WO2008092991A2 - A process for producing gypsum - Google Patents
A process for producing gypsum Download PDFInfo
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- WO2008092991A2 WO2008092991A2 PCT/FI2008/000022 FI2008000022W WO2008092991A2 WO 2008092991 A2 WO2008092991 A2 WO 2008092991A2 FI 2008000022 W FI2008000022 W FI 2008000022W WO 2008092991 A2 WO2008092991 A2 WO 2008092991A2
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- WIPO (PCT)
- Prior art keywords
- calcium sulphate
- gypsum
- water
- hemihydrate
- anhydrite
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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
- C01F11/46—Sulfates
- C01F11/466—Conversion of one form of calcium sulfate to another
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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
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/025—Calcium sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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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
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-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
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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
- C01P2004/51—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
- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the invention relates to a process for the preparation of a gypsum product wherein calcium sulphate hemihydrate and/or calcium sulphate anhydrite and water are contacted so that the calcium sulphate hemihydrate and/or calcium sulphate anhydrite and the water react with each other and form a gypsum product.
- the invention also relates to a product prepared by this process.
- Gypsum or calcium sulphate dihydrate CaSO 4 -2H 2 ⁇ is suitable as material for both coating and filler pigments, especially in paper products. Especially good coating and filler pigment is obtained if the particular gypsum product has crystals, which are small, flat, broad (platy) and of equal size.
- the crystal size of the gypsum product particles is expressed as the weight average diameter D 50 of the particles contained therein. More precisely, D 50 is the diameter of the presumably round particle, smaller than which particles constitute 50 % of the total particle weight. D 5 0 can be measured with an appropriate particle size analyzer, such as Sedigraph 5100.
- the flatness of a crystal means that it has two parallel surfaces larger than the other surfaces.
- the form of flat crystals is suitably expressed by means of the shape ratio SR.
- the SR is the ratio of the crystal length (the longest measure) to the crystal thickness (the shortest transverse measure).
- the SR of the claimed gypsum product is meant the average SR of its individual crystals.
- Plateness is suitably expressed by means of the aspect ratio AR.
- the AR is the ratio between the crystal length (the longest transverse measure) and the crystal width (the longest transverse measure) e.g. the ratio between the length and the diameter of a cylinder tightly surrounding the crystal.
- the AR of the claimed gypsum product is meant the average AR of its individual crystals.
- Both the SR and the AR of the gypsum product can be estimated by examining its scanning electron micrographs.
- a suitable scanning electron microscope is the Philips FEI XL 30 FEG.
- Equal crystal particle size means that the crystal particle size distribution is narrow.
- the width is expressed as the gravimetric weight distribution (D 75 -D 2S )ZD 50 wherein D 75 , D25 and D 50 are the diameters of the presumably round particles, smaller than which particles constitute 75, 25 and 50 %, respectively, of the total weight of the particles.
- the width of the particle distribution is obtained with a suitable particle size analyzer such as the above mentioned type Sedigraph 5100.
- Gypsum occurs as a natural mineral or it is formed as a by-product of chemical processes, e.g. as phosphogypsum or flue gas gypsum.
- phosphogypsum or flue gas gypsum In order to refine the gypsum further by crystallising it into coating pigment or filler, it must first be calcined into calcium sulphate hemihydrate (CaSO 4 - 1 ⁇ H 2 O) after which it may be hydrated back by dissolving the hemihydrate in water and precipitating to give pure gypsum. Calcium sulphate may also occur in the form of anhydrite lacking crystalline water (CaSO 4 ).
- the calcium sulphate hemihydrate may occur in two forms; as ⁇ - and ⁇ -hemihydrate.
- the ⁇ - form is obtained by heat-treating the gypsum raw material at atmospheric pressure while the ⁇ -form is obtained by treating the gypsum raw material at a steam pressure which is higher than atmospheric pressure or by means of chemical wet calcination from salt or acid solutions at 45 0 C.
- WO 88/05423 discloses a process for the preparation of gypsum by hydrating calcium sulphate hemihydrate in an aqueous slurry thereof, the dry matter content of which is between 20 and 25 % by weight. Gypsum is obtained, the largest measure of which is from 100 to 450 ⁇ m and the second larges measure of which is from 10 to 40 ⁇ m.
- AU620857 discloses a process for the preparation of gypsum from a slurry containing not more than 33,33 % by weight of ground hemihydrate, thereby yielding needle-like crystals having an average size of between 2 and 200 ⁇ m and an aspect ratio between 5 and 50. See page 15, lines 5 to 11 , and the examples of this document.
- US 2004/0241082 describes a process for the preparation of small needle-like gypsum crystals (length from 5 to 35 ⁇ m, width from 1 to 5 ⁇ m) from an aqueous slurry of hemihydrate having a dry matter content of between 5 and 25 % by weight.
- the idea in this US document is to reduce the water solubility of the gypsum by means of an additive in order to prevent the crystals from dissolving during e.g. paper manufacture.
- the aim of the invention is to provide a process for the preparation of gypsum crystals of which are intact, small, flat and as equal as possible in size.
- the purpose of the invention is also to provide a process that is simple, scalable, adaptable to reaction conditions and raw materials and thus considerably less expensive than prior art techniques.
