EP0197523A2 - Mixtures of fluidity auxiliaries for the synergistic enhancement of the fluidity of stable aqueous coal suspensions - Google Patents
Mixtures of fluidity auxiliaries for the synergistic enhancement of the fluidity of stable aqueous coal suspensions Download PDFInfo
- Publication number
- EP0197523A2 EP0197523A2 EP86104630A EP86104630A EP0197523A2 EP 0197523 A2 EP0197523 A2 EP 0197523A2 EP 86104630 A EP86104630 A EP 86104630A EP 86104630 A EP86104630 A EP 86104630A EP 0197523 A2 EP0197523 A2 EP 0197523A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- flow aid
- coal
- mixtures according
- ethylene oxide
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/326—Coal-water suspensions
Definitions
- the present invention relates to the use of flow aid mixtures for synergistically increasing the flowability of stable, aqueous coal suspensions with coal contents of at least about 60% by weight.
- aqueous coal suspensions suitable for the pipeline transport of coal must, on the one hand, have viscosities below 1000 cP at shear rates between 10 and 200 lake, on the other hand, their economical use requires the highest possible solids content in the suspension.
- the coal contents of aqueous additive-free coal suspensions are - depending on the properties of the types of coal used - at max. 50 to 55 wt .-%, since higher carbon components to viscometers - tuschserhöhungen and ultimately result in loss of fluidity. It is known that additives which contain surfactants and / or polymers bring about a reduction in viscosity and an improvement in flowability and thus enable higher carbon contents in the suspension. In US Pat. No.
- aqueous coal slurries with coal contents of at least about 60% by weight which contain an additive mixture consisting of an anionic surfactant (e.g. naphthalene sulfonate) and an electrolyte (e.g. NaOH) .
- the viscosities of the suspensions at 60 revolutions per minute are between 300 and 4000 cP (aqueous black Mesa mine coal slurry) and between 200 and 2400 cP (aqueous West Virginia mine coal slurry).
- JP 56/57 891 describes aqueous coal slurries with coal contents of 60% by weight, which contain maleic acid / acrylic acid copolymers as an additive in a concentration of 1% by weight.
- European patent application EP 109740 discloses aqueous coal suspensions with coal contents between 30 and 90% by weight, which contain propylene oxide / ethylene oxide block copolymer condensates of aliphatic or aromatic alcohols.
- the polymer-containing suspensions - regardless of the charcoal properties - have lower viscosities than suspensions in which the block polymer is replaced by sodium or calcium lignin sulfonates.
- JP 58/122991 A2 describes a mixture of glycerol / ethylene oxide / propylene oxide block polymer ether and surfactant (for example sodium naphthalenesulfonate) which is added to aqueous coal suspensions with coal contents of 50 to 80% by weight.
- surfactant for example sodium naphthalenesulfonate
- the stability of the suspensions obtained is more than 4 weeks.
- the object of the present invention was to provide stable, aqueous coal suspensions with coal contents of at least about 60% by weight, the viscosities of which - to achieve sufficient flowability - lie below 1000 cP.
- the flow aid mixtures according to the invention are used in aqueous coal suspensions in concentrations of 0.1 to 2% by weight, preferably 0.3 to 1.2% by weight, in each case based on the amount of coal.
- the amounts of the individual components are chosen so that the weight ratio of components a and b to component c is between 2: 1 and 1: 2 and is preferably about 1: 1.
- the ethylene oxide / propylene oxide block polymers used as nonionic viscosity regulators in the flow aid mixtures have molecular weights between 1000 and 20,000, those with molecular weights between 10,000 and 16,000 being preferred.
- the ethylene oxide content is at least 50% by weight and preferably at least 70% by weight.
- the hydrophilic part of the block polymers consists of at least about 100 ethylene oxide units.
- a block polymer which is offered by Wyandotte Chemicals Corporation under the name Pluronic F 108 and which has the following characteristic data is particularly suitable: molecular weight: 15,500; Ethylene oxide content: 80% by weight; the hydrophilic part consists of about 290 ethylene oxide units.
- ammonium naphthalenesulfonate which is commercially available under the name Lomar D (Diamond Shamrock) and an ammonium ligninsulfonate, which is sold by Lignin-Chemie under the name Hansa AM.
- the maleic acid / acrylic acid copolymers of the flow aid mixture which are used in the form of their alkali, alkaline earth and / or ammonium salts, preferably in the form of their sodium salts, are known in a manner known per se by radical-initiated copolymerization of acrylic acid with maleic acid or its interior Anhydrides obtained, the weight ratio of the copolymers maleic acid-acrylic acid between 2: 1 and 1: 2, preferably between 1: 1 and 1: 2.
- the polymerization temperatures are between 50 and 200 ° C, preferably between 100 and 150 ° C.
- the average molecular weight of the copolymers is characterized by their viscosity in aqueous solution.
