process to reduce black pitch in an aqueous medium generated in a paper or pulp manufacturing proces

专利摘要:
PROCESS TO REDUCE BLACK PEZ IN AN Aqueous MEDIUM GENERATED IN A PAPER OR PULP MANUFACTURING PROCESS, HYDROFOBIZED AND / OR HYDROPHOBIZED PRECIPITATED CALCIUM CARBONATE, USE OF THE SAME, AND PROPOSED COMPOSITION OF THIS SAME PROCESS to reduce black pitch in an aqueous medium generated in a paper or pulp making process, comprising the following steps: a) providing an aqueous medium comprising black pitch generated in a paper or pulp making process; b) providing a ground calcium carbonate or a precipitated calcium carbonate; c) providing a hydrophobizing agent selected from an aliphatic carboxylic acid having between 5 and 24 carbon atoms; d) contacting the ground calcium carbonate and / or precipitated calcium carbonate from step b) with the hydrophobizing agent from step c) to obtain a hydrophobized ground calcium carbonate and / or a hydrophobized precipitated calcium carbonate; and e) contacting the aqueous medium provided in step a) with the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate obtained in step d), for the use of a hydrophobized ground calcium carbonate (...).
公开号:BR112014000657B1
申请号:R112014000657-1
申请日:2012-07-10
公开日:2021-01-26
发明作者:Daniel Gantenbein；Joachim Schoelkopf；Patrick A. C. Gane
申请人:Omya International Ag；
IPC主号:

专利说明:

