Cloud-free stabilization of dispersions of water in hydrocarbon fractions boiling in the diesel or heating oil range
Abstract
This record has no abstract on file.
Term
Term ended
Expired 18 April 2007, 19.4 years ago.
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5 claims: 5 independent, 0 dependent
- 1The use of a multicomponent surfactant mixture for the clouding-free emulsification and stabilization of water in hydrocarbon fractions of the diesel oil or fuel oil range, the surfactant mixture containing at least one alkylphenol polyethylene glycol ether containing 8 or 9 carbon atoms in the alkyl radical, characterized in that the surfactant mixture a) contains at least two components of surfactant class A, if desired in admixture with surfactants of classes B and/or C, surfactant class A including ethoxylates of octylphenol, nonylphenol and isotridecyl alcohol each containing 1 to 7 ethylene oxide units, surfactant class B including coconut oil alcohol ethoxylates containing 1 to 7 ethylene oxide units and surfactant class C including oleyl alcohol ethoxylates containing 1 to 7 ethylene oxide units,b) contains from surfactant class A ethoxylates containing 3 ethylene oxide units in admixture with ethoxylates containing 5 ethylene oxide units,c) has a cloud point of 35 to 70°C, as determined in accordance with DIN 53 917 (5 g surfactant mixture in 25 g of an aqueous 25% butyl diglycol solution). Utilisation d'un mélange d'agents tensioactifs à plusieurs composants pour l'émultion exempte de trouble et la stabilisation d'eau dans des fractions d'hydrocarbures du domaine de fuel ou du mazout pour moteurs diesel, le mélange d'agents tensioactifs comportant au moins un éther d'alkylphénol-polyéthylèneglycol ayant 8 ou 9 atomes de carbone dans le radical alkyle, caractérisée en ce que le mélange d'agents tensioactifs, a) contient au moins deux composants de la classe d'agents tensioactifs A, si on le désire en mélange avec des agents tensioactifs des classes B et/ou C, étant entendu que :Classe d'agents tensioactifs A : produits d'oxyéthylation d'octylphénol, nonylphénol et alcool isotridécylique ayant chacun de 1 à 7 unités oxyde d'éthylène, Classe d'agents tensioactifs B : produits d'oxyéthylation d'alcool de coco ayant de 1 à 7 unités oxyde d'éthylène, Classe d'agents tensioactifs C : produits d'oxyéthylation d'alcool oléylique ayant de 1 à 7 unités oxyde d'éthylène,b) contient dans la classe d'agents tensioactifs A des produits d'oxyéthylation comportant 3 unités oxyde d'éthylène en mélange avec des produits d'oxyéthylation comportant 5 unités oxyde d'éthylène,c) présente une température de trouble de 35 à 70°C, mesurée selon DIN 53917 (5g de mélange d'agents tensioactifs dans 25g d'une solution aqueuse de butyldiglycol à 25 %). Verwendung eines mehrkomponentigen Tensidgemisches zur trübungsfreien Emulgierung und Stabilisierung von Wasser in Kohlenwasserstofffraktionen des Diesel- beziehungsweise Heizölbereichs, wobei das Tensidgemisch mindestens einen Alkylphenolpolyethylenglykolether mit 8 oder 9 C-Atomen im Alkylrest aufweist, dadurch gekennzeichnet, daß das Tensidgemisch a) wenigstens zwei Komponenten der Tensidklasse A, gewünschtenfalls in Abmischung mit Tensiden der Klassen B und/oder C, enthält, wobei gilt: Tensidklasse A: Ethoxylate von Octylphenol, Nonylphenol und Isotridecylalkohol mit jeweils 1 bis 7 Ethylenoxideinheiten, Tensidklasse B: Kokosalkohol-Ethoxylate mit 1 bis 7 Ethylenoxideinheiten, Tensidklasse C: Oleylalkohol-Ethoxylate mit 1 bis 7 Ethylenoxideinheiten,b) aus der Tensidklasse A Ethoxylate mit 3 Ethylenoxideinheiten in Abmischung mit Ethoxylaten mit 5 Ethylenoxideinheiten enthält,c) eine Trübungstemperatur von 35 bis 70 °C - bestimmt nach DIN 53 917 (5 g Tensidgemisch in 25 g einer wäßrigen 25%igen Butyldiglykollösung) - aufweist.
