EP0368041B1 - Coal briquets with diminished water absorption, and process for manufacturing same - Google Patents
Coal briquets with diminished water absorption, and process for manufacturing same Download PDFInfo
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- EP0368041B1 EP0368041B1 EP89119246A EP89119246A EP0368041B1 EP 0368041 B1 EP0368041 B1 EP 0368041B1 EP 89119246 A EP89119246 A EP 89119246A EP 89119246 A EP89119246 A EP 89119246A EP 0368041 B1 EP0368041 B1 EP 0368041B1
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- briquettes
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- starch
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- 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
- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
- C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
- C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
- C10L5/14—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders
Definitions
- the invention relates to hard coal briquettes bound with starch or starch derivatives and having a reduced water absorption capacity, and to processes for producing such briquettes.
- bitumen or sulfite waste liquor in particular have hitherto been used as binders.
- both binders contain a high proportion of sulfur, so that considerable amounts of sulfur dioxide were produced when the briquettes were burned.
- DE-OS 3314764 describes a process for producing fuel briquettes in the presence of synthetic organic compounds as binders, using essentially solid fuel, polyvinyl alcohol and calcium oxide and / or magnesium oxide, in the presence of at least 1% by weight of water mixed together and formed into briquettes in a manner known per se by pressing. This requires about 0.5 to 2% by weight of polyvinyl alcohol, calculated as a dry substance and based on the solid fuel. The combustion exhaust gases of such briquettes contain significantly reduced SO2 contents.
- DE-OS 3445503 relates to a process for the production of briquettes from hard coal and a binder, in which aqueous alkali silicate solutions are used as binders, the solidification taking place by absorption of carbon dioxide and can additionally be accelerated by gassing with carbonic acid.
- DE-PS 1771433 discloses a process for the production of moldings from fine-grained substances, in particular fuels, in which sulfite waste liquor is mixed with higher-temperature solids, water-soluble adhesives, in particular molasses, starch and / or dextrins, being used as binders instead of the sulfite waste liquor be used.
- starch as a binder for briquetting fine coal is also described in DE-OS 3136163 and 3227395. 3 to 8% by weight of sulfite waste liquor or alternatively 1 to 3% by weight of starch, in each case based on coal, are mentioned as binders.
- DE-PS 1010950 shows a process for the production of fuel briquettes in which the starting material is treated with a binder obtained by reacting one or more higher carbohydrates or carbohydrate ethers with a dilute aqueous solution of a carboxylic acid, formed into briquettes under pressure and the Briquettes may be dried.
- starch and starch derivatives in particular have found particular interest.
- Starch is a product available at reasonable prices and in any quantity, which is characterized by particular environmental compatibility in handling and burning.
- a disadvantage of starch is its hydrophilicity. Briquettes bound with starch absorb water from their surroundings, reducing their compressive strength. This affects storage and handling strength in particular. The briquettes also lose calorific value due to water absorption. There is also the risk that briquettes bound with starch, which have a certain water content, will be attacked by microorganisms and mold will form.
- organopolysiloxanes for hydrophobizing inorganic or organic products has been known for a long time.
- silicones for this purpose, however, it is necessary to find silicone preparations which are effective even in small amounts.
- the silicone preparations should be as free of solvents as possible and reduce the water absorption of the briquettes in such a way that the desired storage and handling stability is given.
- the polysiloxanols of the formula I are essentially ⁇ , ⁇ -dimethylsiloxanols, although some methyl radicals can be replaced by phenyl radicals. However, at least 90% of the R 1 radicals are said to be methyl radicals.
- the average chain length of the polysiloxanols is given by the index n. It is 20 to 250, preferably 30 to 80, in particular 50 to 70.
- the silane of formula II is characterized by the presence of the reactive groups OR2 and R3.
- R2 is a lower alkyl radical having 1 to 4 carbon atoms and in particular a straight-chain lower alkyl radical.
- the ethyl radical is particularly preferred.
- the R3 radical is an aminoalkyl radical having 1 to 6 carbon atoms.
- Examples of such aminoalkyl radicals are the aminomethyl, ⁇ -aminopropyl and ⁇ or ⁇ -aminobutyl radical.
- R3 is preferably the ⁇ -aminopropyl radical.
- R3 can also have the meaning of the radical H2N- (CH2) x R4 (CH2) y -, where R4 is an oxygen, sulfur, ⁇ NH ⁇ or ⁇ NH-CH2CH2-NH radical, x ⁇ 3 and y ⁇ 2 is. Examples of this are the Leftovers H2N- (CH2) 3-NH- (CH2) 2 ⁇ , H2N- (CH2) 2-O- (CH2) 2 ⁇ , H2N- (CH2) 3-NH- (CH2) 2-NH- (CH2) 3 -.
- the radical R3 can also be an epoxyalkyl radical of the formula where n is an integer from 1 to 6.
- the glycidyl radical is in particular the epoxyalkyl radical prefers.
- the compounds of the general formula I and the general formula II are mixed with one another in such amounts that an SiOH group of the polysiloxanol corresponds to> 1 to 3 OR 2 groups.
- the molar ratio of 1 SiOH group of the polysiloxanol of the formula I to 2 OR 2 groups of the silane of the formula II is preferred. Reaction products which are obtained when a ratio of 1 SiOH group to 1 SiOR 2 group is observed clearly show poorer properties in reducing the water absorption capacity of the briquettes.
- the organopolysiloxane obtained can be used in the form thus obtained or as an aqueous dispersion.