- the sodium salts of the maleic acid / acrylic acid copolymers in 1% strength aqueous solution at pH 8 and 25 ° C. have specific viscosities between 0.1 and 5, preferably between 0.1 and 0.5, and particularly preferably between 0.17 and 0 , 5 mPa.s.
- the table below summarizes the characteristic data of the preferred maleic acid / acrylic acid copolymers.
- suspensions polysaccharides such as xanthan, guar gum and / or hydroxypropyl guar gum as stabilizers in concentrations of up to 0.3% by weight, based on the coal content - add.
- the viscosities of the additive-containing, aqueous coal suspensions which were prepared by stirring the flow aid mixture into a coal / water mixture, were determined using the Rheomat 30 rotary viscometer (cylindrical measuring body) from Contraves at a shear rate of 40 sec -1 or with the Epprecht - rotary viscometer (anchor-shaped measuring body) determined at a shear rate of 200 sec -1 .
- aqueous coal suspensions with coal contents of at least 64% by weight which contain anionic or nonionic viscosity regulators, have viscosities in the case of naphthalene and / or lignin sulfonates - determined on the Rheomat 30 - of at least 800 cP or Viscosities - determined on the Epprecht viscometer - of at least 2100 cP.
- a viscosity of 870 cP was measured on the Rheomat 30 for the ethylene oxide / propylene oxide block polymer. If the viscosity regulators are replaced by maleic acid / acrylic acid copolymers, the aqueous coal suspensions are no longer flowable.
- coal suspensions with a coal content of 64% by weight have which contain ammonium naphthalenesulfonate (Lomar D) or ammonium ligninsulfonate (Hansa AM) in combination with sodium-maleic acid / acrylic acid copolymer in a weight ratio of 1: 1 in a total concentration of 1% by weight, based on coal, viscosities between 600 and 750 mPa.s.
- Coal suspensions with only one component of the flow aid mixture have much higher viscosities.
- the viscosity is 800 mPa.s and in the case of ammonium ligninsulfonate 930 mPa.s; in the case of the copolymer, the suspension is no longer flowable.
- the viscosity is most strongly reduced in the presence of flow aid mixtures which contain nonionic viscosity regulators in combination with maleic acid / acrylic acid copolymers.
- Coal suspensions with flow aid mixtures according to claim 1 are particularly suitable for the continuous and inexpensive transport of coal in pipelines. Furthermore, the use of these coal slurries has proven to be advantageous in the direct combustion of the suspensions without prior dewatering due to lower pollutant emissions; When gasifying aqueous slurries, dust explosions caused by dry, finely ground coal particles are avoided.
Abstract
Beschrieben wird die Verwendung von Fließhilfsmittelgemischen enthaltend a) an sich bekannte anionische Viskositätsregler auf Basis von Naphthalin- und/oder Ligninsulfonaten und/oder nichtionische Viskositätsregler auf Basis von Ethylenoxid/Propylenoxid-Blockpolymeren und b) gewünschtenfalls an sich bekannte Stabilisatoren aus der Gruppe der Polysaccharide in Kombination mit c) Maleinsäure/Acrylsäure-Copolymeren mit Mischungsverhältnissen der Maleinsäure/Acrylsäure - bezogen auf Gewichtsteile - von 2 : 1 bis 1 : 2 und spezifischen Viskositäten (bestimmt in 1 %iger wäßriger Lösung bei pH 8 und 25°C) zwischen 0,1 und 5 mPa.s zur synergistischen Verstärkung der Fließfähigkeit stabiler wäßriger Kohlesuspension mit Kohlegehalten von mindestens etwa 60 Gew.-%.The use of flow aid mixtures comprising a) known anionic viscosity regulators based on naphthalene and / or lignin sulfonates and / or nonionic viscosity regulators based on ethylene oxide / propylene oxide block polymers and b) if desired known stabilizers from the group of the polysaccharides in is described Combination with c) maleic acid / acrylic acid copolymers with mixing ratios of maleic acid / acrylic acid - based on parts by weight - of 2: 1 to 1: 2 and specific viscosities (determined in 1% aqueous solution at pH 8 and 25 ° C) between 0. 1 and 5 mPa.s for the synergistic enhancement of the flowability of stable aqueous coal suspension with coal contents of at least about 60% by weight.
Description
Die vorliegende Erfindung betrifft die Verwendung von Fließhilfsmittelgemischen zur synergistischen Verstärkung der Fließfähigkeit stabiler, wäßriger Kohlesuspensionen mit Kohlegehalten von mindestens etwa 60 Gew.-%.The present invention relates to the use of flow aid mixtures for synergistically increasing the flowability of stable, aqueous coal suspensions with coal contents of at least about 60% by weight.
