EP0421256B1 - Process for dewaxing waxy mineral-oil products - Google Patents
Process for dewaxing waxy mineral-oil products Download PDFInfo
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- EP0421256B1 EP0421256B1 EP90118450A EP90118450A EP0421256B1 EP 0421256 B1 EP0421256 B1 EP 0421256B1 EP 90118450 A EP90118450 A EP 90118450A EP 90118450 A EP90118450 A EP 90118450A EP 0421256 B1 EP0421256 B1 EP 0421256B1
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- dewaxing
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
- C10G73/04—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils with the use of filter aids
Definitions
- the invention relates to a method for dewaxing, in particular for solvent dewaxing of wax-containing petroleum products using dewaxing aids (dewaxing aids) based on polyacrylate.
- paraffinic waxes in petroleum and petroleum products makes handling very difficult, primarily because of the tendency of the waxes to crystallize below certain temperatures, which vary from case to case. (See Ullmann's Enzyclopadie der techn. Chemie, 4th edition, vol. 20, p. 548 ff, Verlag Chemie 1981). Lighter petroleum fractions can be extracted from the wax simply by cooling to the crystallization temperature of the waxes and pressing through filters.
- the predominantly technically used process for dewaxing wax-containing oils works with solvents, mostly low-boiling aliphatic hydrocarbons such as pentane, hexane, heptane, octane etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and the like, also aromatic hydrocarbons such as benzene, toluene, xylene and the like. and mixtures of solvents.
- solvents mostly low-boiling aliphatic hydrocarbons such as pentane, hexane, heptane, octane etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and the like, also aromatic hydrocarbons such as benzene, toluene, xylene and the like. and mixtures of solvents.
- solvents mostly low-boiling alipha
- Difficulties in practical implementation are caused by the by no means constant throughput capacity in the filtration, which is determined, among other things, by the crystal structure of the wax to be separated. This is influenced by various parameters during the implementation, but most strongly by the type of cooling.
- the nature of the waxes, their crystal size and their appearance give rise to a relatively wide range of variations in the texture and permeability of the filter cake, which of course makes it necessary to adapt the filtration conditions.
- the technique has developed dewaxing aids to improve filtration in general, particularly filtration speed and oil yield, which are added to the oils during the dewaxing process.
- wax-containing distillate oils are particularly suitable, in particular those with a boiling range of approximately 300 to approximately 600 degrees C, a density of approximately 0.08 - 0.09 g / cc at 15 degrees C, a viscosity of approx. 10 - 20 cSt / 100 degrees C, a "pour point" of approx. 30 - 50 degrees C and a wax content (dry) of approx. 10 - approx. 25 wt. -%.
- distillate oils from those fractions that include lubricating oils and special oils in the boiling range 300 - 600 degrees C, especially those with an average boiling point of approx. 400 - 450 degrees C.
- the solvents L used according to the invention for solvent dewaxing also correspond to those which are conventionally used (see prior art).
- aliphatic hydrocarbons with a boiling point ⁇ 150 degrees C including the self-cooling gases such as propane, propylene, butane, pentane, isooctane, etc.
- aromatic hydrocarbons such as Toluene, xylene Ketones such as Acetone, dimethyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, optionally also halogenated hydrocarbons such as methylene chloride, dichloroethane or N-alkylpyrrolidones such as N-methylpyrrolidone, N-ethylpyrrolidone.
- solvents for example ketones and aromatic hydrocarbons such as methyl ethyl ketone / toluene or methyl isobutyl ketone / toluene
- the solvent L in the process according to the invention is added in the customary amounts, for example 0.5-10 parts by volume, preferably 2-7 parts by volume, based on the substrate to be dewaxed.
- the starting monomers for the polymerization P-1 and P-2 (which are already used in the art for the production of polyalkyl (meth) acrylates (PMMA)) are known per se.
- the polymerization of the monomers can also be carried out in a manner known per se.
- the polyalkylacrylates P1 are composed of acrylic esters of C10-C40 alkanols, in particular of acrylic esters of C18-C24 alkanols, for example of the behenyl alcohol type.
- the molecular weight M is advantageously in the range from 10,000 to 1,500,000, preferably from 50,000 to 500,000.
- the determination can be carried out by means of gel permeation chromatography. (See Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol. 18, pg. 209, 749, J. Wiley 1982). It is characteristic of the polyalkyl methacrylates P-2 that they contain more than 10% by weight, preferably more than 15% by weight, of esters of methacrylic acid with branched alkyl radicals.
- the polymers P-2 are esters of C1-C40 alkanols, with preference for the esters of C10-C24, in particular C12-C18 alcohols.
- the polymer P-2 can contain 0.1 to 20% by weight, in particular 1-15% by weight, of C1-C9-alkyl methacrylates.
- Alkanols with C12-C18 hydrocarbon radicals, for example with an average C number 14, for example mixtures of ® DOBANOL 25L (product from Shell AG) and tallow fatty alcohol, and also mixtures of tallow fatty alcohol and other alcohols, for example i-decyl alcohol, are particularly mentioned.
- the molecular weight M (see above) is generally in the range 3,000 to 500,000, preferably 50,000 to 300,000.
- the radical polymerization is advantageously carried out in a solvent which is compatible with the substrate to be dewaxed, such as, for example, in mineral oil.
- a solvent which is compatible with the substrate to be dewaxed
- man uses conventional polymerization initiators such as per compounds, especially peresters such as tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate and the like. in the usual amounts, for example 0.1 to 5, preferably 0.3 to 1% by weight, based on the monomers (cf. Th. Völker, H. Rauch-Puntigam, acrylic and methacrylic compounds, Springer-Verlag 1967).
- Molecular weight regulators in particular sulfur regulators, special mercaptans such as dodecyl mercaptan in the usual amounts, for example 0.01 to 2% by weight, based on the monomers, can also be added to the batches in a manner known per se.
- a protective gas such as CO2.
- the procedure is appropriately such that the monomers are dissolved in a suitable polymerization vessel equipped with a stirrer in the solvent, if appropriate together with the regulator and initiator and first degassed, for example using CO2 snow, and then heated.
