EP0475969B1 - Used of mixed hydroxy ethers as aids for drying solids materials - Google Patents
Used of mixed hydroxy ethers as aids for drying solids materials Download PDFInfo
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- EP0475969B1 EP0475969B1 EP90908227A EP90908227A EP0475969B1 EP 0475969 B1 EP0475969 B1 EP 0475969B1 EP 90908227 A EP90908227 A EP 90908227A EP 90908227 A EP90908227 A EP 90908227A EP 0475969 B1 EP0475969 B1 EP 0475969B1
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- Prior art keywords
- general formula
- water
- mixed ethers
- surfactants
- surfactant
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- 239000007787 solid Substances 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title abstract description 7
- 238000001035 drying Methods 0.000 title abstract description 3
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 239000010419 fine particle Substances 0.000 claims abstract description 6
- 150000002170 ethers Chemical class 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 239000000571 coke Substances 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 8
- 239000006260 foam Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 description 39
- 239000003245 coal Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- OXLXSOPFNVKUMU-UHFFFAOYSA-N 1,4-dioctoxy-1,4-dioxobutane-2-sulfonic acid Chemical class CCCCCCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCCCCCC OXLXSOPFNVKUMU-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B5/00—Drying solid materials or objects by processes not involving the application of heat
- F26B5/005—Drying solid materials or objects by processes not involving the application of heat by dipping them into or mixing them with a chemical liquid, e.g. organic; chemical, e.g. organic, dewatering aids
Definitions
- surfactants as drainage aids for dewatering water-containing fine-particle solids, in particular hard coal, by means of which the residual moisture of fine and fine coal can be reduced.
- the reason for this is the property of the surfactants, to reduce the surface tension and the capillary pressure of the water in the aggregate. At the same time, the work of adhesion to detach the surface water is reduced. When using surfactants, this leads to improved drainage with unchanged energy consumption.
- Dialkyl sulfosuccinates (US Pat. No. 2,266,954) and nonionic surfactants of the alkylphenol polyglycol ether type [Erzmetall 30, 292 (1977)] have been described as surfactant dewatering aids of the type mentioned above.
- these surfactants have the disadvantage of considerable foam formation, which leads to considerable problems in the processing plants, in particular when water is circulated in the usual way.
- the invention is based on the knowledge that nonionic surfactants of the general formula I when used in Water / solids systems without foaming increase the dewatering speed and lower the residual moisture of the dewatered solids.
- the group R 1 of the hydroxy mixed ethers of the general formula I to be used according to the invention is an optionally branched or cyclic alkyl group with 1 to 10 carbon atoms, e.g. a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl group. Alkyl groups with 1 to 4 carbon atoms from the above list are preferred.
- the group R2 in general formula I is an alkyl group with 8 to 20 carbon atoms, e.g.
- x in the general formula I denotes a number in the range from 1 to 20, a range from 2 to 15 being preferred.
- the hydroxy mixed ethers of the general formula I must be water-soluble. It is possible that this water solubility is not sufficient if the hydroxy mixed ethers of the general formula I at long values of x have long-chain radicals R 1 and / or R 2 with chain lengths within the above-mentioned ranges; the required water solubility can, however, be achieved by increasing the value for x within the above-mentioned range.
- hydroxy mixed ethers of the general formula I are described in DE-A 37 23 323; they can be obtained by using ethoxylated alcohols of the general formula II R1O- (CH2CH2O) x -OH (II) with epoxides of alpha olefins of formula III in the presence of catalysts, wherein R1, R2 and x are as defined above.
- the hydroxy mixed ethers of the general formula I to be used according to the invention can also be present as industrial mixtures.
- the hydroxy mixed ethers of the general formula I are used in an amount of 0.5 to 10, in particular 3 to 8 kg per m 3 of the water to be removed from the finely divided solids.
- the hydroxy mixed ethers of the general formula I are particularly suitable for dewatering water-containing, finely divided hard coal or coke; however, they can also be used in the dewatering of other water / solid systems, for example in the case of processed ores or gangue materials in ore mining, sewage sludge or the like.
- a further advantage of the surfactants of the general formula I to be used according to the invention is that they are compatible with any other surfactants present, for example with dialkyl sulfosuccinates such as di-n-octyl sulfosuccinates or polyacrylamides, which were added to the solids to be dewatered in previous treatment stages .
