EP0910697B1 - Method of reusing fillers and coating pigments used in paper, paperboard and cardboard manufacture - Google Patents
Method of reusing fillers and coating pigments used in paper, paperboard and cardboard manufacture Download PDFInfo
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- EP0910697B1 EP0910697B1 EP97915390A EP97915390A EP0910697B1 EP 0910697 B1 EP0910697 B1 EP 0910697B1 EP 97915390 A EP97915390 A EP 97915390A EP 97915390 A EP97915390 A EP 97915390A EP 0910697 B1 EP0910697 B1 EP 0910697B1
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- European Patent Office
- Prior art keywords
- fresh
- weight
- pigment
- fillers
- pigments
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/01—Waste products, e.g. sludge
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F1/00—Wet end of machines for making continuous webs of paper
- D21F1/66—Pulp catching, de-watering, or recovering; Re-use of pulp-water
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S162/00—Paper making and fiber liberation
- Y10S162/09—Uses for paper making sludge
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/928—Paper mill waste, e.g. white water, black liquor treated
Definitions
- the invention relates to a method for recycling fillers and coating pigments from paper, cardboard and cardboard manufacture from the Residual water sludge from the coating waste water, deinking plants, internal Sewage treatment plants or separators as well as the use of such Pigment slurries as a filler for the production of paper or as a pigment slurry for the production of a coating slip for the paper industry.
- the raw material i.e. H. Pulp, wood, straw pulp or harder pulp also waste paper pulp, fillers and pigments added, with which a closed surface is to be achieved to the Properties of the paper, especially the whiteness, the opacity and the Improve the printability of the paper.
- Natural printing papers contain up to 35% by weight of fillers, coated papers 25% to 50% by weight. The amount of filler depends very much Purpose of the paper. Heavily weighted papers have smaller ones Strengths and poorer sizing.
- the proportion of filler in the paper pulp is usually between 5 and 35% by weight. and consists of primary pigment or recirculated coating pigments, which from Remaining coating colors or deleted scrap can come.
- the Whiteness of the filler which is important for white-tinted papers, plays the grain size play an essential role as they greatly increase the filler yield and the physical Properties of the paper, particularly the porosity.
- the one in the paper remaining filler content is between 20 and 80% of that of the fiber suspension amount added.
- the yield depends on the type of filler as well on the material composition, the degree of grinding, the fixation of the filler particles through resin and aluminum sulfate, paper weight, paper machine speed, the type of water extraction and the fineness of the sieve.
- the following products have filler and coating pigment more important today: kaolin, calcium carbonate, artificial aluminum silicates and oxide hydrates, titanium dioxide, satin white, talc and calcium silicate.
- This waste product exists for example from 50% by weight cellulose, 25% by weight kaolin and 20% by weight Calcium carbonate, but also other small proportions of calcium sulfate, titanium dioxide, Talc or other solids can be present, these mixtures may contain more or less large fiber components.
- EP 0 492 121 B1 describes the previous processing of waste paper in such a way that that these waste materials as a wastewater / solid mixture from the Process are separated out, whereby a pure waste product arises that about Contains 50% solids and is stored in landfills.
- a pure waste product arises that about Contains 50% solids and is stored in landfills.
- DE 40 34 054 C1 describes a process for the recovery of raw materials the mechanical residual sewage sludge of the paper industry.
- the residual water sludge is removed after the Coarse dirt is first freed of the black particle content by centrifugation and then using fractional sieving in fibers, fillers, Pigments and agglomerates divided.
- the agglomerates are sheared treated and discarded while the fibers, fillers and pigments, if any can be reused after further treatment.
- EP 0 576 177 A1 describes a method for recycling and reuse of raw materials from the residual water sludges of the paper industry known, which is characterized in that the sludge suspension in one first step of a first screening / cleaning process at relative Subject to low consistency, then thickened, heated and by one Disperser is given before this sludge is used in papermaking again is used.
- the process is characterized by the setting of a defined solids content, the separation of the coarse dirt, the separation of the black particles, the fractionated fine screening of the good content and the recycling of the fiber content and the filler and pigment content in the raw material processing of the paper mill.
- the fillers and coating pigments are often in agglomerated form and have a low whiteness, which limits direct reuse in raw material processing, especially in the coating.
- the object of the invention is to provide a method for Recycling of paper raw materials, especially fillers and Coating pigments while saving energy costs and raw material costs as well as transportation costs.
- the above object is inventively achieved by a process for recycling fillers and coating pigments of paper, paperboard and cardboard from the residual water sludges from coating, deinking plants, internal water treatment plants or separators, to give the filler and coating pigment containing residual water sludges with fresh pigment in Form of powder, fresh filler in the form of powder, fresh pigment-containing and / or fresh filler-containing slurry are mixed and then the fresh pigment or the fresh filler is ground to the desired particle size distribution to form a pigment slurry.
- both the fillers and coating pigments are usually from the manufacturers with the desired whiteness and Grain size distribution provided.
- the essence of the present invention now consists in the delivery of the pigment in a kind of "basic grain", preferably as a solid or as a highly concentrated slurry, for example with a solids content of 70% by weight to 85% by weight or more, for example with an average grain diameter of 50% ⁇ 2 ⁇ m to 10 ⁇ m, especially 2 ⁇ m to 5 ⁇ m and grinding in aqueous phase on site in one Satellite grinding plant to the desired white and grain size.
- the destruction of agglomerates that the The running behavior of a coating color on the blade is disrupted by squeegee strips and the Adversely affecting the properties of the stroke is particularly preferred.
- the residual water sludge including the loaded particles acts as Dispersing aids and grinding aids for the fillers and pigments in the Grinding process, so that the usual amounts of dispersing agents and Grinding aids can be reduced according to the invention.
- the ratio of fillers and / or in the residual water sludge can Pigments to fibers vary in a wide range. Particularly preferred it is residual water sludge with a optionally enriched concentration of fillers and / or pigments to be used in the range from 2% by weight to 80% by weight, in particular 20% by weight is up to 60 wt .-% based on the solids content. So the fiber content on the one hand or the filler and / or pigment content on the other hand for example vary from 2 to 98% by weight or 98 to 2% by weight. Also go without saying Fiber-free residual water sludge can be used according to the invention.
- the waste water from the Production 0.5 to 5 wt .-%, in particular 2.5 wt .-% loss in one special fresh water requirements of 10 to 100 l / kg, in particular 20 l / kg.
- the consistency is preferably 0.02 to 0.5, in particular 0.125% by weight.
- a quantitative ratio of is particularly preferred Fiber content to filler and / or pigment content from 20 to 80 wt .-% or 80 to 20% by weight, in particular fibers to pigment in a ratio of 40 to 60% by weight of one Waste water from production.
- the pH of the residual water sludge used as wastewater from production can vary widely.
- the pH is particularly preferred in the range from 4.5 to 8.5, in particular in the neutral range around pH 7.
- Waste water from the coating plant which can be used according to the invention can, for example a solids content of 0.1 to 20 wt .-%, in particular 1 wt .-% before Precipitation and after precipitation from 1 to 30% by weight, in particular at 5% by weight exhibit.
- the pH can be, for example, in the range from 6.5 to 10, preferably 7.5 before precipitation and 6.0 to 10.0, preferably 7.0 after precipitation be.
- the ash content should in particular be in the range from 60 to 95% by weight, are in particular 90% by weight.
- a typical composition contains 1 up to 90% by weight, in particular 20% by weight of kaolin, 1 to 90% by weight, in particular 60 wt .-% calcium carbonate., 0.5 to 50 wt .-%, in particular 15 wt .-% talc and 0.1 to 40% by weight, in particular 5% by weight of other.
- a fresh pigment and / or fresh filler kaolin natural or precipitated calcium carbonates, artificial or natural aluminum silicates and oxide hydrates, titanium dioxide, satin white, Dolomite, mica, metal flakes, especially aluminum flakes, bentonite, rutile, magnesium hydroxide, Gypsum, layered silicates, talc, calcium silicate and other stones and earth.
- Fresh pigment or fresh filler is preferably used as powder, slurries containing fresh pigment and / or filler in the presence of the Residual water sludges and, if appropriate, customary grinding aids and / or Dispersing aids to form a slurry with a solids content of 30 to 85% by weight, in particular 40 to 75 wt .-% mixed and ground.
- the Pigment slurries from raw material suppliers are usually associated with the number of Weight percentages of particles smaller than 2 ⁇ m characterized, for example as Type: 95, 90, 75, 60, 50 etc.
- the paper manufacturer is therefore able to use pigments as a slurry according to the respective needs, even on site in one Manufacture satellite system.
- This allows a flexible and quick response to Quality and production requirements, for example the different ones Paper raw materials for the pulp, the pigments or slurries for the primer, Top coat and single coat or pigmentation alone, as well as mixing with other pigments. Above all, however, this is a considerable one Reduction in transport costs evident as not necessarily Ready-made slurries with a high water content are transported over long distances Need to become.
- Residual water sludges can be used, such as from EP 0 625 611 A1 are known, the amount required according to the invention significantly reduced compared to the prior art. For one, they contain Residual sewage sludge already contains a certain amount of the above-mentioned agents.
- the wetting, stabilizing, grinding and dispersing aids in usual Orders of magnitude to be used since the time span between production of the slurry and the use can be greatly reduced.
- Another advantage of lower amounts of auxiliary materials is the improved retention of the Pigments in paper production, because larger quantities have a negative influence on the retention.