- the initiator can also be added to the heated mixture in some cases. If necessary, further monomer and initiator and regulator are metered in.
- the temperature generally rises further, for example to 140 ⁇ 10 degrees C.
- suitable conditions for the postpolymerization can be established by adding heat and / or further addition of initiator.
- the total polymerization time is generally less than 12 hours.
- the polymer components P-1 and P-2 can advantageously be used as separately prepared preparations. They are then mixed in the abovementioned weight ratios and the intended proportions of the substrates to be dewaxed, either in bulk or in a compatible solvent such as wax-free mineral oil or one of the solvents or mixtures L, taking care that the cloud point the oils to be dewaxed are exceeded, for example by heating to 50-120 degrees C.
- the polymers P-1 and P-2 can be added together or separately. The addition can take place before cooling or during cooling, but then in cooled solvents. The cooling can take place, for example, in accordance with US Pat. No. 3,773,650.
- the mixture of the polymers P-1 and P-2 is advantageously added together with the dewaxing solvent L in a cooling zone and at a temperature which is matched to the "pour point" of the dewaxed oil to be obtained.
- the cooling step causes the formation of a fluid liquid slurry, which contains solid wax particles, dewaxed oil and solvent L.
- the wax particles usually contain polymer P-1 and P-2.
- the temperature to which cooling must depend on the type of substrate to be dewaxed and the overall procedure. In general, dewaxing is carried out in the temperature range from 0 degrees C to -50 degrees C, when using a solvent mixture L of a ketone and an aromatic hydrocarbon, the dewaxing temperature is to be set at -10 degrees C to -30 degrees C.
- the filtration apparatus consists of a steel filter with a lid and cooling jacket and is cooled in circulation using a cryostat. Filter cloth from the dewaxing plant of the corresponding refinery is used.
- the filter volume is 100 ml.
- the filter is connected to a measuring cylinder via a glass attachment with a 2-way valve.
- a defined vacuum can be applied to the filtration apparatus using an oil rotary vane pump, a pressure reducing valve and a pressure gauge.
- the mineral oil distillate to be dewaxed is mixed with the dewaxing solvents in the heat (above the cloud point) and stirred until a clear solution results. This is carried out with the help of a cryostat with temperature control cooled down to the desired filtration temperature.
- the filter is pre-cooled to this temperature.
- the mixture is transferred to the precooled filter and a vacuum is applied.
- the filtrate volume is measured as a function of time and the filtration rate F is determined as the slope of the linear plot of V / 2S2 against t / V, where V is the filtrate volume, t is the time in seconds and S is the filter area in cm2.
- the dewaxed oil obtained is dried to constant weight and the oil yield is determined gravimetrically.
- the oil content in the filtered paraffin is determined in accordance with ISO 2908.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Entparaffinierung, insbesondere zur Lösungsmittel-Entparaffinierung von wachshaltigen Erdölprodukten unter Verwendung von Entparaffinierungshilfsmitteln (Dewaxing Aids) auf Polyacrylatbasis.The invention relates to a method for dewaxing, in particular for solvent dewaxing of wax-containing petroleum products using dewaxing aids (dewaxing aids) based on polyacrylate.
Das Vorkommen von paraffinischen Wachsen in Erdöl und in Erdölprodukten erschwert die Handhabung ganz erheblich, vorwiegend wegen der Neigung der Wachse zum Kristallisieren unterhalb bestimmter von Fall zu Fall verschiedener Temperaturen. (Vgl. Ullmanns Enzyclopädie der techn. Chemie, 4. Auflage, Bd. 20, S. 548 ff, Verlag Chemie 1981). Leichteren Erdölfraktionen kann das Wachs durch einfaches Abkühlen auf die Kristallisationstemperatur der Wachse und Abpressen über Filter entzogen werden.
Das technisch vorwiegend angewendete Verfahren zur Entparaffinierung von wachshaltigen Ölen arbeitet mit Lösungsmitteln, meistens niedrigsiedenden aliphatischen Kohlenwasserstoffen wie Pentan, Hexan, Heptan, Octan usw., Ketonen wie Aceton, Methylethylketon, Methylisobutylketon u.ä., ferner aromatischen Kohlenwasserstoffen wie Benzol, Toluol, Xylol u.ä. sowie Gemischen von Lösungsmitteln. Auch hier wird das wachshaltige Öl, das mit dem Lösungsmittel vermischt worden war, abgekühlt, bis sich das Wachs in Form feiner Partikel niederschlägt. Die abgeschiedenen Wachspartikel werden auf einen Wachs-Separator, d.h. auf eine Filtervorrichtung aufgegeben und so vom Öl und dem der Wachsentfernung dienenden Lösungsmittel abgetrennt.The presence of paraffinic waxes in petroleum and petroleum products makes handling very difficult, primarily because of the tendency of the waxes to crystallize below certain temperatures, which vary from case to case. (See Ullmann's Enzyclopadie der techn. Chemie, 4th edition, vol. 20, p. 548 ff, Verlag Chemie 1981). Lighter petroleum fractions can be extracted from the wax simply by cooling to the crystallization temperature of the waxes and pressing through filters.
The predominantly technically used process for dewaxing wax-containing oils works with solvents, mostly low-boiling aliphatic hydrocarbons such as pentane, hexane, heptane, octane etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and the like, also aromatic hydrocarbons such as benzene, toluene, xylene and the like. and mixtures of solvents. Here, too, the wax-containing oil that had been mixed with the solvent is cooled until the wax is deposited in the form of fine particles. The separated wax particles are placed on a wax separator, ie on a filter device, and thus separated from the oil and the solvent used to remove the wax.