- a washed fine coal with the following analysis data was used in the examples: 6.8% by weight of water 3.7% by weight of ash (wf; calculated on anhydrous coal) 27.2% volatile components (waf; calculated on water and ash-free coal)
- the sieve analysis of the fine coal gave the following values: - 0.5 mm 1.5% 0.5 - 2.0 mm 23.1% 2.0 - 6.3 mm 51.5% + 6.3 mm 23.9%.
- the fine coal was treated with aqueous solutions of the hydroxy mixed ethers of a defined concentration and dewatered under defined conditions; the residual moisture achieved with and without the addition of surfactants was determined in accordance with DIN 51718 by drying at 106 ° C. and weighing.
- the present examples are laboratory tests in which the amounts of surfactant used in kg are based on 1000 kg of the solids to be dewatered (calculated as anhydrous solids). In practice, the amount of surfactant required will be lower than that used in the examples; in addition, in the practical implementation of solid dewatering, the required amounts of surfactant are used depending on the amount of water to be removed from the solid.
- surfactant used here and below refers to the hydroxy mixed ethers of the general formula I.
- a pressure filter was used, which was a closed filter chute, which was filled with the material to be dewatered.
- the drainage was carried out by applying a pressure of 3 bar to the filter.
- the drainage time was 30 s.
- a filter fabric with a mesh size of 0.2 mm was used as the filter material.
- a cup centrifuge was used here, with which centrifugal values of 15 to 2000 can be achieved at speeds of 300 to 3400 rpm.
- Perforated plates with sieve openings of 0.4 x 4.0 mm were used as the sieve covering for the centrifuge; the surfactants used as filter aids (hydroxy mixed ethers of the general formula I) were dissolved in distilled water in concentrations of 0.1 g / l and 1.0 g / l.
- 400 ml of the surfactant-containing solutions were placed in a glass vessel. 25 g of coal were immersed in each of these solutions. The wetting time was 60 s in each case. This was followed by a constant draining time of 180 s for the pre-dewatering of the samples.
- Table 3 The values obtained in the preliminary dewatering of the samples, the surfactant concentration and the calculated amount of surfactant per 1000 kg of coal are summarized in Table 3.
- a surfactant solution with 0.1 g / l made it possible to lower the residual moisture to 4.0% by weight with a centrifugal value of 111.
- a surfactant solution with 1.0 g / l lowered the residual moisture up to 3.0%. These values can also be achieved with short drainage times.
- Table 4 Centrifugal drainage Speed (rpm) 500 800 1500 500 800 1500 Centrifugal value 43.2 111 389 43.2 111 389
- Surfactant Residual moisture A 5.7 5.3 3.5 3.6 3.1 2.6 B 4.5 4.0 3.7 3.7 3.0 2.5 C.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Extraction Or Liquid Replacement (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
Die Erfindung betrifft die Verwendung von Hydroxymischethern der allgemeinen Formel I
R¹O-(CH₂CH₂O)x-CH₂-CH(OH)R² (I)
in der
- R¹
- eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen,
- R²
- eine Alkylgruppe mit 8 bis 20 Kohlenstoffatomen und
- x
- eine Zahl im Bereich von 1 bis 20
als Hilfsmittel für die Entwässerung wasserhaltiger, feinteiliger Feststoffe.The invention relates to the use of hydroxy mixed ethers of the general formula I.
R¹O- (CH₂CH₂O) x -CH₂-CH (OH) R² (I)
in the
- R¹
- an alkyl group with 1 to 10 carbon atoms,
- R²
- an alkyl group with 8 to 20 carbon atoms and
- x
- a number in the range from 1 to 20
as an aid for the dewatering of water-containing, finely divided solids.
In zahlreichen Industriezweigen, z.B. im Bergbau oder in Klärwerken, fallen große Mengen an stark wasserhaltigen, feinteiligen Feststoffen an, die vor der Weiterverarbeitung der Feststoffe oder ihrer Deponierung entwässert werden müssen. So ist z.B. die Entwässerung von wasserhaltiger Steinkohle bzw. Koks ein zentraler Prozeß innerhalb der Aufbereitung von Brennstoffen auf Kohlebasis. Dabei können die vom Markt geforderten oberen Grenzwerte für den Wassergehalt dieser Materialien oft nur schwer eingehalten werden, da z.B. geförderte Steinkohle aufgrund der weitgehenden Mechanisierung des untertägigen Kohleabbaus sehr feinkörnig anfällt. Zur Zeit bestehen etwa 38 % der Rohförderung aus Feinkohle mit einem Teilchendurchmesser im Bereich von 0,5 bis 10 mm; weitere 14 % bestehen aus Feinstkohle mit einem darunter liegenden Teilchendurchmesser.In numerous branches of industry, for example in mining or in sewage treatment plants, large amounts of highly water-containing, fine-particle solids are produced before further processing the solids or their landfill must be drained. For example, the drainage of water-containing hard coal or coke is a central process in the processing of coal-based fuels. The upper limit values for the water content of these materials required by the market are often difficult to meet because, for example, mined coal is very fine-grained due to the extensive mechanization of underground coal mining. Around 38% of the raw production currently consists of fine coal with a particle diameter in the range from 0.5 to 10 mm; a further 14% consist of fine coal with an underlying particle diameter.
