WO2013142473A1 - Process for preparing scalenohedral precipitated calcium carbonate - Google Patents
Process for preparing scalenohedral precipitated calcium carbonate Download PDFInfo
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- WO2013142473A1 WO2013142473A1 PCT/US2013/032923 US2013032923W WO2013142473A1 WO 2013142473 A1 WO2013142473 A1 WO 2013142473A1 US 2013032923 W US2013032923 W US 2013032923W WO 2013142473 A1 WO2013142473 A1 WO 2013142473A1
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- WIPO (PCT)
- Prior art keywords
- pcc
- process according
- product
- paper
- slaked lime
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/39—Particle morphology extending in three dimensions parallelepiped-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Definitions
- the present invention relates to a method for producing a precipitated calcium carbonate and, in particular, a precipitated calcium carbonate product in substantially scalenohedral form.
- calcium carbonate has found a wide array of uses across many fields.
- calcium carbonate is one of the most widely used minerals in the paper, plastic, paint and coating industries both as a filler and, due to its white color, as a coating pigment.
- calcium carbonate is valued for its high brightness, opacity and gloss and is commonly used as a filler to make bright opaque paper.
- calcium carbonate is frequently used as an extender in paints and is also used as a filler in adhesives, sealants and plastics.
- High grade calcium carbonate has also found uses in formulations of pharmaceuticals.
- Calcium carbonate is known to exist as natural occurring minerals as well as a synthetically produced products.
- Ground natural calcium carbonate in the meaning of the present invention is a calcium carbonate obtained from natural sources including marble, chalk or limestone or dolomite.
- Calcite is a carbonate mineral and the most stable polymorph of calcium carbonate.
- the other polymorphs of calcium carbonate are the minerals aragonite and vaterite. Aragonite will change to calcite at 380-470°C, and vaterite is even less stable.
- Ground calcium carbonate is processed through a treatment such as grinding, screening and/or fractionizing by wet and/or dry, for example, by a cyclone. It is known to the skilled person that ground calcium carbonate can inherently contain a defined concentration of magnesium, such as it is the case for dolomitic limestone.
- Precipitated calcium carbonate in the meaning of the present invention is a synthesized material, generally obtained by precipitation following the reaction of carbon dioxide and lime in an aqueous environment or by precipitation of a calcium and carbonate source in water or by precipitation of calcium and carbonate ions, for example CaCl 2 and Na 2 C0 3 , out of solution.
- Precipitated calcium carbonate exists in three primary crystalline forms: calcite, aragonite and vaterite, and there are many different polymorphs (crystal habits) for each of these crystalline forms.
- Calcite has a trigonal structure with typical crystal habits such as scalenohedral (S-PCC),
- R-PCC rhombohedral
- C-PCC pinacoidal, colloidal
- P-PCC prismatic
- Aragonite is an orthorhombic structure with typical crystal habits of twinned hexagonal prismatic crystals, as well as a diverse assortment of thin elongated prismatic, curved bladed, steep pyramidal, chisel shaped crystals, branching tree, and coral or worm-like forms.
- the scalenohedral form of calcite is particularly desirable for use as a bulking pigment in the paper industry because it is relatively inexpensive to produce and it has desirable light scattering properties.
- Prior art processes for producing scalenohedral PCC product typically rely on the use of additives such as monosaccharides (e.g, simple sugars such as fructose, glucose), disaccharides (e.g., sucrose, maltose, lactose), polysaccharides (e.g, starch, cellulose, glycogen), triethanolamine, mannitol, diethanolamine, bicine, morpholine, tri- isopropanolamine, N-ethyl diethanolamine, ⁇ , ⁇ -diethylethanolamine, sodium
- additives such as monosaccharides (e.g, simple sugars such as fructose, glucose), disaccharides (e.g., sucrose, maltose, lactose), polysaccharides (e.g, starch, cellulose, glycogen), triethanolamine, mannitol, diethanolamine, bicine, morpholine, tri- isopropanolamine, N-ethyl diethanol
- boroheptonate or reagents including a polyhydric alcohol or a polyhydric phenol, during the slaking of the quick lime or prior to carbonation (see, e.g., U.S. Patent Nos.