Schwierigkeiten bei der praktischen Durchführung bereitet die keineswegs konstante Durchsatzkapazität bei der Filtration, die u.a. von der Kristallstruktur des abzutrennenden Wachses bestimmt wird. Diese wird von verschiedenen Parametern bei der Durchführung, am stärksten aber von der Art und Weise des Kühlens beeinflußt. Die Art der Wachse, deren Kristallgröße und -tracht, geben Anlaß zu einer relativ großen Variationsbreite bezüglich der Textur und Permeabilität des Filterkuchens, die natürlich eine Anpassung der Filtrationsbedingungen erforderlich macht. Gefürchtet ist die Ausbildung sehr feiner Wachs-Kristallite, die sich sehr schwer filtrieren lassen und teilweise durch die Filter wandern, um dann im Öl Trübungen zu verursachen. Die Technik hat zur Verbesserung der Filtration allgemein, insbesondere der Filtrationsgeschwindigkeit und der Ölausbeute Entparaffinierungs-Hilfsmittel (Dewaxing Aids) entwickelt, die den Ölen während des Entparaffinierungsprozesses zugesetzt werden.Difficulties in practical implementation are caused by the by no means constant throughput capacity in the filtration, which is determined, among other things, by the crystal structure of the wax to be separated. This is influenced by various parameters during the implementation, but most strongly by the type of cooling. The nature of the waxes, their crystal size and their appearance, give rise to a relatively wide range of variations in the texture and permeability of the filter cake, which of course makes it necessary to adapt the filtration conditions. There is a fear of the formation of very fine wax crystallites, which are very difficult to filter and sometimes migrate through the filters to cause cloudiness in the oil. The technique has developed dewaxing aids to improve filtration in general, particularly filtration speed and oil yield, which are added to the oils during the dewaxing process.
Derartige Entparaffinierungshilfsmittel sind in der Regel Polymere z.B. vom Typ der α-Olefincopolymere (OCP), der Ethylen-Vinylacetat-Copolymere (EVA) und der Polyalkyl(meth)acrylsäureester von C2-C20-Alkoholen. In der US-A 4 451 353 wird ein Entparaffinierungsverfahren vorgeschlagen, bei dem wachshaltige Öl-Destillate mit einem Lösungsmittel (Dewaxing Solvent) und einem Entparaffinierungshilfsmittel (Dewaxing Aid) auf Polyacrylat-Basis gemischt werden, das Gemisch abgekühlt wird, so daß sich ein dünner Brei aus festen Wachspartikeln bildet und durch Filtration Trennung von Wachs und den flüssigen Anteilen aus entparaffiniertem Öl und Lösungsmittel vorgenommen wird. Das Entparaffinierungs-Hilfsmittel besteht dabei aus:
- A. einem Polyacrylat und
- B. einem n-Alkylmethacrylat-Polymeren,
wobei die Komponenten (A) und (B) in einem Gewichtsverhältnis von 1 : 100 bis 100 : 1 angewendet werden.Such dewaxing aids are usually polymers, for example of the type of the α-olefin copolymers (OCP), the ethylene-vinyl acetate copolymers (EVA) and the polyalkyl (meth) acrylic acid esters of C2-C20 alcohols. In US-A 4 451 353 a dewaxing process is proposed in which wax-containing oil distillates are mixed with a solvent (dewaxing solvent) and a dewaxing aid (dewaxing aid) based on polyacrylate, the mixture is cooled so that a thinner Porridge forms from solid wax particles and is separated by filtration from wax and the liquid parts from dewaxed oil and solvent. The dewaxing aid consists of:
- A. a polyacrylate and
- B. an n-alkyl methacrylate polymer,
wherein components (A) and (B) are used in a weight ratio of 1: 100 to 100: 1.
Ansprüche und Beschreibung der US-A lassen keinen Zweifel daran zu, daß die Methacrylat-Komponente aus Estern von im wesentlichen linearen, also unverzweigten Alkoholen mit 10 bis 20 Kohlenstoffatomen bestehen solle.
Der Fachmann mußte demnach von einer besonderen Eignung dieser Gruppe von Methacrylsäureestern als "Dewaxing Aids" ausgehen. Die bestehenden Modellvorstellungen über die Wirkweise derartiger polymerer "Dewaxing Aids" versuchen zwar plausible Erklärungen für den Einfluß des Polymerzusatzes auf das Kristallisationsverhalten der Wachse zu geben. Sie bieten aber keine Auswahlregeln für bestimmte Polymerisatzusammensetzungen an. (Vgl. etwa Ullmann, loc.cit. Bd. 20, Verlag Chemie 1981).
Es bestand daher nach wie vor die Aufgabe, wirkungsvollere "Dewaxing Aids" möglichst auf der Basis an sich bekannter Ausgangsstoffe zur Verfügung zu stellen, die andererseits keine wesentlichen Änderungen bei der Durchführung der Entparaffinierungstechnologie von Erdölen bzw. Erdölprodukten mit sich bringen sollten. Nach den vorliegenden Ergebnissen kann das erfindungsgemäße Verfahren zur Lösung dieser Aufgabe wesentlich beitragen.
Die Erfindung betrifft somit ein Verfahren zur Lösungsmittel-Entparaffinierung von paraffinhaltigen Erdölprodukten, insbesondere Mineralöldestillaten unter Verwendung mindestens eines zur Entparaffinierung geeigneten Lösungsmittels und eines polymeren Entparaffinierungs-Hilfsmittels (Dewaxing Aid) auf Polyacrylatbasis, wobei man die zu entparaffinierenden Produkte mit dem Lösungsmittel und dem polymeren Entparaffinierungsmittel mischt, die erhaltene Mischung abkühlt und das abgeschiedene Wachs abtrennt,
dadurch gekennzeichnet,
daß man als Entparaffinierungs-Hilfsmittel ein Polymergemisch bestehend aus:
- I) einem Polymerisat P-1 aus Estern der Acrylsäure mit C10 - C40-Alkoholen und
- II) einem Polymerisat P-2 aus Estern der Methacrylsäure mit Alkanolen, die einen Anteil von mehr als 10 Gew.-% an verzweigten Alkanolen aufweisen,
verwendet, mit der Maßgabe, daß das Gewichtsverhältnis der Komponenten I) und II) im Gemisch 1 : 20 bis 20 : 1, vorzugsweise 1 : 10 bis 10 : 1 beträgt.
Im allgemeinen liegt die Zusatzmenge an den Polymerisaten P1 und P2 bei 0,01 bis 1 Gew.-% bezogen auf die wachshaltigen Substrate.