Es ist bekannt, zur Entwässerung von wasserhaltigen feinteiligen Feststoffen, insbesondere Steinkohlen, Tenside als Entwässerungshilfsmittel einzusetzen, durch die die Restfeuchte von Fein- und Feinstkohle herabgesetzt werden kann. Als Ursache hierfür ist die Eigenschaft der Tenside, die Oberflächenspannung und den Kapillardruck des Wassers im Haufwerk zu vermindern, anzusehen. Dabei wird gleichzeitig die zur Ablösung des Oberflächenwassers aufzubringende Adhäsionsarbeit verringert. Dies führt beim Einsatz von Tensiden zu einer verbesserten Entwässerung bei unverändertem Energieaufwand.It is known to use surfactants as drainage aids for dewatering water-containing fine-particle solids, in particular hard coal, by means of which the residual moisture of fine and fine coal can be reduced. The reason for this is the property of the surfactants, to reduce the surface tension and the capillary pressure of the water in the aggregate. At the same time, the work of adhesion to detach the surface water is reduced. When using surfactants, this leads to improved drainage with unchanged energy consumption.
Als tensidische Entwässerungshilfsmittel der vorstehend genannten Art sind Dialkylsulfosuccinate (US-C 2 266 954) und nichtionische Tenside vom Typ der Alkylphenol-polyglykolether [Erzmetall 30, 292 (1977)] beschrieben worden. Diese Tenside sind jedoch mit dem Nachteil einer erheblichen Schaumbildung behaftet, die insbesondere bei der üblicherweise angewendeten Kreislaufführung des Wassers in den Aufbereitungsbetrieben zu erheblichen Problemen führt.Dialkyl sulfosuccinates (US Pat. No. 2,266,954) and nonionic surfactants of the alkylphenol polyglycol ether type [Erzmetall 30, 292 (1977)] have been described as surfactant dewatering aids of the type mentioned above. However, these surfactants have the disadvantage of considerable foam formation, which leads to considerable problems in the processing plants, in particular when water is circulated in the usual way.
Die Erfindung beruht auf der Erkenntnis, daß nichtionische Tenside der allgemeinen Formel I bei ihrer Verwendung in Wasser/Feststoff-Systemen ohne Schaumbildung die Entwässerungsgeschwindigkeit erhöhen und die Restfeuchte der entwässerten Feststoffe erniedrigen.The invention is based on the knowledge that nonionic surfactants of the general formula I when used in Water / solids systems without foaming increase the dewatering speed and lower the residual moisture of the dewatered solids.
Die Gruppe R¹ der erfindungsgemäß zu verwendenden Hydroxymischether der allgemeinen Formel I ist eine gegebenenfalls verzweigte oder cyklische Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, z.B. eine Methyl-, Ethyl-, Propyl-, Butyl-, Pentyl-, Hexyl-, Heptyl-, Octyl-, Nonyl- oder Decylgruppe. Bevorzugt sind Alkylgruppen mit 1 bis 4 Kohlenstoffatomen aus der obigen Aufzählung. Die Gruppe R² in der allgemeinen Formel I ist eine Alkylgruppe mit 8 bis 20 Kohlenstoffatomen, z.B. eine Octyl-, Nonyl-, Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl, Pentadecyl-, Hexadecyl, Heptadecyl-, Octadecyl-, Nonadecyl- oder Eicosylgruppe, insbesondere eine Alkylgruppe mit 12 bis 16 Kohlenstoffatomen aus der obigen Aufzählung, wobei geradkettige Reste R² besonders bevorzugt sind. x in der allgemeinen Formel I bedeutet eine Zahl im Bereich von 1 bis 20, wobei ein Bereich von 2 bis 15 bevorzugt ist.The group R 1 of the hydroxy mixed ethers of the general formula I to be used according to the invention is an optionally branched or cyclic alkyl group with 1 to 10 carbon atoms, e.g. a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl group. Alkyl groups with 1 to 4 carbon atoms from the above list are preferred. The group R² in general formula I is an alkyl group with 8 to 20 carbon atoms, e.g. an octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl group, in particular an alkyl group with 12 to 16 carbon atoms from the above list, straight-chain radicals R² are particularly preferred. x in the general formula I denotes a number in the range from 1 to 20, a range from 2 to 15 being preferred.