Fließfähige, für den Pipeline-Transport von Kohle geeignete wäßrige Kohlesuspensionen müssen einerseits Viskositäten unterhalb 1000 cP bei Schergeschwindigkeiten zwischen 10 und 200 See besitzen, andererseits erfordert der wirtschaftliche Einsatz einen möglichst hohen Feststoffgehalt in der Suspension. Die Kohlegehalte wäßriger additivfreier Kohlesuspensionen liegen - in Abhängigkeit von den Eigenschaften der verwendeten Kohlearten - bei max. 50 bis 55 Gew.-%, da höhere Kohleanteile zu Viskosi- tätserhöhungen und schließlich zum Verlust der Fließfähigkeit führen. Es ist bekannt, daß Zusätze, die Tenside und/oder Polymere enthalten, eine Erniedrigung der Viskosität sowie eine Verbesserung der Fließfähigkeit bewirken und somit höhere Kohlegehalte in der Suspension ermöglichen. In der amerikanischen Patentschrift US 4 282 006 werden wäßrige Kohleslurries mit Kohlegehalten von mindestens etwa 60 Gew.-% vorgestellt, die eine Additivmischung enthalten, bestehend aus einem anionischen Tensid (z. B. Naphthalinsulfonat) und einem Elektrolyten (z. B. NaOH). Die Viskositäten der Suspensionen liegen bei 60 Umdrehungen pro' Minute zwischen 300 und 4000 cP (wäßriger Black Mesa mine coal slurry) und zwischen 200 und 2400 cP (wäßriger West Virginia mine coal slurry). Die JP 56/57 891 beschreibt wäßrige Kohleslurries mit Kohlegehalten von 60 Gew.-%, die als Additiv Maleinsäure/Acrylsäure-Copolymere in einer Konzentration von 1 Gew.-% enthalten. Bei einem mittleren Molekulargewicht von 4000 des Copolymeren beträgt die Viskosität 1800 cP. In der europäischen Patentanmeldung EP 109740 werden wäßrige Kohle- suspensionen mit Kohlegehalten zwischen 30 und 90 Gew.-% offenbart, die Propylenoxid/Ethylenoxid-Blockcopolymer-Kondensate aliphatischer oder aromatischer Alkohole enthalten. Die poly- merhaltigen Suspensionen besitzen - unabhängig von den Kohle- eigenschaften - niedrigere Viskositäten als Suspensionen, in denen das Blockpolymer durch Natrium- oder Calcium-Ligninsulfonate ersetzt ist. In der JP 58/122991 A2 wird eine Mischung aus Glycerin-Ethylenoxid/Propylenoxid-Blockpolymerether und Tensid (z. B. Natriumnaphthalinsulfonat) beschrieben, die wäßrigen Kohlesuspensionen mit Kohlegehalten von 50 bis 80 Gew.-% zugesetzt wird. Die Stabilität der erhaltenen Suspensionen beträgt mehr als 4 Wochen.Flowable, aqueous coal suspensions suitable for the pipeline transport of coal must, on the one hand, have viscosities below 1000 cP at shear rates between 10 and 200 lake, on the other hand, their economical use requires the highest possible solids content in the suspension. The coal contents of aqueous additive-free coal suspensions are - depending on the properties of the types of coal used - at max. 50 to 55 wt .-%, since higher carbon components to viscometers - tätserhöhungen and ultimately result in loss of fluidity. It is known that additives which contain surfactants and / or polymers bring about a reduction in viscosity and an improvement in flowability and thus enable higher carbon contents in the suspension. In US Pat. No. 4,282,006, aqueous coal slurries with coal contents of at least about 60% by weight are presented, which contain an additive mixture consisting of an anionic surfactant (e.g. naphthalene sulfonate) and an electrolyte (e.g. NaOH) . The viscosities of the suspensions at 60 revolutions per minute are between 300 and 4000 cP (aqueous black Mesa mine coal slurry) and between 200 and 2400 cP (aqueous West Virginia mine coal slurry). JP 56/57 891 describes aqueous coal slurries with coal contents of 60% by weight, which contain maleic acid / acrylic acid copolymers as an additive in a concentration of 1% by weight. With an average molecular weight of 4000 of the copolymer, the viscosity is 1800 cP. European patent application EP 109740 discloses aqueous coal suspensions with coal contents between 30 and 90% by weight, which contain propylene oxide / ethylene oxide block copolymer condensates of aliphatic or aromatic alcohols. The polymer-containing suspensions - regardless of the charcoal properties - have lower viscosities than suspensions in which the block polymer is replaced by sodium or calcium lignin sulfonates. JP 58/122991 A2 describes a mixture of glycerol / ethylene oxide / propylene oxide block polymer ether and surfactant (for example sodium naphthalenesulfonate) which is added to aqueous coal suspensions with coal contents of 50 to 80% by weight. The stability of the suspensions obtained is more than 4 weeks.
Aufgabe der vorliegenden Erfindung war es, stabile, wäßrige Kohlesuspensionen mit Kohlegehalten von mindestens etwa 60 Gew.-% zur Verfügung zu stellen, deren Viskositäten - zur Erzielung einer ausreichenden Fließfähigkeit - unterhalb 1000 cP lieaen.The object of the present invention was to provide stable, aqueous coal suspensions with coal contents of at least about 60% by weight, the viscosities of which - to achieve sufficient flowability - lie below 1000 cP.