Das vorliegende Verfahren schließt vorteilhaft unmittelbar an dem Stand der Technik, beispielsweise in der US-A 4 451 353 angegebenen an.Claims and description of US-A leave no doubt that the methacrylate component should consist of esters of essentially linear, that is to say unbranched, alcohols having 10 to 20 carbon atoms.
Accordingly, the person skilled in the art had to assume that this group of methacrylic acid esters was particularly suitable as "dewaxing aids". Try the existing model ideas about the mode of action of such polymeric "dewaxing aids" to give plausible explanations for the influence of the polymer additive on the crystallization behavior of the waxes. However, they do not offer any selection rules for certain polymer compositions. (See for example Ullmann, loc.cit. Vol. 20, Verlag Chemie 1981).
It was therefore still the task to provide more effective "dewaxing aids" as far as possible on the basis of known starting materials, which on the other hand should not bring about any significant changes in the implementation of the dewaxing technology of petroleum or petroleum products. According to the present results, the method according to the invention can contribute significantly to solving this problem.
The invention thus relates to a process for solvent dewaxing of petroleum products containing paraffin, in particular mineral oil distillates, using at least one solvent suitable for dewaxing and a polymeric dewaxing aid (dewaxing aid) based on polyacrylate, the products to be dewaxed being treated with the solvent and the polymeric dewaxing agent mixes, the mixture obtained cools and the separated wax separates,
characterized,
that as a dewaxing aid, a polymer mixture consisting of:
- I) a polymer P-1 from esters of acrylic acid with C10 - C40 alcohols and
- II) a polymer P-2 from esters of methacrylic acid with alkanols which have a proportion of more than 10% by weight of branched alkanols,
used, with the proviso that the weight ratio of components I) and II) in the mixture is 1:20 to 20: 1, preferably 1:10 to 10: 1.
In general, the amount of polymer P1 and P2 added is from 0.01 to 1% by weight, based on the wax-containing substrates.
The present method advantageously follows directly from the prior art, for example given in US Pat. No. 4,451,353.
Hinsichtlich der zur Entparaffinierung geeigneten wachshaltigen Substrate auf Erdölbasis ist keine ausgesprochene Limitierung des Verfahrens zu erkennen, jedoch kommen unter praktischen Gesichtspunkten insbesondere wachshaltige Destillatöle infrage, insbesondere solche mit Siedebereich ca. 300 bis ca. 600 Grad C, einer Dichte von ca. 0.08 - 0.09 g/cc bei 15 Grad C, einer Viskosität von ca. 10 - 20 cSt/100 Grad C einem "Pour Point" von ca. 30 - 50 Grad C und einem Wachsgehalt (trocken) von ca. 10 - ca. 25 Gew.-%. Von besonderer Bedeutung sind Destillatöle derjenigen Fraktionen, die Schmieröle und Spezialöle im Siedebereich 300 - 600 Grad C einschließen, insbesondere solche mit einem mittleren Siedepunkt von ca. 400 - 450 Grad C.With regard to the petroleum-based wax-containing substrates suitable for dewaxing, there is no pronounced limitation of the process, but from a practical point of view, wax-containing distillate oils are particularly suitable, in particular those with a boiling range of approximately 300 to approximately 600 degrees C, a density of approximately 0.08 - 0.09 g / cc at 15 degrees C, a viscosity of approx. 10 - 20 cSt / 100 degrees C, a "pour point" of approx. 30 - 50 degrees C and a wax content (dry) of approx. 10 - approx. 25 wt. -%. Of particular importance are distillate oils from those fractions that include lubricating oils and special oils in the boiling range 300 - 600 degrees C, especially those with an average boiling point of approx. 400 - 450 degrees C.
Die erfindungsgemäß zur Lösungsmittel-Entparaffinierung eingesetzten Lösungsmittel L entsprechen ebenfalls den üblicherweise verwendeten (siehe Stand der Technik).The solvents L used according to the invention for solvent dewaxing also correspond to those which are conventionally used (see prior art).
Es handelt sich z.B. um:
aliphatische Kohlenwasserstoffe mit einem Siedepunkt < 150 Grad C, darunter die selbstkühlenden Gase wie Propan, Propylene, Butan, Pentan, ferner Isooctan, u.ä.. aromatische Kohlenwasserstoffe wie z.B.
Toluol, Xylol
Ketone wie z.B.
Aceton, Dimethylketon, Methylethylketon, Methylpropylketon, Methylisobutylketon, gegebenenfalls auch
halogenierte Kohlenwasserstoffe wie Methylenchlorid, Dichlorethan oder N-Alkylpyrrolidone wie N-Methylpyrrolidon, N-Ethylpyrrolidon.For example:
aliphatic hydrocarbons with a boiling point <150 degrees C, including the self-cooling gases such as propane, propylene, butane, pentane, isooctane, etc. aromatic hydrocarbons such as
Toluene, xylene
Ketones such as
Acetone, dimethyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, optionally also
halogenated hydrocarbons such as methylene chloride, dichloroethane or N-alkylpyrrolidones such as N-methylpyrrolidone, N-ethylpyrrolidone.
Vorteilhaft sind auch Gemische von Lösungsmitteln, beispielsweise von Ketonen und aromatischen Kohlenwasserstoffen wie Methylethylketon/Toluol oder Methylisobutylketon/Toluol.
Der Zusatz an Lösungsmitteln L bei dem erfindungsgemäßen Verfahren erfolgt in den üblichen Mengen, beispielsweise 0,5 - 10 Volumteile, vorzugsweise 2 - 7 Volumteile bezogen auf das zu entparaffinierende Substrat.Mixtures of solvents, for example ketones and aromatic hydrocarbons such as methyl ethyl ketone / toluene or methyl isobutyl ketone / toluene, are also advantageous.
The solvent L in the process according to the invention is added in the customary amounts, for example 0.5-10 parts by volume, preferably 2-7 parts by volume, based on the substrate to be dewaxed.