[0001] [0001] The present invention relates to a process for reducing pitch in an aqueous medium generated in a paper or pulp making process, using a hydrophobized ground calcium carbonate and / or a precipitated calcium carbonate hydrophobized to reduce the amount of black pitch in an aqueous medium, as well as hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate and a composite comprising hydrophobized ground calcium carbonate and / or precipitated calcium carbonate hydrophobized and black pitch.
[0002] [0002] In the papermaking industries, fibers from different sources and qualities are obtained through processing and refining, for example, by combinations of milling, heat and chemical treatment, of wood on fibers. During this pulping process, the natural resin contained within the wood is released into the production water circuit in the form of microscopic drops. This wood resin is often referred to as “black pitch”, and can settle on the surface of papermaking equipment which can cause time consuming cleaning of the equipment and result in costly machine downtime. In addition, these deposits occasionally appear as visible stains on the final paper product that vary from yellow to black, or it can lead to a rupture of the web that involves a loss of productivity and a reduction in paper quality.
[0003] [0003] The formation of black pitch can be described conceptually as developing through three main mechanisms. The first route of mechanism is the formation of a film of organic material, which can be transparent or translucent. Its thickness varies according to its concentration and the film needs a core to form an initial coalescence. This type of black pitch, as its formation mechanism suggests, is called veiled. The second type of black pitch is one that is able to coagulate and form globules from 0.1 to 1.0 μm in diameter and, therefore, is called globular pitch. The third commonly developed form of black pitch is a type of black pitch or agglomerated pitch, and is often seen in systems that have the biggest problems with depositing black pitch. The spheres formed are 1 to 120 μm in diameter. In the veiled or globular state, black pitch does not usually cause problems, but once clusters have been formed after the deposition of black pitch begins to occur. This deposition of black pitch can also be a problem in processes of recycled or secondary fibers, where contaminants, such as adhesives, inks, thermoreversible, latex and waxes agglomerate and form deposits in the papermaking equipment.
[0004] [0004] In the art, several attempts have been made to control the deposition of black pitch in papermaking processes. In this regard, a strategy involves the introduction of adsorption materials in the form of various minerals, such as talc, bentonite, or diatomaceous silica for the papermaking process, which will absorb black pitch in the form of small droplets.
[0005] [0005] For example, JP 2004292998 A refers to talc, which is used as the black pitch adsorbent. WO 03/085199 A2 refers to a control system consisting of a deposit of inorganic or organic coagulant and a material of microparticles, such as bentonite clay, crosslinked polymer, colloidal silica, polysilicate for pulp containing black pitch / sticky residue . US 2003/0096143 A1 describes a method of treating talc particles that will improve talc wettability and / or talc affinity for cellulosic fibers. JP 6065892 A refers to an adsorbent black pitch composed of magnesium-modified smectite clay mineral produced by modifying the surface layer of a smectite clay mineral with magnesium. FR. 2 900 410 and FR 2 900 411 refer to the treatment of minerals and / or talc with amphoteric polymers to be used in black pitch control. CA 2205277 refers to a method for minimizing black pitch, ink and sticky particles in particles to be deposited in the papermaking process, causing the retention of such particles in the fiber, comprising the steps of adding an effective amount of control talc. of black pitch, ink, and sticky residues for a fiber suspension in contact with the paper machine and associated parts and adding an effective amount of black pitch control bentonite, ink, and sticky residues to the suspension.
[0006] [0006] This strategy has the advantage that the black pitch is removed together with the final product and therefore cannot concentrate more on the water circuit of the paper machine. In particular, talc is widely accepted as a very effective control agent for black pitch deposits. The action of talc in the control of black pitch, however, is not exactly established. It is assumed that talc reduces the stickiness of black pitch materials or sticky residues so that they are less likely to form agglomerates or settle on papermaking equipment or create stains on the final paper product. In addition, the function of talc is to reduce the stickiness of materials that have already been deposited, so that even more accumulation of sticky materials on these surfaces is delayed. Hereby it is important to add enough talc so that the overall tackiness of the system surfaces is reduced.
[0007] [0007] A problem with talc, however, is that if enough talc is not used, it tends to be merely incorporated into the deposits and clusters of sticky materials. In addition, talc is known to lose some of its affinity for colloidal substances in neutral and alkaline papermaking processes.
[0008] [0008] Another strategy involves the colloidal stabilization of black pitch through the use of dispersants or surfactants. The application of this strategy leads to a concentration of droplets of black pitch in the water circuit of the paper machine. For example, EP 0 740 014 refers to a black pitch control agent that can comprise a candite clay (serpentine group), the particles of which are coated with a homo- or co-polymer comprising melamine formaldehyde. US 5,626,720 A describes a method for the control of black pitch in an aqueous system used in the manufacture of pulp or paper, comprising the addition to the system or to the pulp or papermaking system, of a soluble polymer in water derived from (a) an epihalohydrin, a diepoxide or a precursor of an epihalohydrin or diepoxide, (b) an alkyl amine having a functionality with respect to a 2-epihalohydrin and (c) an amine that has a functionality in which concerns an epihalohydrin greater than 2 and which has no carbonyl group. JP 11043895 A refers to the black pitch suppressor using a cationic compound that is prepared by reacting an alkylenediamine with an epihalohydrin. WO 98/05819 Al refers to a liquid composition for the control of black pitch deposition in the production of pulp and paper, comprising an aqueous solution of (1) a cationic guar polymer, and (2) isobutylene / anhydride copolymer maleic. EP 0 586 755 A1 describes a process for controlling the deposition of black pitch in a pulp or paper production process, in which it is incorporated into the composition comprising papermaking fibers up to 1.0% by weight, based on weight of dry fibers in the composition, of a cationic polyelectrolyte that is a poly (salt of diallyldi (hydrogen or lower alkyl) ammonium) having a numerical average molecular weight greater than 500,000. US 2011/0094695 Al describes a method for controlling the deposition of organic contaminants in papermaking and pulp systems using water-soluble aminoplast ether copolymers. EP 1 950 342 A1 refers to aqueous emulsions comprising dialkylamides and non-ionic surfactants. US 2004/0231816 Al describes a method for the control of black pitch and sticky residues, comprising the steps of adding hydrophobically modified hydroxyethyl cellulose (HMHEC) and cationic polymers to a cellulose fiber slurry (pulp) or to a paper process or a papermaking system and results in a higher degree of inhibition of organic deposition and retention of black pitch in the paper fiber, compared to the inhibition of individual ingredients. US 6,153,049 refers to the ethyleneamine compound (s), or mixtures thereof, which are used in amounts effective to reduce or inhibit the deposition of white pitch on papermaking equipment during processing for recycling coated paper . US 6,051,160 A refers to a liquid composition for controlling the deposition of black pitch in the production of pulp and paper, comprising an aqueous solution of (1) a cationic guar derivative, and (2) styrene and anhydride copolymer maleic. JP 2002212897 A refers to a black pitch problem inhibitor for papermaking comprising a polydialldimethylammonium salt having a molecular weight of 20,000 to 20,000 and an inorganic aluminum compound as active ingredients.
[0009] [0009] However, this strategy often causes problems because changes in temperature, pH or electrolyte concentrations can result in agglomeration with the consequent deposition of droplets of black pitch on the surface of machinery equipment and / or the appearance of stains on the final paper product.
[0010] [00010] Therefore, there is a continuing need for alternative materials, which provide a better performance than the existing adsorbent materials, and effectively reduce the black pitch in aqueous media generated in the paper or pulp manufacturing processes.
[0011] [00011] This and other objects are resolved by the object of the present invention. According to a first aspect of the present invention, a process for reducing pitch in an aqueous medium generated in a paper or pulp making process is provided, in which the process comprises the following steps:
[0012] [00012] a) to provide an aqueous medium comprising black pitch generated in a paper or pulp manufacturing process;
[0013] [00013] b) providing a ground calcium carbonate and / or a precipitated calcium carbonate;
[0014] [00014] c) providing a hydrophobizing agent selected from an aliphatic carboxylic acid having between 5 and 24 carbon atoms;
[0015] [00015] d) contacting the ground calcium carbonate and / or precipitated calcium carbonate from step b) with the hydrophobizing agent from step c) to obtain a hydrophobized ground calcium carbonate and / or a hydrophobized precipitated calcium carbonate ; and
[0016] [00016] e) contacting the aqueous medium provided in step a) with the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate obtained in step d).
[0017] [00017] The inventors have surprisingly found that the previous process according to the present invention leads to an aqueous medium containing an amount of black pitch being less than the amount of black pitch contained in a corresponding aqueous medium obtained by the same process but without contact with a hydrophobized ground calcium carbonate and / or a hydrophobized precipitated calcium carbonate (step e)). More precisely, the inventors have found that the amount of black pitch in an aqueous medium generated in a papermaking or pulping process can be reduced by contacting the aqueous medium with a defined hydrophobized ground calcium carbonate and / or calcium carbonate hydrophobized precipitate.
[0018] [00018] It should be understood that, for the purposes of the present invention, the following terms have the following meaning:
[0019] [00019] "Pez negro" in the sense of the present invention refers to the sticky materials that form insoluble deposits in the paper and pulp manufacturing processes. These sticky materials may come from the wood from which the paper is made. The pitch black components comprise dissolved and colloidal substances (DCS) and are characterized by four classes of lipophilic components, such as i) fats and fatty acids, ii) sterile esters and sterols, iii), and terpenoids iv) compound waxes of fatty alcohols and their esters. The chemical composition of black pitch depends on the fiber source, such as the tree variety, and the seasonal growth from which the sample is produced. These lipophilic pitch black components can be stabilized by the presence of lignosulphonates and polysaccharides. If recycled paper is used in papermaking processes, the term is often used as a more general term, including all sticky materials that are soluble in organic solvents, but are not soluble in water, and include, for example, ink or adhesive material present in the recycled paper. The material from the recycled fiber deposit has also been called “sticky waste”. However, for the purposes of this invention, the term “black pitch” includes not only naturally occurring pitch black particles derived from paper pulp, but also any synthetic or natural sticky materials derived from recycled fibers that form insoluble deposits in papermaking processes.
[0020] [00020] "Ground calcium carbonate" (GCC) in the sense of the present invention is a calcium carbonate obtained from natural sources, such as limestone, marble or chalk or dolomite, and processed through a treatment, such as grinding, sorting and / or fractionation by a wet and / or dry process, for example, by means of a cyclone or classifier.
[0021] [00021] "Precipitated calcium carbonate" (PCC) in the sense of the present invention is a synthesized material, generally obtained by precipitation following the reaction of carbon dioxide and lime in an aqueous medium or by precipitation from a source of calcium ions and water carbonate.
[0022] [00022] An "aqueous medium" in the sense of the present invention is a medium comprising liquid water, insoluble solids, such as fibers and black pitch components.
[0023] [00023] The term "aliphatic carboxylic acid" in the sense of the present invention refers to alicyclic or unsaturated, saturated, straight-chain, branched-chain, carbon and hydrogen compounds. Said organic compound further contains a carboxyl group placed at the end of the carbon skeleton.
[0024] [00024] The term "hydrophobized" ground calcium carbonate and / or "hydrophobized" precipitated calcium carbonate in the sense of the present invention refers to a ground hydrophobized calcium carbonate and / or precipitated calcium carbonate that has been processed through a step additional treatment in order to make the surface of the more hydrophobic calcium carbonate particles.
[0025] [00025] Another aspect of the present invention is directed to a hydrophobized ground calcium carbonate and / or a hydrophobized precipitated calcium carbonate in which between 10% and 19% of the specific surface area of the ground calcium carbonate and / or calcium carbonate precipitate is covered by a coating consisting of an aliphatic carboxylic acid having between 5 and 24 carbon atoms and the reaction products thereof. It is preferred that between 10% and 19% of the specific surface area of the ground calcium carbonate and / or precipitated calcium carbonate is covered by a coating consisting of stearic acid and the reaction products thereof. It is also preferred that between 13% and 17% of the specific surface area of the ground calcium carbonate and / or precipitated calcium carbonate is covered by a coating consisting of an aliphatic carboxylic acid having between 5 and 24 carbon atoms and the products reaction, preferably by a coating consisting of stearic acid and the reaction products thereof. It is also preferred that the source of ground calcium carbonate (GCC) is selected from marble, chalk, calcite, dolomite, limestone and mixtures thereof and / or precipitated calcium carbonate (PCC) is selected from one or more of the forms of aragonitic, characteristic and calcitic mineralogical crystals. It is also preferred that the ground calcium carbonate particles and / or the precipitated calcium carbonate particles have a d50 value of the weight average particle diameter of 0.1 to 50 μm, preferably from 0.1 to 25 pm, more preferably from 0.1 to 15 μm and more preferably from 0.5 to 5 μm, measured according to the sedimentation method. It is also preferable that the ground calcium carbonate particles and / or the precipitated calcium carbonate particles have a specific surface area of 0.5 m2 / g to 25 m2 / g, preferably 0.5 m2 / g to 15 m2 / g, and more preferably 1 m2 / g I, 1 m2 / g, measured using nitrogen and the BET method. It is further preferred that the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate is in the form of powder and / or granules or in the form of a slurry.
[0026] [00026] Another aspect of the present invention is directed to the use of hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate to reduce the amount of black pitch in an aqueous medium generated in a paper or pulp manufacturing process. Yet another aspect of the present invention is directed to a composition comprising hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate and black pitch.
[0027] [00027] According to a preferred embodiment of the process according to the present invention, the source of ground calcium carbonate (GCC) is selected from marble, chalk, calcite, dolomite, limestone and mixtures thereof and / or precipitated calcium carbonate (PCC) is selected from one or more of the crystalline aragonitic, vateritic and calcitic mineral forms.
[0028] [00028] According to another preferred embodiment of the process according to the present invention, the ground calcium carbonate and / or precipitated calcium carbonate is in the form of a powder or in the form of a slurry.
[0029] [00029] According to yet another preferred embodiment of the process according to the present invention, the ground calcium carbonate particles and / or the precipitated calcium carbonate particles have a d50 average weight particle diameter value of 0 , 1 to 50 μm, preferably from 0.1 to 25 μm, more preferably from 0.1 to 15 μm and more preferably from 0.5 to 5 μm, measured according to the sedimentation method.
[0030] [00030] According to a preferred embodiment, the ground calcium carbonate particles and / or the precipitated calcium carbonate particles have a specific surface area of 0.5 m2 / g to 25 m2 / g, preferably of 0.5 m2 / g to 15 m2 / g and more preferably 1 m2 / g to 11 m2 / g, measured using nitrogen and the BET method.
[0031] [00031] According to another preferred embodiment of the process according to the present invention, the hydrophobizing agent is selected from the group consisting of pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid , undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, henicosilic acid, behenic acid, tricosilic acid, lignoceric acid and mixtures thereof, preferably the hydrophobizing agent is selected from the group consisting of octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and mixtures thereof, and more preferably the hydrophobizing agent is selected from from the group consisting of myristic acid, palmitic acid, stearic acid and mixtures thereof.
[0032] [00032] According to yet another preferred embodiment, the hydrophobizing agent comprises a mixture of two aliphatic carboxylic acids having between 5 and 24 carbon atoms, with the proviso that an aliphatic carboxylic acid is stearic acid.