- the method according to the invention is particularly suitable for working up Filling and fiber material existing sewage sludge or Partial suspension of pulp suspension from the waste paper processing paper industry and the reuse of paper scrap, especially in reprocessing of waste paper from the ash removal stage, where particularly great importance is attached to a sorted and size-specific separation of fillers and pigments is laid to recycle them here, and thereby to use the energy and value brought in.
- the coating pigment slurries obtainable with the aid of the present invention can be particularly advantageous in the paper industry, especially for manufacturing a coating color for the paper line or in the paper pulp.
- the use for the production of a coating pigment slurry is particularly preferred for offset paper.
- the inventive Slurries also for making a coating slip for lightweight, coated Papers, especially at high application speeds, as well as for Production of roll offset papers, especially for the production of light-weight, coated roll offset papers, the coating of cardboard and Special paper, such as labels, wallpaper, silicone base paper, self-copying, as well as the admixture for gravure papers.
- Coating pigment slurries obtainable according to the invention in particular usable in sheetfed offset, especially for sheetfed single-stroke, sheetfed double-stroke: Sheetfed pre-coat and sheetfed topcoat; - in web offset, especially for the LWC web offset single line, web offset double line: Web offset primer and web offset top coat; - in gravure, in particular for the LWC rotogravure single line, rotogravure double line: rotogravure pre-coat and rotogravure top coat; - in a box, especially for the double cardboard box: Cardboard primer and cardboard topcoat and for special papers, especially for Labels and flexible packaging.
- the process offers the possibility of the pigment slurries produced according to the invention without any loss of quality in the base paper and coating produced with it and especially to use the final qualities.
- Silos of any size for example from 50 to 1000 m 3, are used to hold and store dry fillers and pigments with a uniform or possibly different basic grain size, for example calcium carbonate. Dispensing of the filler and / or pigment powder with subsequent transport is ensured by metering devices, optionally to day silo container (s), optionally with cleaning devices. Dosing devices for the powder (s), possibly controlled by programmable logic controllers (PLC) with the electronically integrated recipes, determine gravimetrically and / or volumetrically the quantities of the components to be mixed, which are required for mixing with water, fresh water or circulating water from the paper mill.
- PLC programmable logic controllers
- a residual water sludge with a solids content of in particular 0.02 to 50% by weight is used, partially or completely, optionally with the addition of water at a higher concentration of the residual water sludge.
- containers for storing the residual water sludge, dosing devices for the residual water sludge, which determine the amount to be used gravimetrically or volumetrically are also required.
- containers are required to hold the mixture of fresh pigment or filler as a powder, slurry containing fresh pigment and / or filler and residual water sludge / water, optionally grinding aids and dispersion aids or other aids.
- Dispersing devices (dissolvers) or other agitators are required for dispersion and stability adjustment.
- Grinding the fresh pigments and / or fresh fillers as powder, slurry containing fresh pigment and / or filler with the residual water sludge can, according to the invention, continuously in conventional agitator ball mills, for example with a content of 700 to 5000 l or greater become. Grinding media, preferably grinding balls, are used in particular with a diameter of 1 to 4 mm.
- sieves are usually used, preferably curved sieves for separating contaminants (broken balls, separating agents, rust, etc.). Laser measuring instruments are used to determine and control the fineness of grinding during the grinding process and the computer-aided control of the agitator ball mill system. If necessary, further metering injection devices are required for further metering of dispersing and grinding aids on the agitator ball mill. After the pigment slurry has been discharged, sieves may be required for the further separation of pollutants with a size of more than 20 ⁇ m.
- the fresh pigment and / or filler material used in particular calcium carbonate powder used in dry form, has a whiteness according to DIN 53163 of more than 90%, in particular a whiteness of more than 95% in a fineness of d 97 25 25 ⁇ m, a fineness not greater d 97 ⁇ 100 ⁇ m, a purity of the carbonate ⁇ 98%, a proportion of SiO 2 ⁇ 1.0, in particular ⁇ 0.2%.
- Changing proportions of carbonate, for example, mixed with residual water sludge are ground to a slurry that has a solids content, which can be set to a usable coating color, for example. If necessary, the solids content can also be set higher if the pigment slurry should be stored longer.
- the delicacy of the slurry is particular by the dwell time and / or the energy consumption during the Production determined in the agitator ball mill.
- the whiteness of the pigment slurry results, among other things, from the mixing ratio Fresh pigment to residual water sludge and especially the one used Fresh pigment type.
- composition of the residual water sludge is shown in Table 1 below: MgO % 2.15 Al 2 O 3 % 24.38 SiO 2 % 29.84 P 2 O 5 % 0.81 CaO % 27.26 TiO 2 % 0.20 V 2 O 5 % ⁇ 0.01 Cr 2 O 3 % 0.01 MnO % 0.01 Na 2 O % 0.29 K 2 O % 0.82 Fe 2 O 3 % 0.54 SO 4th % 0.14 Cl % 0.01 NiO % ⁇ 0.01 CuO % 0.02 ZnO % 0.01 Ga 2 O 3 % ⁇ 0.01 SrO % 0.02 ZrO 2 % 0.01 PbO % 0.02 BaO % 0.06 Loss on ignition % 13.40 total % 100.00
- a sewage sludge with the composition shown in Table 1 was dried; the fineness and the color value measured.
- the water content of the sewage sludge was 19.5%.
- the pH was in measured in a 10% solution and was 6.8. Part of the dried Sewage sludge was heated at 450 ° C for 2 hours.
- the loss on ignition (organic Shares) was 13.4%.
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Abstract
Description
Gegenstand der Erfindung ist ein Verfahren zur Wiederverwertung von Füllstoffen und Streichpigmenten der Papier-, Pappe- und Kartonherstellung aus den Restwasserschlämmen der Streichereiabwässer, Deinkinganlagen, innerbetrieblichen Kläranlagen oder Abscheidevorrichtungen sowie die Verwendung so anfallender Pigment-Slurries als Füllstoff zur Herstellung von Papier oder als Pigment-Slurry zur Herstellung einer Streichmasse für die Papierindustrie.The invention relates to a method for recycling fillers and coating pigments from paper, cardboard and cardboard manufacture from the Residual water sludge from the coating waste water, deinking plants, internal Sewage treatment plants or separators as well as the use of such Pigment slurries as a filler for the production of paper or as a pigment slurry for the production of a coating slip for the paper industry.
Bei der Herstellung von Papier werden dem Rohstoff, d. h. Zellstoff, Holz, Strohzellstoff oder Hardernhalbstoff auch Altpapierhalbstoff, Füllstoffe und Pigmente zugesetzt, mit denen eine geschlossene Oberfläche erzielt werden soll, um die Eigenschaften des Papiers, insbesondere den Weißgrad, die Opazität und die Bedruckbarkeit des Papiers zu verbessern.In the manufacture of paper, the raw material, i.e. H. Pulp, wood, straw pulp or harder pulp also waste paper pulp, fillers and pigments added, with which a closed surface is to be achieved to the Properties of the paper, especially the whiteness, the opacity and the Improve the printability of the paper.
Fast alle Papiere werden mit Füllstoffen versetzt, die besonders Druck- und Schreibpapieren eine gleichmäßige Formation, bessere Weiche, Weiße und Griff geben. Diese meist "Asche" genannten Füllstoffe, da sie bei der Verbrennunganalyse als Asche zurückbleiben, werden entweder der Fasersuspension zugegeben oder beim Streichen aufgetragen.Almost all papers are filled with fillers that are particularly printing and Writing papers have an even formation, better softness, whiteness and grip give. These mostly called "ashes" fillers because they are used in combustion analysis remaining as ashes are either added to the fiber suspension or applied when painting.
Naturdruckpapiere (ungestrichene Papiere) enthalten bis zu 35 Gew. -% Füllstoffe, gestrichene Papiere 25 Gew-% bis 50 Gew.-%. Die Füllstoffmenge hängt sehr vom Verwendungszweck des Papiers ab. Stark beschwerte Papiere besitzen geringere Festigkeiten und schlechteres Leimungsvermögen.Natural printing papers (uncoated papers) contain up to 35% by weight of fillers, coated papers 25% to 50% by weight. The amount of filler depends very much Purpose of the paper. Heavily weighted papers have smaller ones Strengths and poorer sizing.
Der Füllstoffanteil in der Papiermasse liegt üblicherweise zwischen 5 bis 35 Gew.-% und besteht aus Primärpigment oder aus rezirkulierten Streichpigmenten, die von Reststreichfarben oder gestrichenem Ausschuß stammen können. Neben der Weiße des Füllstoffs, der für weiß-getönte Papiere wichtig ist, spielt die Korngröße eine wesentliche Rolle, da sie die Füllstoffausbeute stark und die physikalischen Eigenschaften des Papiers, insbesondere die Porosität beieinflußt. Der im Papier verbleibende Füllstoffanteil beträgt zwischen 20 und 80 % der der Fasersuspension zugesetzten Menge. Die Ausbeute hängt sowohl von der Füllstoffart als auch von der Stoffzusammensetzung, dem Mahlgrad, der Fixierung der Füllstoffteilchen durch Harz und Aluminiumsulfat, dem Papiergewicht, der Papiermaschinengeschwindigkeit, der Art des Wasserentzuges und der Feinheit des Siebes ab.The proportion of filler in the paper pulp is usually between 5 and 35% by weight. and consists of primary pigment or recirculated coating pigments, which from Remaining coating colors or deleted scrap can come. In addition to the Whiteness of the filler, which is important for white-tinted papers, plays the grain size play an essential role as they greatly increase the filler yield and the physical Properties of the paper, particularly the porosity. The one in the paper remaining filler content is between 20 and 80% of that of the fiber suspension amount added. The yield depends on the type of filler as well on the material composition, the degree of grinding, the fixation of the filler particles through resin and aluminum sulfate, paper weight, paper machine speed, the type of water extraction and the fineness of the sieve.