Entsprechend ihrer Verwendung müssen die Hydroxymischether der allgemeinen Formel I wasserlöslich sein. Es ist möglich, daß diese Wasserlöslichkeit nicht in ausreichendem Ausmaß gegeben ist, wenn die Hydroxymischether der allgemeinen Formel I bei niedrigen Werten von x langkettige Reste R¹ und/oder R² mit Kettenlängen innerhalb der vorstehend genannten Bereiche aufweisen; die geforderte Wasserlöslichkeit läßt sich jedoch dadurch erreichen, daß man den Wert für x innerhalb des vorstehend genannten Bereiches erhöht.Depending on their use, the hydroxy mixed ethers of the general formula I must be water-soluble. It is possible that this water solubility is not sufficient if the hydroxy mixed ethers of the general formula I at long values of x have long-chain radicals R 1 and / or R 2 with chain lengths within the above-mentioned ranges; the required water solubility can, however, be achieved by increasing the value for x within the above-mentioned range.
Die Hydroxymischether der allgemeinen Formel I sind in der DE-A 37 23 323 beschrieben; sie können erhalten werden, indem man ethoxylierte Alkohole der allgemeinen Formel II
R¹O-(CH₂CH₂O)x-OH (II)
mit Epoxiden von alpha-Olefinen der Formel III
in Gegenwart von Katalysatoren umsetzt, wobei R¹, R² und x wie oben definiert sind.The hydroxy mixed ethers of the general formula I are described in DE-A 37 23 323; they can be obtained by using ethoxylated alcohols of the general formula II
R¹O- (CH₂CH₂O) x -OH (II)
with epoxides of alpha olefins of formula III
in the presence of catalysts, wherein R¹, R² and x are as defined above.
Entsprechend ihrer Herstellung und der dabei verwendeten Ausgangsmaterialien, die meist in Form von technischen Gemischen eingesetzt werden, können auch die erfindungsgemäß zu verwendenden Hydroxymischether der allgemeinen Formel I als technische Gemische vorliegen.Depending on their production and the starting materials used, which are mostly used in the form of industrial mixtures, the hydroxy mixed ethers of the general formula I to be used according to the invention can also be present as industrial mixtures.
Gemäß einer vorteilhaften Ausführungsform der Erfindung setzt man die Hydroxymischether der allgemeinen Formel I in einer Menge von 0,5 bis 10, insbesondere 3 bis 8 kg pro m³ des aus den feinteiligen Feststoffen zu entfernenden Wassers ein.According to an advantageous embodiment of the invention, the hydroxy mixed ethers of the general formula I are used in an amount of 0.5 to 10, in particular 3 to 8 kg per m 3 of the water to be removed from the finely divided solids.
Wie eingangs erwähnt, eignen sich die Hydroxymischether der allgemeinen Formel I insbesondere zur Entwässerung von wasserhaltigen, feinteiligen Steinkohlen oder Koks; sie können jedoch auch bei der Entwässerung von anderen Wasser/Feststoff-Systemen, z.B. bei aufbereiteten Erzen oder Gangmaterialien im Erzbergbau, Klärschlämmen oder dergleichen, eingesetzt werden. Dabei ist als weiterer Vorteil der erfindungsgemäß zu verwendenden Tenside der allgemeinen Formel I anzusehen, daß diese mit gegebenenfalls vorhandenen Tensiden anderer Zusammensetzung, z.B. mit Dialkylsulfosuccinaten wie di-n-Octylsulfosuccinaten oder Polyacrylamiden, die den zu entwässernden Feststoffen in vorherigen Aufbereitungsstufen zugesetzt wurden, verträglich sind.As mentioned at the beginning, the hydroxy mixed ethers of the general formula I are particularly suitable for dewatering water-containing, finely divided hard coal or coke; however, they can also be used in the dewatering of other water / solid systems, for example in the case of processed ores or gangue materials in ore mining, sewage sludge or the like. A further advantage of the surfactants of the general formula I to be used according to the invention is that they are compatible with any other surfactants present, for example with dialkyl sulfosuccinates such as di-n-octyl sulfosuccinates or polyacrylamides, which were added to the solids to be dewatered in previous treatment stages .