- a suitable emulsifier e.g. an adduct of 8 to 12 moles of ethylene oxide with dodecyl alcohol or an adduct of 8 to 14 moles of ethylene oxide with nonylphenol or mixtures thereof, in an amount of about 10%, based on the reaction product, and then added in a manner known per se with water to a stable , dilutable, highly concentrated emulsion.
- the concentration of the stock emulsion should advantageously be 30 to 60%. A concentration of 45 to 50% is preferred.
- an acid preferably acetic acid.
- the polyorganosiloxane preparation to be used according to the invention be used with a hardener known per se, such as e.g. Dibutyltin dilaurate or zinc octoate, in amounts of 1 to 8% by weight, based on organopolysiloxane, to be added.
- a hardener known per se, such as e.g. Dibutyltin dilaurate or zinc octoate
- a first process variant is characterized in that the organosilicon compounds, preferably in the form of an aqueous dispersion, are added to the aqueous solution of the gelatinized starch before mixing with the finely divided coal.
- organosilicon compounds preferably in the form of an aqueous dispersion, are mixed with the finely divided coal.
- the briquettes obtained have a water absorption which is uniformly reduced over the entire cross section.
- the shaping of the briquettes, which takes place in a manner known per se by pressing, is not impaired by the addition of the organosilicon compounds.
- Another process variant for producing the briquettes according to the invention is characterized in that the shaped briquettes are sprayed with a solution of the organic compounds or the briquettes are immersed in such a solution.
- Fine coal briquettes in the production of which the organopolysiloxanes to be used according to the invention have been used, or which have been treated with these organopolysiloxanes after being deformed, have excellent storage and handling strength.
- the calorific value of the briquettes is not impaired and there are no annoying emissions caused by the binder when the briquettes are burned.
- starch-bound briquettes are prevented from being attacked by microorganisms and forming mold. The manufacturing process of the fine coal briquettes is not affected.
- a mixture of 1000 g (0.147 mol) of dihydroxydimethylpolysiloxane and 43.4 g of ⁇ -aminopropyltriethoxysilane is heated to 180 ° C. while stirring and passing nitrogen through and kept at this temperature until 13.5 g of ethanol have distilled off. The process takes about 4 hours. The resulting product is cooled.
- 1000 g of this product are mixed with 100 g of an emulsifier mixture of an ethoxylated triglyceride with an HLB value of 18 and an ethoxylated fatty alcohol polyglycol ether with an HLB value of 11 (ratio 60:40) and 900 g of water with an ultrasound device to form an emulsion given.
- the emulsion obtained contains 50% by weight of the organopolysiloxane to be used according to the invention.
- 100 g of anthracite coal are mixed with 10 g of water and 7.5 g of the starch slurry containing the polysiloxane (1. a) or 1. b)).
- the mass is mixed in a kneader until the water content has dropped to 5%.
- the mass has been heated to 95 ° C.
- Pillow-shaped briquettes are produced in a heated stamp press under a short pressure of 100 kp / cm2 and cooled at room temperature. After 3 days of storage in air, the water absorption is determined after 24 hours by pressurized water storage.
- briquettes are made.
- the briquettes obtained are immersed in a solution of the polysiloxane to be used according to the invention, diluted to 5% active ingredient.
- the solution contains 6% by weight, based on organopolysiloxane, of dibutyltin dilaurate.
- the impregnated briquettes thus obtained are air-dried for 3 days. After this, the water absorption is also determined by storing it under pressure after 24 hours.
- starch-bound briquettes are produced analogously to the state of the art, but no polysiloxane is used in their manufacture, and their water absorption is determined.
- the heat resistance of the four briquettes obtained is also determined.
- the heat resistance provides information about the stability of the briquettes in the fire. To determine the briquettes are 20 min in one Muffle furnace heated to 800 ° C and then loaded in a test press until it breaks.
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Description
Die Erfindung betrifft mit Stärke oder Stärkederivaten gebundene Steinkohlenbriketts mit verringertem Wasseraufnahmevermögen sowie Verfahren zur Herstellung solcher Briketts.The invention relates to hard coal briquettes bound with starch or starch derivatives and having a reduced water absorption capacity, and to processes for producing such briquettes.
Bei der Brikettierung von Kohle wurden bisher als Bindemittel insbesondere Bitumen oder Sulfitablauge verwendet. Beide Bindemittel enthalten jedoch einen hohen Anteil an Schwefel, so daß beim Verbrennen der Briketts erhebliche Mengen an Schwefeldioxid entstanden. Im Interesse der Reinhaltung der Luft und zur Erfüllung gesetzgeberischer Auflagen ist man deshalb gezwungen, die bisher verwendeten Bindemittel, insbesondere Bitumen und Sulfitablauge, durch Bindemittel zu ersetzen, welche bei der Verbrennung die Luft geringer belasten und insbesondere keine oder nur geringe Mengen Schwefeldioxid entwickeln.In the briquetting of coal, bitumen or sulfite waste liquor in particular have hitherto been used as binders. However, both binders contain a high proportion of sulfur, so that considerable amounts of sulfur dioxide were produced when the briquettes were burned. In the interest of keeping the air clean and to comply with legislative requirements, it is therefore necessary to replace the binders previously used, in particular bitumen and sulfite waste liquor, with binders which have a lower impact on the air during combustion and in particular produce no or only a small amount of sulfur dioxide.