[0033] [00033] According to another preferred embodiment, the aliphatic carboxylic acid is stearic acid and the other is selected from the group consisting of octanoic acid, myristic acid, palmitic acid, arachidic acid, behenic acid and lignoceric acid.
[0034] [00034] According to a preferred embodiment of the process according to the present invention, step d) is carried out by mixing the ground calcium carbonate and / or precipitated calcium carbonate with the hydrophobizing agent.
[0035] [00035] According to another preferred embodiment of the process according to the present invention, step d) is carried out in which both the ground calcium carbonate and / or precipitated calcium carbonate from step b) and the hydrophobizing agent from step c) are supplied in the dry state or in a solvent.
[0036] [00036] According to yet another preferred embodiment of the process according to the present invention, step d) is carried out in which both the ground calcium carbonate and / or precipitated calcium carbonate from step b) and the hydrophobization of step c) is supplied in a solvent.
[0037] [00037] According to a preferred embodiment of the process according to the present invention, the contact of ground calcium carbonate and / or precipitated calcium carbonate with the hydrophobizing agent of step d) is carried out under elevated temperature conditions , such that the hydrophobizing agent is in a liquid or molten state. Preferably, the contact of step d) is carried out at a temperature of at least 50 ° C, preferably at least 75 ° C, more preferably between 50 ° C and 120 ° C and more preferably between 70 ° C and 100 ° C,
[0038] [00038] According to another preferred embodiment of the process according to the present invention, less than 20% of the specific surface area of the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate obtained in step d) is covered by a coating consisting of the hydrophobizing agent and reaction products thereof.
[0039] [00039] According to yet another preferred embodiment of the process according to the present invention, between 10% and 19% of the specific surface area of the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate obtained in step d ) is covered by a coating consisting of the hydrophobizing agent and reaction products thereof, preferably between 13% and 17% of the specific surface area.
[0040] [00040] According to a preferred embodiment of the process according to the present invention, the aqueous medium to be treated is brought into contact with 0.05 to 20% by weight, preferably with 0.5 to 10% by weight. weight and more preferably with 0.1 to 5% by weight of the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate, based on the total weight of the aqueous medium.
[0041] [00041] According to another preferred embodiment of the process according to the present invention, the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate obtained in step d) is used in the form of powder and / or in the form granules or in the form of a slurry.
[0042] [00042] According to yet another preferred embodiment of the process according to the present invention, the pH of the aqueous medium containing black pitch is adjusted to a value> 6, more preferably> 6.5, and even more preferably > 7 before the addition of the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate.
[0043] [00043] According to a preferred embodiment of the process according to the present invention, the aqueous medium containing black pitch is selected from the group consisting of mechanical pulp, for example, ground wood, TMP (thermo-mechanical pulp) or chemothermomechanical pulp (CTMP), as well as chemical pulps, for example, kraft pulp or sulfate pulp, or recycled pulp used in the papermaking process.
[0044] [00044] As stated above, the process of the invention for reducing black pitch in an aqueous medium generated in a paper or pulp manufacturing process comprises steps a), b), c), d) and e). In the following, it is referred in more detail of the present invention and, in particular, the preceding steps of the process of the invention to reduce black pitch in an aqueous medium generated in papermaking or a pulping process. Step a): Provide an aqueous medium comprising black pitch
[0045] [00045] According to step a) of the process of the present invention, an aqueous medium is provided comprising black pitch generated in a paper or pulp making process.
[0046] [00046] An aqueous medium containing black pitch is understood as a mechanical pulp, for example, ground wood, TMP (thermo-mechanical pulp) or chemothermomechanical pulp (CTMP), as well as chemical pulps, for example, kraft pulp or wood pulp. sulfate, or recycled pulp used in paper or pulp manufacturing processes.
[0047] [00047] "Mechanical pulp" within the meaning of the present invention is prepared by crushing logs and pulp wood chips into the respective fiber components, using mechanical energy. Black powder containing cellulose, which can be subjected to the process of the present invention particularly comes from wood pulp, which is the most common material used to make paper materials. “Ground wood pulp”, as used here, in general, originates from soft wood trees such as spruce, pine, spruce, larch and pine, but also some hard woods such as eucalyptus and is produced by grinding wood in relatively short fibers with grinding stones,
[0048] [00048] "Thermomechanical pulp", as used here, is produced in a thermomechanical process, in which wood chips or sawdust are softened by steam before entering a pressurized refiner.
[0049] [00049] "Quirnitermomecânica pulp", as used herein, is produced by treating wood chips with chemicals, such as sodium sulfite and water vapor and by subsequent mechanical treatment,
[0050] [00050] "Chemical pulp", as used herein, is produced by treating wood chips or sawdust with chemicals to release cellulose fibers by removing binding agents, such as lignin resins and gums. Sulphate or Kraft are two types of chemical pulp production, where Kraft is the predominant pulp production process in the production of chemical pulp.
[0051] [00051] "Recycled pulp", as used here, is derived from recycled paper and cardboard or waste paper.
[0052] [00052] Black pitch, which can be reduced according to the present invention, can be described as dissolved and colloidal substances (DCS) and comprises species such as fats and fatty acids, sterile esters and sterols, terpenes, and compound waxes of fatty alcohols and their esters. The chemical composition depends on the fiber source, such as the tree variety, and the seasonal growth from which the sample is produced.
[0053] [00053] With respect to recycled pulp, it should be noted that the term black pitch is also used to describe the sticky, hydrophobic and / or loaded surface, malleable organic materials found in recycled paper systems. These organic materials comprise a variety of different materials, such as adhesives, styrene - butadiene binders, latex, in general, rubber, vinyl acrylates, polyisoprene, polybutadiene, thermoreversible, etc.
[0054] [00054] Optionally, additives can be added to the sample of aqueous medium containing black pitch to be treated. These may include agents for pH adjustment, etc. Step b): Provide a ground calcium carbonate and / or precipitated calcium carbonate
[0055] [00055] According to step b) of the process of the present invention, a ground calcium carbonate and / or a precipitated calcium carbonate is provided.
[0056] [00056] Milled (or natural) calcium carbonate (GCC) is understood as a natural form of calcium carbonate, extracted from sedimentary rocks, such as limestone or chalk, or metamorphic marble rocks. Calcium carbonate is known to exist as three types of crystal polymorphs: calcite, aragonite and vaterite. Calcite, the most common crystalline polymorph, is considered to be the most stable crystalline form of calcium carbonate. Less common is aragonite, which has a discrete or clustered needle orthorhombic crystalline structure. Vaterita is the rarest polymorph of calcium carbonate and is generally unstable. Ground calcium carbonate is almost exclusively from the calcitic polymorph, which is said to be trigonal - rhombohedral and represents the most stable of the calcium carbonate polymorphs.
[0057] [00057] Preferably, the source of ground calcium carbonate is selected from the group comprising marble, chalk, calcite, dolomite, limestone and mixtures thereof. In a preferred embodiment, the source of ground calcium carbonate is calcite.
[0058] [00058] The term "source" of calcium carbonate in the sense of the present application refers to the naturally occurring mineral material from which calcium carbonate is obtained. The source of calcium carbonate may further comprise naturally occurring components, such as magnesium carbonate, aluminum silicate, etc.
[0059] [00059] Additionally or alternatively, a precipitated calcium carbonate (PCC) is provided. Calcium carbonate polymorphs of the PCC type often include, in addition to calcite, less stable polymorphs of the aragonitic type that have an orthorhombic acicular crystal shape, and the hexagonal vateritic type, which has an even lower stability than aragonite. The different forms of the PCC can be identified according to their characteristic peaks of powder X-ray diffraction (XRD). PCC synthesis most commonly occurs by a synthetic precipitation reaction, which includes a step of contacting carbon dioxide with a solution of calcium hydroxide, the latter being most often provided in the formation of an aqueous suspension of calcium oxide, also known as slaked lime, and the suspension of which is commonly known as lime milk. Depending on the reaction conditions, this PCC can appear in several forms, including both stable and unstable polymorphs. Indeed, PCC is often a thermodynamically unstable calcium carbonate material. When referred to in the context of the present invention, CCP will be understood as the synthetic calcium carbonate products obtained by carbonating a calcium hydroxide slurry, commonly referred to in the art as a lime slurry or lime milk when derived from particulate matter. calcium oxide finely divided into water.
[0060] [00060] Preferred synthetic calcium carbonate is precipitated calcium carbonate, comprising aragonitic, vateritic or calcified crystalline mineral forms or mixtures thereof.
[0061] [00061] In a preferred embodiment, a ground calcium carbonate is provided.
[0062] [00062] In an especially preferred embodiment, the ground calcium carbonate and / or precipitated calcium carbonate provided in step b) of the present process is not a surface-reacted ground calcium carbonate and / or precipitated calcium carbonate reacted in the surface. In particular, the ground calcium carbonate and / or precipitated calcium carbonate provided in step b), in the sense of the present invention, was not treated with an acid and carbon dioxide before step d) of the present process. In addition, it is preferable that the ground calcium carbonate and / or precipitated calcium carbonate have a weight average particle diameter d50 value of 0.1 to 50 μm, preferably from 0.1 to 25 μm, more preferably from 0.1 to 15 μm and more preferably 0.5 to 5 μm, measured according to the sedimentation method. For example, ground calcium carbonate particles and / or precipitated calcium carbonate particles have a weight average particle diameter d50 value of 1.5 μm.
[0063] [00063] The ground calcium carbonate particles and / or the precipitated calcium carbonate particles preferably have a specific surface area of 0.5 m2 / g to 25 m2 / g, preferably 0.5 m2 / g 15 m2 / g, and more preferably 1 m2 / g to 11 m2 / g, measured using nitrogen and the BET method. For example, ground calcium carbonate particles and / or precipitated calcium carbonate particles have a specific surface area of 3.5 m2 / g to 4 m2 / g. Alternatively, the ground calcium carbonate particles and / or the precipitated calcium carbonate particles have a specific surface area of 1.0 m2 / g to 1.5 m2 / g. Alternatively, the ground calcium carbonate particles and / or the precipitated calcium carbonate particles have a specific surface area of 10 m2 / g to 10.5 m2 / g.
[0064] [00064] In a preferred embodiment, the natural ground calcium carbonate particles and / or the precipitated calcium carbonate particles have a specific surface area in the range of 0.5 m2 / g to 25 m2 / g and a d50 value weight average particle diameter within the range of 0.1 to 50 μm. Most preferably, the specific surface area is within the range of 0.5 m2 / g to 15 m2 / g and the d50 weight average particle diameter value is within the range of 0.1 to 25 μm. Even more preferably, the specific surface area is within the range of 0.5 m2 / g to 15 m2 / g and the average weight particle diameter is within the range of 0.1 to 15 μm. Most preferably, the specific surface area is within the range of 1 m2 / g to 11 m2 / g and the d50 weight average particle diameter value is within the range of 0.5 to 5 μm. For example, ground calcium carbonate particles and / or precipitated calcium carbonate particles have a specific surface area in the range of 3.5 m2 / g to 4 m2 / g and a weight average particle diameter d50 value of 1 , 5 μm. Alternatively, the ground calcium carbonate particles and / or the precipitated calcium carbonate particles have a specific surface area within the range of 10 m2 / g to 10.5 m2 / g and a weight average particle diameter d50 value of 0 , 6 μm.
[0065] [00065] In an especially preferred embodiment, the ground calcium carbonate particles are provided with a specific surface area in the range of 3.5 m2 / g to 4 m2 / g and a d50 value of average weight particle diameter of 1.5 pm. In another particularly preferred embodiment, the ground calcium carbonate particles are provided with a specific surface area within the range of 10 m2 / g to 10.5 m2 / g and a d50 average weight particle diameter value of 0.6 μm.
[0066] [00066] In a preferred embodiment, the ground calcium carbonate and / or precipitated calcium carbonate is supplied in the form of a powder.
[0067] [00067] The term '' powder 'as used in the present invention, encompasses solid mineral powders of at least 90% by weight of inorganic mineral matter, based on the total weight of the powder, where the powder particles have a d50 value. weight average particle diameter of 50 μm or less, preferably less than 25 μm, and more preferably less than 15 μm, more preferably between 0.5 μm and 5.0 μm, measured according to sedimentation method.
[0068] [00068] Alternatively or in addition, the ground calcium carbonate and / or precipitated calcium carbonate is supplied in the form of a slurry.
[0069] [00069] The "slurry" within the meaning of the present invention is a suspension containing solids insoluble in water and water and optionally other additives. Suspensions usually contain large amounts of solids and are more viscous and generally of greater density than the liquid from which they are formed. It is accepted in the art that the general term "dispersion" inter alia encompasses "suspensions" as a specific type of dispersion.
[0070] [00070] In order to obtain particles of ground calcium carbonate and / or precipitated calcium carbonate of the respective dimensions, the ground calcium carbonate and / or precipitated calcium carbonate can be subjected to a grinding process, before treatment with a hydrophobizing agent according to step d) of the process of the present invention. The grinding step can be carried out with any conventional grinding device, such as a grinding mill known to the person skilled in the art.
[0071] [00071] Such a grinding step may require drying of the ground calcium carbonate and / or precipitated calcium carbonate, thereby obtaining the ground calcium carbonate and / or precipitated calcium carbonate in the form of a powder.
[0072] [00072] The term "dry" is understood to refer to particles of ground calcium carbonate and / or particles of precipitated calcium carbonate with a total surface moisture content of less than 0.5% by weight, preferably less than 0.2% by weight and more preferably less than 0.1% by weight, based on the total weight of the ground calcium carbonate particles and / or the precipitated calcium carbonate particles. Step c): Provide a hydrophobizing agent
[0073] [00073] According to step c) of the process of the present invention, a hydrophobizing agent selected from an aliphatic carboxylic acid having between 5 and 24 carbon atoms is provided.
[0074] [00074] Aliphatic carboxylic acid, within the meaning of the present invention can be selected from one or more of saturated, straight-chain, branched-chain, saturated, alicyclic and / or unsaturated carboxylic acids. Preferably, the aliphatic carboxylic acid is a monocarboxylic acid, that is, the aliphatic carboxylic acid is characterized in that a single carboxyl group is present. Said carboxyl group is placed at the end of the carbon skeleton.
[0075] [00075] In a preferred embodiment, the hydrophobizing agent is selected from unbranched saturated carboxylic acids, that is, the hydrophobizing agent is preferably selected from the group of carboxylic acids consisting of pentanoic acid, hexanoic acid , heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, hyenic acid, behenic acid, behenic acid , lignoceric acid and mixtures thereof.
[0076] [00076] In another preferred embodiment, the hydrophobizing agent is selected from the group consisting of octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and mixtures thereof. Preferably, the hydrophobizing agent is selected from the group consisting of myristic acid, palmitic acid, stearic acid and mixtures thereof.
[0077] [00077] In an especially preferred embodiment, the hydrophobizing agent is stearic acid.
[0078] [00078] In a preferred embodiment, the hydrophobizing agent comprises a mixture of at least two aliphatic carboxylic acids having between 5 and 24 carbon atoms.
[0079] [00079] Preferably, a mixture of two carboxylic acids with between 5 and 24 carbon atoms is provided, with the proviso that an aliphatic carboxylic acid is stearic acid.
[0080] [00080] In an even more preferred embodiment, the one aliphatic carboxylic acid is from an acid and the other is selected from the group consisting of octanoic acid, myristic acid, palmitic acid, arachidic acid, behenic acid and lignoceric acid.
[0081] [00081] If the hydrophobizing agent according to the present invention comprises a mixture of two aliphatic carboxylic acids having between 5 and 24 carbon atoms, the molar ratio of stearic acid and the second aliphatic carboxylic acid is 99: 1 to 1 ; 99, more preferably from 50: 1 to 1: 50, even more preferably from 25: 1 to 1: 25 and most preferably from 10: 1 to 1: 10. In an especially preferred embodiment of the present invention, the molar ratio of stearic acid and the second aliphatic carboxylic acid is 90: 1 to 1: 1, more preferably 90: 1 to 10: 1 and most preferably 90: 1 to 50: 1. In another form of preferred embodiment, the molar ratio of stearic acid and the second aliphatic carboxylic acid is 1: 1.