Die Ausgangsmonomeren für die Polymerisation P-1 und P-2 (die in der Technik bereits für die Herstellung von Polyalkyl(meth)acrylaten (PMMA) verwendet werden) sind an sich bekannt. Die Polymerisation der Monomeren kann ebenfalls in an sich bekannter Weise durchgeführt werden.The starting monomers for the polymerization P-1 and P-2 (which are already used in the art for the production of polyalkyl (meth) acrylates (PMMA)) are known per se. The polymerization of the monomers can also be carried out in a manner known per se.
Die Polyalkylacrylate P1 sind aus Acrylestern von C10-C40-Alkanolen aufgebaut, insbesondere aus Acrylestern von C18-C24-Alkanolen, z.B. vom Typ des Behenylalkohols. Das Molekulargewicht M liegt vorteilhaft im Bereich 10 000 bis 1 500 000, vorzugsweise 50 000 bis 500 000. Die Bestimmung kann mittels Gelpermeationschromatographie vorgenommen werden. (Vgl. Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd. Ed., Vol. 18, pg. 209, 749, J. Wiley 1982).
Charakteristisch für die Polyalkylmethacrylate P-2 ist, daß diese zu mehr als 10 Gew.-%, vorzugsweise mehr als 15 Gew.-% Ester der Methacrylsäure mit verzweigten Alkylresten enthalten.
Im allgemeinen handelt es sich bei den Polymerisaten P-2 um Ester von C1-C40-Alkanolen, mit Bevorzugung der Ester von C10-C24, insbesondere C12-C18-Alkoholen. Das Polymerisat P-2 kann dabei 0,1 bis 20 Gew.-%, insbesondere von 1 - 15 Gew.-% C1-C9-Alkylmethacrylate enthalten. Besonders genannt seien Alkanole mit C12-C18-Kohlenwasserstoffresten, z.B. mit mittlerer C-Zahl = 14, beispielsweise Mischungen aus ® DOBANOL 25L (Produkt der Shell AG) und Talgfettalkohol, ferner Mischungen aus Talgfettalkohol und anderen Alkoholen, z.B. i-Decylalkohol.
Das Molekulargewicht M (s. oben) liegt im allgemeinen im Bereich 3 000 bis 500 000, vorzugsweise 50 000 bis 300 000.The polyalkylacrylates P1 are composed of acrylic esters of C10-C40 alkanols, in particular of acrylic esters of C18-C24 alkanols, for example of the behenyl alcohol type. The molecular weight M is advantageously in the range from 10,000 to 1,500,000, preferably from 50,000 to 500,000. The determination can be carried out by means of gel permeation chromatography. (See Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol. 18, pg. 209, 749, J. Wiley 1982).
It is characteristic of the polyalkyl methacrylates P-2 that they contain more than 10% by weight, preferably more than 15% by weight, of esters of methacrylic acid with branched alkyl radicals.
In general, the polymers P-2 are esters of C1-C40 alkanols, with preference for the esters of C10-C24, in particular C12-C18 alcohols. The polymer P-2 can contain 0.1 to 20% by weight, in particular 1-15% by weight, of C1-C9-alkyl methacrylates. Alkanols with C12-C18 hydrocarbon radicals, for example with an average C number = 14, for example mixtures of ® DOBANOL 25L (product from Shell AG) and tallow fatty alcohol, and also mixtures of tallow fatty alcohol and other alcohols, for example i-decyl alcohol, are particularly mentioned.
The molecular weight M (see above) is generally in the range 3,000 to 500,000, preferably 50,000 to 300,000.
Vorteilhafterweise wird die radikalische Polymerisation in einem mit dem zu entparaffinierenden Substrat kompatiblen Lösungsmittel, wie z.B. in Mineralöl vorgenommen. Man verwendet übliche Polymerisationsinitiatoren wie z.B. Perverbindungen, insbesondere Perester wie z.B. tert.Butylperpivalat, tert.Butylperoctoat, tert.Butylperbenzoat u.ä. in den üblichen Mengen, beispielsweise 0,1 bis 5, vorzugsweise 0,3 bis 1 Gew.-% bezogen auf die Monomeren (vgl. Th. Völker, H. Rauch-Puntigam, Acryl- und Methacrylverbindungen, Springer-Verlag 1967).The radical polymerization is advantageously carried out in a solvent which is compatible with the substrate to be dewaxed, such as, for example, in mineral oil. Man uses conventional polymerization initiators such as per compounds, especially peresters such as tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate and the like. in the usual amounts, for example 0.1 to 5, preferably 0.3 to 1% by weight, based on the monomers (cf. Th. Völker, H. Rauch-Puntigam, acrylic and methacrylic compounds, Springer-Verlag 1967).
Ebenfalls in an sich bekannter Weise können den Ansätzen Molekulargewichtsregler, insbesondere Schwefelregler spezielle Mercaptane wie z.B. Dodecylmercaptan in den üblichen Mengen, beispielsweise 0,01 bis 2 Gew.-% bezogen auf die Monomeren, zugesetzt werden.
Zweckmäßigerweise arbeitet man unter einem Schutzgas wie z.B. CO₂.
Man geht zweckmäßig so vor, daß man die Monomeren in einem geeigneten mit Rührer ausgestatteten Polymerisationsgefäß im Lösungsmittel löst, gegebenenfalls zusammen mit Regler und Initiator und zunächst entgast, beispielsweise mittels CO₂-Schnee, und anschließend erwärmt. Als Anhalt können z.B. 80 ± 10 Grad C gelten. Der Initiator kann fallweise auch der erwärmten Mischung zugesetzt werden. Gegebenenfalls wird weiteres Monomeres und Initiator sowie Regler zudosiert. Die Temperatur steigt in der Regel weiter an, beispielsweise auf 140 ± 10 Grad C. Gegebenenfalls können durch Wärmezufuhr und/oder weitere Initiatorzugabe für die Nachpolymerisation geeignete Bedingungen hergestellt werden. Die Gesamtpolymerisationsdauer liegt im allgemeinen unter 12 Stunden.Molecular weight regulators, in particular sulfur regulators, special mercaptans such as dodecyl mercaptan in the usual amounts, for example 0.01 to 2% by weight, based on the monomers, can also be added to the batches in a manner known per se.