- 2The use claimed in claim 1, characterized in that hydrocarbon fractions containing up to 5% by weight water are stabilized to clear solutions with 0.5 to 10% by weight of the surfactant mixture, even at temperatures below freezing point. Utilisation selon la revendication 1, caractérisée en ce que les fractions d'hydrocarbures, ayant une teneur en eau allant jusqu'à environ 5 % en poids, sont stabilisées en donnant des solutions limpides même à des températures jusqu'au-dessous du point de congélation, avec utilisation simultanée de 0,5 à 10 % en poids du mélange d'agents tensioactifs. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß Kohlenwasserstofffraktionen eines Wassergehaltes bis zu etwa 5 Gew.-% unter Mitverwendung von 0,5 bis 10 Gew.-% des Tensidgemisches auch bei Temperaturen bis unterhalb des Gefrierpunktes zu klaren Lösungen stabilisiert sind.
- 3The use claimed in claims 1 or 2, characterized in that the surfactant mixtures lie within the following ranges:20 to 60% by weight nonylphenol containing 3 ethylene oxide units, 20 to 80% by weight nonylphenol containing 5 ethylene oxide units, 0 to 30% by weight oleyl and/or coconut oil alcohol containing 5 ethylene oxide units. Utilisation selon la revendication 1 ou 2, caractérisée en ce que les mélanges d'agents tensioactifs se trouvent dans les plages suivantes : - de 20 à 60 % en poids de nonylphénol comportant 3 unités oxyde d'éthylène,- de 20 à 80 % en poids de nonylphénol comportant 5 unités oxyde d'éthylène,- de 0 à 30 % en poids d'alcool oléylique et/ou de coco comportant 5 unités oxyde d'éthylène. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß Tensidmischungen innerhalb der folgenden Bereiche vorliegen: 20 bis 60 Gew.-% Nonylphenol mit 3 Ethylenoxideinheiten, 20 bis 80 Gew.-% Nonylphenol mit 5 Ethylenoxideinheiten, 0 bis 30 Gew. -% Oleyl- und/oder Kokosalkohol mit 5 Ethylenoxideinheiten.
- 4The use claimed in claims 1 to 3, characterized in that the surfactant mixtures used have a cloud point (DIN 53917) of 40 to 60°C and preferably of 45 to 55°C. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que les mélanges d'agents tensioactifs utilisés présentent une température de trouble (DIN 53917) dans la plage de 40 à 60°C, de préférence de 45 à 55°C. Verwendung nach Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die eingesetzten Tensidgemische eine Trübungstemperatur (DIN 53 917) im Bereich von 40 bis 60 °C, vorzugsweise von 45 bis 55 °C, aufweisen.
- 5The use claimed in claims 1 to 4, characterized in that, for water contents of up to 3% by weight, the hydrocarbon mixture contains 1 to 5% by weight of the surfactant mixture. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que dans le cas de teneurs en eau du mélange d'hydrocarbures allant jusqu'à 3 % en poids, sont présents de 1 à 5 % en poids du mélange d'agents tensioactifs. Verwendung nach Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß bei Wassergehalten bis zu 3 Gew.-% im Kohlenwasserstoffgemisch 1 bis 5 Gew.-% des Tensidgemisches vorliegen.
Independent claims5
17 paragraphs, as filed
The invention relates to new possibilities of emulsification and stabilization limited amounts of water in hydrocarbon fractions of daily necessities, especially in those fractions of diesel or heating oil region.