[0082] [00082] If the hydrophobizing agent according to the present invention comprises a mixture of two aliphatic carboxylic acids having between 5 and 24 carbon atoms, the hydrophobizing agent preferably comprises a mixture of stearic acid and myristic acid. In another preferred embodiment, the hydrophobizing agent comprises a mixture of stearic acid and palmitic acid. In yet another preferred embodiment, the hydrophobizing agent comprises a mixture of stearic acid and arachidic acid. In yet another preferred embodiment, the hydrophobizing agent comprises a mixture of stearic acid and behenic acid. In another preferred embodiment, the hydrophobizing agent comprises a mixture of stearic acid and lignoceric acid. In yet another preferred embodiment, the hydrophobizing agent comprises a mixture of stearic acid and octanoic acid.
[0083] [00083] The hydrophobizing agent is preferably supplied in the form of flakes of the respective aliphatic carboxylic acid. Additionally or alternatively, the hydrophobizing agent is supplied in a solvent, that is, the hydrophobizing agent is in a dissolved state. The '"dissolved state" in the sense of the present invention is defined as the state in which the hydrophobizing agent and the solvent form a homogeneous phase.
[0084] [00084] Preferably, the solvent is chosen from groups of alcohol, ketones, carboxyl esters, ethers, alkanes or aryl compounds. Solvents preferably have a melting point of between -90 ° C to 0 ° C. For example, ethanol, acetone or toluene can be chosen.
[0085] [00085] In a preferred embodiment, the hydrophobizing agent is supplied in a liquid or split state of the respective aliphatic carboxylic acid, for example, if the aliphatic carboxylic acid is a solid at room temperature, the hydrophobization agent is heated to a temperature such that the liquid form of aliphatic carboxylic acid is obtained.
[0086] [00086] Preferably, the hydrophobizing agent is heated to a temperature of at least 50 ° C, preferably at least 75 ° C, more preferably between 50 ° C and 120 ° C and most preferably between 70 ° C and 100 ° C. For example, the hydrophobizing agent is heated to a temperature of 80 ° C. Step d): Contact the ground calcium carbonate and / or precipitated calcium carbonate with the hydrophobizing agent
[0087] [00087] According to step d) of the process of the present invention, the ground calcium carbonate and / or precipitated calcium carbonate of step b) is brought into contact with the hydrophobizing agent of step c) to obtain a hydrophobized ground calcium carbonate and / or a hydrophobized precipitated calcium carbonate.
[0088] [00088] In the process of the present invention, contact of a precipitated calcium carbonate and / or precipitated calcium carbonate with the hydrophobizing agent is preferably carried out by mixing the precipitated calcium carbonate and / or precipitated calcium carbonate with the hydrophobizing agent. "Mixing" in the sense of the present invention can be carried out by any conventional mixing process known to the person skilled in the art. Preferably, the mixing is carried out under continuous stirring in order to uniformly contact the ground calcium carbonate particles and / or the precipitated calcium carbonate particles from step b) with the hydrophobizing agent from step c),
[0089] [00089] In a preferred embodiment, the contact of step d) is carried out in which both the ground calcium carbonate and / or precipitated calcium carbonate from step b) and the hydrophobizing agent from step c) is provided in a solvent. That is to say, both the ground calcium carbonate and / or precipitated calcium carbonate from step b) is supplied in the form of a slurry and the hydrophobizing agent from step c) is dissolved in a solvent. For example, if the ground calcium carbonate and / or precipitated calcium carbonate from step b) is supplied in the form of a slurry, the hydrophobizing agent from step c) is supplied in the form of flakes or the hydrophobizing agent from step c ) is supplied in liquid or molten state. Alternatively, if the hydrophobizing agent from step c) is supplied in a solvent, the ground calcium carbonate and / or precipitated calcium carbonate from step b) is supplied as a powder.
[0090] [00090] In a preferred embodiment, the ground calcium carbonate and / or precipitated calcium carbonate from step b) is supplied in the form of a slurry and the hydrophobizing agent from step c) is supplied in the molten state. In a preferred embodiment, the slurry of ground calcium carbonate and / or precipitated calcium carbonate is preheated.
[0091] [00091] In another preferred embodiment, the contact of step d) can be carried out by contacting both the ground calcium carbonate and / or precipitated calcium carbonate from step b) and the hydrophobizing agent of step c) (i) , in the dry state, or (ii) in a solvent.
[0092] [00092] For example, if the contact of step d) is carried out in a solvent, then the hydrophobizing agent of step c) must be in the dissolved state in the solvent, while the ground calcium carbonate and / or precipitated calcium carbonate from step b) is supplied as a slurry. In a preferred embodiment, the slurry of ground calcium carbonate and / or precipitated calcium carbonate is preheated.
[0093] [00093] Alternatively, the contact of step d) is made by contacting the ground calcium carbonate and / or precipitated calcium carbonate from step b) and the hydrophobizing agent of step c) in the dry state. For example, the contact in step d) is carried out in which the ground calcium carbonate and / or precipitated calcium carbonate from step b) is supplied in the form of a powder and the hydrophobizing agent in step c) is provided in the form of flakes or the hydrophobizing agent of step c) is supplied in liquid or molten state. In a preferred embodiment, the ground calcium carbonate and / or precipitated calcium carbonate from step b) is supplied in the form of a powder and the hydrophobizing agent from step c) is supplied in the molten state.
[0094] [00094] In a preferred embodiment of the present process, the contact of the ground calcium carbonate and / or precipitated calcium carbonate with the hydrophobizing agent is carried out at an elevated temperature, such that the hydrophobizing agent is in the liquid or molten state ,
[0095] [00095] The "liquid", or "fused" state in the sense of the present invention is defined as the state in which the hydrophobizing agent is completely liquid, in other words, it is completely fused. Considering that the phenomenon of fusion occurs at a constant temperature in the application of energy, a substance is classified as being melted from the moment after the melting when the temperature starts to rise, as observed in a curve plotting temperature versus energy input obtained by dynamic scanning calorimetry, DSC, ( DIN 51005: 1983-11).
[0096] [00096] Preferably, the ground calcium carbonate and / or precipitated calcium carbonate is contacted with the hydrophobizing agent at a temperature of at least 50 ° C, preferably at least 75 ° C, more preferably between 50 ° C and 120 ° C and more preferably between 70 ° C and 100 ° C. In a preferred embodiment, the ground calcium carbonate and / or precipitated calcium carbonate is brought into contact with the hydrophobizing agent at a temperature of 80 ° C. In an especially preferred embodiment, the ground calcium carbonate and / or precipitated calcium carbonate is brought into contact with the hydrophobizing agent at a constant temperature.
[0097] [00097] For example, if stearic acid is used as the hydrophobizing agent, the ground calcium carbonate and / or precipitated calcium carbonate is preferably brought into contact with the hydrophobization agent at a temperature of at least 70 ° C and more preferably at a temperature of 80 ° C. If octanoic acid or myristic acid is used as the hydrophobizing agent, the ground calcium carbonate and / or precipitated calcium carbonate is preferably brought into contact with the hydrophobizing agent at a temperature of at least 55 ° C and more preferably at a temperature of 65 ° C. If palmitic acid is used as the hydrophobizing agent, the ground calcium carbonate and / or precipitated calcium carbonate is preferably brought into contact with the hydrophobizing agent at a temperature of at least 65 ° C and more preferably at a temperature of at least 65 ° C. temperature of 75 ° C. If arachidic acid is used as the hydrophobizing agent, the ground calcium carbonate and / or precipitated calcium carbonate is preferably brought into contact with the hydrophobizing agent at a temperature of at least 75 ° C and more preferably at a temperature of 85˚C. If behenic acid is used as the hydrophobizing agent, the ground calcium carbonate and / or precipitated calcium carbonate is preferably brought into contact with the hydrophobizing agent at a temperature of at least 80 ° C and more preferably at a temperature of 90 ° C. If lignoceric acid is used as the hydrophobizing agent, the ground calcium carbonate and / or precipitated calcium carbonate is preferably brought into contact with the hydrophobizing agent at a temperature of at least 85 ° C and more preferably at a temperature of 95 ° C.
[0098] [00098] In a preferred embodiment, the hydrophobized ground calcium carbonate is prepared by contacting ground calcium carbonate with stearic acid at a temperature of 80 ° C.
[0099] [00099] In another preferred embodiment, the hydrophobized precipitated calcium carbonate is prepared by contacting precipitated calcium carbonate with stearic acid at a temperature of 80 ° C.
[0100] [000100] In another preferred embodiment, the ground calcium carbonate and / or precipitated calcium carbonate is preheated, that is, the powder or slurry of ground calcium carbonate and / or precipitated calcium carbonate is stirred for a sufficient period of time at an elevated temperature in order to ensure an even distribution of heat within the particles or in the slurry.
[0101] [000101] Preferably, the preheating of the ground calcium carbonate particles and / or the precipitated calcium carbonate particles is carried out under continuous stirring at an elevated temperature. In a preferred embodiment, the preheating of the ground calcium carbonate and / or precipitated calcium carbonate is carried out under continuous stirring at a constant temperature of at least 50 ° C, preferably at least 75 ° C, more than preferably between 50 ° C and 120 ° C and more preferably between 70 ° C and 100 ° C. In another preferred embodiment, the preheating of the ground calcium carbonate and / or precipitated calcium carbonate is carried out under continuous stirring at a constant temperature of 80 ° C
[0102] [000102] In the case that the ground calcium carbonate and / or precipitated calcium carbonate is preheated, the preheating is preferably carried out for a period of time of at least 30 s, more preferably of at least 90 s, and more preferably at least 120 s. In a preferred embodiment, preheating is carried out for a period of time between 1 min and 5 min, preferably between 1 min and 4 min and more preferably between 2 minutes and 3 minutes, for example, for 2 , 5 min. For example, the preheating of the ground calcium carbonate and / or precipitated calcium carbonate is carried out under continuous stirring, at a constant temperature of 80 ° C for a period of 2.5 minutes.
[0103] [000103] After the hydrolobizing agent has been added to the ground calcium carbonate and / or precipitated calcium carbonate, the combination of hydrophobizing agent and ground calcium carbonate and / or precipitated calcium carbonate is preferably brought into contact by mixing for a sufficient period of time at an elevated temperature, in order to ensure an even distribution of the hydrophobizing agent on the surface of the ground calcium carbonate particles and / or the precipitated calcium carbonate particles. In a preferred embodiment, the combination of hydrophobizing agent and ground calcium carbonate and / or precipitated calcium carbonate is mixed at a temperature of at least 50 ° C, preferably at least 75 ° C, more preferably at between 50 ° C and 120 ° C and more preferably between 70 ° C and 100 ° C. For example, the combination of hydrophobizing agent and ground calcium carbonate and / or precipitated calcium carbonate is mixed at a temperature of 80 ° C.
[0104] [000104] The mixture of the combination of hydrophobizing agent and ground calcium carbonate and / or calcium carbonate precipitated at an elevated temperature is preferably carried out for a period of time of at least 1 minute, more preferably of at least , 2 minutes and more preferably at least 4 min.
[0105] [000105] The mixture of the combination of hydrophobizing agent and ground calcium carbonate and / or calcium carbonate precipitated at an elevated temperature is carried out at one or more intervals. The term "an interval", as used herein, refers to a continuous mixing of the combination at elevated temperature for a defined period of time. The term "more intervals" refers to a discontinuous mixing of the combination at elevated temperature for a defined period of time, in which the mixing is stopped at least once.
[0106] [000106] In a preferred embodiment, the mixture of the combination of hydrophobizing agent and ground calcium carbonate and / or calcium carbonate precipitated at an elevated temperature is carried out at an interval. For example, the combination of hydrophobizing agent and ground calcium carbonate and / or precipitated calcium carbonate is continuously mixed for a period of time between 1 min and 10 min, preferably between 2 minutes and 8 minutes and more preferably between 4 and 6 minutes, for example, for 5 min. For example, the contact of the combination of hydrophobizing agent and ground calcium carbonate and / or precipitated calcium carbonate is carried out under continuous stirring, at a temperature of 80 ° C for a 5 min time period.
[0107] [000107] If the mixture of the combination of hydrophobizing agent and ground calcium carbonate and / or calcium carbonate precipitated at an elevated temperature is carried out in more than one time interval, the mixing is preferably carried out in two intervals . In a preferred embodiment, the mixture of the combination of hydrophobizing agent and ground calcium carbonate and / or calcium carbonate precipitated at an elevated temperature is carried out at two equal intervals, that is, the intervals are approximately equal in time. For example, the mixture of the combination of hydrophobizing agent and ground calcium carbonate and / or calcium carbonate precipitated at an elevated temperature is carried out at each interval that has an equal length of between 1 min and 5 min, preferably between 1 min. and 4 min and more preferably between 2 minutes and 3 minutes, for example, 2.5 min.
[0108] [000108] In another preferred embodiment, the mixture of the combination of hydrophobizing agent and calcium carbonate ground at elevated temperature is carried out in two unequal intervals, that is, the intervals are unequal in time. For example, the mixture of the combination of hydrophobizing agent and ground calcium carbonate and / or calcium carbonate precipitated at an elevated temperature is carried out at each interval that has a length of between 1 min and 5 min, preferably between 1 min and 4 min and more preferably between 2 minutes and 3 minutes.
[0109] [000109] The degree of hydrophobization (X) can be adjusted by the percentage of available specific surface area covered by a coating consisting of the hydrophobizing agent and the reaction products thereof. The degree of hydrophobization (X) can be calculated with the following equation. 1 : X = δmExp / (MFA * As * nA) [1]
[0110] [000110] where
[0111] [000111] X: degree of hydrophobization
[0112] [000112] δmExp: experimental mass loss in TGA between 150 ° C and 400 ° C
[0113] [000113] MFA: The molecular mass of carboxylic acid
[0114] [000114] AS: Specific surface area of ground calcium carbonate particles and / or precipitated calcium carbonate particles
[0115] [000115] nA: molecules of carboxylic acid necessary to cover 1 m2 of the particle of ground calcium carbonate and / or precipitated calcium carbonate. Usually 6 μmοl * m -2 for carboxylic acids.
[0116] [000116] Preferably, the degree of hydrophobization is adjusted to a value still allowing the formation of a suspension of the hydrophobized ground calcium carbonate particles and / or the hydrophobized precipitated calcium carbonate particles in the aqueous medium to be treated according to a reasonable degree of agitation. Flotation of hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate on the water surface even under a reasonable degree of agitation should be avoided.
[0117] [000117] The term "reaction products" in the sense of the present invention refers to products normally obtained by contacting a ground calcium carbonate and / or a precipitated calcium carbonate with a hydrophobizing agent selected from a carboxylic acid aliphatic having between 5 and 24 carbon atoms. Said reaction products are preferably formed between the applied hydrophobizing agent and molecules located on the surface of the ground calcium carbonate and / or precipitated calcium carbonate.
[0118] [000118] In particular, less than 20% of the specific surface area of the ground calcium carbonate particles and / or the precipitated calcium carbonate particles obtained in step d) is covered by a coating consisting of the hydrophobizing agent and in their reaction products. In a preferred embodiment, between 10% and 19% of the specific surface area of the ground calcium carbonate particles and / or the precipitated calcium carbonate particles obtained in step d) is covered by a coating consisting of the hydrophobization and its reaction products, preferably between 13% and 17% of the specific surface area. For example, 15% of the specific surface area of the ground calcium carbonate particles and / or the precipitated calcium carbonate particles is covered by a coating consisting of the hydrophobizing agent and the reaction products thereof. In an especially preferred embodiment, 15% of the specific surface area of the ground calcium carbonate particles and / or the precipitated calcium carbonate particles is covered by a coating consisting of stearic acid and its reaction products .
[0119] [000119] The hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate thus obtained can advantageously be implemented in the process of step e) of the present patent application for the reduction of black pitch in an aqueous medium generated in a manufacturing process of paper or pulp. Step e): Contact the aqueous medium with hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate
[0120] [000120] According to step e) of the process of the present invention, the aqueous medium containing black pitch provided in step a) is brought into contact with the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate obtained in step d ).
[0121] [000121] In the process of the present invention, hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate can be brought into contact with the aqueous medium containing black pitch by any conventional feeding medium known to the person skilled in the art.
[0122] [000122] Hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate can be added to the aqueous medium to be treated in any suitable form, for example, in the form of granules or a powder or in the form of a pie . Preferably, the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate is in the form of powder and / or granules. In a preferred embodiment, the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate is in powder form, before being brought into contact with the aqueous medium to be treated. Alternatively, the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate can be added to the aqueous medium to be purified as an aqueous suspension, for example, in the form of a slurry.
[0123] [000123] The "suspension" in the sense of the present invention comprises insoluble solids, i.e. hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate, and water and, optionally, other additives. Suspensions usually contain large amounts of solids and they are more viscous and generally of greater density than the liquid they are formed from. It is recognized in the art that the general term "dispersion" inter alia encompasses "suspensions" as a specific type of dispersion.
[0124] [000124] In a preferred process of the present invention, the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate is suspended in water before being brought into contact with the aqueous medium to be treated. Preferably, the suspension has a content of hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate within the range of 1% by weight to 80% by weight, more preferably 3% by weight to 60% by weight, and even more preferably from 5% by weight to 40% by weight, based on the weight of the suspension.
[0125] [000125] The hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate can be kept in suspension, optionally still stabilized by a dispersant. Conventional dispersants known to the person skilled in the art can be used. A preferred dispersant is polyacrylic acid.
[0126] [000126] Within the context of the present invention, it is also possible to provide an immobile phase, for example, in the form of a pie or layer, comprising hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate, the aqueous medium that goes through the aforementioned immobile phase. In an alternative embodiment, the aqueous medium to be purified is passed through a permeable filter, comprising hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate, and, optionally, talc and being able to retain by means of exclusion of sizes, impurities on the filter surface, the liquid is passed through, by gravity and / or under vacuum and / or under pressure. This process is called "surface filtration".
[0127] [000127] In another preferred technique known as depth filtration, a filter aid consisting of a number of tortuous passages of varying diameter and configuration retains impurities by molecular and / or electrical forces by adsorbing impurities on hydrophobized and ground calcium carbonate / or hydrophobized precipitated calcium carbonate which is present inside said passages, and / or by size exclusion, retaining the impurity particles, if they are too large to pass through the entire thickness of the filter layer.
[0128] [000128] Preferably, the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate is suspended in the aqueous medium containing black pitch, for example, by stirring. The amount of hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate depends on the type of black pitch or species of black pitch to be adsorbed. Preferably, an amount of 0.05 to 25% by weight, more preferably from 0.25 to 10% by weight and more preferably from 0.5 to 2% by weight, based on the weight of kiln-dried fibers. (100 ° C). is added. Alternatively, the amount of hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate to be used for the aqueous treatment is 0.05 to 20% by weight, more preferably from 0.5 to 10% by weight and still more preferably 0.1 to 5% by weight, based on the total weight of the aqueous medium to be treated.
[0129] [000129] In a preferred embodiment, the pH of the aqueous medium containing black pitch is adjusted to a value greater than 6.0, more preferably greater than 6.5 and even more preferably greater than 7.0 prior to the addition of hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate.
[0130] [000130] In a preferred embodiment, the talc is added to the aqueous medium containing black pitch in addition to the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate.
[0131] [000131] Talc, which are useful in the present invention are any commercially available talc, such as, for example, talc from Sotkamo (Finland), Three Springs (Australia), Haicheng (China), from the Alps (Germany), Florence (Italy) ), Tyrol (Austria), Shetland (Scotland), Transvaal (South Africa), the Appalachians, California, Vermont and Texas (USA).
[0132] [000132] Depending on the origin of the thick talc, there may be several impurities contained in it such as chlorite, dolomite and magnesite, amphibole, biotite, olivine, pyroxene, serpentine and quartz.
[0133] [000133] Preferred for use in the present invention are talc having a pure talc content of> 90% by weight, for example,> 95% by weight or> 97% by weight and up to> 100% by weight.
[0134] [000134] The talc particles used in the present invention can have a weight average particle diameter d50, measured according to the sedimentation method, in the range of 0.1 to 50 μm, for example, from 0.2 to 40 μm , preferably from 0.3 to 30 μm, more preferably from 0.4 to 20 μm, particularly from 0.5 to 10 μm, for example, from 1.4 or 7 μm.
[0135] [000135] The specific surface area of the talc can be between 3 and 100 m2 / g, preferably between 7 m2 / g and 80 m2 / g, more preferably between 9 m2 / g and 60 m2 / g, for example, 51 m2 / g, especially between 10 and 50 m2 / g, for example 30 m2 / g, measured using nitrogen and BET.
[0136] [000136] Talc can be used in powder form. Alternatively, it can be kept in suspension, optionally stabilized by a dispersant. Conventional dispersants known to the non-technical person can be used. The dispersant can be anionic or cationic.
[0137] [000137] Preferably, the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate and the talc are mixed, preferably in powder form, before being put in contact with the aqueous medium containing black pitch to be treated. Mixing can be achieved by any conventional means known to those skilled in the art.
[0138] [000138] Alternatively, hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate and talc can be added to the aqueous medium containing black pitch in separate steps.
[0139] [000139] Preferably, the talc is suspended together with the hydrophobized ground calcium carbonate and / or precipitated calcium carbonate hydrophobized in the aqueous medium containing black pitch, for example, by means of stirring. The amount of talc depends on the type of pitch black or contaminating species to be adsorbed. Preferably, an amount of 0.05 to 25% by weight, more preferably from 0.25 to 10% by weight and more preferably from 0.5 to 2% by weight, based on the weight of kiln-dried fibers. (100 ° C) is added. Alternatively, the amount of talc to be used for water treatment is 0.05 to 20% by weight, more preferably from 0.5 to 10% by weight and even more preferably 0.1 to 5% by weight , based on the total weight of the aqueous medium containing black pitch to be treated.
[0140] [000140] After the adsorption process is completed the hydrophobized ground calcium carbonate and / or precipitated hydrophobized calcium carbonate, black pitch, and talc optionally can be separated from the aqueous medium by conventional separation means known to the skilled person in the technique, such as sedimentation and filtration.
[0141] [000141] The aqueous medium obtained in step e) of the present process contains an amount of black pitch that is less than the amount of black pitch contained in an aqueous medium, thus obtained by the same process but without coming into contact with carbonate. hydrophobized ground calcium and / or hydrophobized precipitated calcium carbonate. In a preferred embodiment, the aqueous medium obtained in step e) of the present process contains an amount of colloidal black pitch that is less than the amount of black pitch contained in an aqueous medium, thus obtained by the same process but without contacting hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate.
[0142] [000142] Preferably, the aqueous medium obtained in step d) contains an amount of black pitch that is reduced by at least 20% by weight, more preferably by at least 50% by weight and more preferably by at least 75% by weight, compared to the aqueous medium containing black pitch provided in step a).
[0143] [000143] According to another aspect of the present invention, a compound is provided comprising hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate, black pitch, and optionally talc. As regards the definition of hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate. black pitch, taleo, and preferred embodiments of the same, reference is made to the indications provided above during the discussion of process steps a), b), c), d) and e).
[0144] [000144] The hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate of the present invention has been shown to readily adsorb black pitch species in the papermaking environment. In particular, the aqueous media obtained by the process of the present invention are characterized by the fact that they contain a considerably reduced amount of black pitch or species of black pitch such as colloidal black pitch. Papers made from these aqueous media are characterized by the fact that less stains are created in the final product. As another advantage, hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate reduces the tendency to form deposits on papermaking equipment.
[0145] [000145] In view of the very good results of hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate in reducing black pitch in an aqueous medium generated in the paper or pulp manufacturing process, as defined above, another aspect of the present invention is the use of them in an aqueous medium to reduce the amount of black pitch in it. According to another aspect of the present invention, a hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate is provided in which between 10% and 19% of the specific surface area of the ground calcium carbonate and / or precipitated calcium carbonate it is covered by a coating consisting of an aliphatic carboxylic acid having between 5 and 24 carbon atoms and the reaction products thereof. With regard to the definition of hydrophobized ground calcium carbonate and / or precipitated calcium carbonate and preferred embodiments thereof, reference is made to the indications provided above in the discussion of process steps b), c), d) and e ).
[0146] [000146] The following figures, examples and tests will illustrate the present invention, but are not intended to limit the invention to the exemplified embodiments. The following examples show the effectiveness of hydrophobized ground calcium carbonate and / or precipitated calcium carbonate to reduce black pitch in an aqueous medium generated in a paper or pulp making process according to the present invention. Description of figures:
[0147] [000147] Figure 1: illustrates the normal turbidity after the treatment of minerals from the TMP filtrate. 100% corresponds to 349 NTU.
[0148] [000148] Figure 2: illustrates the normalized chemical oxygen demand (COD), after the treatment of minerals from the TMP filtrate. 100% corresponds to 3644 mg of O2 / dm3.
[0149] [000149] Figure 3: illustrates the thermal gravimetric analysis of the mineral after adsorption. The fraction of weight lost was recorded between 200 and 1 000 ° C and is corrected with the weight loss of the corresponding mineral powder.
[0150] [000150] Figure 4: illustrates the normalized values of chemical oxygen demand (COD), gravimetry and turbidity of a TMP filtrate after an adsorption experiment with mineral powders against the coverage of the surface of mineral powders with stearic acid.
[0151] [000151] Figure 5: illustrates the thermal gravimetric analysis of the mineral phase, after the adsorption experiments against the surface coverage of mineral powders with stearic acid. The weight loss of the starting mineral powders (before the addition to the TMP filtrate) is subtracted (net loss).
[0152] [000152] Figure 6: illustrates the hydrophobicity of the mineral powders tested with their coverage range of stearic acid XSa, also including the talc sample of high surface area (USA). The larger the area on the right side of the line the greater the hydrophobia. The shaded area reflects the situation for talc.
[0153] [000153] Figure 7: illustrates the adsorption isotherm based on turbidity data for treated OMC-1, treated ground calcium carbonate (GCC) (15% surface coverage) and HSA-talc.
[0154] [000154] Figure 8: illustrates the content of petroleum ether extracts in the TMP 4 filtrate before and after adsorption. Extractives are divided into groups: fatty acids, resin acids, lignans, sterols, sterile esters, triglycerides and an unknown fraction.
[0155] [000155] Figure 9: illustrates the relative composition of the extractant groups of the TMP filtrate before and after adsorption.
[0156] [000156] Figure 10: illustrates the content of carbohydrate, soluble acid and insoluble acid in the TMP filtrates before and after adsorption. EXAMPLES A. Materials and methods 1. Pulp containing Pez Negro
[0157] [000157] Four separate tests are provided using unbleached TMP which consisted of 70% fir, the rest being spruce and a small part of the pine. These TMP samples were collected at a paper mill in Switzerland. The mill uses 100% fresh water in its TMP installation. The fresh wet pulp was made from the "accepted '' of the screen at a temperature of 90 ° C, before the bleaching step. The TMP was left overnight to cool to room temperature (RT). The TMP was filtered through a 2 μm pore size filter (circular filter paper 602 EH). The filtrate was checked in an optical microscope (Olympus AX - 70) for the absence of fibers and fibrils. The adsorption tests were performed immediately after filtration. The pH of the filtrates was generally between 6.0 and 7.0. It was adjusted with 0.1 M sodium hydroxide at a pH of 7.0 to 7.5. The pH titration of the electrophoretic mobility was done in order to quantify the colloidal stability of the wood resin drops. This was done in a Malvern ZetaSizer NS using 0.1 M hydrochloric acid and 0.1 M sodium hydroxide solution. In addition, the total electrochemical charge was determined by titrating the TMP filtrate with 0.0025 M poly - D ADM CA [oly - (alildimethyl ammonium chloride), using a current flow detector (SCD) from Miitek (PDC - 03). In addition, the ion content was quantified by ion chromatography on a Dionex DX 120 ion chromatograph.
[0158] [000158] After adjusting the pH, the TMP filtrate was distributed in glass vials each containing 200 cm3 of TMP filtrate. The desired amount and type of mineral was added either as a powder or dispersed in water. In most cases, the dosage was 10 g / dm3 of mineral and, in the case of isotherm, the mineral dosage was varied between 2.5 and 50.0 g / dm3. For all consecutive test samples the same amount of water was added (usually 18 cm3). The flasks were equipped with a magnetic stir bar, closed with an airtight lid and shaken on a magnetic stirrer for 2 hours. After this time, the magnetic stir bar was removed and the experimental mixtures centrifuged (Jouan C 312 by IG Instruments) for 15 minutes at 2600 g. Two phases were collected, an upper liquid phase and a phase containing lower mineral sediment. Centrifugation of the treated TMP filtrate showed no sediment. However, the sedimentation of the pure mineral dispersions showed, in some cases, air bubbles with trapped mineral particles.
[0159] [000159] The upper liquid phase was analyzed for turbidity using a NOVTIN 155 model MNT - S turbidity probe. Particle size was measured by photon correlation spectroscopy in a Malvern ZetaSizer NS without any additional treatment or dilution. Chemical oxygen demand (COD) was measured using a Lange CSB LCK 014, covering a range of 1000 to 10000 mg / dm3 with a LASA 1 / Plus vat. 100 cm3 of the liquid phase was dried in an aluminum beaker at 90 ° C for 12 hours and the residue was weighed to provide a result for the gravimetric residue.
[0160] [000160] The properties of the four TMP samples are summarized in Table 1 below. The ranges presented are based on the standard deviation of three independent experiments.
[0161] [000161] In a test configuration, the upper liquid phase was also analyzed for the content of wood extracts and the content of carbohydrates. The content of wood extracts was determined by extracting the TMP filtrate with petroleum ether (Saltsman et al. 1959, Estimation of tall oil in sulphate black liquor, Tappi, 42 (11), 873). GC-FID analysis to determine the group of wood extracts was performed according to the method of Örsa and Holmbom (Örsa et al, 1994, A convenient method for the determination of Wood extractives in papermaking process Waters and effluents; J Pulp. Pap. Sci., 20 (12), 361). The samples were hydrolyzed with sulfuric acid at 121 ° C in an autoclave according to SCAN - CM 71: 09. The solubilized monosaccharides were quantified using an ion chromatograph coupled to a pulsed amperometric detector (IC-PAD). The acid-insoluble residue was determined gravimetrically and the acid-soluble residue (lignin) was measured by UV spectrophotometry at 205 nm and quantified using an absorption coefficient of 110 dm3 / (gcm).
[0162] [000162] The phase containing the sedimented lower mineral was analyzed by thermo gravimetric analysis (TGA) at Mettler Toledo TGA / STDA 85. The samples were heated from 20 to 1000 ° C with a heating rate of 20 ° C / min. Weight loss was recorded between 200 and 1000 ° C. 2. Minerals
[0163] [000163] Several mineral powders were tested in this study. On the one hand, two types of Finnish talc were used as references. One is the commercially available talc, Finntalc P05 from Mondo Minerals and the other type of talc is derived from Finntalc P05 with subsequent comminution and delamination to generate Fineness, greater aspect ratio and increased specific surface area. (3 Finntalc P05 will be labeled as LSA (low surface area) talc and the laminated quality will be marked as high surface area talc (HSA-talc) talc. Specific surface areas and particle sizes of the various mineral powders are reported in Table 2 below.
