EP0031059A1 - Dispersions of dinitroanthraquinones, process for their preparation and their utilization - Google Patents
Dispersions of dinitroanthraquinones, process for their preparation and their utilization Download PDFInfo
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- EP0031059A1 EP0031059A1 EP80107600A EP80107600A EP0031059A1 EP 0031059 A1 EP0031059 A1 EP 0031059A1 EP 80107600 A EP80107600 A EP 80107600A EP 80107600 A EP80107600 A EP 80107600A EP 0031059 A1 EP0031059 A1 EP 0031059A1
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- dinitroanthraquinones
- dispersions according
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- dispersions
- surfactants
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/22—Other features of pulping processes
- D21C3/222—Use of compounds accelerating the pulping processes
Definitions
- Dinitroanthraquinones have a beneficial effect in certain processes for obtaining and bleaching pulp from lignocellulosic materials such as wood, straw and bagasse when used in amounts of 0.001 to 10% by weight, based on the dry weight of the lignocellulosic material.
- the dinitroanthraquinones are generally in the form of powders.
- the use of such powdered dinitroanthraquinones in processes for the production of pulps from lignocellulosic materials and their bleaching presents difficulties. If the powdered dinitroanthraquinones are added directly to the lignocellulose material to be digested, the finer parts of the dinitroanthraquinones get into the environment in a slightly dusty manner. In this way, they are not only withdrawn from the intended use, but also annoy people working near the addition point and can even cause dust explosions. In addition, one is the same because of the relatively small amounts of the dinitroanthraquinones required moderate distribution difficult. Even distribution of the dinitroanthachinones is essential to achieve uniform pulp quality.
- dinitroanthraquinones have a relatively high specific weight (for example, 2,7-dinitroanthachinone has a specific weight of 1.558 g / cm 3 at 20 ° C.)
- the coarser portions of the powdered dinitroanthraquinones settle rapidly when stirred into water or into the digestion solution After standing briefly on the bottom of the vessel, they form a compact layer that can only be swirled up with difficulty.
- the addition of the dinitroanthraquinones directly to the cooking liquor, in the mixture of lignocellulose materials and cooking liquor or in the form of a slurry in water is therefore not a way to achieve the required uniform distribution of the dinitroanthraquinones.
- the invention therefore relates to dispersions of dinitroanthraquinones for use in processes for the production of pulp from lignocellulosic materials, which are characterized in that they contain dinitroanthraquinones in finely divided form, surfactants and water and / or organic, water-miscible liquids whose boiling point is above 80 ° C. lies included.
- cellulose production is understood to mean all processes and process steps in which lignin in materials containing lignin and cellulose is acted on chemically. Examples of this are alkaline, neutral and acidic digestion processes for lignocellulose materials such as wood, straw, bagasse and grasses, and bleaching processes for partially or largely digested lignocellulose materials.
- dinitroanthraquinones to be dispersed according to the invention are also dinitroanthraquinones which, in addition to the nitro groups, have one or have several further substituents.
- dinitroanthraquinones are also to be understood as meaning partially nuclear-hydrogenated derivatives of dinitroanthraquinones and / or their tautomeric forms.
- the dispersions according to the invention preferably contain mixtures of unsubstituted dinitroanthraquinones. Such mixtures are obtained, for example, in the industrial nitration of anthraquinone and / or mononitroanthraquinones.
- the dispersions according to the invention can contain mixtures of dinitroanthraquinones which are obtained when dinitrating anthraquinone on an industrial scale or nitriding mononitroanthraquinone mixtures and from the resulting nitration products the isomers valuable as dye intermediates, for example. Separates 1-nitro, 1.5-dinitro and / or 1.8-dinitroanthraquinone.
- Mixtures which are particularly preferred as dinitroanthraquinones contain, for example, 0 to 3% by weight of 1-nitroanthraquinone, 5 to 12% by weight of 1,5-dinitroanthraquinone, 15 to 35% by weight of 1,6-dinitroanthraquinone, 15 to 35% by weight of 1,7-dinitroanthraquinone , 15 to 50% by weight of 1,8-dinitroanthraquinone, 0.5 to 3% by weight of 2.6-dinitroanthraquinone and 0.5 to 3% by weight of 2,7-dinitroanthraquinone.
- the dinitroanthraquinones to be dispersed according to the invention preferably consist of 80% by weight of particles with a particle size of less than 10 ⁇ m, in particular less than 5 ⁇ m.
- Cationic, nonionic and above all anionic surfactants are suitable as surfactants for the dispersions according to the invention.
- Quaternary long-chain and / or oxyethylated amines, quaternary pyridinium compounds or long-chain phosphonium compounds may be mentioned as cationic surfactants.
- Long chain means a carbon chain with at least 4 C atoms, preferably with at least 6 C atoms.
- nonionic surfactants are addition products of alkylene oxides, in particular ethylene oxide, with higher fatty acids, alcohols, phenols, acid amides, mercaptans, amines or alkylphenols.
- the adducts can be obtained, for example, from 5 to 50 mol of alkylene oxide and 1 mol of fatty acid, alcohol, phenol, acid amide, mercaptan, amine or alkylphenol, which have at least 4, preferably at least 6, carbon atoms.
- alkylene oxides in particular ethylene oxide, on polypropylene oxide or on sugar, and also oxyethylated and non-oxyethylated sugar derivatives, such as fatty acid esters of pentaerythritol or sucrose, are also suitable as nonionic surfactants.
- the dispersions according to the invention preferably contain anionic surfactants.
- anionic surfactants are alkyl sulfonates, sulfated unsaturated higher fatty acids, sulfonates of polycarboxylic esters, alkylbenzenesulfonates, sulfated aliphatic alcohols, with an inorganic polybasic acid, such as phosphoric acid or especially sulfuric acid, adducts of ethylene oxide with higher amines, acids, phenols or alcohols converted into acidic esters , and lignin sulfonates or derivatives of lignin sulfonates, condensation products from aromatic sulfonic acids and formaldehyde and polyphosphates in question.
- the dispersions according to the invention particularly preferably contain lignin sulfonates and / or as surfactants Condensation products from aromatic sulfonic acids and formaldehyde.
- the dispersions according to the invention can also contain mixtures of anionic and nonionic surfactants.
- Water and / or organic, water-miscible liquids whose boiling point is above 80 ° C., preferably above 100 ° C., are used as dispersants for the dispersions according to the invention.
- Such liquids are, above all, polyhydric alcohols, and also liquid acid amides.
- Examples include: di-, tri- and polyols such as ethylene glycol, propylene glycol, glycerol, and their ethers such as glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; as acid amides formamide and dimethylformamide.
- These organic liquids not only act as dispersants, but when used together with water also serve as a means of reducing the frost sensitivity of the dispersions.
- Water and organic liquids can be present in any mixing ratio in the dispersions according to the invention.
- the content of these organic liquids in the dispersions according to the invention is preferably 5 to 20% by weight, based on the weight of the total dispersion.
- the dispersions according to the invention can contain, for example, 30 to 70% by weight of dinitroanthraquinones finely divided form, 0.5 to 30 wt .-% surfactant or surfactant mixture and at least 30 wt .-% water and / or organic, water-miscible liquid.
- the dispersions according to the invention preferably contain 45 to 65% by weight of dinitroanthraquinones in finely divided form, 1 to 10% by weight of surfactant or surfactant mixtures and at least 35% by weight of water and / or organic, water-miscible liquid.
- the dispersions according to the invention can contain further substances, for example preservatives, drying-out preventatives and / or agents for stabilizing dispersions.