Technical hydrocarbon fractions of the type mentioned are known to contain limited amounts of water, which can for example be in the range of 0.5 to 10 wt .-%. This is most often caused by small amounts of water that are in lines or storage tanks dating from rinsing and cleaning operations already exist, or that they form as a result of humidity as condensation water in the storage tanks. Since water in diesel or heating oil is wt .-% soluble only with less than 0.5, contact with larger amounts of water to separate phases. In practice, this situation if the storage of water containing diesel and heating oil undesirable side effects such as corrosion of the storage tanks.
EP-A-0147506 relates to a process for as complete as possible combustion of fuel mixtures of oil and water. The objective is achieved by the fuel mixture an alkyl phenol polyethylene glycol ether, ie adducts of ethylene oxide with alkylphenols added. As the most important alkylphenol Nonylphenol is called in this context, but which also may be present together with octyl and dodecyl. The additives referred to require a stable emulsification of fuel mixtures. Such fuel mixtures preferably contain up to 100 parts by volume of oil from 1 to 30 parts by volume of water and 0.1 to 0.6 parts by volume of the additive.
In contrast, limited amounts of water of the aforementioned order comes from the invention of the task reliably in hydrocarbon fractions of the type mentioned emulsify and so be able to stabilize that haze-free clear single phase liquids even present when the goods to temperatures below the freezing point, for example to temperatures is cooled to -5 to -10 ° C.
The technical solution of the invention is the use of selected surfactant mixtures intended as emulsifiers and / or stabilizers for the herein described water contents of hydrocarbon fractions of diesel or heating oil region.
The invention is accordingly the use of a multicomponent surfactant mixture to haze-free emulsification and stabilization of water in hydrocarbon fractions of diesel or fuel oil range, wherein the surfactant comprises at least one alkyl phenol polyethylene glycol ether having 8 or 9 carbon atoms in the alkyl radical, characterized in that the surfactant mixture<ul><li>a) at least two components of surfactant class A, optionally in admixture with surfactants of class B and / or C includes, where: Surfactant class A: ethoxylates of octylphenol, nonylphenol and isotridecyl alcohol each containing 1 to 7 ethylene oxide units, Surfactant class B: coconut alcohol ethoxylates having from 1 to 7 ethylene oxide units, Surfactant class C: oleyl ethoxylates having from 1 to 7 ethylene oxide units,</li><li>b) contains from surfactant class A ethoxylates with 3 ethylene in admixture with ethoxylates with 5 ethylene oxide units,</li><li>c) a turbidity temperature of 35 to 70 ° C - determined to DIN 53 917 (5 g surfactant in 25 g of an aqueous 25% butyl ether) - has.</li></ul>
The abbreviation "EO" used hereinafter means "ethylene oxide".
It has been found that by the selection of certain surfactant classes A, B and C in conjunction with the establishment of the hydrophilicity of the surfactant used - determined on the cloud point according to DIN 53917 - a solution of the problem underlying the present invention is achieved.
Necessarily, the invention provides the use of a mixture of at least two surfactants selected from the class A. The concomitant use of surfactants from the classes B and / or C may be desirable, but not required. The proper selection of the mixture components is possible by simple tests the cloud point of each surfactant mixture to be used according to DIN 53917 within the specified classes. Here the cloud point of a solution of 5 g of the surfactant or surfactant mixture in 25 g of an aqueous 25% butyl ether (= diethylene) is determined known. This is done in such a manner that the solution of the sample is heated to above the complete addition turbidity. It is then cooled slowly with stirring. the temperature is kept as a cloud point at which disappear present in the mixture turbidity with whitening and form a clear or slightly opalescenten solution.
According to the invention, the cloud point of the surfactant used for emulsification and stabilization of the classes A and optionally B and / or C preferably in the range of 40 to 60 ° C and in particular in the range of 45 to 55 ° C.