- the above mentioned purposes have now been achieved with a new process of the invention, where calcium sulphate hemihydrate and/or calcium sulphate anhydrite and water are contacted so that they react with each other and form a gypsum product.
- the reaction mixture has a dry matter content of between 34 and 84 % by weight in order to obtain a gypsum product which consists of crystals that are small, flat and of as equal size as possible.
- the gypsum product prepared with the process of the invention has excellent properties for example to coating applications, where small crystals with a smooth surface are a prerequisite for high opacity and gloss.
- the product can be used as plastics filler, and as a raw material in glass industry, cosmetics, printing inks, building materials and paints.
- the process also has the advantage that less pre-treatment and cheaper or no crystallization habit modifier are needed.
- the product need not be crushed or ground.
- the calcium sulphate hemihydrate and/or calcium sulphate anhydrite are preferably used in such an amount that the reaction mixture formed from it/them and the water has a dry matter content of between 40 and 84 % by weight, more preferably between 50 and 80 % and most preferably between 57 and 80 % by weight.
- dry matter content means essentially the same as “solids content”, as the dissolved hemihydrate and/or anhydrite forming a part of the “dry matter” is very small compared to the amount of undissolved hemihydrate and/or anhydrite forming the initial "solids content”.
- water can be contacted with - calcium sulphate hemihydrate
- ⁇ -calcium sulphate hemihydrate is typically used. It may be prepared by heating gypsum raw-material to a temperature of between 140 and 300 ° C, preferably from 150 to 200 0 C. At lower temperatures, the gypsum raw-material is not sufficiently dehydrated and at higher temperatures it is over-dehydrated into anhydrite.
- the calcinated calcium sulphate hemihydrate usually contains impurities in the form of small amounts of calcium sulphate dihydrate and/or calcium sulphate anhydrite. It is preferable to use ⁇ - calcium sulphate hemihydrate, whereby the gypsum raw material is heated to the require temperature as fast as possible.
- anhydrite It is also possible to use calcium sulphate anhydrite as starting material for the process of the invention.
- the anhydrite is obtained by calcination of gypsum raw material.
- the other forms, the so called Anhydrite III, also known as soluble anhydrite has three forms: ⁇ -anhydrite III, ⁇ -anhydrite III', and ⁇ -anhydrite III and Anhydrite ll-s form pure gypsum upon contact with water.
- the temperature of the water in the reaction mixture can be anything between 0 and 100 ° C and it can even be in the form of water vapour.
- the reaction takes place e.g. by mixing, preferably by mixing strongly, said substances together for a sufficient period of time, which can easily be determined experimentally. Strong mixing is necessary because at the claimed high dry matter contents, the slurry is thick and the reagents do not easily come into contact with each other.
- the initial pH is typically between 3.5 and 9.0, preferably between 4.0 and 7.5. If necessary, the pH is regulated by means of an aqueous solution of NaOH and/or HaSO 4 , typically a 10 % solution of NaOH and/or H 2 SO 4 .
- the calcium sulphate hemihydrate and/or calcium sulphate anhydrite, the water and a crystallization habit modifier are contacted.
- the sequence may be of any order. It is, however, preferable to contact the crystallization habit modifier with the water before the hemihydrate and/or the anhydrite.
- the crystallization habit modifier is preferably a compound having in its molecule one or several carboxylic or sulphonic acidic groups, or a salt of such a compound.
- the crystallization habit modifier is an inorganic acid, oxide, base or salt.
- useful inorganic oxides, bases and salts are AIF 3 , AI 2 (SO 4 )S, CaCI 2 , Ca(OH) 2 , H 3 BO 4 , NaCI, Na 2 SO 4 , NaOH, NH 4 OH, (NH 4 ) 2 SO 4 , MgCI 2 , MgSO 4 and MgO.
- the crystallization habit modifier is an organic compound, which is an alcohol, an acid or a salt.
- Suitable alcohols are methanol, ethanol, 1-butanol, 2-butanol, 1-hexanol, 2-octanol, glycerol, i-propanol and alkyl polyglucoside based C 8 -Ci 0 -fatty alcohols.
- organic acids may be mentioned carboxylic acids such as acetic acid, propionic acid, succinic acid, citric acid, tartaric acid, ethylene diamine succinic acid (EDDS), iminodisuccinic acid (ISA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DTPA), nitrilotriacetic acid (NTA), N-bis-(2-aminoethoxylic acids
- carboxylic acids such as acetic acid, propionic acid, succinic acid, citric acid, tartaric acid, ethylene diamine succinic acid (EDDS), iminodisuccinic acid (ISA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DTPA), nitrilotriacetic acid (NTA), N-bis-(2-aric acid, EDDS), iminodisuccinic acid (ISA), ethylene diamine tetraacetic acid (ED
- AES (1 ,2-dicarboxyethoxy)ethyl aspartic acid
- sulphonic acids such as amino-1-naphthol-3,6-disulphonic acid, 8-amino-1-naphthol-3,6-disulphonic acid,
- organic salt may be mentioned the salts of carboxylic acids such as Mg formiate, Na- and NhU -acetate, Na 2 -maleate, NH 4 -citrate, Na 2 -succinate, K- oleate, K-stearate, Na 2 -ethyelendiamine tetraacetic acid (Na 2 -EDTA), Na ⁇ - aspartamic acid ethoxy succinate (Na 6 -AES) and Na 6 -aminotriethoxy succinate (Na 6 -TCA).