In der Literatur ist eine Reihe von Bindemitteln beschrieben, welche an die Stelle der bisher verwendeten Bindemittel treten können. So wird in der DE-OS 3314764 ein Verfahren zur Herstellung von Brennstoffbriketts in Gegenwart von synthetischen organischen Verbindungen als Bindemittel beschrieben, wobei man einen im wesentlichen festen Brennstoff, Polyvinylalkohol und Calciumoxid und/oder Magnesiumoxid, in Gegenwart von mindestens 1 Gew.-% Wasser miteinander vermischt und in an sich bekannter Weise durch Pressen zu Briketts formt. Dabei benötigt man etwa 0,5 bis 2 Gew.-% Polyvinylalkohol, berechnet als Trokkensubstanz und bezogen auf den festen Brennstoff. Die Verbrennungsabgase derartiger Briketts enthalten erheblich reduzierte SO₂-Gehalte.The literature describes a number of binders which can replace the binders used hitherto. For example, DE-OS 3314764 describes a process for producing fuel briquettes in the presence of synthetic organic compounds as binders, using essentially solid fuel, polyvinyl alcohol and calcium oxide and / or magnesium oxide, in the presence of at least 1% by weight of water mixed together and formed into briquettes in a manner known per se by pressing. This requires about 0.5 to 2% by weight of polyvinyl alcohol, calculated as a dry substance and based on the solid fuel. The combustion exhaust gases of such briquettes contain significantly reduced SO₂ contents.
Die DE-OS 3445503 betrifft ein Verfahren zur Herstellung von Briketts aus Steinkohle und einem Bindemittel, bei dem als Bindemittel wäßrige Alkalisilicatlösungen eingesetzt werden, wobei die Verfestigung durch Aufnahme von Kohlendioxid erfolgt und zusätzlich durch Begasen mit Kohlensäure beschleunigt werden kann.DE-OS 3445503 relates to a process for the production of briquettes from hard coal and a binder, in which aqueous alkali silicate solutions are used as binders, the solidification taking place by absorption of carbon dioxide and can additionally be accelerated by gassing with carbonic acid.
Aus der DE-PS 1771433 ist ein Verfahren zur Herstellung von Formkörpern aus feinkörnigen Stoffen, insbesondere Brennstoffen, bei dem Sulfitablauge mit Feststoffen höherer Temperatur vermischt wird, bekannt, wobei anstelle der Sulfitablauge wasserlösliche Kleber, insbesondere Melasse, Stärke und/oder Dextrine, als Bindemittel verwendet werden.DE-PS 1771433 discloses a process for the production of moldings from fine-grained substances, in particular fuels, in which sulfite waste liquor is mixed with higher-temperature solids, water-soluble adhesives, in particular molasses, starch and / or dextrins, being used as binders instead of the sulfite waste liquor be used.
Die Verwendung von Stärke als Bindemittel zum Brikettieren von Feinkohle ist auch in der DE-OS 3136163 und 3227395 beschrieben. Als Bindemittel werden dort 3 bis 8 Gew.-% Sulfitablauge oder alternativ 1 bis 3 Gew.-% Stärke, jeweils bezogen auf Kohle, genannt.The use of starch as a binder for briquetting fine coal is also described in DE-OS 3136163 and 3227395. 3 to 8% by weight of sulfite waste liquor or alternatively 1 to 3% by weight of starch, in each case based on coal, are mentioned as binders.
Der DE-PS 1010950 ist ein Verfahren zur Herstellung von Brennstoffbriketts zu entnehmen, bei dem das Ausgangsmaterial mit einem durch Umsetzung von einem oder mehreren höheren Kohlenhydraten oder Kohlenhydratethern mit einer verdünnten wäßrigen Lösung einer Carbonsäure erhaltenem Bindemittel behandelt, unter Druck zu Briketts geformt wird und die Briketts gegebenenfalls getrocknet werden.DE-PS 1010950 shows a process for the production of fuel briquettes in which the starting material is treated with a binder obtained by reacting one or more higher carbohydrates or carbohydrate ethers with a dilute aqueous solution of a carboxylic acid, formed into briquettes under pressure and the Briquettes may be dried.
Von den vorstehend genannten Bindemitteln haben insbesondere Stärke und Derivate der Stärke besonderes Interesse gefunden. Stärke ist ein zu günstigen Preisen und in beliebiger Menge zur Verfügung stehendes Produkt, das sich durch besondere Umweltverträglichkeit bei der Handhabung und beim Verbrennen auszeichnet. Ein Nachteil der Stärke besteht jedoch in ihrer Hydrophilie. Mit Stärke gebundene Briketts nehmen aus ihrer Umgebung Wasser auf, wodurch ihre Druckfestigkeit verringert wird. Hierdurch ist insbesondere die Lager- und Handhabungsfestigkeit beeinträchtigt. Durch die Wasseraufnahme verlieren die Briketts außerdem an Heizwert. Es besteht außerdem die Gefahr, daß mit Stärke gebundene Briketts, welche einen gewissen Wassergehalt aufweisen, von Mikroorganismen befallen werden und Schimmelbildung einsetzt.Of the binders mentioned above, starch and starch derivatives in particular have found particular interest. Starch is a product available at reasonable prices and in any quantity, which is characterized by particular environmental compatibility in handling and burning. A disadvantage of starch, however, is its hydrophilicity. Briquettes bound with starch absorb water from their surroundings, reducing their compressive strength. This affects storage and handling strength in particular. The briquettes also lose calorific value due to water absorption. There is also the risk that briquettes bound with starch, which have a certain water content, will be attacked by microorganisms and mold will form.