- Substances are suitable as preservatives, e.g. prevent the formation of mold and / or bacteria. Common preservatives are suitable for this, e.g. Pentachlorophenol sodium, addition products of paraformaldehyde to araliphatic alcohols such as benzyl alcohol and / or formaldehyde solutions.
- the preservatives can be added to the dispersions according to the invention, for example in amounts of 0 to 3% by weight, preferably in amounts of 0.05 to 0.5% by weight, based on the weight of the dispersion.
- Suitable drying prevention agents are customary soluble drying prevention agents, such as polyalkylene glycols, for example polyethylene glycols, with molecular weights from 200 to 2000, and polyhydroxyalkyl urethanes and, preferably, those already known as Dispersing agents or organic, water-miscible liquids described as agents for reducing the sensitivity to frost.
- the drying-out preventing agents can be added to the dispersions according to the invention, for example in amounts of 2 to 20, preferably 5 to 10% by weight, based on the weight of the dispersion.
- agents which stabilize the dispersions are: highly disperse silicic acid, magnesium and aluminum silicates, Mömmorillonite, which may also contain organic bases, chalk and / or thickeners such as methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and polyacrylates and / or polymethacrylate and / or their copolymers, polyvinyl alcohols, and combinations of the substances mentioned.
- the stabilizers can be added to the dispersions according to the invention, for example in amounts of 0 to 2, preferably 0.1 to 1,% by weight, based on the total weight of the dispersion.
- the dispersions according to the invention can be prepared, for example, in such a way that the dinitroanthraquinone to be dispersed, the surfactant or the surfactant mixture, water and / or the organic water-miscible liquid, the boiling point of which is above 80 ° C. and, if appropriate, stabilizing agents in the desired ratio mixed, fed to a conventional wet shredder.
- Suitable wet crushers are, for example, kneaders, kneading screws, ball mills, rotor-stator mills, dissolvers, corundum disk mills and Vibrating mills.
- High-speed agitator mills with grinding media are preferably used, the grinding media of which preferably have a diameter of 0.1 to 10 mm.
- the grinding is preferably carried out until at least 80% by weight of the dinitroanthraquinone particles have a grain size below 10 ⁇ m, preferably below 5 ⁇ m.
- the preservatives and / or anti-drying agents can be added to the dispersion before or after grinding.
- the dispersions according to the invention are to be used in cellulose production processes which are carried out in an alkaline medium, it may be advantageous to add small amounts of an alkaline substance to the dispersions.
- alkaline substances are e.g. aqueous sodium hydroxide solution or aqueous potassium hydroxide solution. These substances can be added to the dispersions in amounts of 0 to 2% by weight, based on the total weight of the dispersion.
- the dispersions according to the invention are used in processes for the production of pulp from lignocellulosic materials.
- the dispersions according to the invention can be added to the pulp before the boiling, but advantageously before the impregnation, in which the lignocellulose material is impregnated with the aqueous solution of the digestion chemicals at a temperature of 80 to 100 ° C.
- the aqueous solution is on final chemicals also serves as the conveying medium for loading the impregnator and / or cooker with the lignocellulose material
- the dispersions according to the invention can be metered both into the returning solution or into the solution loaded with chips and also directly into the impregnator or cooker.
- the dispersions according to the invention are generally used in an amount of 0.001 to 10% by weight, based on the weight of the lignocellulose material.
- the desired fine distribution of the dinitroanthraquinones in the digestion liquids is achieved.
- the dispersions of the invention are stable and pumpable, i.e. they can be dosed with the aid of suitable pumps, for example peristaltic pumps, eccentric screw pumps or piston pumps, and can be conveyed through pipelines.
- suitable pumps for example peristaltic pumps, eccentric screw pumps or piston pumps
- they can be stored for several weeks or even months without the dispersed substances settling or floating or only little settling or floating that they can be removed by simple means, e.g. slow running stirrers, can be brought back into the dispersed state.
- the dinitroanthraquinones can be metered by simple volume or quantity measurement.
- dispersions according to the invention fully meet the requirements for use in the production of cellulose, including cellulose bleaching, since the low, but not negligible, solubility of the dinitroanthraquinones in water means that their recrystallization with particle enlargement was not to be expected could be expected. that the finely divided state and thus stable dispersions can be maintained over a long period of time.
- the invention further relates to a process for the production of pulp from lignocellulosic materials in the presence of dinitroanthraquinones, which is characterized in that the dinitroanthraquinones are used in the form of the dispersions according to the invention.
- the processes for the production of cellulose from lignocellulose materials as such are carried out in a manner known per se.
- these processes can be carried out by digesting lignocellulose materials in a sulfite solution, which can be acidic, neutral or alkaline, and adding the dispersions according to the invention to the digest solution before or after adding the lignocellulose material.
- the dispersions according to the invention can also be used in the known pulping processes which are used as Kraft processes, soda processes and polysulfide processes. Procedure.
- the dispersions according to the invention can also be used in the known oxygen-alkali process for pulping and / or in the bleaching processes known for pulping.
- pulps of particularly uniform quality are obtained as a result of the uniform distribution of the dinitroanthraquinones in the digestion solution.
- a flowable, stable dispersion of the dinitroanthraquinone mixture is obtained.
- the dispersion is pumpable and can be easily stirred into wood pulping liquors from the sulfite, power and soda processes.
- a stable, pumpable dispersion is obtained, which can be pumped without difficulty and can be distributed in wood pulping liquors of the sulfite, power and soda process.
- Example 1 600 g of the dinitroanthraquinone mixture described in Example 1, 60 g of ethylene glycol, 313 g of water and 20 g of sodium dinaphthyl methanesulfonate are ground as described in Example 1.
- the suspension is thickened with aluminum silicate and made alkaline with 3 g of 50% sodium hydroxide solution.
- a pumpable, stable dispersion is obtained.
- Example 1 600 g of the mixture of dinitroanthraquinones described in Example 1 are ground with 60 g of propylene glycol, 315 g of water and 20 g of lignin sulfonate as described in Example 1. A preservative based on a formaldehyde addition product with benzyl alcohol is added to the suspension and made alkaline with 3 g of 50% sodium hydroxide solution.
- a stable, flowable dispersion is obtained which can be distributed in the wood digestion liquors of the power and soda process.
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- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
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Abstract
Dispersionen von Dinitroanthrachinonen für die Verwendung in der Zellstoffgewinnung, enthaltend Dinitroanthrachinone in feinverteilter Form, Tenside und Wasser und oder flüssige organische mit Wasser mischbare Verbindungen, deren Siedepunkt über 80°C liegt, Verfahren zur Herstellung der Dispersionen und deren Verwendung zur Gewinmung von Zellstoff aus Lig,ocellulosematerialien.Dispersions of dinitroanthraquinones for use in pulp production, containing dinitroanthraquinones in finely divided form, surfactants and water and or liquid organic water-miscible compounds whose boiling point is above 80 ° C., processes for preparing the dispersions and their use for obtaining pulp from lig , ocellulose materials.
Description
Dinitroanthrachinone üben eine günstige Wirkung bei bestimmten Verfahren zur Gewinnung und Bleichung von Zellstoff aus Lignocellulosematerialien wie Holz, Stroh und Bagasse aus, wenn sie in Mengen von 0,001 bis 10 Gew.-%, bezogen auf das Trockengewicht des Lignocellulosematerials, eingesetzt werden.Dinitroanthraquinones have a beneficial effect in certain processes for obtaining and bleaching pulp from lignocellulosic materials such as wood, straw and bagasse when used in amounts of 0.001 to 10% by weight, based on the dry weight of the lignocellulosic material.