Appropriately, you work under a protective gas such as CO₂.
The procedure is appropriately such that the monomers are dissolved in a suitable polymerization vessel equipped with a stirrer in the solvent, if appropriate together with the regulator and initiator and first degassed, for example using CO₂ snow, and then heated. For example, 80 ± 10 degrees C can be used as a guide. The initiator can also be added to the heated mixture in some cases. If necessary, further monomer and initiator and regulator are metered in. The temperature generally rises further, for example to 140 ± 10 degrees C. If necessary, suitable conditions for the postpolymerization can be established by adding heat and / or further addition of initiator. The total polymerization time is generally less than 12 hours.
Die Polymerkomponenten P-1 und P-2 können vorteilhafterweise als separat hergestellte Präparationen zur Anwendung kommen. Man mischt sie dann in den oben genannten Gewichtsverhältnissen und den beabsichtigten Anteilen den zu entparaffinierenden Substraten zu, entweder in Substanz oder in einem kompatiblen Lösungsmittel wie wachsfreiem Mineralöl oder einem der Lösungsmittel bzw. -gemische L, wobei dafür Sorge zu tragen ist, daß der Trübungspunkt der zu entparaffinierenden Öle überschritten wird, beispielsweise durch Erwärmen auf 50 - 120 Grad C. Die Zugabe der Polymerisate P-1 und P-2 kann gemeinsam oder separat vorgenommen werden. Die Zugabe kann vor dem Abkühlen oder während des Abkühlens, dann aber in gekühlten Lösungsmitteln geschehen. Das Abkühlen kann beispielsweise in Anlehnung an US-A 3 773 650 geschehen. Vorteilhaft setzt man das Gemisch der Polymerisate P-1 und P-2 zusammen mit dem Entparaffinierungs-Lösungsmittel L in einer Kühlzone und bei einer Temperatur zu, die auf den "Pour Point" des zu gewinnenden entparaffinierten Öls abgestimmt ist.
Der Kühlungsschritt bewirkt die Bildung eines leichtflüssigen Breis, der neben festen Wachs-Partikeln entparaffiniertes Öl und Lösungsmittel L enthält. Die Wachs-Partikel enthalten in der Regel Polymerisat P-1 und P-2. Die Temperatur, auf die abgekühlt werden muß, hängt von der Art des zu entparaffinierenden Substrats und der gesamten Vorgehensweise ab. Im allgemeinen arbeitet man bei der Entparaffinierung im Temperaturbereich 0 Grad C bis -50 Grad C, im Falle der Anwendung eines Lösungsmittelgemischs L aus einem Keton und einem arom. Kohlenwasserstoff ist die Entparaffinierungstemperatur bei -10 Grad C bis -30 Grad C anzusetzen.The polymer components P-1 and P-2 can advantageously be used as separately prepared preparations. They are then mixed in the abovementioned weight ratios and the intended proportions of the substrates to be dewaxed, either in bulk or in a compatible solvent such as wax-free mineral oil or one of the solvents or mixtures L, taking care that the cloud point the oils to be dewaxed are exceeded, for example by heating to 50-120 degrees C. The polymers P-1 and P-2 can be added together or separately. The addition can take place before cooling or during cooling, but then in cooled solvents. The cooling can take place, for example, in accordance with US Pat. No. 3,773,650. The mixture of the polymers P-1 and P-2 is advantageously added together with the dewaxing solvent L in a cooling zone and at a temperature which is matched to the "pour point" of the dewaxed oil to be obtained.
The cooling step causes the formation of a fluid liquid slurry, which contains solid wax particles, dewaxed oil and solvent L. The wax particles usually contain polymer P-1 and P-2. The temperature to which cooling must depend on the type of substrate to be dewaxed and the overall procedure. In general, dewaxing is carried out in the temperature range from 0 degrees C to -50 degrees C, when using a solvent mixture L of a ketone and an aromatic hydrocarbon, the dewaxing temperature is to be set at -10 degrees C to -30 degrees C.
Ganz unerwarteterweise geht aus den gewonnenen Ergebnissen mit den Mischungen aus den Polymerisaten P-1 und P-2 hervor, daß bei Verwendung von PAMA-Mischkomponenten mit mehr oder weniger hohen Verzweigungsgraden der Alkylreste deutlich bessere Wirksamkeit und ausgeprägtere synergistische Effekte auftreten als mit im wesentlichen linearen Poly-alkyl(meth)acrylaten. Die Befunde wurden an den unterschiedlichsten Entparaffinierungslösungsmitteln und paraffinhaltigen Substraten d.h. "Feedstocks" gewonnen, wie durch die folgenden Beispiele belegt wird, so daß allgemeine Gültigkeit angenommen werden kann.Quite unexpectedly, the results obtained with the mixtures of the polymers P-1 and P-2 show that when using PAMA mixed components with more or less high degrees of branching of the alkyl radicals, significantly better effectiveness and more pronounced synergistic effects occur than with essentially linear ones Poly-alkyl (meth) acrylates. The findings were made on a wide variety of dewaxing solvents and paraffin-containing substrates, i.e. "Feedstocks" obtained, as evidenced by the following examples, so that general validity can be assumed.
Die folgenden Beispiele dienen zur Erläuterung der Erfindung. Die Bestimmung der spezifischen Viskosität ηsp/c geschieht nach DIN 7745 in Chloroform als Lösungsmittel bei 20 Grad C.The following examples serve to illustrate the invention. The specific viscosity η sp / c is determined in accordance with DIN 7745 in chloroform as a solvent at 20 degrees C.
In einem 100 l-Rührkessel werden 51 kg Behenylacrylat (C18-C24-Acrylat), 9 kg 100 N-Öl und 0,051 kg Dodecylmercaptan vorgelegt, mit CO₂-Eis entgast und auf 70 Grad C erwärmt. Anschließend werden 0,191 kg t-Butylperpivalat und 0,115 kg t-Butylperbenzoat zugegeben, um die Polymerisation zu starten. 1 Stunde nach Erreichen der Temperaturspitze von 134 Grad C wird mit 0,077 kg Dodecylmercaptan und 0,051 kg t-Butylperbenzoat versetzt und bei 130 Grad C 3 Stunden lang nachpolymerisiert.