Die Verwendung von Organopolysiloxanen zur Hydrophobierung von anorganischen oder organischen Produkten ist seit langem bekannt. Für einen technischen Einsatz der Silicone zu diesem Zweck ist es jedoch erforderlich, Siliconzubereitungen zu finden, welche bereits in geringen Mengen wirksam sind. Die Siliconzubereitungen sollen möglichst frei von Lösungsmitteln sein und die Wasseraufnahme der Briketts so verringern, daß die gewünschte Lager- und Handhabungsfestigkeit gegeben ist. Mit der vorliegenden Erfindung sollen diese Anforderungen erfüllt werden.The use of organopolysiloxanes for hydrophobizing inorganic or organic products has been known for a long time. For the technical use of silicones for this purpose, however, it is necessary to find silicone preparations which are effective even in small amounts. The silicone preparations should be as free of solvents as possible and reduce the water absorption of the briquettes in such a way that the desired storage and handling stability is given. These requirements are to be met with the present invention.
Ein Gegenstand der Erfindung sind deshalb mit Stärke oder Stärkederivaten gebundene Steinkohlenbriketts mit verringertem Wasseraufnahmevermögen, welche dadurch gekennzeichnet sind, daß sie, bezogen auf Stärke, 0,2 bis 10 Gew.-% siliciumorganische Verbindungen enthalten, welche dadurch erhältlich sind, daß man ein Polysiloxanol der Formel
- R¹
- im Molekül verschieden sein kann und ein Methyl- oder ein Phenylrest ist, jedoch mindestens 90% der Reste R¹ Methylreste sind und
- n =
- 20 bis 250 ist,
mit einem Silan der Formel
wobei
- R²
- ein niederer Alkylrest mit 1 bis 4 Kohlenstoffatomen,
- R³
- ein Aminoalkylrest mit 1 bis 6 Kohlenstoffatomen, der Rest H₂N-(CH₂)xR⁴(CH₂)y―,
wobei R⁴ einen Sauerstoff-, Schwefel-, ―NH― oder ―NH-CH₂CH₂-NH-Rest bedeutet,
x ≧ 3 und
y ≧ 2 ist,
oder ein Epoxyalkylrest der Formel
wobei n eine ganze Zahl von 1 bis 6 bedeutet, ist,
in solchen Mengen miteinander vermischt und die Mischung gegebenenfalls auf Temperaturen von mindestens 50°C erwärmt, daß einer SiOH-Gruppe des Polysiloxanols > 1 bis 3 OR²-Gruppen entsprechen.The invention therefore relates to hard coal briquettes with reduced water absorption capacity which are bound with starch or starch derivatives and which are characterized in that, based on starch, they contain 0.2 to 10% by weight of organosilicon compounds which are obtainable by preparing a polysiloxanol of the formula
- R¹
- can be different in the molecule and is a methyl or a phenyl radical, but at least 90% of the radicals R 1 are methyl radicals and
- n =
- Is 20 to 250,
with a silane of the formula
in which
- R²
- a lower alkyl radical with 1 to 4 carbon atoms,
- R³
- an aminoalkyl radical having 1 to 6 carbon atoms, the radical H₂N- (CH₂) x R⁴ (CH₂) y -,
where R⁴ is an oxygen, sulfur, ―NH― or ―NH-CH₂CH₂-NH radical,
x ≧ 3 and
y ≧ 2,
or an epoxyalkyl radical of the formula
where n is an integer from 1 to 6,
mixed with one another in such amounts and the mixture is optionally heated to temperatures of at least 50 ° C. such that> 1 to 3 OR 2 groups correspond to an SiOH group of the polysiloxanol.
Bei den Polysiloxanolen der Formel I handelt es sich im wesentlichen um α,ω-Dimethylsiloxanole, wobei jedoch einige Methylreste durch Phenylreste ersetzt sein können. Mindestens 90% der Reste R¹ sollen jedoch Methylreste sein.The polysiloxanols of the formula I are essentially α, ω-dimethylsiloxanols, although some methyl radicals can be replaced by phenyl radicals. However, at least 90% of the R 1 radicals are said to be methyl radicals.
Die mittlere Kettenlänge der Polysiloxanole wird durch den Index n wiedergegeben. Er beträgt 20 bis 250, vorzugsweise 30 bis 80, insbesondere 50 bis 70.The average chain length of the polysiloxanols is given by the index n. It is 20 to 250, preferably 30 to 80, in particular 50 to 70.
Das Silan der Formel II ist durch die Anwesenheit der reaktiven Gruppen OR² und R³ gekennzeichnet. R² ist ein niederer Alkylrest mit 1 bis 4 Kohlenstoffatomen und insbesondere ein geradkettiger niederer Alkylrest. Besonders bevorzugt ist der Ethylrest.The silane of formula II is characterized by the presence of the reactive groups OR² and R³. R² is a lower alkyl radical having 1 to 4 carbon atoms and in particular a straight-chain lower alkyl radical. The ethyl radical is particularly preferred.
Der Rest R³ ist ein Aminoalkylrest mit 1 bis 6 Kohlenstoffatomen. Beispiele solcher Aminoalkylreste sind der Aminomethyl-, γ-Aminopropyl- und γ- oder δ-Aminobutylrest. Bevorzugt ist R³ der γ-Aminopropylrest.The R³ radical is an aminoalkyl radical having 1 to 6 carbon atoms. Examples of such aminoalkyl radicals are the aminomethyl, γ-aminopropyl and γ or δ-aminobutyl radical. R³ is preferably the γ-aminopropyl radical.