- carboxylic acids such as Mg formiate, Na- and NhU -acetate, Na 2 -maleate, NH 4 -citrate, Na 2 -succinate, K- oleate, K-stearate, Na 2 -ethyelendiamine tetraacetic acid (Na 2 -EDTA), Na ⁇ - aspartamic acid ethoxy succinate (Na 6 -AES) and Na
- salt of sulphonic acids are useful, such as Na-n-(Ci O -Ci 3 )-alkylbenzene sulphonate, Cio-C 16 -alkylbenzene sulphonate, Na-1-octyI sulphonate, Na-1- dodecane sulphonate, Na-1-hexadecane sulphonate, the K-fatty acid sulphonates, the Na-C-
- organic salts containing sulphur should also be mentioned the sulphates such as the C-i 2 -Ci 4 -fatty alcohol ether sulphates, Na-2-ethyl hexyl sulphate, Na-n-dodecyl sulphate and Na-lauryl sulphate, and the sulphosuccinates such as the monoalkyl polyglycol ether of Na- sulphosuccinate, Na-dioctyl sulphosuccinate and Na-dialkyl sulphosuccinate.
- the sulphates such as the C-i 2 -Ci 4 -fatty alcohol ether sulphates, Na-2-ethyl hexyl sulphate, Na-n-dodecyl sulphate and Na-lauryl sulphate
- the sulphosuccinates such as the monoalkyl polyglycol ether of Na- sulphosuccinate, Na
- Phosphates may also be used, such as the Na-nonylphenyl- and Na-dinonyl phenylethoxylated phosphate esters, the K-aryl ether phosphates, as well as the triethanolamine salts of polyaryl polyetherphosphate.
- crystallization habit modifier may also be used cationic surfactants such as octyl amine, triethanol amine, di(hydrogenated animal fat alkyl) dimethyl ammonium chloride, and non-ionic surfactants such as a variety of modified fatty alcohol ethoxylates.
- cationic surfactants such as octyl amine, triethanol amine, di(hydrogenated animal fat alkyl) dimethyl ammonium chloride, and non-ionic surfactants such as a variety of modified fatty alcohol ethoxylates.
- polyacrylic acids and polyacrylates examples include the polyacrylic acids and polyacrylates, the acrylate-maleate copolymers, polyacrylamide, poly(2-ethyl-2-oxazoline), polyvinyl phosphonic acid, the copolymer of acrylic acid and allylhydroxypropyl sulphonate (AA-AHPS), poly- ⁇ -hydroxyacrylic acid (PHAS), polyvinyl alcohol, and poly(methyl vinyl ether - alt- maleic acid).
- Especially preferable crystallization habit modifiers are ethylene diamine succinic acid (EDDS), iminodisuccinic acid (ISA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DTPA), nitrilotriacetic acid (NTA), N-bis-(2- (1 ,2-dicarboxyethoxy)ethyl aspartic acid (AES), the di-, tetra- and hexa- aminostilbenesulfonic acids and their salts such as Na-aminotriethoxy succinate (Na ⁇ -TCA), as well as the alkylbenzenesulphonates.
- EDDS ethylene diamine succinic acid
- ISA iminodisuccinic acid
- EDTA ethylene diamine tetraacetic acid
- DTPA diethylene triamine pentaacetic acid
- NTA nitrilotriacetic acid
- the crystallization habit modifier is preferably used in an amount of 0.01 to 5.0 %, most preferably 0.02-1.78 %, based on the weight of the calcium sulphate hemihydrate and/or calcium sulphate anhydrite.
- the method of the invention can be carried on by adding calcium sulphate hemihydrate and/or calcium sulphate anhydrite to the water or a mixture of the water and the crystallization habit modifier.
- the contact can be carried out without stopping or sequentially.
- gypsum has a lower solubility in water than hemihydrate and anhydrite
- the gypsum formed by the reaction of hemihydrate and/or anhydrite with water immediately tends to crystallize from the water medium.
- the recovered gypsum can be left in the water medium as a slurry or it can be recovered in dry form.
- the crystallized and/or recovered gypsum is dispersed with a dispersing agent.
- a dispersing agent are the following: lignosulphonates such as Na lignosulphonate, condensation products of aromatic sulphonic acids with formaldehyde such as the condensed naphthalene sulphonates, dispersing anionic polymers, and copolymers made from anionic monomers or made anionic after polymerization, polymers containing repeating units having anionic charge such as carboxylic and sulphonic acids, their salts and combinations thereof. Also phosphates, non-ionic and cationic polymers, polysaccharides and surfactants may be used.
- anionic polymers described above are e.g. the poly(meth)acrylates, polyacrylate-maleate, polymaleate, poly- ⁇ -hydroxyacrylic acid, polyvinyl sulphonate, polystyrene sulphonate, poly-2-acrylamide-2-methyl propane sulphonate and polyvinyl sulphonate.
- a typical phosphate useful as dispersing agent is Na hexamethaphosphate.