[0164] [000164] The specific surface area, particle size (d50) and electrophoretic mobility are determined in 0.01 M NaCl solution as a medium for the suspension of the investigated minerals.
[0165] [000165] On the other hand, the various types of ground calcium carbonate have been tested. One is commercially available as Omyacarb 10 (OMC - 10), another as Omyacarb 1 (OMC - 1) and a third quality was produced from OMC - 1 by grinding it free of chemical to obtain a ground calcium carbonate high surface area (HSA - GCC) compared to OMC - 1 and OMC - 10, both of which are low - surface area ground calcium carbonates. The samples of ground calcium carbonate were supplied by Omya and originate from Avenza, Italy.
[0166] [000166] The specific surface area was measured by nitrogen adsorption on a Tristar Micromeritics based on the BET adsorption model according to ISO 9277 using nitrogen, followed by conditioning the sample by heating at 250 ° C for a period of 30 minutes. Before such measurements, the sample is filtered through a Buchner funnel, rinsed with deionized water and dried overnight at 90 to 100 ° C in an oven. Subsequently, the dry cake is completely ground in a mortar and the resulting powder placed in a humidity balance at 130 ° C to a constant weight.
[0167] [000167] The average diameter of spherical hydrodynamic particles by weight (d50) was measured under sedimentation with a Micromeritics Sedigraph 5120. The sedimentation method is an analysis of the sedimentation behavior in a gravimetric field. The method and apparatus are known to the person skilled in the art and are normally used to determine the size of filler grains and pigments. The measurement is performed in an aqueous solution of 0.1% by weight of Na4P2O7. The samples were dispersed using a high speed and supersonic stirrer. 3. Treatment with stearic acid
[0168] [000168] Stearic acid was of a high purity from Sigma Aldrich. The GCC powder was introduced into the MTT mixer (Type M3 / l, 5) which was heated to 80 ° C. The powder was stirred for a period of 2.5 minutes at 3000 rpm. Stearic acid was added to the preheated powder. The amount of stearic acid was calculated according to Equation 1, as defined above to obtain a product with a defined expansion factor. The combination was mixed again for 2.5 minutes at 3000 rpm. The mixer was opened, the powder manually mixed to ensure uniform distribution in the mixer and closed again for another 2.5 minutes of mixing time at 3000 rpm. Throughout the procedure, the temperature of the mixer was maintained at 80 ° C.
[0169] [000169] For the calculation of the surface coverage, Eq. 2 was used in which mSA is the mass of stearic acid (SA) that has to be added to treat lg of calcite with a fraction of surface coverage of stearic acid XSA. This is calculated with the specific surface area of the mineral σΜ obtained through nitrogen adsorption, the molecular weight of stearic acid Mwsa, the Avogadro NA constant and the surface area that is covered by a stearic acid molecule Asa which is 0 , 26 nm2.
[0170] [000170] Mixtures of water and ethanol were prepared in volume ratios of 100: 0, 90: 10, 80: 20, 70: 30, 60: 40, 50: 50, 40: 60, 30: 70, 20: 80, 10: 90 and 0: 100. 50 cm3 of each of the mixtures were placed in a 100 cm3 beaker. Approximately 0.5 to 1.0 g of the powder in question was carefully placed on top of the liquid. The wetting behavior was quantified by the time necessary for the powder to be moistened according to the following judgment:
[0171] [000171] 0 → immediate wetting of the powder (sinks within 30 seconds)
[0172] [000172] 0.25 → in 5 minutes all the powder is moistened
[0173] [000173] 0.5 → after 5 minutes, more than 50% of the powder is moistened
[0174] [000174] 0.75 → after 5 minutes, less than 25% of the powder is moistened
[0175] [000175] 1 → the powder is not moistened within 5 minutes B. Results 1. Surface coverage with stearic acid and black pitch adsorption capacity
[0176] [000176] To determine the degree of surface coverage with stearic acid and its black pitch adsorption capacity, several samples, that is, OMC - 10, OMC - 1 and HSA - GCC, were treated with 30% and 60% stearic acid (based on the surface area) and have been studied to track the influence of the degree of treatment of stearic acid and the surface area. For comparison, untreated ground calcium carbonate and LSA talc were also tested.
[0177] [000177] The TMP filtrate used was sample 1 (sampled in November 2009), which was analyzed as described above in Table 1. The electrophoretic mobility of the particles of the TMP 1 filtrate was found to be - 0.5 x 10- 8 m2 / (Vs). The EM remained constant within the relevant pH range 7 to 8.
[0178] [000178] It was found that the calcium carbonate products ground with 60% of the surface covered with stearic acid cannot be moistened by the TMP filtrate, resulting in foam and indefinite phases after centrifugation. Thus, no results were obtained for these products. Even with 30% of the samples treated on the surface, wetting was a problem. Interestingly, wetting improved during the experiments, thus suggesting the adsorption of surface active compounds from the TMP filtrate.
[0179] [000179] The turbidity of the TMP filtrate was clearly reduced as a result of mineral addition (cf. Figure 1). An increase in the specific surface area (SSA) improved the removal efficiency of colloidal material. In the case of ground calcium carbonate with a covered surface of 30%, the turbidity was reduced to 77% of the original 349 NTU with OMC - 10, up to 41% with OMC - 1 and up to 21% with HSA-GCC. Treatment with stearic acid increased the adsorption efficiency of colloidal black pitch. Both surface-treated and untreated surface-ground calcium carbonate products reduced turbidity even more efficiently than LSA talc, which provided only a 50% reduction. The observed effectiveness, however, can also be caused by a process of agglomeration of droplets of wood resin. The particle size before and after adsorption in liquid phase was slightly decreased.
[0180] [000180] As the size analysis in the liquid phase did not include agglomerates that settled during the centrifugation, it is also important to consider other analyzes, such as COD (cf, Figure 2) or TGA (cf. Figure 3). The COD analysis showed a slightly different trend. On the other hand, the values for the WTO - 10, as well as, both the HSA - GCC treated with fatty acid and the untreated HSA - CCG did not show significantly different values. The only difference was observed for OMC -1 so that, unlike turbidity, untreated natural calcium carbonate was seen to be more efficient. A possible explanation for these contrary observations may be that different species are adsorbed on treated and untreated ground carbonate powder. In the case of treated ground calcium carbonate powders, the adsorbable compounds contribute a lot to the turbidity and are, therefore, of a colloidal nature and, in the case of untreated ground carbonate powder, the adsorbable species are instead of dissolved nature , preferably contributing to COD instead of turbidity. In addition, talcum powder shows almost the same efficiency as ground calcium carbonate powders. The analysis of the mineral phase after the adsorption experiment confirmed the turbidity analysis again. The amount adsorbed on the mineral surface increased with the specific surface area. Partly hydrophobized ground calcium carbonate adsorbed slightly more material than native ground calcium carbonate, that is, untreated and unhydrophobized ground calcium carbonate. Both hydrophobized and native natural calcium carbonate adsorbed more material than talc.
[0181] [000181] In addition, it was found that the treatment with ground calcium carbonate clearly increased the pH between 7.0 and 7.8. In addition, conductivity increased from 926 μS / cm to 980 μS / cm. Very important in paper mill water circuits is the concentration of calcium ions. Calcium ions can be a major contributor to the agglomeration of black pitch. The concentration increased from 1.45 mM to 1.90 mM. The addition of talc had no effect on the concentration of calcium ions.
[0182] [000182] Thus, the treatment of the ground calcium carbonate surface with stearic acid is beneficial for adsorption of black pitch, but too much surface treatment with stearic acid can cause wetting problems. 2. The degree of surface coverage with stearic acid
[0183] [000183] We sought to optimize the amount of surface treatment with stearic acid between 0 and 30% of XSA surface coverage. OMC - 1 was used for this optimization. Once again, the TMP 1 filament was used. The electrophoretic mobility (EM) of the particles in the original TMP filtrate is - 0.8 x 10-8 m2 / (Vs) and no dramatic change in MS was observed within the relevant pH range (7 to 8) for this study .
[0184] [000184] During the test, it was observed that, with a top surface coverage with stearic acid, the immersion of the powder in the TMP filtrate was more difficult and, consequently, a foam layer was formed. This undefined phase clearly affected the measurement of turbidity (cf. Figure 4). Optimum turbidity reduction was achieved with a 15% surface coverage. From gravimetric measurements and COD one cannot distinguish between the different degrees of treatment. The thermogravimetric measurement (cf. Figure 5) also showed, the optimal dosage being about 15%. Finally, the semi - quantitative hydrophobicity test (cf. Figure 6) revealed that the sample with a surface coverage of about 15% had a hydrophobicity comparable to that of talc. 3. Isothermal adsorption
[0185] [000185] For further studies, the OMC - 1 product with a specific surface area of 3.9 m2 / g, and a surface coverage with stearic acid of about 15% was used.
[0186] [000186] In order to quantify the effect of treatment with stearic acid, the adsorption isotherms were recorded for an untreated OMC - 1 and a OMC - 1 with a surface coverage of about 15% in stearic acid. As a comparison, high surface area talc (HSA talc) was also included. The isotherm was recorded at 24 ° C. For this work, the TMP 3 filtrate was used providing an electrophoretic mobility of the particles of - 0.8 x 10-8 m2 / (Vs). Within the pH range of 7 to 8, MS changed only slightly. Analyzes of the TMP filtrate prior to the adsorption experiments are shown in Table 1 above.
[0187] [000187] An adsorption isotherm presents the loading of the equilibrium mineral phase (Tcq turb) versus the equilibrium concentration in the liquid phase (CEQ turb), as determined by the turbidity, that is, in this case, the turbidity was the parameter which contained information about the colloid equilibrium concentration. The species load causing “turbidity '''in the mineral was calculated with the following Equation 3, subtracting the equilibrium concentration in the liquid phase (CEQ turb) from the initial turbidity before adsorption (c0turb).
[0188] [000188] The Langmuir adsorption isotherm is given by Equation 4 below. Γ is the charge of adsorbed on the equilibrium (mineral) adsorbent. ceq represents the mass concentration of the adsorbed at equilibrium. The Langmuir constant (KL) indicated that the untreated ground calcium carbonate powder has a higher affinity (0.025 (NTU) -1) for the colloidal material than ο partially hydrophobized (0.013 (NTU) -1) (cf Table 3 ). the degree of HSA-talc had the lowest affinity (0.007 (NTU) -1) with the lowest Kl. The maximum load Γmax increases from the untreated OMC - 1 (25 NTU / g) to the treated OMC - 1 (37 NTU / g), as can be obtained from the following Table 3 and not Figure 7.
[0189] [000189] The adsorption isotene parameters are based on nonlinear least squares (NLLS) adjusted for the Langmuir equation (Eq. 4) performed by TableCurve ® 2D.
[0190] [000190] The differences between the adjusted parameters KL and ΓmaX are significant. As a result of the high specific surface area of the HSA talc (45 m2 / g) the maximum load of colloidal particles in the talc (212 NTU / g) was proportionally higher, in relation to the specific surface area of the OMC - 1, having only about 4 m2 / g. 4. Chemical analysis
[0191] [000191] For the chemical analysis and agglomeration tests, TMP 4 filtrate was collected that had an electrophoretic mobility of the particles at the original pH of 7.2 - 0.6 x 10-8 m2 / (Vs). Again, the EM was stable in the relevant pH range 7 to 8. The properties of the TMP 4 filtrate are listed in Table 1 above.
[0192] [000192] In order to cover the relevant regions of the adsorption isotherms, different amounts of mineral were added to the TMP filtrate. In the case of HSA - talc, a 0.4 g / dm3 talc dosage was provided to represent the region where the dissolved and colloidal substances are in excess and a 4 g / dm3 talc dosage to represent the region where the surface talc is available in excess. Because the specific surface area of the ground calcium carbonate powder is much less (cf. Table 2 above), the mineral addition has been increased to 8 and 40 g / dm3.
[0193] [000193] The content of petroleum ether extracts in the TMP 4 filtrate was 142 mg / dm3, as described in Table 4 below and in Figure 8. Table 4 summarizes the carbohydrate content, soluble acid content (lignin ) and acid insoluble content of the TMP 4 filtrate as described below.
[0194] [000194] The content of petroleum ether extractives in the TMP 4 filtrate is about 4% of the total material in the TMP filtrate. The main constituents of the extracts were triglycerides (44%, triacylglycerides) followed by resin acids (23%) and sterile esters (18%). Free fatty acids (6%), lignans (2%) and sterols (2%) were instead a smaller fraction. The remaining 5% are of unknown origin. As can be seen from figure 5, the addition of 0.4 g / dm3 of HSA - talc reduced the extract content of 120 mg / dm3 and the addition of 4 g / dm3 resulted in an extract content of 32 mg / dm3. The ratio of the extractive groups was in both cases unaffected (see Figure 9). The dosage of 8 g / dm3 of OMC - 1 reduced the content of extractives to 107 mg / dm3 and 40 g / dm3 to 28 mg / dm3, respectively. The ratio of the extractive groups was not affected by the low mineral dosage, but was strongly affected by the high mineral dosage. A similar picture was observed for hydrophobized OMC - 1 ("treated" OMC - 1). The lower mineral dosage led to a residual amount of extracts of 73 mg / dnT and the mineral dosage was higher than 23 mg / dm3, respectively .
[0195] [000195] In addition, the water-soluble part of the TMP filtrate was also analyzed. This analysis is divided into three fractions: i) carbohydrates, ii) soluble in acid (lignin) and iii) insoluble in acid (wood resin, salts, etc.). In this regard, it is used that only lignin in the acid-soluble fraction has its maximum absorption at 280 nm in UV spectroscopy. Thus, by measuring the UV spectrum, the soluble lignin contained in the acid-soluble fraction can be determined. The original TMP 4 filtrate contains 1052 mg / dm of carbohydrates, 527 mg / dm3 of acid-soluble (lignin) and 403 mg / dm3 of acid-insoluble materials (cf. Figure 10, Table 4). The carbohydrate content during treatment with talc was reduced only slightly (1034 mg / dm3) for the low dose of talc, but a large reduction in the carbohydrate content was observed for the high dose of talc (696 mg / dnT). The treated OMC-1 adsorbed only a very small fraction of the carbohydrates. 1024 mg / dnT for the low dosage and 952 mg / dnr for the high dosage of OMC - 1, respectively, were measured. The hydrophobized OMC - 1 also adsorbed a much smaller amount. For both mineral dosages, the carbohydrate content was about 980 mg / dm3. In the case of the acid-soluble fraction (lignin), the reduction after mineral treatment was <3%, except for HSA - talc with 4 g / dm3. In this case, the remaining lignin content was 396 mg / dm3. The acid-insoluble fraction, finally, varied proportionally to the reduction of extractives.
[0196] [000196] The pH of the samples increased as a result of the alkaline nature of the mineral powders. The pH for the lowest dosages of minerals was between 7.3 and 7.6 and for the highest dosages it was between 7.7 and 7.8.
[0197] [000197] The ratios calculated between dissolved and colloidal material in the TMP 4 filtrate before and after adsorption are given in Table 5 below.
[0198] [000198] The ratios of the amount of extractives and the amount of carbohydrates, in addition to acid-soluble lignin are calculated similar to Eq. 2. It can be seen in Table 5, that, in the case of high talc dosage (excess surface of talc), the dissolution ratio of colloidal substances is clearly shifted to the dissolved fraction (4.4). One possible explanation may be that the black pitch droplets adsorb together with their stabilizing carbohydrate layer (low mineral dosage), thus resulting in a constant ratio. After most of the colloidal fraction (high mineral dosage) has been removed, talc also adsorbs dissolved materials such as carbohydrates, lignins and dissolved wood resin constituents (resin acids, etc.), while ground calcium carbonate does not adsorb the material from the dissolved fraction. Also, the adsorption isotherms for colloidal substances in the form of the Langmuir constant showed these different adsorption preferences. Talc showed the lowest affinity for the colloidal fraction and the untreated GCC the highest affinity. Interestingly, the affinity of the hydrophobized GCC was intermediate.
[0199] [000199] Another observation is that, at high dosages of ground calcium carbonate, a substantial amount of resin acids was found in the aqueous phase. One possible explanation may be that the resin acids were dissolved during the adsorption experiment. It is well known that about 20 to 30 mg / dm3 are dissolved in the pH range 7 to 8. The pH after the adsorption experiments was measured to be 7.8 for the high dosages of mineral. Once the pH before the extraction procedure is acidified, the resin acids become insoluble again and will be measured as a part of the extracts.
[0200] [000200] Thus, the effective reduction of colloidal material, that is, black pitch from the sample is favored by hydrophobized ground calcium carbonate, while the uptake of fractions of dissolved carbohydrates is favored by talc.
[0201] [000201] Consequently, a specially hydrophobized ground calcium carbonate has been shown to readily adsorb black pitch species in the papermaking environment. Typical black pitch control talc seems to have enough area to handle all the likely components contained in a pulp. Hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate or combinations thereof with talc provides possibilities for treatments of the synergistic water system such as TMP black wood pitch.