Die Aufgabe wird gelöst durch Additivmischungen, die den Kohle-Wasser-Suspensionen zugesetzt werden. Gegenstand der Erfindung ist somit die Verwendung von Fließhilfsmittelgemischen enthaltend
- a) an sich bekannte anionische Viskositätsregler auf Basis von Naphthalin- und/oder Ligninsulfonaten und/oder nichtionische Viskositätsregler auf Basis von EthylenoxidlPropylenoxid-Blockpolymeren und
- b) gewünschtenfalls an sich bekannte Stabilisatoren aus der Gruppe der Polysaccharide
in Kombination mit
- c) Maleinsäure/Acrylsäure-Copolymeren mit Mischungsverhältnissen der Maleinsäure/Acrylsäure - bezogen auf Gewichtsteile - von 2 : 1 bis 1 : 2 und spezifischen Viskositäten (bestimmt in 1 %iger wäßriger Lösung bei pH 8 und 25 °C) zwischen 0,1 und 5 mPa.s
zur synergistischen Verstärkung der Fließfähigkeit stabiler, wäßriger Kohlesuspensionen mit Kohlegehalten von mindestens etwa 60 Gew.-%.The object is achieved by means of additive mixtures which are added to the coal-water suspensions. The invention thus relates to the use of flow aid mixtures comprising
- a) known anionic viscosity regulators based on naphthalene and / or lignin sulfonates and / or nonionic viscosity regulators based on ethylene oxide / propylene oxide block polymers and
- b) if desired, known stabilizers from the group of the polysaccharides
in combination with
- c) Maleic acid / acrylic acid copolymers with mixing ratios of maleic acid / acrylic acid - based on parts by weight - from 2: 1 to 1: 2 and specific viscosities (determined in 1% aqueous solution at pH 8 and 25 ° C) between 0.1 and 5 mPa.s
for synergistically increasing the flowability of stable, aqueous coal suspensions with coal contents of at least about 60% by weight.
Die erfindungsgemäßen Fließhilfsmittelmischungen werden in wäßrigen Kohlesuspensionen in Konzentrationen von 0,1 bis 2 Gew.-%, vorzugsweise von 0,3 bis 1,2 Gew.-% - jeweils bezogen auf die Kohlemenge - verwendet. Die Mengen der einzelnen Komponenten werden dabei so gewählt, daß das Gewichtsverhältnis der Komponenten a und b zur Komponente c zwischen 2 : 1 und 1 : 2 liegt und vorzugsweise etwa 1 : 1 beträgt.The flow aid mixtures according to the invention are used in aqueous coal suspensions in concentrations of 0.1 to 2% by weight, preferably 0.3 to 1.2% by weight, in each case based on the amount of coal. The amounts of the individual components are chosen so that the weight ratio of components a and b to component c is between 2: 1 and 1: 2 and is preferably about 1: 1.
Die in den Fließhilfsmittelgemischen als nichtionische Viskositätsregler verwendeten Ethylenoxid/Propylenoxid-Blockpolymere besitzen Molekulargewichte zwischen 1000 und 20 000, wobei solche mit Molekulargewichten zwischen 10 000 und 16 000 bevorzugt werden. Der Ethylenoxid-Gehalt beträgt wenigstens 50 Gew.-% und vorzugsweise wenigstens 70 Gew.-%. Der hydrophile Teil der Blockpolymeren besteht aus mindestens etwa 100 Ethylenoxid-Einheiten. Besonders geeignet ist ein Blockpolymer, das von Wyandotte Chemicals Corporation unter dem Namen Pluronic F 108 angeboten wird und das folgende charakteristische Daten besitzt: Molekulargewicht: 15 500; Ethylenoxidgehalt: 80 Gew.-%; der hydrophile Teil besteht aus etwa 290 Ethylenoxid-Einheiten. Als anionische Viskositätsregter finden alle bekannten Alkali-, Erdalkali- und/oder Ammonium-Salze von Naphthalin- undloder Ligninsulfonsäuren Verwendung. Bevorzugt wird ein Ammoniumnaphthalinsulfonat, das im Handel unter der Bezeichnung Lomar D (Diamond Shamrock) erhältlich ist sowie ein Ammoniumligninsulfonat, das von der Lignin-Chemie unter der Bezeichnung Hansa AM vertrieben wird.The ethylene oxide / propylene oxide block polymers used as nonionic viscosity regulators in the flow aid mixtures have molecular weights between 1000 and 20,000, those with molecular weights between 10,000 and 16,000 being preferred. The ethylene oxide content is at least 50% by weight and preferably at least 70% by weight. The hydrophilic part of the block polymers consists of at least about 100 ethylene oxide units. A block polymer which is offered by Wyandotte Chemicals Corporation under the name Pluronic F 108 and which has the following characteristic data is particularly suitable: molecular weight: 15,500; Ethylene oxide content: 80% by weight; the hydrophilic part consists of about 290 ethylene oxide units. All known alkali, alkaline earth and / or ammonium salts of naphthalene and / or lignin sulfonic acids are used as anionic viscosity regulators. Preferred is an ammonium naphthalenesulfonate, which is commercially available under the name Lomar D (Diamond Shamrock) and an ammonium ligninsulfonate, which is sold by Lignin-Chemie under the name Hansa AM.