Die Dinitroanthrachinone liegen im allgemeinen in Form von Pulvern vor. Die Anwendung derartiger pulverförmiger Dinitroanthrachinone in Verfahren zur Gewinnung von Zellstoffen aus Lignocellulosematerialien und deren Bleichung bereitet jedoch Schwierigkeiten. Setzt man die pulverförmigen Dinitroanthrachinone dem aufzuschließenden Lignocellulosematerial unmittelbar zu, so gelangen die feineren Anteile der Dinitroanthrachinone leicht staubförmig in die Umgebung. Auf diese Weise werden sie nicht nur der zugedachten Verwendung entzogen, sondern führen auch zur Belästigung der in der Nähe der Zugabestelle arbeitenden Menschen und können sogar Staubexplosionen verursachen. Außerdem ist wegen der relativ geringen Mengen der benötigten Dinitroanthrachinone eine gleichmäßige Verteilung schwierig. Eine gleichmäßige Verteilung der Dinitroanthachinone ist jedoch zur Erzielung einer einheitlichen Zellstoffqualität unerläßlich.The dinitroanthraquinones are generally in the form of powders. However, the use of such powdered dinitroanthraquinones in processes for the production of pulps from lignocellulosic materials and their bleaching presents difficulties. If the powdered dinitroanthraquinones are added directly to the lignocellulose material to be digested, the finer parts of the dinitroanthraquinones get into the environment in a slightly dusty manner. In this way, they are not only withdrawn from the intended use, but also annoy people working near the addition point and can even cause dust explosions. In addition, one is the same because of the relatively small amounts of the dinitroanthraquinones required moderate distribution difficult. Even distribution of the dinitroanthachinones is essential to achieve uniform pulp quality.
Eine gleichmäßige Verteilung der Dinitroanthachinone wird auch dadurch erschwert, daß diese in Wasser und in den in der Zellstoffgewinnung verwendeten wäßrigen Aufschlußlösungen im allgemeinen.nicht nur sehr wenig löslich sind, sondern auch schlecht benetzt werden. Infolge der schlechten Benetzung lassen sich die feineren Anteile der pulverförmigen Dinitroanthrachinone nicht oder nur schlecht einrühren und schwimmen stattdessen unbenetzt, gegebenenfalls unter Einschluß von Luft, auf der Oberfläche.Uniform distribution of the dinitroanthachinones is also made more difficult by the fact that they are not only very slightly soluble in water and in the aqueous pulping solutions used in pulp production, but are also poorly wetted. As a result of poor wetting, the finer portions of the powdered dinitroanthraquinones cannot be stirred in or can only be stirred in poorly and instead float on the surface without wetting, if appropriate with the inclusion of air.
Da Dinitroanthrachinone ein relativ hohes spezifisches Gewicht haben (z.B. hat 2.7-Dinitroanthachinon bei 20°C ein spezifisches Gewicht von 1,558 g/cm3), setzen sich die gröberen Anteile der pulverförmigen Dinitroanthrachinone, beim Einrühren in Wasser oder in die Aufschlußlösung, rasch ab und bilden nach kurzem Stehen am Gefäßboden eine kompakte, nur mit Schwierigkeiten wieder aufwirbelbare Schicht. Die Zugabe der Dinitroanthrachinone direkt zur Kochlauge, in die Mischung von Lignocellulosematerialien und Kochlauge oder in Form einer Anschlämmung in Wasser ist also kein Weg, die erforderliche gleichmäßige Verteilung der Dinitroanthrachinone zu erreichen.Since dinitroanthraquinones have a relatively high specific weight (for example, 2,7-dinitroanthachinone has a specific weight of 1.558 g / cm 3 at 20 ° C.), the coarser portions of the powdered dinitroanthraquinones settle rapidly when stirred into water or into the digestion solution After standing briefly on the bottom of the vessel, they form a compact layer that can only be swirled up with difficulty. The addition of the dinitroanthraquinones directly to the cooking liquor, in the mixture of lignocellulose materials and cooking liquor or in the form of a slurry in water is therefore not a way to achieve the required uniform distribution of the dinitroanthraquinones.
Es wurde nun gefunden, daß sich die vorstehend beschriebenen Schwierigkeiten bei der Anwendung der Dinitroanthrachinone vermeiden lassen, wenn man diese in Form bestimmter Dispersionen einsetzt. Diese Dispersionen werden dadurch erhalten, daß man Dinitroanthrachinone in feinverteilter Form zusammen mit Tensiden in Wasser und/oder organischen, mit Wasser mischbaren Flüssigkeiten, deren Siedepunkt über 80°C liegt, dispergiert.It has now been found that the difficulties described above in using the dinitroanthraquinones can be avoided by using them in the form of certain dispersions. These dispersions are obtained by dispersing dinitroanthraquinones in finely divided form together with surfactants in water and / or organic, water-miscible liquids whose boiling point is above 80.degree.
Die Erfindung betrifft daher Dispersionen von Dinitroanthrachinonen für die Verwendung in Verfahren zur Gewinnung von Zellstoff aus Lignocellulosematerialien, die dadurch gekennzeichnet sind, daß sie Dinitroanthrachinone in feinverteilter Form, Tenside und Wasser und/ oder organische, mit Wasser mischbare Flüssigkeiten, deren Siedepunkt über 80°C liegt, enthalten.The invention therefore relates to dispersions of dinitroanthraquinones for use in processes for the production of pulp from lignocellulosic materials, which are characterized in that they contain dinitroanthraquinones in finely divided form, surfactants and water and / or organic, water-miscible liquids whose boiling point is above 80 ° C. lies included.
Im Rahmen der Erfindung werden unter dem Begriff "Zellstoffgewinnung" alle Verfahren und Verfahrensstufen verstanden, bei denen auf Lignin in Lignin und Cellulose enthaltenden Materialien auf chemische Weise eingewirkt wird. Beispiele hierfür sind alkalische, neutrale und saure Aufschlußverfahren für Lignocellulosematerialien wie Holz, Stroh, Bagasse und Gräser, sowie Bleichverfahren für teilweise oder weitgehend aufgeschlossene Lignocellulosematerialien.In the context of the invention, the term “cellulose production” is understood to mean all processes and process steps in which lignin in materials containing lignin and cellulose is acted on chemically. Examples of this are alkaline, neutral and acidic digestion processes for lignocellulose materials such as wood, straw, bagasse and grasses, and bleaching processes for partially or largely digested lignocellulose materials.
Als Vertreter der erfindungsgemäß zu dispergierenden Dinitroanthrachinone kommen auch Dinitroanthrachinone in Betracht, die zusätzlich zu den Nitrogruppen einen oder mehrere weitere Substituenten aufweisen.Representatives of the dinitroanthraquinones to be dispersed according to the invention are also dinitroanthraquinones which, in addition to the nitro groups, have one or have several further substituents.
Als Vertreter der erfindungsgemäß zu dispergierenden Dinitroanthrachinone seien beispielsweise genannt:
- 1.5-, 1.6-, 1.7-, 1.8-, 2.6- und 2.7-Dinitroanthrachinon; 1.3-Dinitro-4-aminoanthrachinon; 1.5-Dinitro-4.8-dihydroxy-anthrachinon; 1.8-Dinitro-4.5-dihydroxy- anthrachinon.
- 1.5-, 1.6-, 1.7-, 1.8-, 2.6- and 2.7-dinitroanthraquinone; 1,3-dinitro-4-aminoanthraquinone; 1,5-dinitro-4.8-dihydroxyanthraquinone; 1.8-Dinitro-4.5-dihydroxyanthraquinone.
Unter Dinitroanthrachinonen sind im Rahmen der vorliegenden Erfindung auch partiell kernhydrierte Derivate von Dinitroanthrachinonen und/oder deren tautomere Formen zu verstehen.In the context of the present invention, dinitroanthraquinones are also to be understood as meaning partially nuclear-hydrogenated derivatives of dinitroanthraquinones and / or their tautomeric forms.