- Typical non-ionic polymers are polyvinyl alcohol, polyvinyl pyrrolidone, the polyalkoxysilanes, and the polyethoxyalcohols.
- Cationically charged dispersing polymers are, for example, the dicyandiamide-formaldehyde polymers.
- polysaccharides should be mentioned native and modified starch, or modified cellulose such as carboxymethyl cellulose, and their derivatives.
- Useful surfactants are anionic surfactants such as carboxylic acids, sulphonic acids sulphuric acid esters, phosphoric acids and polyphosphoric acid esters and their salts, non-ionic surface active substances such as ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated carboxylic acid esters and ethoxylated carboxylic acid amides, and cationic surface active substances such as acid-free amines, amines containing oxygen, amines containing an amide bond, and quaternary ammonium salts.
- anionic surfactants such as carboxylic acids, sulphonic acids sulphuric acid esters, phosphoric acids and polyphosphoric acid esters and their salts
- non-ionic surface active substances such as ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated carboxylic acid esters and ethoxylated carboxylic acid amides
- the amount of dispersing agent used is preferably from 0.01 to 5.0 %, preferably from 0.05 to 3.0 %, based on the weight of the gypsum.
- the gypsum product of the invention is also treated with other additives.
- a typical additive is a biocide which prevents the activity of micro organisms when storing and using the gypsum product.
- the formed, recovered, dispersed and/or additive-treated gypsum product may be sieved or sentrifuged in order to obtain gypsum particles having the desired size.
- a final bleaching step may also be included.
- a new gypsum product is obtained.
- the new gypsum product is characterized in that it consists of essentially intact crystals having an average size (D5 0 ) between 0.1 and below 2.0 ⁇ m (0.1 ⁇ D 50 ⁇ 2.0).
- the size of the crystals obtained with prior art crystallisation technique is usually considerably bigger.
- essentially intact crystals is meant crystal particles which are not mechanically broken, but the crystal surfaces of which are preserved.
- Figure 33 shows gypsum with broken particles, obtained by grinding
- Figures 23 to 27 and 30 show gypsum having intact crystals, prepared by crystallization according to embodiments of the invention.
- Preferred crystal sizes range from 0.2 to below 2.0 ⁇ m.
- the shape ratio SR of the crystals of the claimed gypsum product is preferably at least 2.0, more preferably between 2.0 and 50, most preferably between 3.0 and 40.
- the aspect ratio AS of the crystals is preferably between 1.0 and 10, most preferably between 1.0 and below 5.0.
- the narrower the width of the particle size distribution WPDS (D 7 5-D 25 )/D 5 o is the more homogenic the gypsum product is.
- a homogenic product has, in addition to high scattering, also an improved opacity.
- the width of the particle size distribution is preferably below 2.0, more preferably below 1.25, most preferably below 1.10, which ensures that the product is homogeneous.
- Figure 33 shows that a ground product according to the state of the art has particles of very different sizes (broad size distribution).
- the gypsum product of the invention is typically a coating or a filler pigment.
- the gypsum product is a coating pigment consisting of crystals having an average size of 0.1 - 1.0 ⁇ m, preferably an average size of 0.5 - 1.0 ⁇ m.
- the gypsum product is a filler pigment consisting of crystals having an average size of 1.0 - 2.0 ⁇ m.
- Figures 1-22 present the electron microscope photographs of the gypsum products of examples 1-22 taken with a scanning electron microscope.
- Pictures 23-27 present photographs from the gypsum products of examples 23-27 taken with a microscope. Please see also the explanation of the examples later in the text.
- figures 28-32 are shown results from the application of platy calcium sulphate pigments according to the invention in the coating and filling application of paper.
- FIGS 1- 5 are shown electron microscope micrographs of the crystallized gypsum products obtained in examples 1-5 with fluidized bed calcined ⁇ -calcium sulphate hemihydrate in different dry matter contents and temperatures.
- figures 6 and 7 are shown electron microscope micrographs of the crystallized gypsum products obtained in examples 6 and 7 with rotary kiln calcined ⁇ -calcium sulphate hemihydrate in different dry matter contents and temperatures.
- figures 8 and 9 are shown electron microscope micrographs of the crystallized gypsum products obtained in examples 8 and 9 with wet calcined ⁇ -calcium sulphate hemihydrate in different dry matter contents and temperatures.
- figures 10-12 are shown electron microscope micrographs of the crystallized gypsum products obtained in examples 10-12 with fluidized bed calcined ⁇ - calcium sulphate hemihydrate in different dry matter contents and reaction conditions (temperature, pH)
- figures 13 and 14 are shown electron microscope micrographs of the crystallized gypsum products obtained in examples 13 and 14 with calcium sulphate anhydrite in different dry matter contents and temperatures.
- figures 15 and 16 are shown electron microscope micrographs of the crystallized gypsum products obtained in examples 15 and 16 with a mixture of calcined ⁇ -calcium sulphate hemihydrate and dried calcium sulphate dihydrate in different dry matter contents.
- figures 17 and 18 are shown electron microscope micrographs of the crystallized gypsum products obtained in examples 17 and 18 with a mixture of acid oven calcined calcium sulphate anhydrite and calcium sulphate dihydrate in different dry matter contents and temperatures.