.Die Maleinsäure/Acrylsäure-Copolymeren des Fließhilfsmittelgemisches, die in Form ihrer Alkali-, Erdalkali- und/oder Ammoniumsalze, vorzugsweise in Form ihrer Natriumsalze, eingesetzt werden, werden in an sich bekannter Weise durch radikalisch initiierte Copolymerisation von Acrylsäure mit Maleinsäure oder deren inneren Anhydriden erhalten, wobei das Gewichtsverhältnis der Copolymere MaleinsäurelAcrylsäure zwischen 2 : 1 und 1 :2, bevorzugt zwischen 1 : 1 und 1 : 2 liegt. Die Polymerisationstemperaturen liegen zwischen 50 und 200 °C, vorzugsweise zwischen 100 und 150 °C. Das mittlere Molekulargewicht der Copolymeren wird durch ihre Viskosität in wäßriger Lösung charakterisiert. Die Natriumsalze der Maleinsäure/Acrylsäure-Copolymerisate weisen in 1%iger wäßriger Lösung bei pH 8 und 25 °C spezifische Viskositäten zwischen 0,1 und 5, bevorzugt zwischen 0,1 und 0,5, und besonders bevorzugt zwischen 0,17 und 0,5 mPa.s auf. In der nachfolgenden Tabelle sind die charakteristischen Daten der bevorzugten Maleinsäure/Acrylsäure-Copolymerisate zusammengefaßt.
Um ein Sedimentieren der wäßrigen Kohlesuspensionen während einer möglichen Lagerung zu verhindern, kann es vorteilhaft sein, den Suspensionen Polysaccharide wie Xanthan, Guar Gum und/oder Hydroxypropyl-Guar gum als Stabilisatoren in Konzentrationen bis zu 0,3 Gew.-% - bezogen auf Kohlegehalt - zuzusetzen.In order to prevent sedimentation of the aqueous coal suspensions during possible storage, it may be advantageous to use the suspensions polysaccharides such as xanthan, guar gum and / or hydroxypropyl guar gum as stabilizers in concentrations of up to 0.3% by weight, based on the coal content - add.
Die Viskositäten der additivhaltigen, wäßrigen Kohlesuspensionen, die durch Einrühren des Fließhilfsmittelgemisches in eine Kohle/Wassermischung hergestellt wurden, wurden mit dem Rota- tionsviskosimeter Rheomat 30 (zylinderförmiger Meßkörper) der Firma Contraves bei einer Schergeschwindigkeit von 40 Sec-1 oder mit dem Epprecht - Rotationsviskosimeter (ankerförmiger Meßkörper) bei einer Schergeschwindigkeit von 200 Sec-1 ermittelt. Wie aus den Tabellen 2 und 3 hervorgeht, besitzen wäßrige Kohlesuspensionen mit Kohlegehalten von wenigstens 64 Gew.-%, die anionische oder nichtionische Viskositätsregler enthalten, im Falle von Naphthalin- und/oder Ligninsulfonaten Viskositäten - ermittelt am Rheomat 30 - von wenigstens 800 cP bzw. Viskositäten - ermittelt am Epprecht-Viskosimeter - von wenigstens 2100 cP. Für das Ethylenoxid/Propylenoxid-Blockpolymere wurde am Rheomat 30 eine Viskosität von 870 cP gemessen. Werden die Viskositätsregler durch Maleinsäure/Acrylsäure-Copolymerisate ersetzt, sind die wäßrigen Kohlesuspensionen nicht mehr fließfähig.The viscosities of the additive-containing, aqueous coal suspensions, which were prepared by stirring the flow aid mixture into a coal / water mixture, were determined using the Rheomat 30 rotary viscometer (cylindrical measuring body) from Contraves at a shear rate of 40 sec -1 or with the Epprecht - rotary viscometer (anchor-shaped measuring body) determined at a shear rate of 200 sec -1 . As can be seen from Tables 2 and 3, aqueous coal suspensions with coal contents of at least 64% by weight, which contain anionic or nonionic viscosity regulators, have viscosities in the case of naphthalene and / or lignin sulfonates - determined on the Rheomat 30 - of at least 800 cP or Viscosities - determined on the Epprecht viscometer - of at least 2100 cP. A viscosity of 870 cP was measured on the Rheomat 30 for the ethylene oxide / propylene oxide block polymer. If the viscosity regulators are replaced by maleic acid / acrylic acid copolymers, the aqueous coal suspensions are no longer flowable.