Die Erfindung wird im folgenden anhand von bevorzugten Ausführungsbeispielen näher erläutert.The invention is explained in more detail below on the basis of preferred exemplary embodiments.
In den Beispielen wurde eine gewaschene Feinkohle mit folgenden Analysendaten verwendet:
6,8 Gew.-% Wasser
3,7 Gew.-% Asche (wf; berechnet auf wasserfreie Kohle)
27,2 % flüchtige Bestandteile (waf; berechnet auf wasser- und aschefreie Kohle)
Die Siebanalyse der Feinkohle lieferte die folgenden Werte:
6.8% by weight of water
3.7% by weight of ash (wf; calculated on anhydrous coal)
27.2% volatile components (waf; calculated on water and ash-free coal)
The sieve analysis of the fine coal gave the following values:
Zur Ermittlung der Wirksamkeit der Hydroxymischether der allgemeinen Formel I bei der Entwässerung wurde die Feinkohle mit wässrigen Lösungen der Hydroxymischether definierter Konzentration behandelt und unter definierten Bedingungen entwässert; die mit und ohne Tensidzusatz erreichte Restfeuchte wurde nach DIN 51718 durch Trocknung bei 106°C und Wägung bestimmt.To determine the effectiveness of the hydroxy mixed ethers of the general formula I in dewatering, the fine coal was treated with aqueous solutions of the hydroxy mixed ethers of a defined concentration and dewatered under defined conditions; the residual moisture achieved with and without the addition of surfactants was determined in accordance with DIN 51718 by drying at 106 ° C. and weighing.
Bei den vorliegenden Beispielen handelt es sich um Laborversuche, bei denen die eingesetzten Tensidmengen in kg auf je 1000 kg der zu entwässernden Feststoffe (berechnet als wasserfreie Feststoffe) bezogen sind. In der Praxis werden die erforderlichen Tensidmengen niedriger sein als die in den Beispielen eingesetzten; zudem werden bei der praktischen Durchführung der Feststoffentwässerung die erforderlichen Tensidmengen in Abhängigkeit von der Menge des den Feststoffen zu entziehenden Wassers eingesetzt.The present examples are laboratory tests in which the amounts of surfactant used in kg are based on 1000 kg of the solids to be dewatered (calculated as anhydrous solids). In practice, the amount of surfactant required will be lower than that used in the examples; in addition, in the practical implementation of solid dewatering, the required amounts of surfactant are used depending on the amount of water to be removed from the solid.
Die Struktur der getesteten Hydroxymischether der allgemeinen Formel I und ihre im folgenden verwendeten Abkürzungen ergeben sich aus der Tabelle 1.The structure of the hydroxy mixed ethers of the general formula I tested and their abbreviations used below are shown in Table 1.
Der hier und nachfolgend verwendete Begriff "Tensid" bezieht sich auf die Hydroxymischether der allgemeinen Formel I.
50 g Kohle wurden in 400 ml destilliertem Wasser bzw. Tensidlösungen in destilliertem Wasser gegeben und nach einer Einwirkzeit von 60 s gefiltert. Hierzu wurde ein Druckfilter verwendet, bei dem es sich um eine geschlossene Filternutsche handelte, die mit dem zu entwässernden Gut befüllt wurde. Die Entwässerung erfolgte, indem der Filter mit einem Druck von 3 bar beaufschlagt wurde. Die Entwässerungszeit betrug 30 s. Als Filtermaterial wurde ein Filtergewebe mit einer Maschenweite von 0,2 mm eingesetzt.50 g of coal were placed in 400 ml of distilled water or surfactant solutions in distilled water and filtered after an exposure time of 60 s. For this purpose, a pressure filter was used, which was a closed filter chute, which was filled with the material to be dewatered. The drainage was carried out by applying a pressure of 3 bar to the filter. The drainage time was 30 s. A filter fabric with a mesh size of 0.2 mm was used as the filter material.
Die geprüften Tenside, die Tensidkonzentration der Lösung, mit der die Kohle behandelt wurde, die errechnete Tensidmenge pro 1000 kg Kohle sowie die ermittelte Restfeuchte sind in der Tabelle 2 zusammengefaßt.
Wie sich aus Tabelle 2 ergibt, wird die Restfeuchte beim Einsatz der erfindungsgemäß einzusetzenden Tenside im Vergleich zu ohne Tensidzusatz entwässerter Kohle deutlich herabgesetzt.As can be seen from Table 2, the residual moisture when using the surfactants to be used according to the invention is significantly reduced in comparison to coal dewatered without the addition of surfactants.