Bevorzugt enthalten die erfindungsgemäßen Dispersionen Mischungen-von unsubstituierten Dinitroanthrachinonen. Solche Mischungen fallen.beispielsweise bei der technischen Nitrierung von Anthrachinon und/oder Mononitroanthrachinonen an. Insbesondere können die erfindungsgemäßen Dispersionen Mischungen von Dinitroanthrachinonen enthalten, die anfallen, wenn man Anthrachinon in technischem Maßstab dinitriert oder Mononitroanthrachinongemische nitriert und aus den dabei anfallenden Nitrierungsprodukten die als Farbstoffzwischenprodukte wertvollen Isomeren, z..B. 1-Nitro-, 1.5-Dinitro- und/oder 1.8-Dinitroanthrachinon abtrennt. Diese letztgenannten Mischungen enthalten als wesentliche Bestandteile 1.5-, 1.6-, 1.7-, 1.8-, 2.6- und 2.7-Dinitroanthrachinon. Als Dinitroanthrachinone besonders bevorzugte Mischungen enthalten beispielsweise 0 bis 3 Gew.-% 1-Nitroanthrachinon, 5 bis 12 Gew.-% 1.5-Dinitroanthrachinon, 15 bis 35 Gew.-% 1.6-Dinitroanthrachinon, 15 bis 35 Gew.-% 1.7-Dinitroanthrachinon, 15 bis 50 Gew.-% 1.8-Dinitroanthrachinon, 0,5 bis 3 Gew.-% 2.6-Dinitroanthrachinon und 0,5 bis 3 Gew.-% 2.7-Dinitroanthrachinon.The dispersions according to the invention preferably contain mixtures of unsubstituted dinitroanthraquinones. Such mixtures are obtained, for example, in the industrial nitration of anthraquinone and / or mononitroanthraquinones. In particular, the dispersions according to the invention can contain mixtures of dinitroanthraquinones which are obtained when dinitrating anthraquinone on an industrial scale or nitriding mononitroanthraquinone mixtures and from the resulting nitration products the isomers valuable as dye intermediates, for example. Separates 1-nitro, 1.5-dinitro and / or 1.8-dinitroanthraquinone. These latter mixtures ent hold as essential components 1.5-, 1.6-, 1.7-, 1.8-, 2.6- and 2.7-dinitroanthraquinone. Mixtures which are particularly preferred as dinitroanthraquinones contain, for example, 0 to 3% by weight of 1-nitroanthraquinone, 5 to 12% by weight of 1,5-dinitroanthraquinone, 15 to 35% by weight of 1,6-dinitroanthraquinone, 15 to 35% by weight of 1,7-dinitroanthraquinone , 15 to 50% by weight of 1,8-dinitroanthraquinone, 0.5 to 3% by weight of 2.6-dinitroanthraquinone and 0.5 to 3% by weight of 2,7-dinitroanthraquinone.
Die erfindungsgemäß zu dispergierenden Dinitroanthrachinone bestehen vorzugsweise zu 80 Gew.-% aus Teilchen einer Korngröße unter 10um, insbesondere unter 5um.The dinitroanthraquinones to be dispersed according to the invention preferably consist of 80% by weight of particles with a particle size of less than 10 µm, in particular less than 5 µm.
Als Tenside kommen für die erfindungsgemäßen Dispersionen kationische, nichtionische und vor allem anionische Tenside in Frage.Cationic, nonionic and above all anionic surfactants are suitable as surfactants for the dispersions according to the invention.
Als kationische Tenside seien beispielsweise quarternäre langkettige und/oder oxethylierte Amine, quarternäre Pyridiniumverbindungen oder langkettige Phosphoniumverbindungen genannt. Langkettig bedeutet dabei eine Kohlenstoffkette mit mindestens 4 C-Atomen, vorzugsweise mit mindestens 6 C-Atomen.Quaternary long-chain and / or oxyethylated amines, quaternary pyridinium compounds or long-chain phosphonium compounds may be mentioned as cationic surfactants. Long chain means a carbon chain with at least 4 C atoms, preferably with at least 6 C atoms.
Beispiele für kationische Tenside sind insbesondere:
- Trimethyl-hexadecyl-ammoniumbromid, Cetyl-pyridiniumbromid, Lauryl-dimethylbenzyl-ammoniumchlorid, Monoester des Triethanolamins mit Stearinsäure als ameisensaure oder essigsaure Salze, N-Lauryl-methylbenzimidazol-chlorhydrat und Dodecyl-trimethyl-phosphoniumbromid.
- Trimethyl-hexadecyl-ammonium bromide, cetyl-pyridinium bromide, lauryl-dimethylbenzyl-ammonium chloride, monoesters of triethanolamine with stearic acid as formic acid or acetic acid salts, N-lauryl-methylbenzimidazole chlorohydrate and dodecyl-trimethyl-phosphonium bromide.
Als nichtionische Tenside kommen beispielsweise Anlagerungsprodukte von Alkylenoxiden, insbesondere Ethylenoxid, an höhere Fettsäuren, Alkohole, Phenole, Säureamide, Mercaptane, Amine oder Alkylphenole, in Frage. Die Anlagerungsprodukte können beispielsweise aus 5 bis 50 Mol Alkylenoxid und 1 Mol Fettsäure, Alkohol, Phenol, Säureamid, Mercaptan, Amin oder Alkylphenol, die mindestens 4, vorzugsweise mindestens 6 C-Atome aufweisen, erhalten werden. Als nichtionogene Tenside kommen auch Anlagerungsprodukte von Alkylenoxiden, insbesondere Ethylenoxid, an Polypropylenoxid oder an Zucker, sowie oxethylierte und nichtoxethylierte Zuckerderivate, wie Fettsäureester des Pentaerythrits oder der Saccharose, in Frage.Examples of suitable nonionic surfactants are addition products of alkylene oxides, in particular ethylene oxide, with higher fatty acids, alcohols, phenols, acid amides, mercaptans, amines or alkylphenols. The adducts can be obtained, for example, from 5 to 50 mol of alkylene oxide and 1 mol of fatty acid, alcohol, phenol, acid amide, mercaptan, amine or alkylphenol, which have at least 4, preferably at least 6, carbon atoms. Addition products of alkylene oxides, in particular ethylene oxide, on polypropylene oxide or on sugar, and also oxyethylated and non-oxyethylated sugar derivatives, such as fatty acid esters of pentaerythritol or sucrose, are also suitable as nonionic surfactants.
Beispiele für nichtionogene Tenside sind insbesondere:
- Anlagerungsprodukte von 5 bis 20 Mol Ethylenoxid an Stearinsäure, Oleylalkohol, Polypropylenglykol, Nonylphenol, ölsäureamid und Dodecylamin.
- Addition products of 5 to 20 moles of ethylene oxide with stearic acid, oleyl alcohol, polypropylene glycol, nonylphenol, oleic acid amide and dodecylamine.
Ein großer Teil dieser Verbindungen und weitere in Betracht kommende nichtionogene Tenside sind z.B. in N. Schönfeldt, Grenzflächenaktive Ethylenoxid-Addukte, Seiten 42 bis 95 (1976) und in K. Lindner, Tenside-Textilhilfsmittel-Waschrohstoffe, Band 1, Seiten 837 bis 917 (1964), beschrieben.A large part of these compounds and other suitable nonionic surfactants are e.g. in N. Schönfeldt, interfacially active ethylene oxide adducts, pages 42 to 95 (1976) and in K. Lindner, tenside-textile auxiliary washing raw materials, volume 1, pages 837 to 917 (1964).