Entsprechend dem Verbrauch haben folgende Produkte als Füllstoff und Streichpigment heute größere Bedeutung: Kaolin, Calciumcarbonat, künstliche Aluminiumsilikate und -oxidhydrate, Titandioxid, Satin-Weiß, Talkum und Calciumsilicat.According to consumption, the following products have filler and coating pigment more important today: kaolin, calcium carbonate, artificial aluminum silicates and oxide hydrates, titanium dioxide, satin white, talc and calcium silicate.
Bei der Verwertung von Altpapier fallen die Füllstoffe und Pigmente als Abfallprodukt insbesondere in Deinkinganlagen an. Dieses Abfallprodukt besteht beispielsweise aus 50 Gew.-% Zellulose, 25 Gew.-% Kaolin und 20 Gew.-% Calciumcarbonat, wobei aber auch weitere geringe Anteile Calciumsulfat, Titandioxid, Talkum oder andere Feststoffe vorliegen können, wobei diese Gemische mehr oder weniger große Faseranteile enthalten können.When recycling waste paper, the fillers and pigments fall into waste especially in deinking facilities. This waste product exists for example from 50% by weight cellulose, 25% by weight kaolin and 20% by weight Calcium carbonate, but also other small proportions of calcium sulfate, titanium dioxide, Talc or other solids can be present, these mixtures may contain more or less large fiber components.
In EP 0 492 121 B1 wird die bisherige Aufbereitung von Altpapier derart beschrieben, daß diese Abfallstoffe als ein Abwasser- Feststoffgemisch aus dem Prozeß ausgesondert werden, wobei ein reines Abfallprodukt entsteht, daß etwa 50 % Feststoffanteile enthält und auf Deponien gelagert wird. Hier wird vorgeschlagen, das schlammartige Wasser-Feststoffgemisch intensiv zu mischen und dann anschließend dieses Gemisch aus Wasser und Feststoff grob, fein beziehungsweise feinst zu zerkleinern und erst dann die Weiterverwendung unter Zugabe entsprechender Zuschläge durchzuführen. Es wird der Einsatz dieses Materials aus Ausgangsstoff für Farbstoffe, Kleber, Füllstoffe und hydraulische Bindemittel vorgeschlagen.EP 0 492 121 B1 describes the previous processing of waste paper in such a way that that these waste materials as a wastewater / solid mixture from the Process are separated out, whereby a pure waste product arises that about Contains 50% solids and is stored in landfills. Here it is suggested to mix the sludge-like water-solid mixture intensively and then this mixture of water and solid coarse, fine or finely shredded and only then reused under Add appropriate supplements. It will use this Materials from raw material for dyes, adhesives, fillers and hydraulic Binder proposed.
In DE 40 34 054 C1 wird ein Verfahren zur Rückgewinnung von Rohstoffen aus dem mechanischen Restabwasserschlamm der Papierindustrie vorgeschlagen. Bei diesem Verfahren wird der Restwasserschlamm nach Abscheidung des Grobschmutzes zunächst mittels Zentrifugieren vom Schwarzpartikelgehalt befreit und daran anschließend mittels fraktioniertem Sieben in Fasern, Füllstoffe, Pigmente und Agglomerate aufgeteilt. Die Agglomerate werden mittels Scherung behandelt und verworfen, während die Fasern, Füllstoffe und Pigmente gegebenenfalls nach weiterer Behandlung einem gezielten Wiedereinsatz zugeführt werden.DE 40 34 054 C1 describes a process for the recovery of raw materials the mechanical residual sewage sludge of the paper industry. In this process, the residual water sludge is removed after the Coarse dirt is first freed of the black particle content by centrifugation and then using fractional sieving in fibers, fillers, Pigments and agglomerates divided. The agglomerates are sheared treated and discarded while the fibers, fillers and pigments, if any can be reused after further treatment.
Aus EP 0 576 177 A1 ist ein Verfahren zur Wiederverwertung und Wiederverwendung von Rohmaterialien aus den Restwasserschlämmen der Papierindustrie bekannt, das dadurch gekennzeichnet ist, daß die Schlammsuspension in einem ersten Verfahrensschritt einem ersten Sieb-/Reinigungsverfahren bei relativ niedriger Konsistenz unterworfen, anschließend eingedickt, erhitzt und durch einen Dispergierer gegeben wird, bevor dieser Schlamm in der Papierherstellung wieder eingesetzt wird.EP 0 576 177 A1 describes a method for recycling and reuse of raw materials from the residual water sludges of the paper industry known, which is characterized in that the sludge suspension in one first step of a first screening / cleaning process at relative Subject to low consistency, then thickened, heated and by one Disperser is given before this sludge is used in papermaking again is used.
In EP 0 554 285 B1 wird berichtet, daß alle Rückgewinnungsverfahren auf die Entstoffung an sich wenig verschmutzter Kreisläufe gerichtet sind, da der Wiedereinsatz des aus Faser- und Füllstoff bestehenden sogenannten Fang- oder Dickstoffes in den Papierherstellungsprozeß ein höherer Schmutzanteil verbietet. Demgemäß wird ein Verfahren beschrieben, die im Restabwasserschlamm der mechanischen Kläranlage enthaltenen brauchbaren Fasern und Füllstoffe zurückzugewinnen.In EP 0 554 285 B1 it is reported that all recovery processes are based on the removal of substances Circuits that are not very dirty are addressed because they are reused the so-called capture or thick matter consisting of fiber and filler prohibits a higher proportion of dirt in the paper production process. Accordingly a method is described which in the residual sewage sludge of the mechanical Waste water treatment plant contain useful fibers and fillers.
Das Verfahren ist gekennzeichnet durch die Einstellung eines definierten Feststoffgehalts,
das Abscheiden der Grobschmutzanteile, das Abscheiden der
Schwarzpartikelanteile, das fraktionierte Feinsieben des Gutanteils und die
Rückführung des Faseranteils und des Füllstoff- und Pigmentanteils in die Rohstoffaufbereitung
der Papierfabrik.
In den Restwasserschlämmen der Streichereiabwässer, Deinkinganlagen, innerbetrieblichen
Anlagen oder Abscheidevorrichtungen liegen die Füllstoffe und
Streichpigmente häufig in agglomerierter Form und mit geringer Weiße vor, die
eine direkte Wiederverwendung in der Rohstoffaufbereitung, insbesondere im
Strich einschränkt.The process is characterized by the setting of a defined solids content, the separation of the coarse dirt, the separation of the black particles, the fractionated fine screening of the good content and the recycling of the fiber content and the filler and pigment content in the raw material processing of the paper mill.
In the residual water sludge of the coating wastewater, deinking plants, in-house plants or separators, the fillers and coating pigments are often in agglomerated form and have a low whiteness, which limits direct reuse in raw material processing, especially in the coating.
Die Aufgabe der Erfindung besteht in der Bereitstellung eines Verfahrens zur Wiederverwertung von Papierrohstoffen, insbesondere der Füllstoffe und der Streichpigmente bei gleichzeitiger Einsparung von Energiekosten und Rohstoffkosten sowie Transportkosten.The object of the invention is to provide a method for Recycling of paper raw materials, especially fillers and Coating pigments while saving energy costs and raw material costs as well as transportation costs.
Die vorstehend genannte Aufgabe wird erfindungsgemäß gelöst durch ein Verfahren zur Wiederverwertung von Füllstoffen und Streichpigmenten der Papier-, Pappe- und Kartonherstellung aus den Restwasserschlämmen der Streichereiabwässer, Deinkinganlagen, innerbetrieblichen Kläranlagen oder Abscheidevorrichtungen, wobei man die Füllstoff- und Streichpigment-haltigen Restwasserschlämme mit Frischpigment in Form von Pulver, Frischfüllstoff in Form von Pulver, frischpigmenthaltiger und/oder frischfüllstoffhaltiger Slurry vermischt und anschließend das Frischpigment oder den Frischfüllstoff auf die gewünschte Korngrößenverteilung zu einer Pigment-Slurry vermahlt.The above object is inventively achieved by a process for recycling fillers and coating pigments of paper, paperboard and cardboard from the residual water sludges from coating, deinking plants, internal water treatment plants or separators, to give the filler and coating pigment containing residual water sludges with fresh pigment in Form of powder, fresh filler in the form of powder, fresh pigment-containing and / or fresh filler-containing slurry are mixed and then the fresh pigment or the fresh filler is ground to the desired particle size distribution to form a pigment slurry.
Mit Hilfe der vorliegenden Erfindung des oben beschriebenen Verfahrens wird eine definierte, konzentrierte Pigment-Slurry oder Füllstoffslurry erhalten, die in der Papier-, Pappe- und Kartonherstellung eingesetzt werden kann.With the help of the present invention of the method described above, a get defined, concentrated pigment slurry or filler slurry, which in the Paper, cardboard and cardboard manufacturing can be used.