Through selection and combination of the present invention given surfactant succeed safe emulsification and stabilization of the present in the hydrocarbon mixture water content - of typically up to about 5 may be wt .-% - with the concomitant use of 0.5 to 10 wt .-% of the surfactant to clear , resistant solutions even when the water-containing hydrocarbon fractions are cooled to temperatures just below room temperature and even below 0 ° C. Frequently, the water content of the question here hydrocarbon fractions is not more than about 3 wt .-%. This then can be used together up to about 5 wt .-%, in particular about 1 to 5 wt .-% of the surfactant mixtures according to the invention - in each case based on 100 parts by weight of diesel or heating oil fraction - clear solutions are prepared at temperatures to -4 comprise ° C and even below unchanged single-phase texture. The described Vulnerabilities Inherent in the practical handling of the question here hydrocarbon fractions are thus eliminated reliable for the practical needs of everyday life.
at least 2 surfactants are used in combination with each other as indicated from the surfactant class A, wherein the surfactant comprises ethoxylates of said type with 3 EO in combination with ethoxylates of the type mentioned with 5 EO. It can get nonylphenol ethoxylates of said type are particularly important.
Preferred surfactant for use herein are made within the following ranges: <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">20 to 60 wt .-%</entry><entry namest="col2" nameend="col2" align="left">Nonylphenol-3 EO</entry></row><row><entry namest="col1" nameend="col1" align="right">20 to 80 wt .-%</entry><entry namest="col2" nameend="col2" align="left">Nonylphenol EO 5</entry></row><row><entry namest="col1" nameend="col1" align="right">0 to 30 wt .-%</entry><entry namest="col2" nameend="col2" align="left">Oleyl and / or coconut alcohol 5 EO</entry></row></tbody></tgroup></table></tables> The surfactant component B is based in the preferred embodiment on a coconut alcohol the following C chain distribution: C₁₂- 55 wt .-%, C₁₄ - 25 wt .-%, C₁₆- 10 wt .-% and 10 wt .-% C₁₈-.
The Oleylalkoholbasis the surfactant component C may have iodine numbers in the range of 40 to 170th
The surfactant used in the invention for water stabilization are inexpensive commercial products. In the intended use of the corresponding laden hydrocarbon fractions - especially the combustion of these KohIenwasserstofffraktionen for energy - do not interfere with these components.
<b>example</b>
Using various surfactant mixtures according to the invention the quality of diesel / water mixtures is judged. The following table shows the composition of the surfactant mixture, the haze temperature (DIN 53917) of the surfactant and the assessment of the emulsion composition at 20 ° C with the following basic formulation:<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Diesel hydrocarbon mixture</entry><entry namest="col2" nameend="col2" align="right">95 wt .-%</entry></row><row><entry namest="col1" nameend="col1" align="left">surfactant mixture according to the invention</entry><entry namest="col2" nameend="col2" align="right">4 wt .-%</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="right">1 wt .-%</entry></row></tbody></tgroup></table></tables><tables id="tabl0003" num="0003"><table frame="all"><title>table</title><tgroup cols="5" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">Examples</entry><entry namest="col2" nameend="col2" align="center">Composition of the surfactant</entry><entry namest="col3" nameend="col3" align="center">Wt .-%</entry><entry namest="col4" nameend="col4" align="center">Trübungstempera- (DIN 53917)</entry><entry namest="col5" nameend="col5" align="center">Assessment of the emulsion at 20 ° C</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" morerows="2" align="right">1.