Vorzugsweise enthalten die erfindungsgemäßen Dispersionen anionische Tenside. Als anionische Tenside kommen beispielsweise Alkylsulfonate, sulfatierte ungesättigte höhere Fettsäuren, Sulfonate von Polycarbonsäureestern, Alkylbenzolsulfonate, sulfatierte aliphatische Alkohole, mit einer anorganischen mehrbasigen Säure, wie Phosphorsäure oder insbesondere Schwefelsäure, in saure Ester überführte Anlagerungsprodukte von Ethylenoxid an höhere Amine, Säuren, Phenole oder Alkohole, sowie Ligninsulfonate oder Derivate von Ligninsulfonaten, Kondensationsprodukte aus aromatischen Sulfonsäuren und Formaldehyd und Polyphosphate in Frage.The dispersions according to the invention preferably contain anionic surfactants. Examples of anionic surfactants are alkyl sulfonates, sulfated unsaturated higher fatty acids, sulfonates of polycarboxylic esters, alkylbenzenesulfonates, sulfated aliphatic alcohols, with an inorganic polybasic acid, such as phosphoric acid or especially sulfuric acid, adducts of ethylene oxide with higher amines, acids, phenols or alcohols converted into acidic esters , and lignin sulfonates or derivatives of lignin sulfonates, condensation products from aromatic sulfonic acids and formaldehyde and polyphosphates in question.
Beispiele für anionische Tenside sind insbesondere:
- Natriumdodecylsulfonat, Natriumlaurylsulfat, Natriumdodecylbenzolsulfonat, Natriumdibutylnaphthalinsulfonat, saure Schwefelsäureester des Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol Nonylphenol, Natriumdioctylsulfosuccinat, Kondensationsprodukte aus Kresol, 2-Naphthol-6-sulfonsäure und Formaldehyd, sowie Sulfonsäuren von Naphthalin, Terphenyl oder Ditolylether.
- Sodium dodecyl sulfonate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dibutylnaphthalenesulfonate, acidic sulfuric acid esters of the adduct of 2 moles of ethylene oxide with 1 mole of nonylphenol, sodium dioctylsulfosuccinate, condensation products of cresol, 2-naphthalenylphonyl ether, and 6-naphthalenol-formaldehyde;
Ein großer Teil dieser Verbindungen und weitere in Betracht kommende anionische Tenside sind in K. Lindner, Tenside-Textilhilfsmittel-Waschrohstoffe, Band 1, Seiten 571 bis 835 (1964), beschrieben.A large part of these compounds and further anionic surfactants that can be considered are described in K. Lindner, Tenside-Textile Aid Wash Raw Materials, Volume 1, pages 571 to 835 (1964).
Die erfindungsgemäßen Dispersionen enthalten als Tenside besonders bevorzugt Ligninsulfonate und/oder Kondensationsprodukte aus aromatischen Sulfonsäuren und Formaldehyd.The dispersions according to the invention particularly preferably contain lignin sulfonates and / or as surfactants Condensation products from aromatic sulfonic acids and formaldehyde.
Die erfindungsgemäßen Dispersionen können auch Mischungen von anionischen und nichtionischen Tensiden enthalten.The dispersions according to the invention can also contain mixtures of anionic and nonionic surfactants.
Als Dispersionsmittel werden für die erfindungsgemäßen Dispersionen Wasser und/oder organische, mit Wasser mischbare Flüssigkeiten verwendet, deren Siedepunkt über 80°C, vorzugsweise über 100°C, liegt.Water and / or organic, water-miscible liquids whose boiling point is above 80 ° C., preferably above 100 ° C., are used as dispersants for the dispersions according to the invention.
Als solche Flüssigkeiten kommen vor al-lem mehrwertige Alkohole, ferner flüssige Säureamide, in Betracht. Beispielsweise seien genannt: Di-, Tri- und Polyole wie Ethylenglykol, Propylenglykol, Glycerin, und deren Ether wie Glykolmonoethylether, Diethylenglykolmonomethylether und Diethylenglykolmonoethylether; als Säureamide Formamid und Dimethylformamid. Diese organischen Flüssigkeiten wirken nicht nur als Dispergiermittel sondern dienen bei ihrer gemeinsamen Verwendung mit Wasser zugleich als Mittel zur Herabsetzung der Frostempfindlichkeit der Dispersionen. In den erfindungsgemäßen Dispersionen können Wasser und organische Flüssigkeiten in beliebigen Mischungsverhältnissen vorliegen. Der Gehalt der erfindungsgemäßen Dispersionen an diesen organischen Flüssigkeiten beträgt vorzugsweise 5 bis 20 Gew.-%, bezogen auf das Gewicht der Gesamtdispersion.Such liquids are, above all, polyhydric alcohols, and also liquid acid amides. Examples include: di-, tri- and polyols such as ethylene glycol, propylene glycol, glycerol, and their ethers such as glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; as acid amides formamide and dimethylformamide. These organic liquids not only act as dispersants, but when used together with water also serve as a means of reducing the frost sensitivity of the dispersions. Water and organic liquids can be present in any mixing ratio in the dispersions according to the invention. The content of these organic liquids in the dispersions according to the invention is preferably 5 to 20% by weight, based on the weight of the total dispersion.
Die erfindungsgemäßen Dispersionen können beispielsweise 30 bis 70 Gew.-% Dinitroanthrachinone in feinverteilter Form, 0,5 bis 30 Gew.-% Tensid oder Tensidgemisch und mindestens 30 Gew.-% Wasser und/oder organische, mit Wasser mischbare Flüssigkeit enthalten. Vorzugsweise enthalten die erfindungsgemäßen Dispersionen 45 bis 65 Gew.-% Dinitroanthrachinone in feinverteilter Form, 1 bis 10 Gew.-% Tensid oder Tensidgemische und mindestens 35 Gew.-% Wasser und/ oder organische, mit Wasser mischbare Flüssigkeit.The dispersions according to the invention can contain, for example, 30 to 70% by weight of dinitroanthraquinones finely divided form, 0.5 to 30 wt .-% surfactant or surfactant mixture and at least 30 wt .-% water and / or organic, water-miscible liquid. The dispersions according to the invention preferably contain 45 to 65% by weight of dinitroanthraquinones in finely divided form, 1 to 10% by weight of surfactant or surfactant mixtures and at least 35% by weight of water and / or organic, water-miscible liquid.
Die erfindungsgemäßen Dispersionen können zusätzlich zu den vorstehend genannten Komponenten weitere Stoffe enthalten, beispielsweise Konservierungsmittel, Eintrocknungsverhinderungsmittel und/oder Mittel zur Stabilisierung von Dispersionen.In addition to the components mentioned above, the dispersions according to the invention can contain further substances, for example preservatives, drying-out preventatives and / or agents for stabilizing dispersions.
Als Konservierungsmittel kommen Stoffe in Frage, welche z.B. die Schimmelbildung und/oder den Bakterienbefall verhindern. Hierfür.sind übliche Konservierungsmittel geeignet, z.B. Pentachlorphenolnatrium, Additionsprodukte von Paraformaldehyd an araliphatische Alkohole wie Benzylalkohol und/oder Formaldehydlösungen. Die Konservierungsmittel können den erfindungsgemäßen Dispersionen beispielsweise in Mengen von 0 bis 3 Gew.-%, vorzugsweise in Mengen von 0,05 bis 0,5 Gew.-%, bezogen auf das Gewicht der Dispersion zugesetzt werden.Substances are suitable as preservatives, e.g. prevent the formation of mold and / or bacteria. Common preservatives are suitable for this, e.g. Pentachlorophenol sodium, addition products of paraformaldehyde to araliphatic alcohols such as benzyl alcohol and / or formaldehyde solutions. The preservatives can be added to the dispersions according to the invention, for example in amounts of 0 to 3% by weight, preferably in amounts of 0.05 to 0.5% by weight, based on the weight of the dispersion.
