalent metal with a solids content of about 50% or higher.
    [0025]
    25. Use of an aqueous suspension as defined in any of claims 13 or 15 to 24 or of the dry precipitated divalent metal ion carbonate as defined in any of claims 14 to 24, characterized in that it is as a pigment in formulations of coating or as fillers in the paper, plastic and ink manufacturing industries.
    [0026]
    26. Use of a dry precipitated divalent metal ion carbonate as defined in any of claims 14 to 24, characterized in that it is in the field of paints, rubber, plastics, building materials, and paints.
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    同族专利:
    公开号 | 公开日
    CO6801806A2|2013-11-29|
    KR20130138847A|2013-12-19|
    SI2709951T1|2019-07-31|
    PL2524898T3|2016-02-29|
    US20160229702A1|2016-08-11|
    SI2524898T1|2015-10-30|
    PT2709951T|2019-06-19|
    CL2013003267A1|2014-07-25|
    US9944535B2|2018-04-17|
    WO2012156231A1|2012-11-22|
    MX346652B|2017-03-28|
    KR20150058558A|2015-05-28|
    CA2836197A1|2012-11-22|
    CA2836197C|2016-07-05|
    HRP20190938T1|2019-07-26|
    CN103534207B|2015-08-19|
    PT2524898E|2015-11-03|
    RU2596827C2|2016-09-10|
    DK2524898T3|2015-12-14|
    ES2730148T3|2019-11-08|
    ES2549029T3|2015-10-22|
    MX2013013024A|2013-12-02|
    EP2709951B1|2019-03-27|
    ZA201308068B|2015-01-28|
    EP2709951A1|2014-03-26|
    EP2524898B1|2015-09-02|
    KR101558725B1|2015-10-07|
    AR086330A1|2013-12-04|
    JP5778858B2|2015-09-16|
    UY34064A|2013-01-03|
    JP2014523839A|2014-09-18|
    RU2013155614A|2015-06-27|
    CN103534207A|2014-01-22|
    EP2524898A1|2012-11-21|
    US9409788B2|2016-08-09|
    AU2012257864B2|2014-08-14|
    US20140186241A1|2014-07-03|
    BR112013029361A2|2017-01-31|
    AU2012257864A1|2013-11-14|
    TR201908236T4|2019-06-21|
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    法律状态:
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C01F 11/18 (2006.01), B82Y 30/00 (2011.01), C01B 3 |
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-07-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-04-28| B09A| Decision: intention to grant|
    2020-10-06| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/05/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11166216.9A|EP2524898B1|2011-05-16|2011-05-16|Method for the production of precipitated calcium carbonate from pulp mill waste|
    EP11166216.9|2011-05-16|
    US201161490128P| true| 2011-05-26|2011-05-26|
    US61/490128|2011-05-26|
    PCT/EP2012/058432|WO2012156231A1|2011-05-16|2012-05-08|Precipitated calcium carbonate from pulp mill waste having an improved brightness, method for the production and use thereof|
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