R³ kann auch die Bedeutung des Restes H₂N-(CH₂)xR⁴(CH₂)y― haben, wobei R⁴ einen Sauerstoff-, Schwefel-, ―NH― oder ―NH-CH₂CH₂-NH-Rest bedeutet, x ≧ 3 und y ≧ 2 ist. Beispiele hierfür sind die Reste
H₂N-(CH₂)₃-NH-(CH₂)₂―, H₂N-(CH₂)₂-O-(CH₂)₂―, H₂N-(CH₂)₃-NH-(CH₂)₂-NH-(CH₂)₃―.R³ can also have the meaning of the radical H₂N- (CH₂) x R⁴ (CH₂) y -, where R⁴ is an oxygen, sulfur, ―NH― or ―NH-CH₂CH₂-NH radical, x ≧ 3 and y ≧ 2 is. Examples of this are the Leftovers
H₂N- (CH₂) ₃-NH- (CH₂) ₂―, H₂N- (CH₂) ₂-O- (CH₂) ₂―, H₂N- (CH₂) ₃-NH- (CH₂) ₂-NH- (CH₂) ₃ -.
Der Rest R³ kann ferner ein Epoxyalkylrest der Formel
sein, wobei n eine ganze Zahl von 1 bis 6 bedeutet. Als Epoxyalkylrest ist insbesondere der Glycidylrest
bevorzugt.The radical R³ can also be an epoxyalkyl radical of the formula
where n is an integer from 1 to 6. The glycidyl radical is in particular the epoxyalkyl radical
prefers.
Bevorzugt enthalten die erfindungsgemäßen Steinkohlenbriketts siliciumorganische Verbindungen, welche dadurch erhältlich sind, daß man ein Polysiloxanol der Formel
wobei n = 20 bis 250 ist,
mit γ-Aminotriethoxysilan vermischt und gegebenenfalls erwärmt.The hard coal briquettes according to the invention preferably contain organosilicon compounds which can be obtained by using a polysiloxanol of the formula
where n = 20 to 250,
mixed with γ-aminotriethoxysilane and optionally heated.
Die Verbindungen der allgemeinen Formel I und der allgemeinen Formel II werden in solchen Mengen miteinander vermischt, daß einer SiOH-Gruppe des Polysiloxanols > 1 bis 3 OR²-Gruppen entsprechen. Bevorzugt ist das molare Mengenverhältnis von 1 SiOH-Gruppe des Polysiloxanols der Formel I zu 2 OR²-Gruppen des Silans der Formel II. Umsetzungsprodukte, die man erhält, wenn man ein Mengenverhältnis von 1 SiOH-Gruppe zu 1 SiOR²-Gruppe einhält, zeigen deutlich schlechtere Eigenschaften in bezug auf die Verringerung des Wasseraufnahmevermögens der Briketts.The compounds of the general formula I and the general formula II are mixed with one another in such amounts that an SiOH group of the polysiloxanol corresponds to> 1 to 3 OR 2 groups. The molar ratio of 1 SiOH group of the polysiloxanol of the formula I to 2 OR 2 groups of the silane of the formula II is preferred. Reaction products which are obtained when a ratio of 1 SiOH group to 1 SiOR 2 group is observed clearly show poorer properties in reducing the water absorption capacity of the briquettes.
Es genügt, die Verbindungen der Formel I und II miteinander zu vermischen. Es tritt bereits bei Raumtemperatur zeitabhängig eine partielle Reaktion der beiden Verbindungen miteinander ein. Man kann jedoch, und dies bevorzugt, die Mischung des Polysiloxanols mit dem Silan auch auf Temperaturen von mindestens 50°C, vorzugsweise 80 bis 180°C, erwärmen und das Gemisch dann abkühlen lassen. Bei der Reaktion des Polysiloxanols mit dem Silan wird der Alkohol R²OH freigesetzt. Bei einem Reaktionsverhältnis von 2 bis 3 SiOR-Gruppen je SiOH-Gruppe wird der Alkohol R²OH vorzugsweise vollständig abdestilliert. Bei einem SiOR: SiOH-Verhältnis von < 2 werden zur Vermeidung einer möglichen Vergelung nur Teilmengen des gebildeten Alkohols abdestilliert, z.B. bei einem SiOR: SiOH-Verhältnis von > 1 bis etwa 1,5 nur 30% der Alkoholmenge.It is sufficient to mix the compounds of the formula I and II with one another. Depending on the time, a partial reaction of the two compounds with one another already occurs at room temperature. However, one can, and this is preferred to heat the mixture of the polysiloxanol with the silane to temperatures of at least 50 ° C., preferably 80 to 180 ° C., and then to allow the mixture to cool. When the polysiloxanol reacts with the silane, the alcohol R²OH is released. With a reaction ratio of 2 to 3 SiOR groups per SiOH group, the alcohol R²OH is preferably completely distilled off. If the SiOR: SiOH ratio is <2, only partial amounts of the alcohol formed are distilled off to avoid possible gelling, for example if the SiOR: SiOH ratio is> 1 to about 1.5, only 30% of the amount of alcohol is distilled off.
Das erhaltene Organopolysiloxan kann in der so erhaltenen Form oder als wäßrige Dispersion verwendet werden. Im letzteren Fall wird dem Umsetzungsprodukt zweckmäßig ein geeigneter Emulgator, z.B. ein Anlagerungsprodukt von 8 bis 12 Mol Ethylenoxid an Dodecylalkohol oder ein Anlagerungsprodukt von 8 bis 14 Mol Ethylenoxid an Nonylphenol oder Gemische hiervon, in einer Menge von etwa 10%, bezogen auf Umsetzungsprodukt, zugesetzt und dann in an sich bekannter Weise mit Wasser zu einer stabilen, verdünnbaren, hochkonzentrierten Emulsion emulgiert. Die Konzentration der Stammemulsion soll zweckmäßig 30 bis 60% betragen. Bevorzugt ist eine Konzentration von 45 bis 50%.The organopolysiloxane obtained can be used in the form thus obtained or as an aqueous dispersion. In the latter case, a suitable emulsifier, e.g. an adduct of 8 to 12 moles of ethylene oxide with dodecyl alcohol or an adduct of 8 to 14 moles of ethylene oxide with nonylphenol or mixtures thereof, in an amount of about 10%, based on the reaction product, and then added in a manner known per se with water to a stable , dilutable, highly concentrated emulsion. The concentration of the stock emulsion should advantageously be 30 to 60%. A concentration of 45 to 50% is preferred.