Als Eintrocknungsverhinderungsmittel kommen übliche lösliche Eintrocknungsverhinderungsmittel wie Polyalkylenglykole, z.B. Polyethylenglykole, mit Molekulargewichten von 200 bis 2000, und Polyhydroxyalkylurethane sowie, vorzugsweise, die bereits als Dispersionsmittel bzw. als Mittel zur Herabsetzung der Frostempfindlichkeit beschriebenen organischen, mit Wasser mischbaren Flüssigkeiten in Betracht. Die Eintrocknungsverhinderungsmittel können den erfindungsgemäßen Dispersionen beispielsweise in Mengen von.2 bis 20, vorzugsweise 5 bis 10 Gew.-%, bezogen auf das Gewicht der Dispersion, zugesetzt werden.Suitable drying prevention agents are customary soluble drying prevention agents, such as polyalkylene glycols, for example polyethylene glycols, with molecular weights from 200 to 2000, and polyhydroxyalkyl urethanes and, preferably, those already known as Dispersing agents or organic, water-miscible liquids described as agents for reducing the sensitivity to frost. The drying-out preventing agents can be added to the dispersions according to the invention, for example in amounts of 2 to 20, preferably 5 to 10% by weight, based on the weight of the dispersion.
Als Mittel, die eine Stabilisierung der Dispersionen bewirken, seien beispielsweise genannt: hochdisperse Kieselsäure, Magnesium- und Aluminium-Silikate, Möntmorillonite, die auch organische Basen enthalten können, Kreide und/oder Verdickungsmittel wie Methylcellulose, Hydroxymethylcellulose, Hydroxyethylcellulose, Carboxymethylcellulose, sowie Polyacrylate und/ oder Polymethacrylat und/oder deren Mischpolymerisate, Polyvinylalkohole, sowie Kombinationen der genannten Stoffe. Die Stabilisierungsmittel können den erfindungsgemäßen Dispersionen beispielsweise in Mengen von 0 bis 2, vorzugsweise 0,1 bis 1 Gew.-%, bezogen auf das Gesamtgewicht der Dispersion, zugesetzt werden.Examples of agents which stabilize the dispersions are: highly disperse silicic acid, magnesium and aluminum silicates, Mömmorillonite, which may also contain organic bases, chalk and / or thickeners such as methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and polyacrylates and / or polymethacrylate and / or their copolymers, polyvinyl alcohols, and combinations of the substances mentioned. The stabilizers can be added to the dispersions according to the invention, for example in amounts of 0 to 2, preferably 0.1 to 1,% by weight, based on the total weight of the dispersion.
Die erfindungsgemäßen Dispersionen können z.B. in der Weise hergestellt werden, daß man das zu dispergierende Dinitroanthrachinon, das Tensid bzw. das Tensidgemisch, Wasser und/oder die organische, mit Wasser mischbare Flüssigkeit, deren Siedepunkt über 80°C liegt und gegebenenfalls Stabilisierungsmittel im gewünschten Verhältnis gemischt, einem üblichen Naßzerkleinerungsapparat zugeführt. Geeignete Naßzerkleinerungsapparate sind z.B. Kneter, Knetschnecken, Kugelmühlen, Rotor-Stator-Mühlen, Dissolver, Korundscheibenmühlen und Schwingmühlen. Vorzugsweise werden schnell laufende Rührwerksmühlen mit Mahlkörpern verwendet, deren Mahlkörper vorzugsweise einen Durchmesser von 0,1 bis 10 mm aufweisen. Die Mahlung erfolgt vorzugsweise solange, bis die Dinitroanthrachinon-Partikel zu mindestens 80 Gew.-% eine Korngröße unter 10um, vorzugsweise unter 5gm aufweisen. Die Konservierungsmittel und/oder Eintrocknungsverhinderungsmittel können der Dispersion vor oder nach der Mahlung zugesetzt werden.The dispersions according to the invention can be prepared, for example, in such a way that the dinitroanthraquinone to be dispersed, the surfactant or the surfactant mixture, water and / or the organic water-miscible liquid, the boiling point of which is above 80 ° C. and, if appropriate, stabilizing agents in the desired ratio mixed, fed to a conventional wet shredder. Suitable wet crushers are, for example, kneaders, kneading screws, ball mills, rotor-stator mills, dissolvers, corundum disk mills and Vibrating mills. High-speed agitator mills with grinding media are preferably used, the grinding media of which preferably have a diameter of 0.1 to 10 mm. The grinding is preferably carried out until at least 80% by weight of the dinitroanthraquinone particles have a grain size below 10 μm, preferably below 5 μm. The preservatives and / or anti-drying agents can be added to the dispersion before or after grinding.
Falls die erfindungsgemäßen Dispersionen in Zellstoffgewinnungsverfahren eingesetzt werden sollen, die in alkalischem Medium durchgeführt werden, kann es vorteilhaft sein, den Dispersionen kleine Mengen eines alkalisch reagierenden Stoffes zuzusetzen. Solche alkalisch reagierenden Stoffe sind z.B. wäßrige Natronlauge oder wäßrige Kalilauge. Diese Stoffe können den Dispersionen in Mengen von 0 bis 2 Gew.-%, bezogen auf das Gesamtgewicht der Dispersion, zugesetzt werden.If the dispersions according to the invention are to be used in cellulose production processes which are carried out in an alkaline medium, it may be advantageous to add small amounts of an alkaline substance to the dispersions. Such alkaline substances are e.g. aqueous sodium hydroxide solution or aqueous potassium hydroxide solution. These substances can be added to the dispersions in amounts of 0 to 2% by weight, based on the total weight of the dispersion.
Die erfindungsgemäßen Dispersionen werden in Verfahren zur Gewinnung von Zellstoff aus Lignocellulosematerialien verwendet. Die erfindungsgemäßen Dispersionen können bei der Zellstoffgewinnung vor der Kochung, vorteilhaft jedoch bereits vor der Imprägnierung zugesetzt werden, in der das Lignocellulosematerial bei einer Temperatur von 80 bis 100°C mit der wäßrigen Lösung der Aufschlußchemikalien imprägniert wird. In den Fällen, in denen die wäßrige Lösung der Aufschlußchemikalien auch als Fördermedium zur Beschickung der Imprägnierer und/oder Kocher mit dem Lignocellulosematerial dient, können die erfindungsgemäßen Dispersionen sowohl in die rücklaufende Lösung oder in die mit Hackschnitzeln beladene Lösung als auch unmittelbar in den Imprägnierer oder Kocher eindosiert werden.The dispersions according to the invention are used in processes for the production of pulp from lignocellulosic materials. The dispersions according to the invention can be added to the pulp before the boiling, but advantageously before the impregnation, in which the lignocellulose material is impregnated with the aqueous solution of the digestion chemicals at a temperature of 80 to 100 ° C. In cases where the aqueous solution is on final chemicals also serves as the conveying medium for loading the impregnator and / or cooker with the lignocellulose material, the dispersions according to the invention can be metered both into the returning solution or into the solution loaded with chips and also directly into the impregnator or cooker.
Die erfindungsgemäßen Dispersionen werden beim Einsatz in Verfahren zur Zellstoffgewinnung im allgemeinen in einer Menge von 0,001 bis 10 Gew.-%, bezogen auf das Gewicht des Lignocellulosematerials, eingesetzt.When used in processes for the production of cellulose, the dispersions according to the invention are generally used in an amount of 0.001 to 10% by weight, based on the weight of the lignocellulose material.