Hier wurde eine Becherzentrifuge eingesetzt, mit der bei Drehzahlen von 300 bis 3400 U/min Zentrifugalkennwerte von 15 bis 2000 realisierbar sind. Als Siebbelag für die Zentrifuge wurden Lochplatten mit Sieböffnungen von 0,4 x 4,0 mm verwendet; die als Filterhilfsmittel eingesetzten Tenside (Hydroxymischether der allgemeinen Formel I) wurden in Konzentrationen von 0,1 g/l und 1,0 g/l in destilliertem Wasser gelöst. Zur Durchführung der Tests wurden jeweils 400 ml der tensidhaltigen Lösungen in ein Glasgefäß gefüllt. In diese Lösungen wurden jeweils 25 g Kohle eingetaucht. Die Benetzungszeit betrug jeweils 60 s. Hieran schloß sich zur Vorentwässerung der Proben eine konstante Abtropfzeit von 180 s an. Die bei der Vorentwässerung der Proben erhaltenen Werte, die Tensidkonzentration sowie die errechnete Tensidmenge pro 1000 kg Kohle sind in Tabelle 3 zusammengefaßt.A cup centrifuge was used here, with which centrifugal values of 15 to 2000 can be achieved at speeds of 300 to 3400 rpm. Perforated plates with sieve openings of 0.4 x 4.0 mm were used as the sieve covering for the centrifuge; the surfactants used as filter aids (hydroxy mixed ethers of the general formula I) were dissolved in distilled water in concentrations of 0.1 g / l and 1.0 g / l. To carry out the tests, 400 ml of the surfactant-containing solutions were placed in a glass vessel. 25 g of coal were immersed in each of these solutions. The wetting time was 60 s in each case. This was followed by a constant draining time of 180 s for the pre-dewatering of the samples. The values obtained in the preliminary dewatering of the samples, the surfactant concentration and the calculated amount of surfactant per 1000 kg of coal are summarized in Table 3.
Für die Entwässerung der vorentwässerten Proben in der Becherzentrifuge wurden Zentrifugalkennwerte von 43,2, 111 und 389 (entsprechend Drehzahlen von 500, 800 und 1500 U/min) eingestellt. Die Entwässerungsdauer betrug 30 s. Die erhaltenen Ergebnisse sind in Tabelle 4 zusammengefaßt.Centrifugal parameters of 43.2, 111 and 389 (corresponding to speeds of 500, 800 and 1500 rpm) were set for the dewatering of the pre-dewatered samples in the cup centrifuge. The drainage time was 30 s. The results obtained are summarized in Table 4.
In einer zweiten Versuchsreihe wurde eine Tensidkonzentration von 1,0 g/l bei einem Zentrifugalkennwert von 111 (entsprechend einer Drehzahl von 800 U/min) bei Entwässerungszeiten von 5, 10 und 30 s getestet; die erhaltenen Ergebnisse sind in Tabelle 5 zusammengefaßt.In a second series of tests, a surfactant concentration of 1.0 g / l with a centrifugal value of 111 (corresponding to a speed of 800 rpm) with dewatering times tested from 5, 10 and 30 s; the results obtained are summarized in Table 5.
Wie sich aus den Tabellen 3 bis 5 ergibt, weisen sämtliche getesteten Tenside eine sehr gute Wirkung auf die Entwässerung auf. Schon in der Vorentwässerung (Tabelle 3) wurde die Wirksamkeit der Tenside im Vergleich zu einer Probe ohne Tensidzusatz deutlich; während die unbehandelte Probe nach der Abtropfzeit von 180 s eine Restfeuchte von 43,6 % aufwies, ließ sich dieser Wert durch die erfindungsgemäß eingesetzten Tenside auf bis zu 26,5 % reduzieren. Dies entspricht einer relativen Absenkung der Restfeuchte um 39 %.As can be seen from Tables 3 to 5, all tested surfactants have a very good effect on drainage. Even in the pre-dewatering (Table 3), the effectiveness of the surfactants was clear in comparison to a sample without added surfactants; While the untreated sample had a residual moisture of 43.6% after the draining time of 180 s, this value could be reduced to up to 26.5% by the surfactants used according to the invention. This corresponds to a relative reduction in residual moisture by 39%.