In der Papierherstellung ist es üblich, die Füllstoffe und Streichpigmente sowohl als Pulver oder in Form einer konzentrierten Slurry, die 50 bis 80 Gew.-% Feststoffanteile aufweist, einzusetzen. Diese Füllstoffe und Pigmente werden üblicherweise von den Herstellern mit der gewünschten Weiße und Korngrößenverteilung zur Verfügung gestellt. Der Kern der vorliegenden Erfindung besteht nunmehr in der Anlieferung des Pigments in einer Art "Grundkörnung", vorzugsweise als Feststoff oder auch als hochkonzentrierte Slurry, beispielsweise mit einem Feststoffgehalt von 70 Gew.-% bis 85 Gew.-% oder mehr, beispielsweise mit einem mittleren Korndurchmesser von 50% <2µm bis 10µm, insbesondere 2 µm bis 5 µm und Vermahlung in wäßriger Phase vor Ort in einer Satellitenmahlanlage auf die gewünschte Weiße und Korngröße. Somit werden die obengenannten Restwasserschlämme nicht den fertig angelieferten oder fertig zubereiteten Rohstoffen beigemischt, sondern diese zunächst durch Vermischung und anschließend der Vermahlung von Frischpigment oder Frischfüllstoff als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry auf die gewünschte Weiße und Feinheit vermahlen und dann als Füllstoff oder Streichpigment eingesetzt. Die genannten mineralischen Füllstoffe und Pigmente werden üblicherweise in Naß- oder Trockenverfahren auf die gewünschte Korngröße vermahlen. Bei der Naßverrnahlung ist naturgemäß ein großer Anteil Wasser erforderlich. Erfindungsgemäß wurde nun festgestellt, daß ein Teil oder die gesamte Menge des notwendigen Wassers zur Vermischung und anschließend der Vermahlung der Frischpigmente oder Frischfüllstoffe als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry durch die Restwasserschlämme ersetzt werden kann, die gegebenenfalls Fasern enthalten. Üblicherweise in den Restwasserschlämmen vorliegende Agglomerate der Füllstoffe oder Pigmente stören hierbei wenig, da diese im Verlauf des Naßmahlprozesses auf die gewünschten Korngrößen zerkleinert werden. Weitere Vorteile der Erfindung bestehen in der gegenüber dem Stand der Technik erhöhten Flexibilität der erhältlichen gewünschten Korngrößen vor Ort, den geringeren Frachtkosten durch Wegfall des Transports von Wasser in marktüblicher Slurry, sowie die verbesserte Stabilität der selbst hergestellten Pigment-Slurry.In papermaking, it is common for both the fillers and coating pigments as a powder or in the form of a concentrated slurry containing 50 to 80% by weight Has solids content to use. These fillers and pigments are usually from the manufacturers with the desired whiteness and Grain size distribution provided. The essence of the present invention now consists in the delivery of the pigment in a kind of "basic grain", preferably as a solid or as a highly concentrated slurry, for example with a solids content of 70% by weight to 85% by weight or more, for example with an average grain diameter of 50% <2 µm to 10 µm, especially 2 µm to 5 µm and grinding in aqueous phase on site in one Satellite grinding plant to the desired white and grain size. So be the above-mentioned residual water sludge is not the one delivered or ready prepared raw materials, but these first by mixing and then grinding fresh pigment or filler as powder, Slurry containing fresh pigment and / or filler to the desired whiteness and fineness are ground and then used as filler or coating pigment. The Mineral fillers and pigments mentioned are usually wet or dry process to the desired grain size. In the Wet grinding naturally requires a large proportion of water. According to the invention it has now been found that part or all of the amount the water necessary for mixing and then grinding the fresh pigments or fillers as powder, fresh pigment and / or fresh filler-containing slurry can be replaced by the residual water sludge, which may contain fibers. Usually in the residual water sludge Existing agglomerates of the fillers or pigments do not bother here because this in the course of the wet grinding process to the desired grain sizes be crushed. Further advantages of the invention consist in the over the State of the art increased flexibility of the available desired grain sizes on site, the lower freight costs by eliminating the transport of water in standard slurry, as well as the improved stability of the self-made Pigment slurry.
Bei der Aufbereitung von Restwasserschlämmen ist es naturgemäß erforderlich, den Grobschmutzanteil, der aus Splittern, Sandkörnern und sonstigen Unreinheiten besteht, abzutrennen und zu verwerfen. Der so erhaltene Siebdurchgang besteht aus Fasern, Füllstoffen, Pigmenten, Feinsand, Schwarzpartikeln und Agglomeraten aus Füllstoffen und Pigmenten oder Pigmenten, Fasern und Füllstoffen. Unter Füllstoff werden dabei üblicherweise die in der Papiermasse eingesetzten Feinteilchen verstanden; unter Pigment werden die in der Streichfarbe eingesetzten feinen Teilchen verstanden. Die normalerweise nicht brauchbaren Schwarzpartikel weisen eine große Korngrößenvariation auf. Sie bestehen in der Hauptsache aus grau- bis schwarz gefärbtem Sand, Bodenabrieb, Maschinenabrieb, verkokten Schmiermitteln, sauer attackierten organischen Teilchen, Rost und agglomeriertem Staub oder einer Mischung daraus. Üblicherweise ist eine Abscheidung dieser Schwarzpartikel mittels Zentrifugieren oder Flottieren erforderlich, wenn die Abwasserschlämme der Rohstoffaufbereitung zugeführt werden sollen. Erfindungsgemäß ist jedoch eine entsprechende Abtrennung der Schwarzpartikel nicht notwendigerweise erforderlich, da diese Partikel bei der Vermahlung der Frischfüllstoffe und Frischpigmente in der Regel derart zerkleinert werden, daß der Weißgrad durch die Schwarzpartikel weniger stark beeinflußt wird.When processing residual water sludge, it is naturally necessary the coarse dirt that comes from chips, sand grains and other impurities exists to separate and discard. The sieve pass obtained in this way exists from fibers, fillers, pigments, fine sand, black particles and agglomerates from fillers and pigments or pigments, fibers and fillers. Under Filler are usually those used in the pulp Understood fine particles; pigment is used in the coating color understood fine particles. The normally unusable black particles have a large grain size variation. They mainly consist of gray to black colored sand, soil abrasion, machine abrasion, coking Lubricants, acid attacked organic particles, rust and agglomerated Dust or a mixture thereof. Usually this is a separation Black particles required by centrifugation or floatation if the Waste water sludge should be fed to the raw material processing. According to the invention, however, there is a corresponding separation of the black particles not necessarily necessary as these particles are used in the grinding of the Fresh fillers and fresh pigments are usually crushed so that the Whiteness is less affected by the black particles.
Dennoch ist selbstverständlich auch eine Abscheidung der Schwarzpartikel insbesondere mittels Zentrifugieren, wie beispielsweise in EP 0 554 285 B1 beschrieben, auch im Sinne der vorliegenden Erfindung möglich, um ganz besondere Qualitäten der Füllstoffe oder Pigmente im Sinne der Erfindung zu erhalten.Nevertheless, a separation of the black particles is of course also particularly important by centrifugation, as for example in EP 0 554 285 B1 described, also possible in the sense of the present invention, to complete special qualities of the fillers or pigments in the sense of the invention receive.
In gleicher Weise ist es gegebenenfalls sinnvoll, Faserabtrennungsverfahren insbesondere bei der Aufbereitung von Restwasserschlämmen aus Deinkinganlagen, Kläranlagen und Abscheidevorrichtungen durchzuführen. Als bekannte Verfahren bieten sich hier die Flockung und Sedimentation, die Filtrierung, Siebung, Zentrifugierung sowie sonstige chemische Behandlungsverfahren, wie beispielsweise die Oxidation an. In diesem Falle liegt dann üblicherweise ein Gemisch unterschiedlicher Pigmente vor, das häufig Kaolin, Calciumcarbonat und Talkum enthält. Durch Flockung und Umladung bilden sich bei den Abtrennungsverfahren häufig Aggtomerate. Die Restwasserschlämme mit niedrigem Feststoffgehalt sind an sich dementsprechend kaum als Rohstoff einsetzbar.In the same way, it may be appropriate to use fiber separation methods in particular in the treatment of residual water sludge from deinking plants, Sewage treatment plants and separation devices. As a known method flocculation and sedimentation, filtration, sieving, Centrifugation and other chemical treatment processes, such as for example, the oxidation. In this case there is usually a Mixture of different pigments, which are often kaolin, calcium carbonate and Contains talc. Due to flocculation and transhipment the Separation processes often agglomerates. The residual water sludge with Accordingly, low solids content can hardly be used as a raw material.
Zur Herstellung von Streichfarben ist daher eine Anhebung des Feststoffgehalts des Pigmentgemisches sowie in der Regel eine Anhebung der Weiße nach an sich bekannten Verfahren erforderlich. Die Zerstörung von Agglomeraten, die das Laufverhalten einer Streichfarbe am Blade durch Rakelstreifen stören und die Eigenschaften des Strichs negativ beeinflussen, ist besonders bevorzugt. Die Pigment- und Füllstoffteilchen des Restwasserschlamms, die zum Einsatz als Füllstoff oder Pigment vorgesehen sind, wirken hierbei als Mahlhilfsmittel und Dispergierhilfsmittel für die Zerstörung der Agglomerate bei dem Mahlprozeß. Gleichzeitig wirkt der Restwasserschlamm inklusive der beladenen Partikel als Dispergierhilfsmittel und Mahlhilfsmittel für die Füllstoffe und Pigmente bei dem Mahlprozeß, so daß die an sich üblichen Mengen an Dispergierhilfsmitteln und Mahlhilfsmitteln erfindungsgemäß verringert werden können.For the production of coating colors, an increase in the solids content is therefore necessary of the pigment mixture and usually an increase in whiteness per se known methods required. The destruction of agglomerates that the The running behavior of a coating color on the blade is disrupted by squeegee strips and the Adversely affecting the properties of the stroke is particularly preferred. The Pigment and filler particles of the residual water sludge, which are used as Filler or pigment are provided, act as grinding aids and Dispersing aids for the destruction of the agglomerates in the grinding process. At the same time, the residual water sludge including the loaded particles acts as Dispersing aids and grinding aids for the fillers and pigments in the Grinding process, so that the usual amounts of dispersing agents and Grinding aids can be reduced according to the invention.