Überraschenderweise wurde nun gefunden, daß Fließhilfsmittelgemische, enthaltend an sich bekannte, anionische Viskositätsregler auf Basis von Naphthalin- und /oder Ligninsulfonaten und/oder nichtionische Viskositätsregler auf Basis von Ethytenoxid/Propytenoxid-Blockpolymeren und gewünschtenfalls an sich bekannte Stabilisatoren aus der Gruppe der Polysaccharide in Kombination mit Mateinsäure/Acrylsäure-Copotymerisaten, eine synergistische Verstärkung der Fließfähigkeit stabiler, wäßriger Kohtesuspensionen bewirken. Wie aus Tabelle 2 hervorgeht, besitzen Kohlesuspensionen mit einem Kohlegehalt von 64 Gew.-%, die Ammoniumnaphthalinsulfonat (Lomar D) oder Ammoniumligninsulfonat (Hansa AM) in Kombination mit Natrium-Maleinsäure/Acrylsäure-Copolymer in einem Gewichtsverhältnis von 1 : 1 in einer Gesamtkonzentration von 1 Gew.-% - bezogen auf Kohle - enthalten, Viskositäten zwischen 600 und 750 mPa.s. Kohlesuspensionen mit nur einer Komponente des Fließhilfsmittelgemisches weisen dagegen sehr viel höhere Viskositäten auf. Im Fall des Ammoniumnaphthalinsulfonats beträgt die Viskosität 800 mPa.s und im Fall des Ammoiumligninsulfonats 930 mPa.s; im Fall des Copolymerisats ist die Suspension nicht mehr fließfähig. Am stärksten wird die Viskosität in Gegenwart von Fließhilfsmittelgemischen reduziert, die nichtionische Viskositätsregler in Kombination mit Maleinsäure/Acrylsäure-Copolymerisaten enthalten.Surprisingly, it has now been found that flow aid mixtures containing anionic viscosity regulators based on naphthalene and / or lignin sulfonates and / or nonionic viscosity regulators based on ethylene oxide / propytenoxide block polymers and, if desired, known stabilizers from the group of the polysaccharides in combination with maleic acid / acrylic acid copolymers, a synergistic enhancement of the flowability of stable, aqueous coal suspensions. As can be seen from Table 2, coal suspensions with a coal content of 64% by weight have which contain ammonium naphthalenesulfonate (Lomar D) or ammonium ligninsulfonate (Hansa AM) in combination with sodium-maleic acid / acrylic acid copolymer in a weight ratio of 1: 1 in a total concentration of 1% by weight, based on coal, viscosities between 600 and 750 mPa.s. Coal suspensions with only one component of the flow aid mixture, on the other hand, have much higher viscosities. In the case of ammonium naphthalenesulfonate the viscosity is 800 mPa.s and in the case of ammonium ligninsulfonate 930 mPa.s; in the case of the copolymer, the suspension is no longer flowable. The viscosity is most strongly reduced in the presence of flow aid mixtures which contain nonionic viscosity regulators in combination with maleic acid / acrylic acid copolymers.
Die synergistische Verstärkung der Fließfähigkeit, die eine Erhöhung des Kohlegehaltes in der Suspension ermöglicht und die Wirtschaftlichkeit beim Transport und der anschließenden direkten Verarbeitung der Kohle verbessert, wurde an mehreren Kohletypen mit unterschiedlich guter Dispergierbarkeit beobachtet (siehe Tabellen 2 und 3). Die russische Kohle, die eine Teilchengröße kleiner 200 µm, einen Heizwert von 6500 bis 7000 kcal und einen Aschegehalt von etwa 10 % besitzt, weist sehr ungünstige Dispergiereigenschaften auf. Kohlearten mit geringerem Aschegehalt, wie zum Beispiel die Ruhr-Fettkohle mit einem Aschegehalt von 6,8 % (Teilchengröße: 90 % größer 200 µm), besitzen günstigere Dispergiereigenschaften.The synergistic enhancement of the flowability, which enables an increase in the coal content in the suspension and improves the economy during transport and the subsequent direct processing of the coal, has been observed in several coal types with different dispersibility (see Tables 2 and 3). Russian coal, which has a particle size of less than 200 µm, a calorific value of 6500 to 7000 kcal and an ash content of around 10%, has very unfavorable dispersing properties. Coals with a lower ash content, such as Ruhr fat coal with an ash content of 6.8% (particle size: 90% larger than 200 µm), have more favorable dispersing properties.