Wie sich aus den Tabellen 4 und 5 ergibt, ließ sich eine Reduzierung der Restfeuchte sowohl durch Erhöhung des Zentrifugalkennwertes als auch durch die Zugabe der erfindungsgemäß zu verwendenden Tenside erreichen.As can be seen from Tables 4 and 5, a reduction in the residual moisture could be achieved both by increasing the centrifugal value and by adding the surfactants to be used according to the invention.
Eine Tensidlösung mit 0,1 g/l ermöglichte bei einem Zentrifugalkennwert von 111 ein Absenken der Restfeuchte auf 4,0 Gew.-%. Eine Tensidlösung mit 1,0 g/l senkte die Restfeuchte auf bis zu 3,0 %. Diese Werte sind auch bei kurzen Entwässerungszeiten erreichbar.
Claims (6)
- The use of hydroxy mixed ethers corresponding to general formula I
R¹O-(CH₂CH₂O)x-CH₂-CH(OH)R² (I)
in which
R¹ is a C₁₋₁₀ alkyl group,
R² is a C₈₋₂₀ alkyl group and
x is a number of 1 to 20,
as auxiliaries for dewatering water-containing fine-particle solids. - The use claimed in claim 1, characterized in that hydroxy mixed ethers corresponding to formula I, in which R¹ is a C₁₋₄ alkyl group, are used.
- The use claimed in claim 1 or 2, characterized in that hydroxy mixed ethers corresponding to general formula I, in which R² is a C₁₂₋₁₆ alkyl group, are used.
- The use claimed in at least one of claims 1 to 3, characterized in that hydroxy mixed ethers corresponding to general formula I, in which x is a number of 2 to 15, are used.
- The use claimed in at least one of claims 1 to 4, characterized in that the hydroxy mixed ethers are used in a quantity of 0.5 to 10 kg and more particularly in a quantity of 3 to 8 kg per m³ of the water to be removed from the fine-particle solid.
- The use claimed in at least one of claims 1 to 5 for dewatering water-containing fine-particle mineral coals or coke.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3918274A DE3918274A1 (en) | 1989-06-05 | 1989-06-05 | USE OF HYDROXYMISCHETHERS AS A SOLVENT FOR SOLIDS HEATING |
| DE3918274 | 1989-06-05 | ||
| PCT/EP1990/000851 WO1990015295A1 (en) | 1989-06-05 | 1990-05-28 | Used of mixed hydroxy ethers as aids for drying solids materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0475969A1 EP0475969A1 (en) | 1992-03-25 |
| EP0475969B1 true EP0475969B1 (en) | 1994-04-27 |
Family
ID=6382085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90908227A Expired - Lifetime EP0475969B1 (en) | 1989-06-05 | 1990-05-28 | Used of mixed hydroxy ethers as aids for drying solids materials |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5215669A (en) |
| EP (1) | EP0475969B1 (en) |
| AU (1) | AU631647B2 (en) |
| BR (1) | BR9007418A (en) |
| CA (1) | CA2058440C (en) |
| DE (2) | DE3918274A1 (en) |
| NO (1) | NO178838C (en) |
| PT (1) | PT94261A (en) |
| TR (1) | TR24599A (en) |
| WO (1) | WO1990015295A1 (en) |
| ZA (1) | ZA904275B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4019174A1 (en) * | 1990-06-15 | 1992-01-02 | Henkel Kgaa | EXTRACTS FOR FILTRATION AND / OR DEHUMIDIFICATION OF MINERAL AND CARBON SUSPENSIONS |
| DE4218050A1 (en) * | 1992-06-01 | 1993-12-02 | Henkel Kgaa | Process for dewatering fine particulate suspensions |
| DE4218074A1 (en) * | 1992-06-01 | 1993-12-02 | Henkel Kgaa | Process for dewatering fine particulate suspensions |
| US5670056A (en) * | 1995-04-17 | 1997-09-23 | Virginia Tech Intellectual Properties, Inc. | Chemical-mechanical dewatering process |
| US6855260B1 (en) | 1999-06-07 | 2005-02-15 | Roe-Hoan Yoon | Methods of enhancing fine particle dewatering |
| US6526675B1 (en) | 1999-06-07 | 2003-03-04 | Roe-Hoan Yoon | Methods of using natural products as dewatering aids for fine particles |