Dementsprechend ist es erfindungsgemäß besonders bevorzugt, den Restwasserschlamm mit einer Feststoffkonzentration von 0,02 Gew.-% bis 50 Gew.-%, insbesondere 1 Gew.-% bis 30 Gew.-% zur Vermischung und anschließend der Vermahlung mit Frischpigment oder Frischfüllstoff als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry einzustellen. Bei einer zu geringen Konzentration wird das Wiederverwertungsverfahren unwirtschaftlich. Accordingly, it is particularly preferred according to the invention, the residual water sludge with a solids concentration of 0.02% by weight to 50% by weight, in particular 1% by weight to 30% by weight for mixing and then the Grinding with fresh pigment or fresh filler as powder, containing fresh pigment and / or adjust slurry containing fresh filler. If the rate is too low Concentration makes the recycling process uneconomical.
In den Restwasserschlämmen kann das Verhältnis von Füllstoffen und/oder Pigmenten zu Fasern in einer großen Bandbreite variieren. Besonders bevorzugt ist es im Sinne der vorliegenden Erfindung Restwasserschlämme mit einer gegebenenfalls angereicherten Konzentration an Füllstoffen und/oder Pigmenten einzusetzen, die im Bereich von 2 Gew.-% bis 80 Gew.-%, insbesondere 20 Gew.-% bis 60 Gew.-% bezogen auf den Feststoffgehalt liegt. So kann der Faseranteil einerseits oder der Füllstoff- und/oder Pigmentanteil andererseits beispielsweise von 2 bis 98 Gew.-% oder 98 bis 2 Gew.-% variieren. Auch sind selbstverständlich Faser-freie Restwasserschlämme erfindungsgemäß einsetzbar.The ratio of fillers and / or in the residual water sludge can Pigments to fibers vary in a wide range. Particularly preferred it is residual water sludge with a optionally enriched concentration of fillers and / or pigments to be used in the range from 2% by weight to 80% by weight, in particular 20% by weight is up to 60 wt .-% based on the solids content. So the fiber content on the one hand or the filler and / or pigment content on the other hand for example vary from 2 to 98% by weight or 98 to 2% by weight. Also go without saying Fiber-free residual water sludge can be used according to the invention.
Beispielhaft seien hier die bevorzugten Zusammensetzungen verschiedener Abwasserschlämme erläutert. Vorzugsweise umfaßt das Abwasser aus der Produktion 0,5 bis 5 Gew.-%, insbesondere 2,5 Gew.-% Stoffverlust bei einem speziellen Frischwasserbedarf von 10 bis 100 l/kg, insbesondere 20 l/kg. Die Stoffdichte beträgt vorzugsweise 0,02 bis 0,5, insbesondere 0,125 Gew.-%. Besonders bevorzugt im Sinne der Erfindung ist hier ein Mengenverhältnis von Faseranteil zu Füllstoff und/oder Pigmentanteil von 20 zu 80 Gew.-% oder 80 zu 20 Gew.-%, insbesondere Fasem zu Pigment im Verhältnis 40 zu 60 Gew.-% eines Abwassers aus der Produktion.The preferred compositions of different ones are exemplary here Sewage sludge explained. Preferably, the waste water from the Production 0.5 to 5 wt .-%, in particular 2.5 wt .-% loss in one special fresh water requirements of 10 to 100 l / kg, in particular 20 l / kg. The The consistency is preferably 0.02 to 0.5, in particular 0.125% by weight. For the purposes of the invention, a quantitative ratio of is particularly preferred Fiber content to filler and / or pigment content from 20 to 80 wt .-% or 80 to 20% by weight, in particular fibers to pigment in a ratio of 40 to 60% by weight of one Waste water from production.
Der pH-Wert der Restwasserschlämme, die als Abwasser aus der Produktion anfallen, kann in weiten Grenzen variieren. Besonders bevorzugt wird der pH-Wert im Bereich von 4,5 bis 8,5, insbesondere im neutralen Bereich um pH 7 eingestellt.The pH of the residual water sludge used as wastewater from production can vary widely. The pH is particularly preferred in the range from 4.5 to 8.5, in particular in the neutral range around pH 7.
Erfindungsgemäß einsetzbares Abwasser aus der Streicherei kann beispielsweise einen Feststoffgehalt von 0,1 bis 20 Gew.-%, insbesondere 1 Gew.-% vor der Fällung und nach der Fällung von 1 bis 30 Gew.-%, insbesondere bei 5 Gew.-% aufweisen. Der pH-Wert kann beispielsweise im Bereich von 6,5 bis 10, vorzugsweise 7,5 vor der Fällung und 6,0 bis 10,0, vorzugsweise 7,0, nach der Fällung betragen. Der Aschegehalt sollte insbesondere im Bereich von 60 bis 95 Gew.-%, insbesondere bei 90 Gew.-% liegen. Eine typische Zusammensetzung enthält 1 bis 90 Gew.-%, insbesondere 20 Gew.-% Kaolin, 1 bis 90 Gew.-%, insbesondere 60 Gew.-% Calciumcarbonat., 0,5 bis 50 Gew.-%, insbesondere 15 Gew.-% Talkum und 0,1 bis 40 Gew.-%, insbesondere 5 Gew.-% Sonstiges.Waste water from the coating plant which can be used according to the invention can, for example a solids content of 0.1 to 20 wt .-%, in particular 1 wt .-% before Precipitation and after precipitation from 1 to 30% by weight, in particular at 5% by weight exhibit. The pH can be, for example, in the range from 6.5 to 10, preferably 7.5 before precipitation and 6.0 to 10.0, preferably 7.0 after precipitation be. The ash content should in particular be in the range from 60 to 95% by weight, are in particular 90% by weight. A typical composition contains 1 up to 90% by weight, in particular 20% by weight of kaolin, 1 to 90% by weight, in particular 60 wt .-% calcium carbonate., 0.5 to 50 wt .-%, in particular 15 wt .-% talc and 0.1 to 40% by weight, in particular 5% by weight of other.
Im Rahmen der vorliegenden Erfindung werden vorzugsweise als Frischpigment und/oder Frischfüllstoff Kaolin, natürliche oder gefällte Calciumcarbonate, künstliche oder natürliche Aluminiumsilikate und -oxidhydrate, Titandioxid, Satin-Weiß, Dolomit, Glimmer, Metall-, insbesondere Aluminiumflakes, Bentonit, Rutil, Magnesiumhydroxid, Gips, Schichtsilikate, Talkum, Calciumsilikat sowie sonstige Steine und Erden einsetzt.In the context of the present invention are preferably used as a fresh pigment and / or fresh filler kaolin, natural or precipitated calcium carbonates, artificial or natural aluminum silicates and oxide hydrates, titanium dioxide, satin white, Dolomite, mica, metal flakes, especially aluminum flakes, bentonite, rutile, magnesium hydroxide, Gypsum, layered silicates, talc, calcium silicate and other stones and earth.
Bevorzugterweise wird Frischpigment oder Frischfüllstoff als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurries in Anwesenheit der Restwasserschlämme und gegebenenfalls üblichen Mahlhilfsmitteln und/oder Dispergierhilfsmitteln zu einer Slurry mit einem Feststoffgehalt von 30 bis 85 Gew.-%, insbesondere 40 bis 75 Gew.-% vermischt und vermahlt.Fresh pigment or fresh filler is preferably used as powder, slurries containing fresh pigment and / or filler in the presence of the Residual water sludges and, if appropriate, customary grinding aids and / or Dispersing aids to form a slurry with a solids content of 30 to 85% by weight, in particular 40 to 75 wt .-% mixed and ground.
Die Frischpigmente oder Frischfüllstoffe als Pulver, frischpigmenthaltige und/oder
frischfüllstoffhaltige Slurries werden vorzugsweise zu einer Korngrößenverteilung
von
Aus EP 0 625 611 A1 sind Komgrößenverteilungen für Streichpigmente bekannt,
die auch mit Hilfe der vorliegenden Erfindung vorzugsweise eingestellt werden.