Mit Hilfe der erfindungsgemäßen Dispersionen wird die gewünschte Feinverteilung der Dinitroanthrachinone in den Aufschlußflüssigkeiten erreicht. Die erfindungsgemäßen Dispersionen sind stabil und pumpfähig, d.h. sie können mit Hilfe geeigneter Pumpen, beispielsweise Schlauchquetschpumpen, Exzenterschneckenpumpen oder Kolbenpumpen dosiert und durch Rohrleitungen gefördert werden. Infolge ihrer Stabilität können sie mehrere Wochen oder sogar Monate gelagert werden, ohne daß sich die dispergierten Stoffe absetzen bzw. aufschwimmen bzw. nur sowenig absetzen oder aufschwimmen, daß sie mit einfachen Mitteln, z.B. langsam laufenden Rührern, wieder in den dispergierten Zustand gebracht werden können. In Form der erfindungsgemäßen Dispersionen lassen sich die Dinitroanthrachinone durch einfache Volumen- oder Mengenmessung dosieren.With the aid of the dispersions according to the invention, the desired fine distribution of the dinitroanthraquinones in the digestion liquids is achieved. The dispersions of the invention are stable and pumpable, i.e. they can be dosed with the aid of suitable pumps, for example peristaltic pumps, eccentric screw pumps or piston pumps, and can be conveyed through pipelines. As a result of their stability, they can be stored for several weeks or even months without the dispersed substances settling or floating or only little settling or floating that they can be removed by simple means, e.g. slow running stirrers, can be brought back into the dispersed state. In the form of the dispersions according to the invention, the dinitroanthraquinones can be metered by simple volume or quantity measurement.
Durch die Verwendung der erfindungsgemäßen Dispersionen in Verfahren zur Zellstoffgewinnung einschließlich der Zellstoffbleichung kann die günstige Wirkung der Dinitroanthrachinone optimal genutzt werden.By using the dispersions according to the invention in processes for pulp production including Cellulose bleaching can make optimal use of the beneficial effects of dinitroanthraquinones.
Es ist als ausgesprochen überraschend zu bezeichnen, daß die erfindungsgemäßen Dispersionen die Anforderungen für den Einsatz bei der Zellstoffgewinnung einschließlich der Zellstoffbleichung vollständig erfüllen, da wegen der geringen, doch nicht vernachlässigbaren Löslichkeit der Dinitroanthrachinone in Wasser mit deren Rekristallisation unter Teilchenvergrößerung zu rechnen war und deshalb nicht erwartet werden konnte,. daß der feinverteilte Zustand und damit stabile Dispersionen über längere Zeit aufrechterhalten werden können.It can be described as extremely surprising that the dispersions according to the invention fully meet the requirements for use in the production of cellulose, including cellulose bleaching, since the low, but not negligible, solubility of the dinitroanthraquinones in water means that their recrystallization with particle enlargement was not to be expected could be expected. that the finely divided state and thus stable dispersions can be maintained over a long period of time.
Die Erfindung betrifft weiterhin ein Verfahren zur Gewinnung von ` Zellstoff aus Lignocellulosematerialien in Gegenwart.von Dinitroanthrachinonen, das dadurch gekennzeichnet ist, daß man die Dinitroanthrachinone in Form der erfindungsgemäßen Dispersionen anwendet.The invention further relates to a process for the production of pulp from lignocellulosic materials in the presence of dinitroanthraquinones, which is characterized in that the dinitroanthraquinones are used in the form of the dispersions according to the invention.
Die Verfahren zur Zellstoffgewinnung aus Lignocellulosematerialien als solche werden in an sich bekannter Weise durchgeführt. Beispielsweise können diese Verfahren durchgeführt werden, indem man Lignocellulosematerialien in einer Sulfitlösung, die sauer, neutral oder alkalisch sein kann, digeriert und der Digerierlösung vor oder nach Zugabe des Lignocellulosematerials die erfindungsgemäßen Dispersionen zusetzt. Man kann die erfindungsgemäßen Dispersionen auch in den bekannten Zellstoffgewinnungsverfahren einsetzen, die als Kraft-Verfahren, Soda-Verfahren und Polysulfid-Verfahren bezeichnet werden. Man kann die erfindungsgemäßen Dispersionen weiterhin in dem bekannten Sauerstoff-Alkali-Verfahren zur Zellstoffgewinnung und/oder in den für die Zellstoffgewinnung bekannten Bleichverfahren einsetzen.The processes for the production of cellulose from lignocellulose materials as such are carried out in a manner known per se. For example, these processes can be carried out by digesting lignocellulose materials in a sulfite solution, which can be acidic, neutral or alkaline, and adding the dispersions according to the invention to the digest solution before or after adding the lignocellulose material. The dispersions according to the invention can also be used in the known pulping processes which are used as Kraft processes, soda processes and polysulfide processes. Procedure. The dispersions according to the invention can also be used in the known oxygen-alkali process for pulping and / or in the bleaching processes known for pulping.
Mit Hilfe des erfindungsgemäßen Verfahrens werden infolge der gleichmäßigen Verteilung der Dinitroanthrachinone in der Aufschlußlösung Zellstoffe besonders einheitlicher Qualität erhalten.With the aid of the method according to the invention, pulps of particularly uniform quality are obtained as a result of the uniform distribution of the dinitroanthraquinones in the digestion solution.
600 g einer technischen Mischung von Dinitroanthrachinonen (Zusammensetzung: 30,7 Gew.-% 1.8-, 27,1 Gew.-% 1.6-, 23,0 Gew.-% 1.7-, 10,0 Gew.-% 1.5-, 1,1 Gew.-% 2.7-, 1,0 Gew.-% 2.6-Dinitroanthrachinon; 0,7 Gew.-% 1-Nitroanthrachinon und 6,4 Gew.-% sonstige Nitroanthrachinone), 318 g Wasser, 60 g Ethylenglykol und 20 g eines Kondensationsproduktes aus 1 Mol Naphthalinsulfonat und 1 Mol Formaldehyd und 2 g eines Konservierungsmittels auf Basis einer formaldehydabspaltendep Verbindung werden in einem Dissolver (hochtouriges Rührwerk) vorgemischt und in einer Rührwerksmühle vermahlen, bis 80 % des Dinitroanthrachinons eine Korngröße unter 10µm aufweist.600 g of a technical mixture of dinitroanthraquinones (composition: 30.7% by weight 1.8-, 27.1% by weight 1.6-, 23.0% by weight 1.7-, 10.0% by weight 1.5-, 1.1 wt.% 2.7-, 1.0 wt.% 2.6-dinitroanthraquinone; 0.7 wt.% 1-nitroanthraquinone and 6.4 wt.% Other nitroanthraquinones), 318 g water, 60 g ethylene glycol and 20 g of a condensation product of 1 mol of naphthalene sulfonate and 1 mol of formaldehyde and 2 g of a preservative based on a compound which releases formaldehyde are premixed in a dissolver (high-speed stirrer) and ground in a stirrer mill until 80% of the dinitroanthraquinone has a particle size of less than 10 μm.
Es wird eine fließfähige, stabile Dispersion des Dinitroanthrachinongemisches erhalten. Die Dispersion ist pumpbar und läßt sich ohne Schwierigkeiten in Holzaufschlußlaugen des Sulfit-, Kraft- und Sodaprozesses einrühren.A flowable, stable dispersion of the dinitroanthraquinone mixture is obtained. The dispersion is pumpable and can be easily stirred into wood pulping liquors from the sulfite, power and soda processes.