- the present invention provides a process for producing low cost precipitated PCC in the scalenohedral form that has a stronger resistance of the PCC clusters/crystals during processing (i.e. lesser tendency to form discrete PCC particles), and leads to improved stiffness and/or bulk in woodfree paper applications than conventional scalenohedral PCC.
- the present invention accomplishes these requirements by utilizing a two stage manufacturing process.
- the first stage includes the step of slaking quick lime to obtain slaked lime.
- the second stage includes the step of subjecting the slaked lime, without agitation, without prior cooling in a heat exchanger, and in the absence of any additives, to carbonation with carbon dioxide gas to produce PCC.
- the product of this two stage process overcomes the deficiencies of prior PCC production processes and results in a scalenohedral PCC product that has a stronger resistance of the PCC clusters/crystals during processing (i.e. lesser tendency to form discrete PCC particles), and leads to improved stiffness and/or bulk in woodfree paper applications than conventional scalenohedral PCC.
- the present invention also provides a PCC or PCC product prepared by the process of the present invention.
- the present invention provides a material comprising the PCC or PCC product of the present invention.
- the material may include, for example, products in which it is desirable to include calcium carbonate as a filler, such as paper, paper coatings, paper products, inks, paints, coatings, plastics, adhesives, building products, foodstuffs, cosmetics and pharmaceutical products.
- the present invention also provides a paper coating comprising the PCC or PCC product of the present invention.
- the PCC or PCC product of the present invention is believed to result in higher gloss and improved opacity.
- the present invention is directed to uses of the PCC or the PCC product of the present invention for the manufacture of a material in which it is desirable to use scalenohedral PCC as a filler.
- Figure 1 represents a graph of the particle size distribution comparing the PCC prepared in accordance with the conventional process (old) with the PCC prepared in accordance with the present invention (new) both before and after centrifugation (after CF).
- Figure 2 represents an SEM photograph taken of the PCC prepared in accordance with the present invention before centrifugation.
- Figure 3 represents an SEM photograph taken of the PCC prepared in accordance with the present invention after centrifugation.
- a precipitated calcium carbonate product is prepared in a two-stage process.
- quick lime (CaO) is slaked in water to obtain a calcium hydroxide (Ca(OH) 2 ) slurry, or milk of lime.
- This reaction is shown in reaction (1) and preferably takes place in a slaker tank:
- the source of quick lime (CaO) used in the slaking reaction is preferably obtained by subjecting crushed limestone to heat (calcination) to form lime (CaO) and carbon dioxide (C0 2 ).
- the reaction is preferably performed at an initial temperature of about 85°F to 120°F, and preferably 95°F to 110°F. Since the reaction is exothermic, the temperature typically raises to 180°F to 210°F, and preferably to 195°F to 205 °F.
- the reaction also is desirably performed with mixing or agitation. The duration of the reaction may vary but is typically about 5 to 15 minutes.
- the solids content of the slurry is typically about 10 to 20 wt.-% solids, and preferably 12 to 18 wt.-% solids. It is within the confines of the present invention that additional water may be introduced during the slaking reaction in order to control and/or maintain and/or achieve the desired solids concentration.
- the calcium hydroxide slurry or slaked lime from the slaking reaction may then be screened if desired in order to remove oversize particles.
- a suitable screen can include, for example, a screen having an about 30-50 mesh screen size.
- the calcium hydroxide slurry or slaked lime may then be transferred to an intermediate tank if desired.
- the temperature of the calcium hydroxide slurry or slaked lime is then reduced by about 40°F to 70°F, and more preferably about 60°F, resulting in slurry temperature of 125°F to 165°F, and preferably 135°F to 155°F.
- the carbonation is conducted in the absence of any additives.
- the "absence of any additives” means the absence of any additives that may be added prior to or during carbonation, including additives that may be added during the slaking of the quick lime or the resulting calcium hydroxide slurry.
- additives include, for example, a carbohydrate, a monosaccharide, a disaccharide, a polysaccharide, triethanolamine, mannitol, diethanolamine, bicine, morpholine, tri-isopropanolamine, N-ethyl
- the absence of any additive means the absence of a monosaccharide or a disaccharide, and most preferably, the absence of any additive means the absence of a disaccharide (e.g., sucrose).