So ist es besonders bevorzugt im Sinne der vorliegenden Erfindung, daß die
Pigmente folgende Korngrößenverteilung aufweisen:
Erfindungsgemäß ist darüber hinaus eine große Variation der Weiße und Korngrößenverteilungen möglich, die insbesondere durch die Art und Dauer der Mahlung gesteuert werden kann. So ist es möglich, vor Ort relativ groben Frischfüllstoff mit einer großen Menge an Restwasserschlamm zu vermischen, um diese Slurry nach der Vermahlung in die Papiermasse einzubringen. In gleicher Weise ist es möglich, vor Ort durch Einsatz einer geringeren Menge an Restwasserschlamm diese zur feineren Vermahlung mit Frischpigment einzusetzen, was dann als Streichpigment und/oder Füllstoff dient. Der Papierhersteller ist somit nicht mehr an vorgegebene Teilchengrößen der Frischpigmente und/oder Frischfüllstoffe sowie Pigment-Slurries von Anbietern der Rohstoffe gebunden. Die Pigment-Slurries der Rohstoffanbieter werden üblicherweise mit der Zahl der Gewichtsprozente an Teilchen kleiner als 2 µm charakterisiert, beispielsweise als Typ: 95, 90, 75, 60, 50 etc.. Der Papierhersteller ist somit in der Lage, Pigmente als Slurry den jeweiligen Bedürfnissen entsprechend selbst vor Ort in einer Satellitenanlage herzustellen. Dies erlaubt eine flexible und schnelle Reaktion auf Qualitäts- und Produktionsanforderungen, beispielsweise der verschiedenen Papierrohstoffe für die Papiermasse, die Pigmente oder Slurries für den Vorstrich, Deckstrich und Einfachstrich oder die Pigmentierung allein, sowie die Vermischung mit anderen Pigmenten. Vor allem aber ist hierdurch eine beträchtliche Reduzierung der Transportkosten ersichtlich, da nicht notwendigerweise Fertigslurries mit hohem Wassergehalt über große Entfernungen transportiert werden müssen.According to the invention there is also a large variation in the whiteness and grain size distributions possible, in particular by the type and duration of the Grinding can be controlled. So it is possible to be relatively rough on site To mix fresh filler with a large amount of residual water sludge insert this slurry into the paper pulp after grinding. In the same Way it is possible to use a smaller amount on site Residual water sludge to use for fine grinding with fresh pigment, which then serves as a coating pigment and / or filler. The paper manufacturer is thus no longer to predetermined particle sizes of the fresh pigments and / or Fresh fillers and pigment slurries from suppliers of the raw materials bound. The Pigment slurries from raw material suppliers are usually associated with the number of Weight percentages of particles smaller than 2 µm characterized, for example as Type: 95, 90, 75, 60, 50 etc. The paper manufacturer is therefore able to use pigments as a slurry according to the respective needs, even on site in one Manufacture satellite system. This allows a flexible and quick response to Quality and production requirements, for example the different ones Paper raw materials for the pulp, the pigments or slurries for the primer, Top coat and single coat or pigmentation alone, as well as mixing with other pigments. Above all, however, this is a considerable one Reduction in transport costs evident as not necessarily Ready-made slurries with a high water content are transported over long distances Need to become.
Auch wenn im Sinne der vorliegenden Erfindung an sich bekannte Netzmittel, Stabilisierungsmittel, Mahlhilfsmittel und Dispergierhilfsmittel während der Vermischung und der Vermahlung der Frischpigmente oder Frischfüllstoffe als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry mit Restwasserschlämmen eingesetzt werden können, wie sie beispielsweise aus EP 0 625 611 A1 bekannt sind, so ist doch erfindungsgemäß die erforderliche Menge gegenüber dem Stand der Technik deutlich verringert. Zum einen enthalten die Restabwasserschlämme bereits eine gewisse Menge der genannten Mittel. Zum anderen ist es aufgrund der Möglichkeit der direkten Vermahlung vor Ort nicht notwendig, die Netz-, Stabilisierungs-, Mahl- und Dispergierhilfsmittel in üblichen Größenordnungen einzusetzen, da die Zeitspanne zwischen Herstellung der Slurry und der Verwendung stark verkürzt werden kann. Ein weiterer Vorteil der geringeren Einsatzmengen an Hilfsmitteln ist die verbesserte Retention der Pigmente bei der Papierherstellung, da größere Mengen einen negativen Einfluß auf die Retention haben.Even if wetting agents known per se in the sense of the present invention, Stabilizing agents, grinding aids and dispersing aids during the Mixing and grinding of the fresh pigments or fillers as Powder, slurry containing fresh pigment and / or fresh filler Residual water sludges can be used, such as from EP 0 625 611 A1 are known, the amount required according to the invention significantly reduced compared to the prior art. For one, they contain Residual sewage sludge already contains a certain amount of the above-mentioned agents. To the others are not due to the possibility of direct grinding on site necessary, the wetting, stabilizing, grinding and dispersing aids in usual Orders of magnitude to be used since the time span between production of the slurry and the use can be greatly reduced. Another advantage of lower amounts of auxiliary materials is the improved retention of the Pigments in paper production, because larger quantities have a negative influence on the retention.
Das erfindungsgemäße Verfahren eignet sich besonders für die Aufarbeitung aus Füll- und Faserstoff bestehenden Abwasserschlämmen oder Faserstoffsuspensions-Teilströmen der Altpapier-verarbeitenden Papierindustrie und der Wiederverwertung von Papierausschuß, insbesondere bei der Aufbereitung von Altpapier aus der Stufe der Entaschung, wo besonders großen Wert auf eine sortenreine und komgrößenspezifische Auftrennung der Füllstoffe und Pigmente gelegt wird, um diese hier durch Wiedereinsatz zu verwerten, und dadurch eingebrachte Energie und Wertigkeit zu nutzen. The method according to the invention is particularly suitable for working up Filling and fiber material existing sewage sludge or Partial suspension of pulp suspension from the waste paper processing paper industry and the reuse of paper scrap, especially in reprocessing of waste paper from the ash removal stage, where particularly great importance is attached to a sorted and size-specific separation of fillers and pigments is laid to recycle them here, and thereby to use the energy and value brought in.
Die mit Hilfe der vorliegenden Erfindung erhältlichen Streichpigment-Slurries können besonders vorteilhaft in der Papierindustrie, insbesondere zur Herstellung einer Streichfarbe für den Papierstrich oder in der Papiermasse eingesetzt werden. Besonders bevorzugt ist die Verwendung zur Herstellung einer Streichpigment-Slurry für Offsetpapier. Darüber hinaus eignen sich die erfindungsgemäßen Slurries auch zur Herstellung einer Streichmasse für leichtgewichtige, gestrichene Papiere, insbesondere auch bei hoher Auftragsgeschwindigkeit, sowie zur Herstellung von Rollen-Offsetpapieren, insbesondere zur Herstellung von leicht-gewichtigen, gestrichenen Rollen-Offsetpapieren, das Streichen von Karton und Spezialpapier, wie Etiketten, Tapeten, Silikonrohpapier, selbstdurchschreibend, sowie der Beimischung bei Tiefdruckpapieren. In diesem Sinne sind die erfindungsgemäß erhältlichen Streichpigment-Slurries, insbesondere einsetzbar im Bogenoffset, insbesondere für den Bogenoffset-Einfachstrich, Bogenoffset-Doppelstrich: Bogenoffset-Vorstrich und Bogenoffset-Deckstrich;- im Rollenoffset, insbesondere für den LWC-Rollenoffset-Einfachstrich, Rollenoffset-Doppelstrich: Rollenoffset-Vorstrich und Rollenoffset-Deckstrich; - im Tiefdruck, insbesondere für den LWC-Tiefdruck-Einfachstrich, Tiefdruck-Doppelstrich: Tiefdruck-Vorstrich und Tiefdruck-Deckstrich; - im Karton, insbesondere für den Karton-Doppelstrich: Karton-Vorstrich und Karton-Deckstrich und für Spezialpapiere, insbesondere für Etiketten und flexible Verpackungen.The coating pigment slurries obtainable with the aid of the present invention can be particularly advantageous in the paper industry, especially for manufacturing a coating color for the paper line or in the paper pulp. The use for the production of a coating pigment slurry is particularly preferred for offset paper. In addition, the inventive Slurries also for making a coating slip for lightweight, coated Papers, especially at high application speeds, as well as for Production of roll offset papers, especially for the production of light-weight, coated roll offset papers, the coating of cardboard and Special paper, such as labels, wallpaper, silicone base paper, self-copying, as well as the admixture for gravure papers. In this sense they are Coating pigment slurries obtainable according to the invention, in particular usable in sheetfed offset, especially for sheetfed single-stroke, sheetfed double-stroke: Sheetfed pre-coat and sheetfed topcoat; - in web offset, especially for the LWC web offset single line, web offset double line: Web offset primer and web offset top coat; - in gravure, in particular for the LWC rotogravure single line, rotogravure double line: rotogravure pre-coat and rotogravure top coat; - in a box, especially for the double cardboard box: Cardboard primer and cardboard topcoat and for special papers, especially for Labels and flexible packaging.
Das Verfahren bietet die Möglichkeit, die erfindungsgemäß hergestellten Pigment-Slurries ohne Qualitätseinbuße bei den damit hergestellten Rohpapieren, Strichen und insbesondere den Endqualitäten einzusetzen.The process offers the possibility of the pigment slurries produced according to the invention without any loss of quality in the base paper and coating produced with it and especially to use the final qualities.