Mw (GPC, PMMA-Eichung) = 560 000 g/mol
ηsp/c (CHCl₃, 20 Grad C) = 48 ml/g51 kg of behenyl acrylate (C18-C24 acrylate), 9 kg of 100N oil and 0.051 kg of dodecyl mercaptan are placed in a 100 l stirred kettle, degassed with CO₂ ice and heated to 70 ° C. Then 0.191 kg of t-butyl perpivalate and 0.115 kg of t-butyl perbenzoate are added to start the polymerization. 1 hour after the temperature peak of 134 degrees C has been reached, 0.077 kg of dodecyl mercaptan and 0.051 kg of t-butyl perbenzoate are added and the polymerization is continued at 130 degrees C for 3 hours.
Mw (GPC, PMMA calibration) = 560,000 g / mol
ηsp / c (CHCl₃, 20 degrees C) = 48 ml / g
In einem 150 l-Rührkessel werden 2,967 kg eines C12-C18-Alkylmethacrylates (mittlere C-Zahl 14, 17,9 % verzweigt, z.B. auf Basis einer Mischung aus Dobanol 25 L ® der Shell und Talgfettalkohol), 26,7 kg 100 N-Öl und 0,083 kg t-Butylperoctoat vorgelegt, mit CO₂-Eis entgast und auf 85 Grad C erwärmt. Innerhalb von 3,5 Stunden werden dann 37,033 kg C12-C18-Alkylmethacrylat und 0,0741 kg t-Butylperoctoat zudosiert. 2 Stunden nach Zulaufende werden erneut 0,08 kg t-Butylperoctoat zugegeben. Nach weiteren 5 Stunden wird mit 33,3 kg 100 N-Öl verdünnt.
Mw (GPC, PMMA-Eichung) = 410 000 g/mol
ηsp/c (CHCl₃, 20 Grad C) = 65 ml/g
Gew.-Anteil verzweigter Ester = 17,9 %In a 150 l stirred kettle, 2.967 kg of a C12-C18 alkyl methacrylate (average C number 14, 17.9% are branched, for example based on a mixture of Dobanol 25 L ® from Shell and tallow fatty alcohol), 26.7 kg 100 N -Oil and 0.083 kg Submitted t-butyl peroctoate, degassed with CO₂ ice and heated to 85 degrees C. 37.033 kg of C12-C18-alkyl methacrylate and 0.0741 kg of t-butyl peroctoate are then metered in within 3.5 hours. 2 hours after the end of the feed, 0.08 kg of t-butyl peroctoate are again added. After a further 5 hours, the mixture is diluted with 33.3 kg of 100 N oil.
Mw (GPC, PMMA calibration) = 410,000 g / mol
ηsp / c (CHCl₃, 20 degrees C) = 65 ml / g
Weight fraction of branched esters = 17.9%
Die Herstellung erfolgt wie in Beispiel 2 beschrieben. Statt Dobanol/Talgfettalkohol werden andere Alkoholgemische eingesetzt. Die folgende Tabelle faßt die Eigenschaften der Polymeren zusammen.
In einem 100 l Rührkessel werden 37 kg 100 N-Öl, 4,111 kg eines Methacrylsäureesters eines Alkoholgemisches aus 57,9 Gew.-% Talgfettalkohol und 42,1 Gew.-% i-Decylalkohol vorgelegt und auf 85 Grad C erwärmt. Anschließend wird durch Zugabe von CO₂-Eis entgast und 0,016 kg Dodecylmercaptan und 0,032 kg t-Butylperoctoat werden zugegeben. Innerhalb von 3,5 Stunden werden dann weitere 58,889 kg des Methacrylsäureesters, 0,236 kg Dodecylmercaptan und 0,177 kg t-Butylperoctoat zudosiert. 2 Stunden nach Zulaufende werden erneut 0,126 kg t-Butylperoctoat zugegeben. Nach weiteren 5 Stunden ist die Polymerisation beendet.
ηsp/c (CHCl₃, 20 Grad C) = 22 ml/g
Gew.-Anteil verzweigter Ester = 45,2 %37 kg of 100 N oil, 4.111 kg of a methacrylic acid ester of an alcohol mixture of 57.9% by weight of tallow fatty alcohol and 42.1% by weight of i-decyl alcohol are placed in a 100 l stirred kettle and heated to 85 ° C. It is then degassed by adding CO₂ ice and 0.016 kg of dodecyl mercaptan and 0.032 kg of t-butyl peroctoate are added. A further 58.889 kg of the methacrylic acid ester, 0.236 kg of dodecyl mercaptan and 0.177 kg of t-butyl peroctoate are then metered in within 3.5 hours. 2 hours after the end of the feed, 0.126 kg of t-butyl peroctoate are again added. The polymerization is complete after a further 5 hours.
ηsp / c (CHCl₃, 20 degrees C) = 22 ml / g
Weight fraction of branched esters = 45.2%
In einem 100 l-Rührkessel werden 1,976 kg C12-C18-Alkylmethacrylat (mittlere C-Zahl 14, 17,9 verzweigt, z.B. auf Basis einer Mischung aus Dobanol 25 L ® der Shell und Talgfettalkohol), 0,0297 kg Methylmethacrylat, 17,8 kg 100 N-Öl und 0,0551 kg t-Butylperoctoat vorgelegt, mit CO₂-Eis entgast und auf 85 Grad C erwärmt. Innerhalb von 3,5 Stunden werden dann 24,664 kg C12-C18-Alkylmethacrylat, 6,223 kg von Methylmethacrylat und 0,0494 kg t-Butylperoctoat zudosiert. 2 Stunden nach Zulaufende werden erneut 0,053 kg t-Butylperoctoat zugegeben. Nach weiteren 5 Stunden wird mit 22,18 kg 100 N-0l verdünnt.