- the carbon dioxide (C0 2) is selected from gaseous carbon dioxide, liquid carbon dioxide, solid carbon dioxide or a gaseous mixture of carbon dioxide and at least one other gas, and is preferably gaseous carbon dioxide.
- the gaseous mixture is a carbon dioxide containing flue gas exhausted from industrial processes like combustion processes or calcination processed or alike.
- C0 2 can also be produced by reacting an alkali- and/or earth alkali carbonate with acid. Furthermore, it can be produced by the combustion of organics, such as ethyl alcohol, wood and the like, or by fermentation.
- the carbon dioxide is present in the range of 8 to about 99% by volume, and preferably in the range of 10 to 25% by volume, for example 20% by volume.
- the C0 2 is obtained from an external source, and is more preferably captured from the calcination of the crushed calcium carbonate.
- the carbonation reaction is preferably conducted at an initial temperature of 130°F to 160°F, and more preferably at an initial temperature of 135°F to 145°F.
- the medium particle size of the calcium carbonate can be controlled by adjusting the starting temperature upwards or downwards 1-2 °F.
- the reaction desirably precedes until all or substantially all of the calcium hydroxide or slaked lime has been converted into calcium carbonate slurry. In the preferred embodiment, the reaction is stopped when the conductivity of the reaction mixture increases.
- the PCC slurry obtained from the carbonation reaction is then isolated. This is preferably accomplished by transferring the PCC slurry to a holding tank.
- the PCC slurry may then be subjected to additional processing steps, including, for example, screening, dewatering, dispersion and/or grinding steps to obtain a PCC product having desired characteristics.
- the PCC slurry is passed through one or more screens in order to remove larger particles.
- the PCC slurry is passed through a screen to separate particles >45 microns or particles >75 microns.
- the resulting PCC product preferably contains 85%> or more scalenohedral particles, and more preferably 90% or more scalenohedral particles, and most preferably 95% or more scalenohedral particles.
- the resulting PCC product also preferably has a medium particle size (dso) of 2.0 to 3.0 microns, and more preferably a medium particle size (dso) of 2.2 to 2.8 microns, and most preferably a medium particle size (dso) of 2.5 microns.
- dso medium particle size
- the "particle size" of a calcium carbonate product is described by its distribution of particle sizes.
- the value d x represents the diameter relative to which x % by weight of the particles have diameters less than d x .
- the dso value is thus the weight median particle size, i.e. 50 wt.-% of all grains are bigger or smaller than this particle size.
- the particle size is specified as weight median particle size dso unless indicated otherwise.
- a Sedigraph 5100 device from the company Micromeritics, USA can be used.
- the resulting PCC product also preferably has a BET surface area of 4.0 to 7.0 m 2 /g.
- the PCC product obtained in accordance with the process of the present invention has a stronger resistance of the PCC clusters/crystals during processing (i.e. lesser tendency to form discrete PCC particles), and leads to improved stiffness and/or bulk in woodfree paper applications than PCC products prepared using conventional processes.
- the PCC product may be dry ground and/or wet ground.
- Wet grinding refers to grinding the PCC in a liquid medium (e.g., slurry). Wet grinding may be carried out in the absence of a grinding aid or in the presence of a grinding aid.
- One or more grinding agents can be included, such as, e.g., sodium polyacrylate, a salt of polyacrylate acid, and/or a salt of a copolymer of acrylic acid.
- Drying may take place using any suitable drying equipment and can, for example, include thermal drying and/or drying at reduced pressure using equipment such as an evaporator, a flash drier, an oven, a spray drier (such as a spray drier sold by Niro and/or Nara), and/or drying in a vacuum chamber. Dispersants also can be included to prepare dispersions if desired.
- the PCC or PCC product produced according to the present invention may be used in various materials in which it is desirable to use calcium carbonate as a filler.
- the scalenohedral PCC or PCC product may be used in the pharmaceutical field with products such as medicines, in human or animal foodstuffs, in the papermaking field as a filler or in the coating of paper, in water-based or non-water-based paints, in plastics, or in printing inks (e.g., offset printing, rotogravure printing).
- the PCC or PCC product is used as a filler in paper, and more preferably as a filler in uncoated woodfree paper.