Nachfolgend werden beispielhaft einige Streichrezepturen angegeben, die mit Hilfe der vorliegenden Erfindung erhalten werden können (alle Angaben in Gewichtsteile fest gerechnet (atro/Wirkstoff)): In the following, some coating formulations are given as examples, which can be used with the help of the present invention (all parts by weight calculated (atro / active ingredient):
Die erfindungsgemäße Prozeßdurchführung in einer üblichen Papierfabrik kann wie folgt beschrieben werden:The process implementation according to the invention in a conventional paper mill can can be described as follows:
Silos in einer beliebigen Größe, beispielsweise von 50 bis 1000 m3 dienen zur Aufnahme und Lagerung von trockenen Füllstoffen und Pigmenten einer einheitlichen oder gegebenenfalls unterschiedlichen Grundkörnung, beispielsweise Calciumcarbonat. Durch Dosiervorrichtungen wird ein Austrag des Füllstoff- und/oder Pigmentpulvers mit anschließendem Transport gewährleistet, gegebenenfalls zu Tagessilobehälter(n), gegebenenfalls mit Reinigungsvorrichtungen. Dosierungsvorrichtungen für das/die Pulver, gegebenenfalls gesteuert durch speicherprogrammierbare Steuerungen (SPS) mit den elektronisch integrierten Rezepten bestimmen gravimetrisch und/oder volumetrisch die zur Vermischung mit Wasser, Frischwasser oder Kreislaufwasser der Papierfabrik erforderlichen Mengen der zu mischenden Bestandteile. Erfindungsgemäß wird anstelle des Frischwassers oder des Kreislaufwassers teilweise oder vollständig ein Restwasserschlamm mit einem Feststoffgehalt von insbesondere 0,02 bis 50 Gew.-%, gegebenenfalls unter Zugabe von Wasser bei höherer Konzentration des Restwasserschlamms eingesetzt. Dementsprechend sind weiterhin erforderlich, Behälter zur Lagerung des Restwasserrschlamms, Dosiervorrichtungen für den Restwasserschlamm, die die einzusetzende Menge gravimetrisch oder volumetrisch bestimmen. Daneben sind erforderlich Behälter zur Aufnahme des Gemisches aus Frischpigment oder Frischfüllstoff als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry und Restwasserschlamm/Wasser, gegebenenfalls Mahlhilfsmittel und Dispergierhilfsmittel oder sonstige Hilfsmittel. Zur Dispergierung und Stabilitätseinstellung sind Dispergiereinrichtungen (Dissolver) oder sonstige Rührwerke erforderlich.Silos of any size, for example from 50 to 1000 m 3, are used to hold and store dry fillers and pigments with a uniform or possibly different basic grain size, for example calcium carbonate. Dispensing of the filler and / or pigment powder with subsequent transport is ensured by metering devices, optionally to day silo container (s), optionally with cleaning devices. Dosing devices for the powder (s), possibly controlled by programmable logic controllers (PLC) with the electronically integrated recipes, determine gravimetrically and / or volumetrically the quantities of the components to be mixed, which are required for mixing with water, fresh water or circulating water from the paper mill. According to the invention, instead of the fresh water or the circulating water, a residual water sludge with a solids content of in particular 0.02 to 50% by weight is used, partially or completely, optionally with the addition of water at a higher concentration of the residual water sludge. Accordingly, containers for storing the residual water sludge, dosing devices for the residual water sludge, which determine the amount to be used gravimetrically or volumetrically, are also required. In addition, containers are required to hold the mixture of fresh pigment or filler as a powder, slurry containing fresh pigment and / or filler and residual water sludge / water, optionally grinding aids and dispersion aids or other aids. Dispersing devices (dissolvers) or other agitators are required for dispersion and stability adjustment.
Das Vermahlen der Frischpigmente und/oder Frischfüllstoffe als Pulver, frischpigmenthaltige und/oder frischfüllstoffhaltige Slurry mit den Restwasserschlämmen, kann erfindungsgemäß kontinuierlich in üblichen Rührwerkskugelmühlen, beispielsweise mit einem Inhalt von 700 bis 5000 l oder größer durchgeführt werden. Zum Einsatz kommen Mahlmedien, vorzugsweise Mahlkugeln, insbesondere mit einem Durchmesser von 1 bis 4 mm.Grinding the fresh pigments and / or fresh fillers as powder, slurry containing fresh pigment and / or filler with the residual water sludge, can, according to the invention, continuously in conventional agitator ball mills, for example with a content of 700 to 5000 l or greater become. Grinding media, preferably grinding balls, are used in particular with a diameter of 1 to 4 mm.
Zur Aufbereitung der Restwasserschlärnme werden üblicherweise Siebe, vorzugsweise Bogensiebe zum Abscheiden von Verunreinigungen (Kugelbruch, Trennstoffe, Rost etc.) eingesetzt. Lasermeßinstrumente dienen der Bestimmung und Steuerung der Mahlfeinheit während des Mahlvorgangs und der Rechner-gestützten Steuerung der Rührwerkskugelmühlenanlage. Gegebenenfalls sind weitere Dosierinjektionseinrichtungen zum Nachdosieren von Dispergier- und Mahlhilfsmitteln an der Rührwerkskugelmühle erforderlich. Nach dem Austrag der Pigment-Slurry sind gegebenenfalls Siebe zur nochmaligen Trennung von Schadstoffen mit einer Größe von mehr als 20 µm erforderlich. Typischerweise weist das eingesetzte Frischpigment- und/oder Füllstoffmaterial, insbesondere eingesetzes Calciumcarbonatpulver in trockener Form einen Weißgrad nach DIN 53163 von mehr als 90 %, insbesondere einen Weißgrad von mehr als 95 % in einer Feinheit von d97 ≤ 25 µm, eine Feinheit nicht größer d97 ≤100 µm, eine Reinheit des Carbonats ≥ 98 %, einen Anteil SiO2 ≤ 1,0, insbesondere ≤ 0,2% auf.To process the residual water sludge, sieves are usually used, preferably curved sieves for separating contaminants (broken balls, separating agents, rust, etc.). Laser measuring instruments are used to determine and control the fineness of grinding during the grinding process and the computer-aided control of the agitator ball mill system. If necessary, further metering injection devices are required for further metering of dispersing and grinding aids on the agitator ball mill. After the pigment slurry has been discharged, sieves may be required for the further separation of pollutants with a size of more than 20 μm. Typically, the fresh pigment and / or filler material used, in particular calcium carbonate powder used in dry form, has a whiteness according to DIN 53163 of more than 90%, in particular a whiteness of more than 95% in a fineness of d 97 25 25 μm, a fineness not greater d 97 ≤100 µm, a purity of the carbonate ≥ 98%, a proportion of SiO 2 ≤ 1.0, in particular ≤ 0.2%.
Wechselnde Anteile von beispielsweise Carbonat, vermischt mit Restwasserschlamm werden zu einer Slurry vermahlen, die einen Feststoffgehalt aufweist, der beispielsweise auf eine gebrauchsfähige Streichfarbe eingestellt werden kann. Gegebenenfalls ist der Feststoffgehalt auch höher einstellbar, wenn die Pigment-Slurry länger zwischengelagert werden soll. Die Feinheit der Slurry wird insbesondere durch die Verweilzeit und/oder die Energieaufnahme während der Produktion in der Rührwerkskugelmühle bestimmt.Changing proportions of carbonate, for example, mixed with residual water sludge are ground to a slurry that has a solids content, which can be set to a usable coating color, for example. If necessary, the solids content can also be set higher if the pigment slurry should be stored longer. The delicacy of the slurry is particular by the dwell time and / or the energy consumption during the Production determined in the agitator ball mill.
Der Weißgrad der Pigment-Slurry ergibt sich unter anderem aus dem Mischungsverhältnis Frischpigment zu Restwasserschlamm und insbesondere dem eingesetzten Frischpigmenttyp.The whiteness of the pigment slurry results, among other things, from the mixing ratio Fresh pigment to residual water sludge and especially the one used Fresh pigment type.
Eine Ausführungsform der Zusammensetzung der Restwasserschlämme, wie sie
erfindungsgemäß eingesetzt werden können, ist nachfolgend in der Tabelle 1
wiedergegeben:
Ein Abwasserschlamm mit der in Tabelle 1 dargestellten Zusammensetzung wurde getrocknet; die Feinheit und der Farbwert gemessen.A sewage sludge with the composition shown in Table 1 was dried; the fineness and the color value measured.
Die gefundenen Werte lauten:
D50-Wert = 15,0 µm
D3,2-Wert = 1,0 µm
(Helligkeit Ry, C/2° DIN 53163)
Ry-Wert = 84,1
Gelbwert: (C/2°) = -5,6
D 50 value = 15.0 µm
D 3.2 value = 1.0 µm
(Brightness R y , C / 2 ° DIN 53163)
R y value = 84.1
Yellowness index: (C / 2 °) = -5.6
Der Wassergehalt des Abwasserschlamms betrug 19,5 %. Der pH-Wert wurde in einer 10 %igen Lösung gemessen und betrug 6,8. Ein Teil des getrockneten Abwasserschlamms wurde 2 Stunden bei 450°C erhitzt. Der Glühverlust (organische Anteile) betrug 13,4%.The water content of the sewage sludge was 19.5%. The pH was in measured in a 10% solution and was 6.8. Part of the dried Sewage sludge was heated at 450 ° C for 2 hours. The loss on ignition (organic Shares) was 13.4%.
Im Labormaßstab wurde anschließend der Abwasserschlamm zu 40 Gew.-% mit 60 Gew.-% Frischpigment Calcicell® , einem natürlichen, kristallinen Calciumcarbonat (Komgrößenbereich 0 - 20 µm, D50-Wert = 5,5 µm, Weißgrad C/2° DIN 53163 = 95 ±1) aufgeschlämmt und in der Mühle kurz vermahlen.The wastewater sludge was then 40% by weight with 60% by weight of Calcicell® fresh pigment, a natural, crystalline calcium carbonate (grain size range 0 - 20 µm, D 50 value = 5.5 µm, whiteness C / 2 ° DIN) on a laboratory scale 53163 = 95 ± 1) slurried and briefly ground in the mill.
Danach wurde am vermahlenen und getrockneten Produkt die Feinheit und der Farbwert gemessen.Then the fineness and the Color value measured.
Feinheit: (Cilas 850)
D50-Wert = 9,2 µm
D9-Wert = 1,0 µmFineness : (Cilas 850)
D 50 value = 9.2 µm
D 9 value = 1.0 µm
Der Weißgrad (Helligkeit Ry, C/2° DIN 53163) nach der Vermahlung betrug:
Ry-Wert = 92,0
Gelbwert: (C/2°) = -2,6The degree of whiteness (brightness R y , C / 2 ° DIN 53163) after grinding was:
R y value = 92.0
Yellowness index: (C / 2 °) = -2.6
(Alle genannten Feinheitsmerkmale wurden durch Lagersedimentationsanalyse mit dem Gerät Cilas 850 der Firma Cilas, Frankreich, bestimmt. Die Dispergierung der Proben in Alkohol wurde mittels Schnellrührer und Ultraschall vorgenommen.)(All the fineness characteristics mentioned were determined by storage sedimentation analysis with the Cilas 850 device from Cilas, France. The dispersion the samples in alcohol were made using a high-speed stirrer and ultrasound.)