</entry><entry namest="col2" nameend="col2" align="left">Nonylphenol-3 EO</entry><entry namest="col3" nameend="col3" align="right">60</entry><entry namest="col4" nameend="col4" morerows="2" align="right">48 ° C</entry><entry namest="col5" nameend="col5" morerows="2" align="left">clear</entry></row><row><entry namest="col2" nameend="col2" align="left">Nonylphenol EO 5</entry><entry namest="col3" nameend="col3" align="right">30</entry></row><row><entry namest="col2" nameend="col2" align="left">Coconut alcohol 7EO</entry><entry namest="col3" nameend="col3" align="right">10</entry></row><row><entry namest="col1" nameend="col1" morerows="2" align="right">. 2</entry><entry namest="col2" nameend="col2" align="left">Nonylphenol-3 EO</entry><entry namest="col3" nameend="col3" align="right">50</entry><entry namest="col4" nameend="col4" morerows="2" align="right">47 ° C</entry><entry namest="col5" nameend="col5" morerows="2" align="left">clear</entry></row><row><entry namest="col2" nameend="col2" align="left">Nonylphenol EO 5</entry><entry namest="col3" nameend="col3" align="right">30</entry></row><row><entry namest="col2" nameend="col2" align="left">Coconut alcohol 5 EO</entry><entry namest="col3" nameend="col3" align="right">20</entry></row><row><entry namest="col1" nameend="col1" morerows="2" align="right">. 3</entry><entry namest="col2" nameend="col2" align="left">Nonylphenol-3 EO</entry><entry namest="col3" nameend="col3" align="right">50</entry><entry namest="col4" nameend="col4" morerows="2" align="right">50 ° C</entry><entry namest="col5" nameend="col5" morerows="2" align="left">clear</entry></row><row><entry namest="col2" nameend="col2" align="left">Nonylphenol EO 5</entry><entry namest="col3" nameend="col3" align="right">30</entry></row><row><entry namest="col2" nameend="col2" align="left">Oleyl-7 EO</entry><entry namest="col3" nameend="col3" align="right">20</entry></row><row><entry namest="col1" nameend="col1" morerows="2" rowsep="1" align="right">. 4</entry><entry namest="col2" nameend="col2" align="left">Nonylphenol-3 EO</entry><entry namest="col3" nameend="col3" align="right">25</entry><entry namest="col4" nameend="col4" morerows="2" rowsep="1" align="right">57 ° C</entry><entry namest="col5" nameend="col5" morerows="2" rowsep="1" align="left">clear</entry></row><row><entry namest="col2" nameend="col2" align="left">Nonylphenol EO 5</entry><entry namest="col3" nameend="col3" align="right">25</entry></row><row><entry namest="col2" nameend="col2" align="left">Oleyl-5 EO</entry><entry namest="col3" nameend="col3" align="right">50</entry></row></tbody></tgroup></table></tables>
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| Document | Relation | Office | Cited during |
|---|---|---|---|
| US7413583B2 | Cited by | United States of America | Search report |
7 members in 4 offices
Priority claims5
| Document | Office | Kind | Date |
|---|---|---|---|
| 3614040 | Germany | A | |
| 3614040 | Germany | A | |
| 3614040 | Germany | – | |
| 3614040 | – | – | – |
| DE19863614040 | – | – | – |
Members7
| Document | Office | Kind | |
|---|---|---|---|
| EP0242832A2 | European Patent Office (EPO) | A2 | |
| DE3614040A1 | Germany | A1 | |
| JPS62260890A | Japan | A | |
| EP0242832A3 | European Patent Office (EPO) | A3 | |
| CA1288412C | Canada | C | |
| EP0242832B1This record | European Patent Office (EPO) | B1 | |
| DE3774613D1 | Germany | D1 |
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Numbers
- Publication
- 0242832
- Publication, DOCDB
- 0242832
- Publication, EPODOC
- EP0242832
- Application
- 87105776
- Application, DOCDB
- 87105776
- Application, EPODOC
- EP19870105776
Titles3
- German
- Trübungsfreie Stabilisierung von Wasser in Kohlenwasserstofffraktionen des Diesel- bzw. Heizölbereichs
- English
- Cloud-free stabilization of dispersions of water in hydrocarbon fractions boiling in the diesel or heating oil range
- French
- Stabilisation de dispersions d'eau en hydrocarbures bouillant dans la gamme d'huile diesel respectivement d'huile de chauffage en obtenant des dispersions claires
Classification
- CPC, 5
- C10L1/328
- C09K23/42
- F02B3/06
- C09K23/00
- C09K23/018
- IPC, 6
- C10L1 183
- C09K23 00
- C10L1 182
- C10L1 185
- C10L1 32
- F02B3 06
Designated states5
- Contracting states, 5
- Belgium
- Germany
- France
- United Kingdom
- Italy