- the PCC product of the present invention offers an improvement over conventional PCC in uncoated wood free paper, by allowing better bulk (+ 5-10%), higher opacity and stiffness than conventional PCC.
- the PCC or PCC product of the present invention is believed to result in higher gloss and improved opacity.
- Particle size distribution (mass % particles with a diameter ⁇ X) and weight medium diameter d ) of mineral material.
- the weight median diameter and the particle size distribution characteristics of the mineral material were determined via the sedimentation method, i.e. an analysis of sedimentation behavior in a gravimetric field. The measurement was made using a SedigraphTM 5100 of
- the method and the instrument are known to the skilled person and are commonly used to determine grain size of fillers and pigments.
- the measurement was carried out in an aqueous solution of 0.1 wt.-% Na 4 P 2 0 7 .
- the samples were dispersed using a high speed stirrer and supersonics.
- SSA Specific Surface Area of a material.
- the specific surface area was measured via the BET (Brunauer, Emmett, Teller) method according to ISO 9277 using nitrogen, following conditioning of the sample by heating at 250°C (482°F) for a period of 30 minutes. Prior to such measurements, the sample was filtered, rinsed and dried at 90 to 100°C (194 to 212°F) in an oven for at least 12 hours before being broken down in a mortar with a pestle, and then placed in a mass balance at 130°C (266°F) until a constant weight was observed.
- BET Brunauer, Emmett, Teller
- Carbon dioxide from the host paper mill's lime kiln was then introduced into the bottom of the reactor with the agitators turned on to convert the slaked lime into calcium carbonate slurry.
- the calcium carbonate slurry was then screened to remove particles >45 microns, and resulting product was then pumped into a storage tank.
- Two products were prepared using this process by varying the carbonation start temperature.
- One product had a medium particle size ⁇ dso) of a 2.5 micron, a BET specific surface area of 4.9 m 2 /g, and a of 1.49.
- the other product had a medium particle size ⁇ dso) of 2.9 micron, a BET specific surface area of 3.8 m 2 /g, and a of 1.44.
- the PCC according to the present invention was prepared as in Example 1 with the following differences. First, the slaked lime was not pumped through a heat exchanger to cool the slurry. Second, sugar was not added to the slaked lime. Third, the carbonation reaction was performed with the agitators turned off. The product prepared by this process had a medium particle size ⁇ dso) of 2.5 micron, a BET specific surface area of 4.7 m 2 /g, and a of 1.5.
- the conventional PCC from Example 1 and the PCC according to the present invention from Example 2 were used to prepare handsheets for further testing. More specifically, the handsheets were prepared by first combining 80% hardwood pulp with 20%) softwood pulp to achieve a 100% pulp mix. Hanksheets were then made using 80% of the pulp and 20% of either the conventional PCC or the PCC according to the present invention. The handsheets were then subjected to the following tests. [0046] Gurley porosity. This test measured the time for a 100 cc of air to pass through a paper sample, and used a Gurley-Hill Porosity Meter (Model 4190)(Gurley Precision Instruments, New York) in accordance with Tappi T460 om-96.
- Gurley porosity This test measured the time for a 100 cc of air to pass through a paper sample, and used a Gurley-Hill Porosity Meter (Model 4190)(Gurley Precision Instruments, New York) in accordance with Tappi T460 om-96
- Scott Bond test This test measured the internal fiber bond strength of paper, and gave an indication of expected performance of the strength in the Z direction. This test was performed with the Scott Internal Bond Tester (Model # B, version AV- 2)(Huygen Corporation, Illinois) in accordance with Tappi T569.
- Taber Stiffness This tests evaluated the stiffness and resilency of paper, and used a Tabler V-5 Stiffness Tester (Model # 150B) (Teledyne/Taber Inc., New York) in accordance with Tappi T-543 pm-84.
- Tensile Strength This test measured the maximum tensile strength developed at rupture, and more specifically, the force per unit width required to break a paper sample. This test used the Instron Testing System (Model #101 l)(Instron Corporation, Massachusetts) in accordance with Tappi T-498 om-88.