Unabhängig von den Eigenschaften der Kohlesorten fällt bei allen Kohlesuspensionen der synergistische Effekt der Fließhilfsmittelgemische hinsichtlich der Viskositätsreduzierung auf. Kohleslurries mit Additivmischungen bestehend aus anionischen und/ oder nichtionischen Viskositätsreglern in Kombination mit MaleinsäurelAcrylsäure-Copolymeren im Gewichtsverhältnis von 2 : 1 bis 1 : 2, vorzugsweise 1 : 1, besitzen gegenüber Kohiesturries mit nur einer Komponente - Viskositätsregler oder Maleinsäure/Acryfsäure-Copolymerisat - eine um bis zu 50 % ge' ingere Viskosität.Regardless of the properties of the coal types, the synergistic effect of the flow aid mixtures with regard to the reduction in viscosity is noticeable in all coal suspensions. Coal slurries with additive mixtures consisting of anionic and / or nonionic viscosity regulators in combination with maleic acid / acrylic acid copolymers in a weight ratio of 2: 1 to 1: 2, preferably 1: 1, have Kohiesturries with only one component - viscosity regulators or maleic acid / Acryfsäure copolymer - a ge by up to 50% 'ingere viscosity.
Kohlesuspensionen mit Fließhilfsmittelgemischen nach Anspruch 1 eignen sich besonders gut für den kontinuierlichen und kostengünstigen Kohletransport in Pipelines. Weiterhin erweist sich der Einsatz dieser Kohleslurries bei der direkten Verbrennung der Suspensionen ohne vorherige Entwässerung aufgrund geringerer Schadstoffemissionen als vorteilhaft; bei der Kohlevergasung wäßriger Slurries werden Staubexplosionen, die durch trockene, feingemahlene Kohlepartikel hervorgerufen werden, vermieden.
Claims (10)
nichtionische Viskositätsregler auf Basis von Ethylenoxid/Propylenoxid-Blockpolymeren
und
in Kombination mit
zur synergistischen Verstärkung der Fließfähigkeit stabiler wäßriger Kohlesuspensionen mit Kohlegehalten von mindestens etwa 60 Gew.-%.1. Use of flow aid mixtures containing
non-ionic viscosity regulators based on ethylene oxide / propylene oxide block polymers
and
in combination with
for synergistically increasing the flowability of stable aqueous coal suspensions with coal contents of at least about 60% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3513045 | 1985-04-12 | ||
| DE19853513045 DE3513045A1 (en) | 1985-04-12 | 1985-04-12 | FLOW AGENT MIXTURES FOR SYNERGISTICALLY REINFORCING THE FLOWABILITY OF STABLE, AQUEOUS CARBON SUSPENSIONS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0197523A2 true EP0197523A2 (en) | 1986-10-15 |
| EP0197523A3 EP0197523A3 (en) | 1987-11-19 |
| EP0197523B1 EP0197523B1 (en) | 1990-05-23 |
Family
ID=6267758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86104630A Expired - Lifetime EP0197523B1 (en) | 1985-04-12 | 1986-04-04 | Mixtures of fluidity auxiliaries for the synergistic enhancement of the fluidity of stable aqueous coal suspensions |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4652271A (en) |
| EP (1) | EP0197523B1 (en) |
| JP (1) | JPH0710986B2 (en) |
| DE (2) | DE3513045A1 (en) |
| ZA (1) | ZA862743B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3603207A1 (en) * | 1986-02-03 | 1987-08-06 | Kurt Bertram | METHOD FOR PRODUCING AN ADDITIVE FOR LUBRICANTS AND FOR AQUEOUS HEATING AND FUEL SYSTEMS AND THEIR SPECIFIC APPLICATIONS |
| AU589752B2 (en) * | 1986-06-27 | 1989-10-19 | Kawasaki Jukogyo K.K. | Dispersant for carbonaceous solid water slurry |
| AU3422189A (en) * | 1988-04-29 | 1989-11-24 | Dow Chemical Company, The | Coal slurry composition and treatment |
| JPH01313594A (en) * | 1988-06-10 | 1989-12-19 | Kao Corp | Ultraheavy oil emulsion fuel |
| GB2230207A (en) * | 1989-04-14 | 1990-10-17 | Coal Ind | Dispersants for coal water mixtures |
| USH1161H (en) | 1989-10-30 | 1993-04-06 | The United States Of America As Represented By The United States Department Of Energy | Aqueous coal slurry |
| EP0878446A1 (en) * | 1993-01-26 | 1998-11-18 | National Starch And Chemical Investment Holding Corporation | A proces for sequestration of water hardness ions |
| CN115197759A (en) * | 2022-06-20 | 2022-10-18 | 天津正达科技有限责任公司 | Water-coal-coke slurry doped with high-proportion petroleum coke, additive and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5657891A (en) * | 1979-10-17 | 1981-05-20 | Kao Corp | Dispersing agent for aqueous slurry of coal powder |
| US4470828A (en) * | 1982-01-19 | 1984-09-11 | Kao Corporation | Aqueous coal slurry composition |
| EP0132712A2 (en) * | 1983-07-21 | 1985-02-13 | OXCE Fuel Company | Coal-aqueous slurry |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104035A (en) * | 1975-12-11 | 1978-08-01 | Texaco Inc. | Preparation of solid fuel-water slurries |
| US4282006A (en) * | 1978-11-02 | 1981-08-04 | Alfred University Research Foundation Inc. | Coal-water slurry and method for its preparation |