500 g einer Mischung von Dinitroanthrachinonen (Zusammensetzung: 33 Gew.-% 1.6-, 21,7 Gew.-% 1.8-, 21,6 Gew.-% 1.7-, 6,5 Gew.-% 1.5-, 1,9 Gew.-% 2.6- und 1,8 Gew.-% 2.7-Dinitroanthrachinon und 1,4 Gew.-% 1-Nitroanthrachinon) werden mit 480 g Ethylenglykol und 20 g Natriumdinaphthylmethansulfonat in einem Dissolver vorgemischt und anschließend in einer Perlmühle vermahlen, bis 80 % des Dinitroanthrachinongemisches eine Korngröße unter 5gm aufweist.500 g of a mixture of dinitroanthraquinones (composition: 33% by weight 1.6-, 21.7% by weight 1.8-, 21.6% by weight 1.7-, 6.5% by weight 1.5-, 1.9 % By weight of 2.6- and 1.8% by weight of 2,7-dinitroanthraquinone and 1.4% by weight of 1-nitroanthraquinone) are premixed with 480 g of ethylene glycol and 20 g of sodium dinaphthyl methanesulfonate in a dissolver and then in one Bead mill until 80% of the dinitroanthraquinone mixture has a grain size below 5gm.
Es wird eine stabile pumpfähige Dispersion erhalten, die sich ohne Schwierigkeiten pumpen und in Holzaufschlußlaugen des Sulfit-, Kraft- und Sodaprozesses verteilen läßt.A stable, pumpable dispersion is obtained, which can be pumped without difficulty and can be distributed in wood pulping liquors of the sulfite, power and soda process.
600 g der in Beispiel 1 beschriebenen Dinitroanthrachinon-Mischung, 60 g Ethylenglykol, 313 g Wasser und 20 g Natriumdinaphthylmethansulfonat werden wie in Beispiel 1 beschrieben vermahlen. Die Suspension wird mit Aluminiumsilikat verdickt und mit 3 g 50 %iger Natronlauge alkalisch gestellt.600 g of the dinitroanthraquinone mixture described in Example 1, 60 g of ethylene glycol, 313 g of water and 20 g of sodium dinaphthyl methanesulfonate are ground as described in Example 1. The suspension is thickened with aluminum silicate and made alkaline with 3 g of 50% sodium hydroxide solution.
Es wird eine pumpfähige, stabile Dispersion erhalten.A pumpable, stable dispersion is obtained.
600 g der in Beispiel 1 beschriebenen Mischung von Dinitroanthrachinonen wird mit 60 g Propylenglykol, 315 g Wasser und 20 g Ligninsulfonat wie in Beispiel 1 beschrieben vermahlen. Die Suspension wird mit einem Konservierungsmittel auf Basis eines Formaldehydadditionsproduktes an Benzylalkohol versetzt und mit 3 g 50 %iger Natronlauge alkalisch gestellt.600 g of the mixture of dinitroanthraquinones described in Example 1 are ground with 60 g of propylene glycol, 315 g of water and 20 g of lignin sulfonate as described in Example 1. A preservative based on a formaldehyde addition product with benzyl alcohol is added to the suspension and made alkaline with 3 g of 50% sodium hydroxide solution.
Es wird eine stabile, fließfähige Dispersion erhalten, die sich in den Holzaufschlußlaugen des Kraft- und Sodaprozesses verteilen läßt.A stable, flowable dispersion is obtained which can be distributed in the wood digestion liquors of the power and soda process.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT80107600T ATE2094T1 (en) | 1979-12-17 | 1980-12-04 | DISPERSIONS OF DINITROANTHRACHINONES, PROCESS FOR THEIR PREPARATION AND THEIR USE. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19792950693 DE2950693A1 (en) | 1979-12-17 | 1979-12-17 | DISPERSIONS OF DINITROANTHRACHINONES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| DE2950693 | 1979-12-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0031059A1 true EP0031059A1 (en) | 1981-07-01 |
| EP0031059B1 EP0031059B1 (en) | 1982-12-22 |
Family
ID=6088693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80107600A Expired EP0031059B1 (en) | 1979-12-17 | 1980-12-04 | Dispersions of dinitroanthraquinones, process for their preparation and their utilization |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0031059B1 (en) |
| JP (1) | JPS5696981A (en) |
| AT (1) | ATE2094T1 (en) |
| AU (1) | AU6522280A (en) |
| BR (1) | BR8008214A (en) |
| DE (2) | DE2950693A1 (en) |
| ES (1) | ES8200423A1 (en) |
| FI (1) | FI803903A7 (en) |
| NO (1) | NO803624L (en) |
| NZ (1) | NZ195838A (en) |
| ZA (1) | ZA807831B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035522C (en) * | 1989-02-01 | 1997-07-30 | 王建忠 | Separating method of vegetable cellulose and non-cellulose |
| WO1995029288A1 (en) * | 1994-04-26 | 1995-11-02 | Harima Chemicals, Inc. | Pulp digestion aid |
| DE10002331C2 (en) * | 2000-01-20 | 2003-03-06 | Infineon Technologies Ag | Rotation angle measuring device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2524747C3 (en) * | 1975-06-04 | 1980-12-18 | Basf Ag, 6700 Ludwigshafen | Process for the isolation of 1,5- / 1,8-dinitroanthraquinone with a high content of a, a '-duutro compounds |
| US4036680A (en) * | 1976-12-14 | 1977-07-19 | Canadian Industries, Ltd. | Delignification of lignocellulosic material with a soda pulping liquor containing a Diels Alder adduct of benzoquinone or naphthoquinone in admixture with a nitro aromatic compound |
| DE2854427A1 (en) * | 1978-12-16 | 1980-06-26 | Bayer Ag | METHOD AND APPARATUS FOR THE RECOVERY OF DRY 1,5- AND / OR 1,8- DINITROANTHRAQUINONE FROM SUSPENSIONS CONTAINING SOLID 1,5- AND / OR 1,8-DINITROANTHRAQUINONE AND LIQUID NITROBENZENE |
-
1979
- 1979-12-17 DE DE19792950693 patent/DE2950693A1/en not_active Withdrawn
-
1980
- 1980-12-01 NO NO803624A patent/NO803624L/en unknown
- 1980-12-04 DE DE8080107600T patent/DE3061447D1/en not_active Expired
- 1980-12-04 EP EP80107600A patent/EP0031059B1/en not_active Expired
- 1980-12-04 AT AT80107600T patent/ATE2094T1/en not_active IP Right Cessation
- 1980-12-10 AU AU65222/80A patent/AU6522280A/en not_active Abandoned
- 1980-12-12 JP JP17475880A patent/JPS5696981A/en active Pending
- 1980-12-15 FI FI803903A patent/FI803903A7/en not_active Application Discontinuation
- 1980-12-15 NZ NZ195838A patent/NZ195838A/en unknown
- 1980-12-15 ZA ZA00807831A patent/ZA807831B/en unknown
- 1980-12-16 ES ES497799A patent/ES8200423A1/en not_active Expired
- 1980-12-16 BR BR8008214A patent/BR8008214A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR8008214A (en) | 1981-07-07 |
| DE3061447D1 (en) | 1983-01-27 |
| FI803903L (en) | 1981-06-18 |
| DE2950693A1 (en) | 1981-06-25 |
| AU6522280A (en) | 1981-06-25 |
| ES497799A0 (en) | 1981-11-01 |
| NZ195838A (en) | 1983-03-15 |
| FI803903A7 (en) | 1981-06-18 |
| ATE2094T1 (en) | 1983-01-15 |
| NO803624L (en) | 1981-06-18 |
| ZA807831B (en) | 1981-12-30 |
| ES8200423A1 (en) | 1981-11-01 |
| EP0031059B1 (en) | 1982-12-22 |
| JPS5696981A (en) | 1981-08-05 |
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