- PCC prepared by the conventional process
- new PCC PCC prepared by the process of the present invention
- the old PCC generated an increase of 56% of particles having a dp ⁇ 2 ⁇ , while the new PCC generated an increase of 48.9% of particles having a dp ⁇ 2 ⁇ .
- the old PCC generated an increase of 34.6%> of particles having a dp ⁇ 1.5 ⁇
- the new PCC generated an increase of 27.8% of particles having a dp ⁇ 1.5 ⁇ .
- the old PCC generated an increase of 13% of particles having a having a dp ⁇ ⁇
- the new PCC generated an increase of 10.1% particles having a dp ⁇ ⁇ .
- the reduction in fines for the new PCC in comparison to the old PCC as a result of centrifugation demonstrates that the new PCC has a stronger resistance of the PCC clusters/crystals during processing than the old PCC.
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Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112014021592-8A BR112014021592B1 (en) | 2012-03-23 | 2013-03-19 | process for the preparation of precipitated calcium carbonate |
KR1020147028622A KR101720401B1 (en) | 2012-03-23 | 2013-03-19 | Process for preparing scalenohedral precipitated calcium carbonate |
CN201380015854.0A CN104204351B (en) | 2012-03-23 | 2013-03-19 | The method for being used to prepare scalenohedron winnofil |
JP2015501844A JP5893795B2 (en) | 2012-03-23 | 2013-03-19 | Method for preparing declinated trihedral precipitated calcium carbonate |
IN2048MUN2014 IN2014MN02048A (en) | 2012-03-23 | 2013-03-19 | |
RU2014142635/05A RU2596763C2 (en) | 2012-03-23 | 2013-03-19 | Process for preparing scalenohedral precipitated calcium carbonate |
US14/379,110 US9428398B2 (en) | 2012-03-23 | 2013-03-19 | Process for preparing scalenohedral precipitated calcium carbonate |
CA2865647A CA2865647C (en) | 2012-03-23 | 2013-03-19 | Process for preparing scalenohedral precipitated calcium carbonate |
MX2014011125A MX2014011125A (en) | 2012-03-23 | 2013-03-19 | Process for preparing scalenohedral precipitated calcium carbonate. |
PL13764704T PL2828434T3 (en) | 2012-03-23 | 2013-03-19 | Process for preparing scalenohedral precipitated calcium carbonate |
EP13764704.6A EP2828434B1 (en) | 2012-03-23 | 2013-03-19 | Process for preparing scalenohedral precipitated calcium carbonate |
AU2013235257A AU2013235257B2 (en) | 2012-03-23 | 2013-03-19 | Process for preparing scalenohedral precipitated calcium carbonate |
US14/873,924 US9981855B2 (en) | 2012-03-23 | 2015-10-02 | Process for preparing scalenohedral precipitated calcium carbonate |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261614644P | 2012-03-23 | 2012-03-23 | |
US61/614,644 | 2012-03-23 | ||
EP12164041.1 | 2012-04-13 | ||
EP12164041 | 2012-04-13 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/379,110 A-371-Of-International US9428398B2 (en) | 2012-03-23 | 2013-03-19 | Process for preparing scalenohedral precipitated calcium carbonate |
US14/873,924 Division US9981855B2 (en) | 2012-03-23 | 2015-10-02 | Process for preparing scalenohedral precipitated calcium carbonate |
Publications (1)
Publication Number | Publication Date |
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WO2013142473A1 true WO2013142473A1 (en) | 2013-09-26 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US2013/032923 WO2013142473A1 (en) | 2012-03-23 | 2013-03-19 | Process for preparing scalenohedral precipitated calcium carbonate |
Country Status (13)
Country | Link |
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US (2) | US9428398B2 (en) |
EP (1) | EP2828434B1 (en) |
JP (2) | JP5893795B2 (en) |
KR (1) | KR101720401B1 (en) |
CN (1) | CN104204351B (en) |
AU (2) | AU2013235257B2 (en) |
CA (1) | CA2865647C (en) |
CO (1) | CO7051025A2 (en) |
IN (1) | IN2014MN02048A (en) |
MX (1) | MX2014011125A (en) |
PL (1) | PL2828434T3 (en) |
RU (1) | RU2596763C2 (en) |
WO (1) | WO2013142473A1 (en) |
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