- figures 19 and 20 are shown electron microscope micrographs of the crystallized gypsum products obtained in examples 19 and 20 with a mixture of rotary kiln calcined ⁇ -calcium sulphate hemihydrate and calcium sulphate anhydrite in different dry matter contents.
- figure 21 and 22 are shown electron microscope micrographs of the crystallized gypsum products obtained in example 21 with a mixture of rotary kiln calcined ⁇ - calcium sulphate hemihydrate, calcium sulphate dihydrate and calcium sulphate anhydrite in different dry matter contents.
- figures 28-33 are shown examples of the application of platy calcium sulphate pigments according to the invention in the coating and filling application of paper.
- figure 28 is shown an electron microscope image of the precipitated calcium sulphate pigment used in coating tests of wood free fine paper.
- the studied property was paper gloss.
- figure 30 is shown an electron microscope image of the precipitated calcium sulphate pigment used in SC-paper filler tests.
- the studied properties were opacity, porosity and tensile strength of paper.
- figure 31 is shown the opacity as a function of tensile strength in filler application.
- Precipitated gypsum pigment was used together with titanium dioxide. Higher tensile strength with gypsum pigment enables increased filler level and similar opacity with reference pigments.
- figure 32 is shown the brightness as a function of tensile strength in filler application.
- Precipitated gypsum pigment was used together with titanium dioxide. Higher tensile strength with gypsum pigment enables increased filler level. Similar brightness with PCC can be obtained at higher tensile strength.
- the reaction was carried out either at system pH or the pH was adjusted to the desired value by addition of small amounts of 10 % NaOH or 10 % H 2 SO 4 .
- the reactions are carried out in an unjacketed reactor, the temperature of the water being 12-100 0 C.
- the hemihydrate/anhydrite is added as batch to the water resulting a slurry with an initial solids content of 57-84 w-%.
- the slurry is stirred using a Hobart-mixer model N50CE (ca. 250- 500 rpm).
- the pH of the reactor was monitored by a Knick Portamess 911 pH-electrode.
- the morphology of calcium sulphate dihydrate was studied by using a FEI XL 30 FEG scanning electron microscope. Conversion of the hemihydrate to dihydrate gypsum was analyzed using a Mettler Toledo TGA/SDTA85 1/1100- thermogravimetric analyzer (TG). The crystal structure was determined with Philips X'pert x-ray powder diffractometer (XRD).
- Sample preparation 2 g of gypsum (dry matter content of which is approximately 68 %) is weighted in a decanter, 50 ml of methanol is added (e.g. JT. Baker 8045). The mixture is stirred with a magnetic stirrer utilizing ultrasound for 10 min.
- Density of the sample the density of dihydrate gypsum, 2.3 g/cm 3 was used
- the lengths/diameters and thickness as defined in the description were measured from scanning electron microscope photographs for at least 20 particles.
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1.
- the total amount of hemihydrate added is 855.0 g. After the addition the operation speed of the stirrer is raised to position 2.
- the precipitated product is dispersed using a Diaf dissolver and
- Average particle size (D50) is 0.90 ⁇ m
- the shape ratio is 9.18
- the aspect ratio is 3.27 Width of the particle size distribution is 0.73
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1.
- the total amount of hemihydrate added is 720.0 g. After the addition the operation speed of the stirrer is raised to position 2.
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size (D50) is 1.13 ⁇ m
- the shape ratio is 7.03
- the aspect ratio is 2.55 Width of the particle size distribution is 0.91
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size (D50) is 1.13 ⁇ m
- the shape ratio is 6.46
- the aspect ratio is 3.06
- Width of the particle size distribution is 1.45
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1.
- the total amount of hemihydrate added is 1200 g. After the addition the operation speed of the stirrer is raised to position 2.
- the precipitated product is dispersed using a Diaf dissolver and
- Average particle size (D50) is 0.81 ⁇ m
- the shape ratio is 3.18
- the aspect ratio is 3.18 Width of the particle size distribution is 2.54
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1.
- the total amount of hemihydrate added is 1008 g. After the addition the operation speed of the stirrer is raised to position 2.
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size (D50) is 0.97 ⁇ m
- the shape ratio is 4.11
- the aspect ratio is 4.11 Width of the particle size distribution is 3.68
- Rotary kiln calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer being set to position 1.
- the total amount of hemihydrate added is 855.0 g.
- the rotation speed of the stirrer is raised to position 2 after the addition of sulphate hemihydrate.
- the precipitated product is dispersed using a Diaf dissolver and
- Average particle size (D50) is 1.04 ⁇ m
- the shape ratio is 10.48
- the aspect ratio is 3.30 Width of the particle size distribution is 1.09
- Rotary kiln calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer being set to position 1.
- the total amount of hemihydrate added is 1200.0 g.
- the rotation speed of the stirrer is raised to position 2 after the addition of sulphate hemihydrate. 3. Wait for the formation of calcium sulphate dihydrate.
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size (D50) is 0.91 ⁇ m
- the shape ratio is 6.64
- the aspect ratio is 4.41 Width of the particle size distribution is 2.08
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- the obtained dihydrate gypsum is shown in figure 8.