Zur Erhöhung der Lagerstabilität der Dispersion kann es vorteilhaft sein, die Dispersion mit einer Säure, vorzugsweise Essigsäure, zu neutralisieren.To increase the storage stability of the dispersion, it may be advantageous to neutralize the dispersion with an acid, preferably acetic acid.
Es empfiehlt sich, der erfindungsgemäß zu verwendenden Polyorganosiloxanzubereitung vor der Verwendung einen an sich bekannten Härter, wie z.B. Dibutylzinndilaurat oder Zinkoctoat, in Mengen von 1 bis 8 Gew.-%, bezogen auf Organopolysiloxan, zuzusetzen.It is recommended that the polyorganosiloxane preparation to be used according to the invention be used with a hardener known per se, such as e.g. Dibutyltin dilaurate or zinc octoate, in amounts of 1 to 8% by weight, based on organopolysiloxane, to be added.
Eine erste Verfahrensvariante ist dadurch gekennzeichnet, daß man die siliciumorganischen Verbindungen, vorzugsweise in Form einer wäßrigen Dispersion, der wäßrigen Lösung der verkleisterten Stärke vor dem Vermischen mit der feinteiligen Kohle zugibt.A first process variant is characterized in that the organosilicon compounds, preferably in the form of an aqueous dispersion, are added to the aqueous solution of the gelatinized starch before mixing with the finely divided coal.
Eine weitere Verfahrensvariante ist dadurch gekennzeichnet, daß man die siliciumorganischen Verbindungen, vorzugsweise in Form einer wäßrigen Dispersion, mit der feinteiligen Kohle vermischt.Another process variant is characterized in that the organosilicon compounds, preferably in the form of an aqueous dispersion, are mixed with the finely divided coal.
In beiden Fällen weisen die erhaltenen Briketts eine über den gesamten Querschnitt gleichmäßig reduzierte Wasseraufnahme auf. Die in an sich bekannter Weise durch Verpressung erfolgende Formgebung der Briketts wird durch den Zusatz der siliciumorganischen Verbindungen nicht beeinträchtigt.In both cases, the briquettes obtained have a water absorption which is uniformly reduced over the entire cross section. The shaping of the briquettes, which takes place in a manner known per se by pressing, is not impaired by the addition of the organosilicon compounds.
Eine weitere Verfahrensvariante zur Herstellung der erfindungsgemäßen Briketts ist dadurch gekennzeichnet, daß man die geformten Briketts mit einer Lösung der organischen Verbindungen besprüht oder die Briketts in eine solche Lösung taucht.Another process variant for producing the briquettes according to the invention is characterized in that the shaped briquettes are sprayed with a solution of the organic compounds or the briquettes are immersed in such a solution.
Bei dieser Verfahrensweise wird nur die äußere Schicht der Briketts hydrophobiert. Dies reicht in vielen Fällen bereits aus, um die Wasseraufnahme der Briketts in gewünschter Weise zu senken.With this procedure, only the outer layer of the briquettes is made hydrophobic. In many cases this is sufficient to reduce the water absorption of the briquettes in the desired way.
Feinkohlenbriketts, bei deren Herstellung die erfindungsgemäß zu verwendenden Organopolysiloxane eingesetzt worden sind oder die nach ihrer Verformung mit diesen Organopolysiloxanen behandelt worden sind, weisen eine ausgezeichnete Lager- und Handhabungsfestigkeit auf. Der Heizwert der Briketts wird nicht beeinträchtigt, und es entstehen beim Verbrennen der Briketts keine störenden und durch das Bindemittel verursachten Emissionen. Gleichzeitig wird verhindert, daß mit Stärke gebundene Steinkohlenbriketts von Mikroorganismen befallen werden und Schimmel bilden. Der fabrikatorische Herstellungsprozeß der Feinkohlenbriketts wird nicht beeinträchtigt.Fine coal briquettes, in the production of which the organopolysiloxanes to be used according to the invention have been used, or which have been treated with these organopolysiloxanes after being deformed, have excellent storage and handling strength. The calorific value of the briquettes is not impaired and there are no annoying emissions caused by the binder when the briquettes are burned. At the same time, starch-bound briquettes are prevented from being attacked by microorganisms and forming mold. The manufacturing process of the fine coal briquettes is not affected.
Die folgenden Beispiele belegen die guten Eigenschaften der erfindungsgemäß zu verwendenden Organopolysiloxane.The following examples demonstrate the good properties of the organopolysiloxanes to be used according to the invention.