| US4441888A (en) * | 1982-05-21 | 1984-04-10 | Nalco Chemical Company | Coal-water slurry viscosity reduction using olefin/maleic acid salt copolymers |
| US4488881A (en) * | 1982-09-10 | 1984-12-18 | The Standard Oil Company | Coal-aqueous mixtures having a particular coal particle size distribution |
| US4436528A (en) * | 1982-09-17 | 1984-03-13 | Diamond Shamrock Chemicals Company | Aqueous slurries of carbonaceous materials |
-
1985
- 1985-04-12 DE DE19853513045 patent/DE3513045A1/en not_active Withdrawn
- 1985-05-14 US US06/734,004 patent/US4652271A/en not_active Expired - Fee Related
-
1986
- 1986-04-04 EP EP86104630A patent/EP0197523B1/en not_active Expired - Lifetime
- 1986-04-04 DE DE8686104630T patent/DE3671466D1/en not_active Expired - Fee Related
- 1986-04-11 ZA ZA862743A patent/ZA862743B/en unknown
- 1986-04-12 JP JP61084854A patent/JPH0710986B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5657891A (en) * | 1979-10-17 | 1981-05-20 | Kao Corp | Dispersing agent for aqueous slurry of coal powder |
| US4470828A (en) * | 1982-01-19 | 1984-09-11 | Kao Corporation | Aqueous coal slurry composition |
| EP0132712A2 (en) * | 1983-07-21 | 1985-02-13 | OXCE Fuel Company | Coal-aqueous slurry |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN, Band 5, Nr. 120 (C-65)[792], 4. August 1981, Seite 109 C 65; & JP-A-56 57 891 (KAO SEKKEN K.K.) 20-05-1981 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0197523A3 (en) | 1987-11-19 |
| US4652271A (en) | 1987-03-24 |
| EP0197523B1 (en) | 1990-05-23 |
| JPS61245830A (en) | 1986-11-01 |
| JPH0710986B2 (en) | 1995-02-08 |
| DE3671466D1 (en) | 1990-06-28 |
| DE3513045A1 (en) | 1986-10-30 |
| ZA862743B (en) | 1986-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3135892C2 (en) | Non-aqueous slurries useful as thickeners | |
| US4358293A (en) | Coal-aqueous mixtures | |
| DE19546515C2 (en) | Process for forming stable bimodal emulsions | |
| EP0197523B1 (en) | Mixtures of fluidity auxiliaries for the synergistic enhancement of the fluidity of stable aqueous coal suspensions | |
| DE3932707A1 (en) | SUPER HEAVY OIL EMULSION FUEL | |
| CH643880A5 (en) | STABILIZED CARBON BROTH AND METHOD FOR THE PRODUCTION THEREOF. | |
| US4432771A (en) | Combustible coal/water mixtures for fuels and methods of preparing the same | |
| DE2727943C2 (en) | Solid fuel / water slurry | |
| DE2942122C2 (en) | ||
| DE2648769A1 (en) | METHOD FOR MANUFACTURING A FUEL | |
| EP0066817B1 (en) | Mixed fuels | |
| DE1521386B2 (en) | Promoter compound for applying metallic coatings to metallic objects | |
| KR850001963B1 (en) | Aqueous coal suspension | |
| EP0045342B1 (en) | Fuel composition with particular fluidity at low temperatures | |
| DD288758A5 (en) | DISPERSION OF COAL IN WATER | |
| EP1577372A1 (en) | Stable aqueous dispersion of particles , its use and its process of production | |
| US4488881A (en) | Coal-aqueous mixtures having a particular coal particle size distribution | |
| JPS60229993A (en) | Coal-water mixture | |
| EP0176920B1 (en) | Aqueous coal dispersions | |
| DE3426395A1 (en) | AQUEOUS COAL DISPERSIONS | |
| DE1058849B (en) | Process for the preparation of a foam fire extinguishing agent containing a stable mixture of a soluble alginate and hydrolyzed protein | |
| DE3636118C2 (en) | ||
| DE3225784A1 (en) | Method of producing a coal slurry | |
| RU2100267C1 (en) | Method of preparation and transportation of concentrated mixtures of coal and water along pipelines | |
| EP0062843B1 (en) | Coal diesel fuel suspensions which contain wax-like polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): DE FR GB SE |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): DE FR GB SE |
|
| 17P | Request for examination filed |
Effective date: 19880511 |
|
| 17Q | First examination report despatched |
Effective date: 19890621 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB SE |
|
| REF | Corresponds to: |
Ref document number: 3671466 Country of ref document: DE Date of ref document: 19900628 |
|
| ET | Fr: translation filed | ||
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19920320 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19920330 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19920408 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19920416 Year of fee payment: 7 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19930404 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19930405 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19930404 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19931229 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19940101 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| EUG | Se: european patent has lapsed |
Ref document number: 86104630.8 Effective date: 19931110 |