- Average particle size (D50) is 2.43 ⁇ m
- the shape ratio is 6.96
- the aspect ratio is 3.37 Width of the particle size distribution is 0.77
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size (D50) is 1.09 ⁇ m
- the shape ratio is 5.27
- the aspect ratio is 5.27
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1.
- the total amount of hemihydrate added is 855.0 g. After the addition the operation speed of the stirrer is raised to position 2.
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size (D50) is 3.18 ⁇ m
- the shape ratio is 7.89
- the aspect ratio is 3.69
- Width of the particle size distribution is 1.17
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1. The total amount of hemihydrate added is 1200 g. After the addition the operation speed of the stirrer is raised to position 2. 3. Wait for the formation of calcium sulphate dihydrate.
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size (D50) is 1.19 ⁇ m
- the shape ratio is 5.28
- the aspect ratio is 2.95 Width of the particle size distribution is 1.98
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1.
- the total amount of hemihydrate added is 855 g. After the addition the operation speed of the stirrer is raised to position 2.
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- the obtained dihydrate gypsum is shown in figure 12.
- Average particle size (D50) is 1.06 ⁇ m
- the shape ratio is 14.22
- the aspect ratio is 4.40 Width of the particle size distribution is 0.99
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size (D50) is 0.89 ⁇ m
- the shape ratio is 7.82
- the aspect ratio is 3.61
- Width of the particle size distribution is 1.34 Example 14
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- the obtained dihydrate gypsum is shown in figure 14.
- Average particle size (D50) is 0.61 ⁇ m
- the shape ratio is 5.77
- the aspect ratio is 2.90 Width of the particle size distribution is 1.84
- a mixture (50:50) of calcium sulphate hemihydrate and calcium sulphate dihydrate is evenly added to the reactor with the operation speed of the stirrer being set to position 1.
- the total amount of hemihydrate and dihydrate added is 800 g. After the addition the operation speed of the stirrer is raised to position 2.
- Average particle size (D50) is 0.85 ⁇ m
- the shape ratio is 15.12
- the aspect ratio is 4.79
- Width of the particle size distribution is 7.22
- a mixture (50:50) of calcium sulphate hemihydrate and calcium sulphate dihydrate is evenly added to the reactor with the operation speed of the stirrer being set to position 1.
- the total amount of hemihydrate and dihydrate added is 1000 g. After the addition the operation speed of the stirrer is raised to position 2.
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- the obtained dihydrate gypsum is shown in figure 16.
- Average particle size (D50) is 2.02 ⁇ m
- the shape ratio is 3.36
- the aspect ratio is 3.36
- Width of the particle size distribution is 6.95
- a mixture (50:50) of calcium sulphate anhydrite and calcium sulphate dihydrate is evenly added to the reactor with the operation speed of the stirrer being set to position 1.
- the total amount of anhydrite and dihydrate added is 870 g. After the addition the operation speed of the stirrer is raised to position 2.
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size (D50) is 5.14 ⁇ m
- the shape ratio is 12.50
- the aspect ratio is 3.84
- a mixture (50:50) of calcium sulphate anhydrite and calcium sulphate dihydrate is evenly added to the reactor with the operation speed of the stirrer being set to position 1.
- the total amount of anhydrite and dihydrate added is 737 g. After the addition the operation speed of the stirrer is raised to position 2.
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size (D50) is 5.17 ⁇ m
- the shape ratio is 7.48
- the aspect ratio is 2.23
- Width of the particle size distribution is 5.43
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size (D50) is 1.51 ⁇ m
- the shape ratio is 16.27
- the aspect ratio is 4.08 Width of the particle size distribution is 2.04
- a mixture (50:50) of rotary kiln calcinated ⁇ -calcium sulphate hemihydrate and calcium sulphate anhydrite is evenly added to the reactor with the operation speed of the stirrer being set to position 1.
- the total amount of hemihydrate and anhydrite added is 712 g. After the addition the operation speed of the stirrer is raised to position 2.
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- the obtained dihydrate gypsum is shown in figure 20.
- Average particle size (D50) is 2.38 ⁇ m
- the shape ratio is 3.51
- the aspect ratio is 3.51 Width of the particle size distribution is 2.45
- a mixture (1:1 :1) of rotary kiln calcinated ⁇ -calcium sulphate hemihydrate, calcium sulphate dihydrate and calcium sulphate anhydrite is evenly added to the reactor with the operation speed of the stirrer being set to position 1.
- the total amount of hemihydrate, dihydrite and anhydrite added is 680 g. After the addition the operation speed of the stirrer is raised to position 2.
- the precipitated product is dispersed using a Diaf dissolver and
- Average particle size (D50) is 27.09 ⁇ m
- the shape ratio is 12.19
- the aspect ratio is 2.38 Width of the particle size distribution is 1.04
- a mixture (1 :1 :1 ) of rotary kiln calcinated ⁇ -calcium sulphate hemihydrate, calcium sulphate dihydrate and calcium sulphate anhydrite is evenly added to the reactor with the operation speed of the stirrer being set to position 1.
- the total amount of hemihydrate, dihydrite and anhydrite added is 1000 g. After the addition the operation speed of the stirrer is raised to position 2.