1000 g (0,147 Mol) Dihydroxydimethylpolysiloxan werden mit 43,4 g γ-Aminopropyltriethoxysilan vermischt und 30 Min. bei Raumtemperatur gerührt. Anschließend werden 500 g dieser Mischung mit 450 g Wasser und 50 g eines Emulgatorgemisches aus einem ethoxylierten Triglycerid mit einem HLB-Wert von 18 und einem ethoxylierten Fettalkoholpolyglykolether mit einem HLB-Wert von 11 (Mengenverhältnis 60: 40) versetzt und in dreimaligem Umlauf in einem Hochdruckhomogenisator emulgiert. Die erhaltene Emulsion enthält 50% des erfindungsgemäß einzusetzenden Organopolysiloxans. Zur Erhöhung der Lagerstabilität wird unter Rühren der pH-Wert der Emulsion mit verdünnter Essigsäure auf 6,5 eingestellt.1000 g (0.147 mol) of dihydroxydimethylpolysiloxane are mixed with 43.4 g of γ-aminopropyltriethoxysilane and stirred for 30 minutes at room temperature. 500 g of this mixture are then mixed with 450 g of water and 50 g of an emulsifier mixture of an ethoxylated triglyceride with an HLB value of 18 and an ethoxylated fatty alcohol polyglycol ether with an HLB value of 11 (ratio 60:40) and in three circulations in one High pressure homogenizer emulsifies. The emulsion obtained contains 50% of the organopolysiloxane to be used according to the invention. To increase the storage stability, the pH of the emulsion is adjusted to 6.5 with dilute acetic acid.
Ein Gemisch aus 1000 g (0,147 Mol) Dihydroxydimethylpolysiloxan und 43,4 g γ-Aminopropyltriethoxysilan wird unter Rühren und Durchleiten von Stickstoff auf 180°C erwärmt und bei dieser Temperatur gehalten, bis 13,5 g Ethanol abdestilliert sind. Der Vorgang dauert etwa 4 Stunden. Das entstandene Produkt wird abgekühlt.A mixture of 1000 g (0.147 mol) of dihydroxydimethylpolysiloxane and 43.4 g of γ-aminopropyltriethoxysilane is heated to 180 ° C. while stirring and passing nitrogen through and kept at this temperature until 13.5 g of ethanol have distilled off. The process takes about 4 hours. The resulting product is cooled.
1000 g dieses Produktes werden mit 100 g eines Emulgatorgemisches aus einem ethoxylierten Triglycerid mit einem HLB-Wert von 18 und einem ethoxylierten Fettalkoholpolyglykolether mit einem HLB-Wert von 11 (Mengenverhältnis 60: 40) versetzt und mit 900 g Wasser mit einem Ultraschallgerät zu einer Emulsion gegeben. Die erhaltene Emulsion enthält 50 Gew.-% des erfindungsgemäß einzusetzenden Organopolysiloxans.1000 g of this product are mixed with 100 g of an emulsifier mixture of an ethoxylated triglyceride with an HLB value of 18 and an ethoxylated fatty alcohol polyglycol ether with an HLB value of 11 (ratio 60:40) and 900 g of water with an ultrasound device to form an emulsion given. The emulsion obtained contains 50% by weight of the organopolysiloxane to be used according to the invention.
Während des Misch- und Emulgiervorgangs hat eine Teilkondensation zwischen dem Dihydroxydimethylpolysiloxan und dem γ-Aminopropyltriethoxysilan stattgefunden, bei dem 2,6 g Ethanol frei wurden.During the mixing and emulsification process, partial condensation between the dihydroxydimethylpolysiloxane and the γ-aminopropyltriethoxysilane took place, releasing 2.6 g of ethanol.
Zu 99 Gew.-Teilen einer 40%igen Aufschlämmung granulärer Maisstärke in Wasser wird 1 Gew.-Teil der nach 1. a) oder 1. b) erhaltenen Organopolysiloxandispersion gegeben.1 part by weight of the organopolysiloxane dispersion obtained according to 1. a) or 1. b) is added to 99 parts by weight of a 40% slurry of granular corn starch in water.
100 g Anthrazitkohle werden mit 10 g Wasser und 7,5 g der das Polysiloxan (1. a) oder 1. b)) enthaltenden Stärkeaufschlämmung vermischt. Bei einer Temperatur von 130°C wird in einem Knetwerk die Masse so lange gemischt, bis der Wasseranteil auf 5% gesunken ist. Die Masse ist dabei auf 95°C erwärmt worden. In einer beheizten Stempelpresse werden unter kurzem Druck von 100 kp/cm² kissenförmige Briketts hergestellt und bei Raumtemperatur abgekühlt. Nach 3 Tagen Lagerung an der Luft wird die Wasseraufnahme durch Druckwasserlagerung nach 24 Stunden bestimmt.100 g of anthracite coal are mixed with 10 g of water and 7.5 g of the starch slurry containing the polysiloxane (1. a) or 1. b)). At a temperature of 130 ° C, the mass is mixed in a kneader until the water content has dropped to 5%. The mass has been heated to 95 ° C. Pillow-shaped briquettes are produced in a heated stamp press under a short pressure of 100 kp / cm² and cooled at room temperature. After 3 days of storage in air, the water absorption is determined after 24 hours by pressurized water storage.
In einem weiteren Versuch werden 100 g Anthrazitkohle mit 10 g Wasser und 15 g einer 40 gew.-%igen granulären Maisstärkeaufschlämmung, welche kein Polysiloxan enthielt, vermischt. Wie im vorstehenden Beispiel beschrieben, werden Briketts hergestellt. Die erhaltenen Briketts werden in eine auf 5% Wirkstoffanteil verdünnte Lösung des erfindungsgemäß zu verwendenden Polysiloxans getaucht. Die Lösung enthält als Katalysator 6 Gew.-%, bezogen auf Organopolysiloxan, Dibutylzinndilaurat. Die so erhaltenen, imprägnierten Briketts werden 3 Tage an der Luft getrocknet. Danach wird ebenfalls die Wasseraufnahme durch Druckwasserlagerung nach 24 Stunden bestimmt.In a further experiment, 100 g of anthracite coal are mixed with 10 g of water and 15 g of a 40% by weight granular maize starch slurry which did not contain any polysiloxane. As described in the previous example, briquettes are made. The briquettes obtained are immersed in a solution of the polysiloxane to be used according to the invention, diluted to 5% active ingredient. As a catalyst, the solution contains 6% by weight, based on organopolysiloxane, of dibutyltin dilaurate. The impregnated briquettes thus obtained are air-dried for 3 days. After this, the water absorption is also determined by storing it under pressure after 24 hours.