权利要求:
Claims (24)
[0001]
Process to reduce black pitch in an aqueous medium generated in a paper or pulp manufacturing process, characterized by the fact that it comprises the following steps: a) providing an aqueous medium comprising black pitch generated in a paper or pulp manufacturing process; b) supply a ground calcium carbonate and / or a precipitated calcium carbonate, in which the source of ground calcium carbonate (GCC) is selected from marble, chalk, calcite, dolomite, limestone and mixtures thereof and / or precipitated calcium carbonate (PCC) is selected from one or more of the aragonitic, vateritic and calcitic crystalline mineral forms; c) providing a hydrophobizing agent selected from an aliphatic carboxylic acid having between 5 and 24 carbon atoms; d) contacting the ground calcium carbonate and / or precipitated calcium carbonate from step b) with the hydrophobizing agent of step c) to obtain a hydrophobized ground calcium carbonate and / or a hydrophobized precipitated calcium carbonate; and e) contacting the aqueous medium provided in step a) with the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate obtained in step d).
[0002]
Process according to claim 1, characterized in that the ground calcium carbonate and / or precipitated calcium carbonate is in the form of a powder or in the form of a slurry.
[0003]
Process according to any one of the preceding claims, characterized in that the particles of ground calcium carbonate and / or the particles of precipitated calcium carbonate have a d50 average weight particle diameter value of 0.1 to 50 μm, preferably from 0.1 to 25 μm, more preferably from 0.1 to 15 μm and more preferably from 0.5 to 5 μm, measured according to the sedimentation method.
[0004]
Process according to any one of the preceding claims, characterized in that the ground calcium carbonate particles and / or the precipitated calcium carbonate particles have a specific surface area of 0.5 m2 / g to 25 m2 / g, preferably 0.5 m2 / g to 15 m2 / g, and more preferably 1 m2 / g to 11 m2 / g, measured using nitrogen and the BET method.
[0005]
Process according to any one of the preceding claims, characterized in that the hydrophobizing agent is selected from the group consisting of pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, acid lauric, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, henicosilic acid, behenic acid, tricosilic acid, lignoceric acid and mixtures thereof, preferably the hydrophobizing agent is selected from the group consisting of octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and mixtures thereof, and more preferably the hydrophobizing agent is selected from the group consisting of myristic acid, palmitic acid, stearic acid and mixtures thereof.
[0006]
Process according to any one of the preceding claims, characterized in that the hydrophobizing agent comprises a mixture of two aliphatic carboxylic acids having between 5 and 24 carbon atoms, with the proviso that an aliphatic carboxylic acid is stearic acid .
[0007]
Process according to claim 6, characterized in that one aliphatic carboxylic acid is stearic acid and the other is selected from the group consisting of octanoic acid, myristic acid, palmitic acid, arachidic acid, behenic acid and lignoceric acid .
[0008]
Process according to any one of the preceding claims, characterized in that step d) is carried out by mixing the ground calcium carbonate and / or a precipitated calcium carbonate with the hydrophobizing agent.
[0009]
Process according to any one of the preceding claims, characterized in that step d) is carried out in which both the ground calcium carbonate and / or precipitated calcium carbonate from step b) and the hydrophobizing agent from step c) are carried out. supplied in a dry state or in a solvent.
[0010]
Process according to any one of claims 1 to 9, characterized in that step d) is carried out in which both the ground calcium carbonate and / or precipitated calcium carbonate from step b) and the hydrophobizing agent of step c ) is provided in a solvent.
[0011]
Process according to any one of the preceding claims, characterized by the fact that step d) is carried out under conditions of elevated temperature, such that the hydrophobizing agent is in liquid or molten state.
[0012]
Process according to claim 11, characterized in that step d) is carried out at a temperature of at least 50 ° C, preferably at least 75 ° C, more preferably between 50 ° C and 120 ° C and more preferably between 70 ° C and 100 ° C.
[0013]
Process according to any one of the preceding claims, characterized in that the aqueous medium to be treated is placed in contact with 0.05 to 20% by weight, preferably with 0.5 to 10% by weight and more preferably with 0.1 to 5% by weight of the hydrophobized ground calcium carbonate and / or the hydrophobized precipitated calcium carbonate, based on the total weight of the aqueous medium.
[0014]
Process according to any one of the preceding claims, characterized in that the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate obtained in step d) is used in the form of powder and / or in the form of granules or in the form of granules. fluid paste form.
[0015]
Process according to any one of the preceding claims, characterized in that the pH of the aqueous medium containing black pitch is adjusted to a value> 6, more preferably> 6.5, and even more preferably> 7 before adding the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate.
[0016]
Process according to any one of the preceding claims, characterized by the fact that the aqueous medium containing black pitch is selected from the group comprising mechanical pulp, for example, ground wood, TMP (thermo-mechanical pulp) or chemothermomechanical pulp ( CTMP), as well as chemical pulps, for example, kraft pulp or sulfate pulp, or recycled pulp used in the papermaking process.
[0017]
Hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate as defined in claim 1, characterized by the fact that between 10% and 19% of the specific surface area of the ground calcium carbonate and / or precipitated calcium carbonate is covered by a coating consisting of an aliphatic carboxylic acid having between 5 and 24 carbon atoms and the reaction products thereof, and in which the source of ground calcium carbonate (GCC) is selected from marble, chalk, calcite, dolomite, limestone and mixtures thereof and / or precipitated calcium carbonate (PCC) is selected from one or more of the aragonitic, vateritic and calcitic mineralogical forms.
[0018]
Hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate according to claim 17, characterized in that between 10% and 19% of the specific surface area of the ground calcium carbonate and / or precipitated calcium carbonate is covered by a coating consisting of stearic acid and the reaction products thereof.
[0019]
Hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate according to claim 17 or 18, characterized in that between 13% and 17% of the specific surface area of the ground calcium carbonate and / or precipitated calcium carbonate is covered by a coating consisting of an aliphatic carboxylic acid having between 5 and 24 carbon atoms and the reaction products thereof, preferably by a coating consisting of stearic acid and the reaction products thereof.
[0020]
Hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate according to any one of claims 17 to 19, characterized in that the ground calcium carbonate particles and / or the precipitated calcium carbonate particles have a d50 value the weight average particle diameter from 0.1 to 50 μm, preferably from 0.1 to 25 μm, more preferably from 0.1 to 15 μm and more preferably from 0.5 to 5 μm, measured according to the sedimentation method.
[0021]
Hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate according to any one of claims 17 to 20, characterized in that the ground calcium carbonate particles and / or the precipitated calcium carbonate particles have an area of specific surface of 0.5 m2 / g to 25 m2 / g, preferably from 0.5 m2 / g to 15 m2 / g, and more preferably from 1 m2 / g to 11 m2 / g, measured using nitrogen and the BET method.
[0022]
Hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate according to any one of claims 17 to 21, characterized in that the hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate is in the form of powder and / either in the form of granules or in the form of a slurry.
[0023]
Use of hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate, as defined in any one of claims 17 to 22, characterized by the fact that it is to reduce the amount of black pitch in an aqueous medium generated in a manufacturing process. paper or pulp.
[0024]
Composite, characterized in that it comprises hydrophobized ground calcium carbonate and / or hydrophobized precipitated calcium carbonate, as defined in any one of claims 17 to 22, and black pitch.