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size (D50) is 23.54 ⁇ m
- the shape ratio is 8.06
- the aspect ratio is 1.78
- Width of the particle size distribution is 1.40
- the reaction was carried out either at system pH or the pH was adjusted to the desired value by addition of 10 % NaOH or 10 % H 2 SO 4 .
- the amount of habit modifier chemical is calculated as per cent of the precipitated calcium sulphate dihydrate (%/DH).
- the raw material in all examples was ⁇ -hemihydrate obtained by fluidized bed flash heating.
- the dispersing agent in all examples was Fennodispo A41.
- the hemihydrate is added as a batch to the water containing the crystallization habit modifier and other possible chemicals.
- the slurry containing 57-60 % dry matter is stirred using a Heidolph- mixer (ca. 250 - 500 rpm).
- the reactor was of Hobart type N50CE, keeping the temperature of the reaction between 10-100 0 C.
- the hemihydrate and the chemicals are added batch wise to the aqueous liquid phase and a hemihydrate slurry with an initial solids of 57-80 w- % is obtained.
- Mixing speed is ca. 250 - 500 rpm.
- the reaction is carried out at system pH.
- a MLH 12 MAP type laboratory mixer The hemihydrate is added batch wise to the reactor and water with chemicals is added into the hemihydrate without mixing. Mixing (ca. 200 rpm) is then turned on and the starting solids content of the slurry is 57-80 w-%. The reaction is carried out at system pH. Analysis
- the pH and temperature of the reactor were monitored by Knick Portamess 911 pH-electrode.
- the morphology of the calcium sulphate dihydrate was studied by using FEI XL 30 FEG scanning electron microscope.
- the conversion of hemihydrate to dihydrate was analyzed using Mettier Toledo TGA/SDTA85
- TG 1/1100-thermogravimetric analyzer
- XRD Philips X'pert x-ray powder diffractometer
- Sedigraph 5100 particle sizer The samples were prepared in methanol. The shape ratio and aspect ratio was measured by examining at least ten particles found in the electron microscope micrographs.
- NABS Na-n-alkyl(C10-13)benzene sulfonate
- pH of the hemihydrate slurry is adjusted to 7-7.3 using 10 % NaOH-solution.
- the precipitated product is dispersed using a Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size is 0.57 ⁇ m
- the shape ratio is ca. 27.8
- the aspect ratio is ca. 3.46
- Width of the particle size distribution is 0.775
- pH of the hemihydrate slurry is adjusted to 7-7.3 using 10 % NaOH-solution.
- the precipitated product is dispersed using Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Average particle size is 0.838 ⁇ m
- Shape ratio is ca. 6.2
- pH of the hemihydrate slurry is adjusted to 7-7.3 using 10 % NaOH-solution.
- the precipitated product is dispersed using Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
- Shape ratio is ca. 6.3
- Width of the particle size distribution is 0.658
- Water - habit modifier mixture is added to hemihydrate and mixing is started and speed is gradually increased to 225 rpm. Reaction is run at system pH.
- the precipitated product is dispersed using MLH12 MAP laboratory mixer and Fennodispo A41 polyacrylate dispersant.
- Average particle size is 0.88 ⁇ m
- the width of the particle size distribution is 1.06
- the precipitated product is dispersed using Diaf dissolver and Fennodispo A41 polyacrylate dispersant.
Abstract
Description
Claims
Priority Applications (4)
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CA002676418A CA2676418A1 (en) | 2007-02-02 | 2008-02-01 | A process for producing gypsum |
EP08718492A EP2118013A2 (en) | 2007-02-02 | 2008-02-01 | A process for producing gypsum |
US12/525,149 US20100034727A1 (en) | 2007-02-02 | 2008-02-01 | Process for producing gypsum |
JP2009547719A JP2010517906A (en) | 2007-02-02 | 2008-02-01 | Gypsum manufacturing method |
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FI20070093A FI20070093A0 (en) | 2007-02-02 | 2007-02-02 | Plaster product and process for making the same |
FI20070093 | 2007-02-02 |
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PCT/FI2008/000022 WO2008092991A2 (en) | 2007-02-02 | 2008-02-01 | A process for producing gypsum |
PCT/FI2008/000021 WO2008092990A2 (en) | 2007-02-02 | 2008-02-01 | Gypsum product and process for its preparation |
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PCT/FI2008/000021 WO2008092990A2 (en) | 2007-02-02 | 2008-02-01 | Gypsum product and process for its preparation |
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US (2) | US20100034727A1 (en) |
EP (2) | EP2118013A2 (en) |
JP (2) | JP2010517905A (en) |
KR (2) | KR20090115747A (en) |
CN (2) | CN101622197A (en) |
CA (2) | CA2676418A1 (en) |
FI (1) | FI20070093A0 (en) |
RU (2) | RU2448906C2 (en) |
WO (2) | WO2008092991A2 (en) |
Cited By (4)