Claims (15)
- A process for recycling fillers and coating pigments from the preparation of paper, paperboard and cardboard found in the residual water sludges from coating plant waste waters, deinking plants, internal water treatment plants or separators, characterized in that the residual water sludges containing the fillers and coating pigments are subjected to mixing with fresh pigments in the form of powder, fresh fillers in the form of powder, fresh-pigment containing slurries and/or fresh-filler containing slurries, followed by milling said fresh pigment or said fresh filler to the desired grain size distribution to yield a pigment slurry.
- The process according to claim 1, characterized in that residual water sludges having a ratio of fiber content to filler and/or pigment content of from 2 to 98% by weight to from 98 to 2% by weight are employed.
- The process according to claim 1, characterized in that residual water sludges derived from deinking plants, internal water treatment plants and separators are subjected to fiber separation.
- The process according to claim 3, characterized in that said fiber separation is effected by flocculation and sedimentation, filtering, screening, centrifuging and/or chemical treatment, especially oxidation.
- The process according to one or more of claims 1 to 4, characterized in that residual water sludges having a solids concentration of from 0.02% by weight to 50% by weight, especially from 1% by weight to 30% by weight, are employed.
- The process according to one or more of claims 1 to 5, characterized in that residual water sludges having a concentration of fillers and/or coating pigments of from 2 to 80% by weight, especially from 20 to 60% by weight, based on the solids content, are employed.
- The process according to one or more of claims 1 to 6, characterized in that china clay, natural or precipitated calcium carbonates, artificial or natural aluminum silicates and oxide hydrates, titanium dioxide, satin white, dolomite, mica, metal flakes, especially aluminum flakes, bentonite, rutile, magnesium hydroxide, gypsum, sheet silicates, talcum, calcium silicate and other rocks and earths are used as said fresh pigment and/or fresh filler.
- The process according to one or more of claims 1 to 7, characterized in that said fresh pigments or fresh fillers are mixed and milled in the form of powders, fresh-pigment containing slurries and/or fresh-filler containing slurries in the presence of said residual water sludges and optionally usual milling aids and/or dispersing aids to yield a slurry having a solids content of from 30 to 85% by weight, especially from 40 to 75% by weight.
- The process according to one or more of claims 1 to 8, characterized in that said fresh pigments or fresh fillers are milled in the form of powders, fresh-pigment containing slurries and/or fresh-filler containing slurries to give a grain size distribution offrom 10 to 99% by weight of particles < 1 µm, especiallyfrom 10 to 95% by weight of particles < 1 µm,respectively based on the equivalent diameter.
- The process according to one or more of claims 1 to 8, characterized in that said fresh pigments and/or fresh fillers are milled in the form of powders, fresh-pigment containing slurries and/or fresh-filler containing slurries to give a grain size distribution of:a) from 95 to 100% by weight of particles < 10 µm;b) from 50 to 100% by weight of particles < 2 µm, especially from 50 to 95% by weight of particles < 2 µm;c) from 27 to 95% by weight of particles < 1 µm, especially from 27 to 75% by weight of particles < 1 µm; andd) from 0.1 to 55% by weight of particles < 0.2 µm, especially from 0.1 to 35% by weight of particles < 0.2 µm;
- The process according to one or more of claims 1 to 10, characterized in that the whiteness of said pigment slurries is adjusted via the ratio of milled or unmilled fresh pigment or fresh filler in the form of powders, fresh-pigment containing slurries and/or fresh-filler containing slurries to residual water sludge.
- The process according to one or more of claims 1 to 11, characterized in that the whiteness of said pigment slurries is adjusted by selecting the chemical purity, especially the whiteness and/or the yellowness index, of said fresh pigments or fresh fillers in the form of powders, fresh-pigment containing slurries and/or fresh-filler containing slurries.
- Use of a pigment slurry according to one or more of the preceding claims for the preparation of a coating compound for the paper industry, especially of coating compounds for various segments, such as sheet-fed offset papers, rotary offset papers, intaglio printing papers, cardboard and special papers.
- The use according to claim 13 for the preparation of usual coating compounds to replace part or all of the coating pigments.
- Use of a pigment slurry according to one or more of claims 1 to 11 in the paper stock for papermaking.
Priority Applications (1)
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SI9730180T SI0910697T1 (en) | 1996-07-09 | 1997-03-19 | Method of reusing fillers and coating pigments used in paper, paperboard and cardboard manufacture |
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DE19627523A DE19627523C1 (en) | 1996-07-09 | 1996-07-09 | Preparation of filler or pigment coating material for paper, pulp or board from waste sludge |
DE19627523 | 1996-07-09 | ||
PCT/EP1997/001375 WO1998001621A1 (en) | 1996-07-09 | 1997-03-19 | Method of reusing fillers and coating pigments used in paper, paperboard and cardboard manufacture |
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US (3) | US6214166B1 (en) |
EP (1) | EP0910697B1 (en) |
JP (1) | JP4046764B2 (en) |
CN (1) | CN1120262C (en) |
AT (1) | ATE202810T1 (en) |
AU (1) | AU2288997A (en) |
BR (1) | BR9710866A (en) |
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DE (2) | DE19627523C1 (en) |
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EP1734174A2 (en) | 2005-06-13 | 2006-12-20 | Andritz AG | Process for the recycling of fillers and coating pigments at the production of paper and board |
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- 1997-03-19 PL PL97331011A patent/PL187463B1/en unknown
- 1997-03-19 TR TR1999/00012T patent/TR199900012T2/en unknown
- 1997-03-19 JP JP50468698A patent/JP4046764B2/en not_active Expired - Fee Related
- 1997-03-19 AT AT97915390T patent/ATE202810T1/en active
- 1997-03-19 PT PT97915390T patent/PT910697E/en unknown
- 1997-03-19 CZ CZ0002299A patent/CZ298816B6/en not_active IP Right Cessation
- 1997-03-19 HU HU9903637A patent/HU221442B/en not_active IP Right Cessation
- 1997-03-19 BR BR9710866-9A patent/BR9710866A/en not_active IP Right Cessation
- 1997-03-19 CN CN97196175A patent/CN1120262C/en not_active Expired - Lifetime
- 1997-03-19 CA CA002250475A patent/CA2250475C/en not_active Expired - Lifetime
- 1997-03-19 DE DE59703962T patent/DE59703962D1/en not_active Expired - Lifetime
- 1997-03-19 DK DK97915390T patent/DK0910697T3/en active
- 1997-03-19 AU AU22889/97A patent/AU2288997A/en not_active Abandoned
- 1997-03-19 EP EP97915390A patent/EP0910697B1/en not_active Expired - Lifetime
- 1997-03-19 WO PCT/EP1997/001375 patent/WO1998001621A1/en active IP Right Grant
- 1997-03-19 ES ES97915390T patent/ES2160936T3/en not_active Expired - Lifetime
-
1999
- 1999-01-08 US US09/227,533 patent/US6214166B1/en not_active Expired - Lifetime
- 1999-01-08 NO NO19990074A patent/NO324375B1/en not_active IP Right Cessation
-
2000
- 2000-12-21 US US09/741,023 patent/US6444092B1/en not_active Expired - Lifetime
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2001
- 2001-07-05 GR GR20010401005T patent/GR3036174T3/en not_active IP Right Cessation
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2002
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EP1734174A2 (en) | 2005-06-13 | 2006-12-20 | Andritz AG | Process for the recycling of fillers and coating pigments at the production of paper and board |
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US20020088587A1 (en) | 2002-07-11 |
ES2160936T3 (en) | 2001-11-16 |
PT910697E (en) | 2001-10-30 |
HUP9903637A3 (en) | 2001-04-28 |
NO990074D0 (en) | 1999-01-08 |
US6444092B1 (en) | 2002-09-03 |
CA2250475C (en) | 2005-12-27 |
CN1120262C (en) | 2003-09-03 |
TR199900012T2 (en) | 1999-04-21 |
BR9710866A (en) | 2000-01-11 |
HU221442B (en) | 2002-10-28 |
US7887629B2 (en) | 2011-02-15 |
DK0910697T3 (en) | 2001-09-24 |
CN1225144A (en) | 1999-08-04 |
HUP9903637A2 (en) | 2000-03-28 |
JP2000514510A (en) | 2000-10-31 |
NO324375B1 (en) | 2007-10-01 |
ATE202810T1 (en) | 2001-07-15 |
AU2288997A (en) | 1998-02-02 |
PL331011A1 (en) | 1999-06-21 |
CA2250475A1 (en) | 1998-01-15 |
NO990074L (en) | 1999-01-08 |
US20030041990A1 (en) | 2003-03-06 |
DE19627523C1 (en) | 1997-10-23 |
CZ298816B6 (en) | 2008-02-13 |
JP4046764B2 (en) | 2008-02-13 |
PL187463B1 (en) | 2004-07-30 |
CZ2299A3 (en) | 1999-06-16 |
DE59703962D1 (en) | 2001-08-09 |
EP0910697A1 (en) | 1999-04-28 |
WO1998001621A1 (en) | 1998-01-15 |
US6214166B1 (en) | 2001-04-10 |
GR3036174T3 (en) | 2001-10-31 |
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