In einem dritten Versuch werden entsprechend dem Stand der Technik in analoger Weise stärkegebundene Briketts hergestellt, bei deren Herstellung jedoch kein Polysiloxan verwendet wird, und deren Wasseraufnahme bestimmt.In a third experiment, starch-bound briquettes are produced analogously to the state of the art, but no polysiloxane is used in their manufacture, and their water absorption is determined.
Von den vier erhaltenen Briketts wird außerdem die Warmfestigkeit bestimmt. Die Warmfestigkeit gibt Aufschluß über die Standfestigkeit der Briketts im Feuer. Zur Bestimmung werden die Briketts 20 Min. in einem Muffelofen auf 800°C erhitzt und anschließend in einer Prüfpresse bis zum Bruch belastet.The heat resistance of the four briquettes obtained is also determined. The heat resistance provides information about the stability of the briquettes in the fire. To determine the briquettes are 20 min in one Muffle furnace heated to 800 ° C and then loaded in a test press until it breaks.
Bei der Bewertung der Warmfestigkeit ist zu beachten, daß es bekannt ist, daß die Warmfestigkeit von Briketts durch Siloxanzusatz sinkt. Es ist deshalb besonders überraschend, daß bei den erfindungsgemäß imprägnierten Briketts, welche unter Zusatz von Organopolysiloxanen (nach Methode 1. a)) erhalten worden sind, die Warmfestigkeit nahezu den Wert der unbehandelten Briketts erreicht.
Claims (5)
with a silane of the formula
where
R⁴ being oxygen, sulphur, ―NH― or an ―NH-CH₂CH₂-NH radical,
x ≧ 3 and
y ≧ 2,
or an epoxyalkyl radical of the formula
with one another in such quantities, and heating the mixture, if necessary, to temperatures of at least 50°C, that more than 1 to 3 OR² groups correspond to one SiOH group of the polysiloxanol.
Applications Claiming Priority (2)
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DE3836940 | 1988-10-29 | ||
DE3836940A DE3836940C1 (en) | 1988-10-29 | 1988-10-29 |
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EP0368041A1 EP0368041A1 (en) | 1990-05-16 |
EP0368041B1 true EP0368041B1 (en) | 1992-01-08 |
Family
ID=6366190
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP89119246A Expired - Lifetime EP0368041B1 (en) | 1988-10-29 | 1989-10-17 | Coal briquets with diminished water absorption, and process for manufacturing same |
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EP (1) | EP0368041B1 (en) |
DE (2) | DE3836940C1 (en) |
Cited By (1)
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KR101946343B1 (en) | 2010-07-12 | 2019-02-11 | 프리메탈스 테크놀로지스 오스트리아 게엠베하 | Method for producing pressed articles containing coal particles |
Families Citing this family (3)
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US7569716B2 (en) | 2004-04-08 | 2009-08-04 | Dow Corning Corporation | Method of selecting silicon having improved performance |
US7737082B2 (en) | 2004-09-17 | 2010-06-15 | James Alan Rabe | Siloxane composition, agglomerate, and method of preparing |
AT510135B1 (en) * | 2010-07-12 | 2016-11-15 | Primetals Technologies Austria GmbH | PROCESS FOR PREPARING PRESS LENDS CONTAINING COAL PARTICLES |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2330887A1 (en) * | 1973-06-16 | 1975-01-09 | Goldschmidt Ag Th | USE OF ALKYL / ARYL-ALCOXY POLYSILOXANES FOR IMPRAEGNATION |
DE3227395A1 (en) * | 1981-07-23 | 1983-11-10 | Gewerkschaft Sophia-Jacoba Steinkohlenbergwerk, 5142 Hückelhoven | Process for producing briquettes for the fixed bed of a gasifier reactor or shaft furnace |
DE3136163A1 (en) * | 1981-09-12 | 1983-03-31 | Gewerkschaft Sophia-Jacoba Steinkohlenbergwerk, 5142 Hückelhoven | Process for cold briquetting of fine coal |
DE3314764A1 (en) * | 1983-04-23 | 1984-10-31 | Akzo Gmbh, 5600 Wuppertal | FUEL BRIQUETTES |
DE3445503A1 (en) * | 1984-12-13 | 1986-06-19 | Woellner-Werke GmbH & Co, 6700 Ludwigshafen | Process for producing briquettes |
FR2625749B1 (en) * | 1988-01-11 | 1992-03-27 | Roquette Freres | WATER RESISTANT COMBUSTIBLE AGGLOMERATE, PROCESS FOR PREPARING THE SAME AND COMPOSITION OF MATERIALS USED IN THIS PROCESS |
-
1988
- 1988-10-29 DE DE3836940A patent/DE3836940C1/de not_active Expired - Lifetime
-
1989
- 1989-10-17 EP EP89119246A patent/EP0368041B1/en not_active Expired - Lifetime
- 1989-10-17 DE DE8989119246T patent/DE58900703D1/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101946343B1 (en) | 2010-07-12 | 2019-02-11 | 프리메탈스 테크놀로지스 오스트리아 게엠베하 | Method for producing pressed articles containing coal particles |
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DE58900703D1 (en) | 1992-02-20 |
EP0368041A1 (en) | 1990-05-16 |
DE3836940C1 (en) | 1990-05-17 |
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