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WO2011098672A1 (en) | 2010-02-10 | 2011-08-18 | Kemira Oyj | Process for the preparation of a pigment -fibre composite |
WO2011141632A1 (en) | 2010-05-10 | 2011-11-17 | Kemira Oyj | Gypsum -fibre composite product |
WO2011141630A1 (en) | 2010-05-10 | 2011-11-17 | Kemira Oyj | Process for the preparation of gypsym |
WO2012062967A1 (en) | 2010-11-08 | 2012-05-18 | Kemira Oyj | Use of composition for improving inkjet printing properties and an inkjet recording sheet |
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FI20070093A0 (en) * | 2007-02-02 | 2007-02-02 | Kemira Oyj | Plaster product and process for making the same |
MX2011001116A (en) | 2008-07-31 | 2011-05-23 | Yoshino Gypsum Co | Process for continuous modification of dihydrate gypsum and modified dihydrate gypsum obtained by the process. |
EP2163590B1 (en) * | 2008-09-12 | 2011-07-06 | Rohm and Haas Company | Wood adhesives comprising protein and oxazoline polymer or resin |
TWI486510B (en) | 2009-01-26 | 2015-06-01 | Henry Co Llc | Mixtures and emulsions to reduce energy in gypsum wallboard manufacture |
US8748515B2 (en) | 2010-04-15 | 2014-06-10 | Henry Company Llc | Mixtures and emulsions for use in providing strength to gypsum compositions |
WO2012115688A1 (en) | 2011-02-24 | 2012-08-30 | Henry Company Llc | Aqueous wax emulsions having reduced solids content for use in gypsum compositions and building products |
GB2497574B (en) * | 2011-12-15 | 2019-10-02 | Saint Gobain Placo Sas | A method of forming a gypsum based product |
US8343273B1 (en) * | 2012-03-30 | 2013-01-01 | United States Gypsum Company | Method of modifying beta stucco using diethylene-triamine-pentaacetic acid |
CN102675919B (en) * | 2012-05-07 | 2013-12-18 | 长沙理工大学 | Preparation method for calcium sulfate whisker papermaking coating pigment |
DK2722368T3 (en) | 2012-10-16 | 2016-10-24 | Omya Int Ag | A method for the controlled chemical reaction of a solid filler material surface and additives to produce a surface treated filler material product |
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KR20160094940A (en) * | 2013-10-14 | 2016-08-10 | 써튼티드 집섬, 인크. | Struvite-k and syngenite composition for use in building materials |
CN110629279B (en) * | 2018-06-22 | 2020-12-22 | 北新集团建材股份有限公司 | Self-assembled lamellar anhydrous gypsum single crystal material and preparation method thereof |
CN110963729A (en) * | 2020-01-03 | 2020-04-07 | 龙蟒佰利联集团股份有限公司 | Method for preparing titanium dioxide byproduct gypsum and reducing standard thickening water consumption |
CN112390555A (en) * | 2020-11-11 | 2021-02-23 | 杭州归领医疗器械有限公司 | Alpha calcium sulfate hemihydrate and preparation method thereof |
EP4105178A1 (en) * | 2021-06-16 | 2022-12-21 | Saint-Gobain Placo | A process for the continuous preparation of alpha-calcium sulphate hemihydrate and an apparatus |
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- 2008-02-01 US US12/525,149 patent/US20100034727A1/en not_active Abandoned
- 2008-02-01 JP JP2009547719A patent/JP2010517906A/en active Pending
- 2008-02-01 RU RU2009130787/05A patent/RU2448906C2/en not_active IP Right Cessation
- 2008-02-01 CN CN200880003698A patent/CN101622197A/en active Pending
- 2008-02-01 WO PCT/FI2008/000022 patent/WO2008092991A2/en active Application Filing
- 2008-02-01 KR KR1020097018391A patent/KR20090115747A/en not_active Application Discontinuation
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- 2008-02-01 EP EP08718491A patent/EP2118012A2/en not_active Withdrawn
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011098672A1 (en) | 2010-02-10 | 2011-08-18 | Kemira Oyj | Process for the preparation of a pigment -fibre composite |
WO2011141632A1 (en) | 2010-05-10 | 2011-11-17 | Kemira Oyj | Gypsum -fibre composite product |
WO2011141630A1 (en) | 2010-05-10 | 2011-11-17 | Kemira Oyj | Process for the preparation of gypsym |
WO2012062967A1 (en) | 2010-11-08 | 2012-05-18 | Kemira Oyj | Use of composition for improving inkjet printing properties and an inkjet recording sheet |
Also Published As
Publication number | Publication date |
---|---|
WO2008092990A3 (en) | 2008-10-30 |
RU2448906C2 (en) | 2012-04-27 |
US20100062255A1 (en) | 2010-03-11 |
US20100034727A1 (en) | 2010-02-11 |
KR20090115747A (en) | 2009-11-05 |
WO2008092991A3 (en) | 2008-11-06 |
WO2008092990A2 (en) | 2008-08-07 |
KR20090115748A (en) | 2009-11-05 |
RU2009130790A (en) | 2011-03-10 |
EP2118012A2 (en) | 2009-11-18 |
RU2448049C2 (en) | 2012-04-20 |
EP2118013A2 (en) | 2009-11-18 |
CA2676578A1 (en) | 2008-08-07 |
RU2009130787A (en) | 2011-03-10 |
FI20070093A0 (en) | 2007-02-02 |
JP2010517905A (en) | 2010-05-27 |
CA2676418A1 (en) | 2008-08-07 |
CN101636350A (en) | 2010-01-27 |
CN101622197A (en) | 2010-01-06 |
JP2010517906A (en) | 2010-05-27 |
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