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BR112016023731B1|2022-02-08|USE OF A COLOIDAL PRECIPATED CALCIUM CARBONATE FOR ADSORPTION AND/OR REDUCTION OF THE QUANTITY OF AT LEAST ONE ORGANIC MATERIAL IN AN AQUEOUS MEDIUM

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Gantenbein et al.2012|The development of hydrophobised ground calcium carbonate particles for the effective adsorption of dissolved and colloidal substances | from thermo mechanical pulp | filtrates

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RU2574242C2|2016-02-10|Method for manufacturing calcium carbonate-containing material with processed surface and thereof application for removal of organic material from water medium

同族专利:

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公开号 | 公开日

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RU2556517C1|2015-07-10|

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HRP20140078T1|2014-04-11|

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DK2732092T3|2016-07-25|

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MY165112A|2018-02-28|

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SI2546410T1|2014-03-31|

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AU2012282543B2|2015-07-09|

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US20190256377A1|2019-08-22|

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EP2546410B1|2013-11-13|

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BR112014000657A2|2017-02-14|

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DK2546410T3|2014-02-03|

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CA2839848C|2018-05-01|

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HRP20160787T1|2016-08-12|

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TWI527953B|2016-04-01|

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CA2839848A1|2013-01-17|

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PT2732092T|2016-07-13|

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RS55049B1|2016-12-30|

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PL2546410T3|2014-05-30|

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CN103748282A|2014-04-23|

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EP2546410A1|2013-01-16|

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ES2446390T3|2014-03-07|

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CA2998017C|2020-06-30|

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US10322946B2|2019-06-18|

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CA2998017A1|2013-01-17|

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TWI479064B|2015-04-01|

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KR101529445B1|2015-06-16|

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AR088137A1|2014-05-14|

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CL2014000038A1|2014-08-22|

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WO2013007717A1|2013-01-17|

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CN103748282B|2016-04-13|

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CO6842014A2|2014-01-20|

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EP2732092A1|2014-05-21|

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ES2581483T3|2016-09-06|

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TW201311967A|2013-03-16|

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PL2732092T3|2016-10-31|

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EP2732092B1|2016-04-06|

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UY34192A|2013-02-28|

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RS53163B|2014-06-30|

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AU2012282543A1|2014-01-16|

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JP2014518340A|2014-07-28|

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US20150044127A1|2015-02-12|

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KR20140027510A|2014-03-06|

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AU2012282543A8|2014-02-06|

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SI2732092T1|2016-07-29|

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PT2546410E|2014-02-17|

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TW201447070A|2014-12-16|

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JP5882460B2|2016-03-09|

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-20| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2021-01-05| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-01-26| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/07/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP11173471.1A|EP2546410B1|2011-07-11|2011-07-11|Hydrophobised calcium carbonate particles|

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EP11173471.1|2011-07-11|

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US201161508730P| true| 2011-07-18|2011-07-18|

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US61/508730|2011-07-18|

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PCT/EP2012/063461|WO2013007717A1|2011-07-11|2012-07-10|Hydrophobised calcium carbonate particles|

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