| US6375853B1 (en) * | 2000-03-17 | 2002-04-23 | Roe-Hoan Yoon | Methods of using modified natural products as dewatering aids for fine particles |
| US6799682B1 (en) | 2000-05-16 | 2004-10-05 | Roe-Hoan Yoon | Method of increasing flotation rate |
| WO2002026340A2 (en) | 2000-09-28 | 2002-04-04 | Yoon Roe Hoan | Methods of using natural products as dewatering aids for fine particles |
| JP4022595B2 (en) * | 2004-10-26 | 2007-12-19 | コニカミノルタオプト株式会社 | Imaging device |
| US8007754B2 (en) * | 2005-02-04 | 2011-08-30 | Mineral And Coal Technologies, Inc. | Separation of diamond from gangue minerals |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2266954A (en) * | 1939-08-26 | 1941-12-23 | American Cyanamid Co | Wetting agent in settling of oe pulps |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2975123A (en) * | 1957-11-04 | 1961-03-14 | Int Nickel Co | Dewatering metal ore concentrates |
| US3194758A (en) * | 1961-05-24 | 1965-07-13 | Petrolite Corp | Method of agglomerating finely divided solids in an aqueous medium |
| US3327402A (en) * | 1964-12-28 | 1967-06-27 | Shell Oil Co | Solvent drying of coal fines |
| LU47975A1 (en) * | 1965-02-12 | 1966-08-12 | ||
| US4014104A (en) * | 1975-06-23 | 1977-03-29 | Continental Oil Company | Drying of lignite using nonaqueous solvents |
| JPS5613099A (en) * | 1979-07-10 | 1981-02-07 | Nichireki Chem Ind Co Ltd | Treating method of sludge |
| JPS5784708A (en) * | 1980-11-18 | 1982-05-27 | Kao Corp | Improving agent for filtration/dehydration property of metal hydroxide slurry |
| CA1252016A (en) * | 1984-01-09 | 1989-04-04 | Kay E. Cawiezel | Mineral dewatering method |
| DE3723323C2 (en) * | 1987-07-15 | 1998-03-12 | Henkel Kgaa | Hydroxy mixed ethers, processes for their preparation and their use |
| US4866856A (en) * | 1987-10-13 | 1989-09-19 | The Standard Oil Company | Solids dewatering process and apparatus |
| US4990264A (en) * | 1989-10-13 | 1991-02-05 | Sherex Chemical Company, Inc. | Ore dewatering process and compositions therefor |
-
1989
- 1989-06-05 DE DE3918274A patent/DE3918274A1/en not_active Withdrawn
-
1990
- 1990-05-28 BR BR909007418A patent/BR9007418A/en not_active Application Discontinuation
- 1990-05-28 WO PCT/EP1990/000851 patent/WO1990015295A1/en active IP Right Grant
- 1990-05-28 EP EP90908227A patent/EP0475969B1/en not_active Expired - Lifetime
- 1990-05-28 DE DE59005545T patent/DE59005545D1/en not_active Expired - Fee Related
- 1990-05-28 CA CA002058440A patent/CA2058440C/en not_active Expired - Fee Related
- 1990-05-28 AU AU56685/90A patent/AU631647B2/en not_active Ceased
- 1990-05-28 US US07/777,389 patent/US5215669A/en not_active Expired - Fee Related
- 1990-06-01 TR TR90/0510A patent/TR24599A/en unknown
- 1990-06-04 ZA ZA904275A patent/ZA904275B/en unknown
- 1990-06-04 PT PT94261A patent/PT94261A/en not_active Application Discontinuation
-
1991
- 1991-10-11 NO NO914001A patent/NO178838C/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2266954A (en) * | 1939-08-26 | 1941-12-23 | American Cyanamid Co | Wetting agent in settling of oe pulps |
Also Published As
| Publication number | Publication date |
|---|---|
| US5215669A (en) | 1993-06-01 |
| NO914001L (en) | 1991-10-11 |
| WO1990015295A1 (en) | 1990-12-13 |
| BR9007418A (en) | 1992-06-16 |
| NO178838B (en) | 1996-03-04 |
| NO178838C (en) | 1996-06-12 |
| TR24599A (en) | 1992-01-01 |
| NO914001D0 (en) | 1991-10-11 |
| EP0475969A1 (en) | 1992-03-25 |
| DE59005545D1 (en) | 1994-06-01 |
| AU631647B2 (en) | 1992-12-03 |
| AU5668590A (en) | 1991-01-07 |
| CA2058440C (en) | 2001-03-27 |
| ZA904275B (en) | 1991-02-27 |
| DE3918274A1 (en) | 1990-12-06 |
| CA2058440A1 (en) | 1990-12-06 |
| PT94261A (en) | 1991-02-08 |
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