ηsp/c (CHCl₃, 20 Grad C) = 34 ml/g
Gew.-Anteil verzweigter Ester = 14,5 %In a 100 l stirred tank, 1.976 kg of C12-C18 alkyl methacrylate (average C number 14, 17.9 are branched, for example based on a mixture of Dobanol 25 L ® from Shell and tallow fatty alcohol), 0.0297 kg of methyl methacrylate, 17. 8 kg of 100 N oil and 0.0551 kg of t-butyl peroctoate are introduced, Degassed with CO₂ ice and heated to 85 degrees C. 24.664 kg of C12-C18 alkyl methacrylate, 6.223 kg of methyl methacrylate and 0.0494 kg of t-butyl peroctoate are then metered in within 3.5 hours. 2 hours after the end of the feed, 0.053 kg of t-butyl peroctoate are again added. After a further 5 hours, it is diluted with 22.18 kg of 100N-0l.
ηsp / c (CHCl₃, 20 degrees C) = 34 ml / g
Weight fraction of branched esters = 14.5%
In einem 150 l-Rührkessel wurden 4,889 kg C16-C18-Alkylmethacrylat (z.B. auf Basis Alfol 1618 S ®-Alkohol der Condea), 44,0 kg 100 N-Öl und 0,172 kg t-Butylperoctoat vorgelegt. Nach dem Entgasen mit CO₂-Eis wird auf 85 Grad C erwärmt. Anschließend werden innerhalb von 3,5 Stunden 51,111 kg C16-C18-Alkylmethacrylat und 0,153 kg t-Butylperoctoat mittels einer Dosierpumpe zugegeben. 2 Stunden nach Zulaufende werden erneut 0,112 kg t-Butylperoctoat zugegeben. Nach weiteren 5 Stunden ist die Polymerisation abgeschlossen.
Mw (GPC, PMMA-Eichung) = 220 000 g/mol
ηsp/c (CHCl₃, 20 Grad C) = 44 ml/g
Gew.-Anteil verzweigter Ester = 0 %In a 150 l stirred kettle, 4,889 kg of C16-C18 alkyl methacrylate (for example based on Alfol 1618 S ® alcohol from Condea), 44.0 kg of 100 N oil and 0.172 kg of t-butyl peroctoate were placed submitted. After degassing with CO₂ ice, the temperature is raised to 85 degrees C. Then 51.111 kg of C16-C18 alkyl methacrylate and 0.153 kg of t-butyl peroctoate are added by means of a metering pump within 3.5 hours. 2 hours after the end of the feed, 0.112 kg of t-butyl peroctoate are again added. The polymerization is complete after a further 5 hours.
Mw (GPC, PMMA calibration) = 220,000 g / mol
ηsp / c (CHCl₃, 20 degrees C) = 44 ml / g
Weight fraction of branched ester = 0%
Die Filtrationsapparatur besteht aus einem Stahlfilter mit Deckel und Kühlmantel und wird mit Hilfe eines Kryostaten im Umlauf gekühlt. Es wird Filtertuch aus der Entparaffinierungsanlage der entsprechenden Raffinerie verwendet. Das Filtervolumen beträgt 100 ml. Der Filter ist über einen Glasaufsatz mit 2-Wegehahn mit einem Meßzylinder verbunden. Mittels einer Öl-Drehschieberpumpe, einem Druckminderventil und einem Manometer kann ein definiertes Vakuum an die Filtrationsapparatur angelegt werden. Das zu entparaffinierende Mineralöldestillat wird in der Wärme (oberhalb des Cloud Point) mit den Entparaffinierungs-Lösungsmitteln versetzt und gerührt bis eine klare Lösung resultiert. Diese wird unter Zuhilfenahme eines Kryostaten mit Temperatursteuerung mit definierter Geschwindigkeit auf die gewünschte Filtrationstemperatur abgekühlt. Der Filter wird auf diese Temperatur vorgekühlt.The filtration apparatus consists of a steel filter with a lid and cooling jacket and is cooled in circulation using a cryostat. Filter cloth from the dewaxing plant of the corresponding refinery is used. The filter volume is 100 ml. The filter is connected to a measuring cylinder via a glass attachment with a 2-way valve. A defined vacuum can be applied to the filtration apparatus using an oil rotary vane pump, a pressure reducing valve and a pressure gauge. The mineral oil distillate to be dewaxed is mixed with the dewaxing solvents in the heat (above the cloud point) and stirred until a clear solution results. This is carried out with the help of a cryostat with temperature control cooled down to the desired filtration temperature. The filter is pre-cooled to this temperature.
Sämtliche Filtrationsbedingungen wie Lösungsmittel: Feedstock-Verhältnis, Verhältnis der Lösungsmittel bei Gemischen, Abkühlraten und Filtrationstemperatur entsprechen den in der jeweiligen Raffinerie angewandten Bedingungen. Da das Arbeiten mit Propan im Labor problematisch ist, wurde in solchen Fällen Isooctan anstelle von Propan eingesetzt.All filtration conditions such as solvent: feedstock ratio, solvent ratio for mixtures, cooling rates and filtration temperature correspond to the conditions used in the respective refinery. Since working with propane in the laboratory is problematic, isooctane was used instead of propane in such cases.
Nach Erreichen der Filtrationstemperatur wird das Gemisch in den vorgekühlten Filter überführt und Vakuum wird angelegt. Das Filtratvolumen wird in Abhängigkeit von der Zeit gemessen und die Filtrationsrate F wird als Steigung der linearen Auftragung von V/2S² gegen t/V bestimmt, wobei V das Filtratvolumen, t die Zeit in sec. und S die Filterfläche in cm² ist.After the filtration temperature has been reached, the mixture is transferred to the precooled filter and a vacuum is applied. The filtrate volume is measured as a function of time and the filtration rate F is determined as the slope of the linear plot of V / 2S² against t / V, where V is the filtrate volume, t is the time in seconds and S is the filter area in cm².
Nach Abdestillieren der Lösungsmittel mittels eines Rotationsverdampfers, gegebenenfalls azeotrop unter Zuhilfenahme eines weiteren Lösungsmittels wird das erhaltene entparaffinierte Öl zur Gewichtskonstanz getrocknet und gravimetrisch die Ölausbeute bestimmt. Die Bestimmung des Ölgehalts im abfiltrierten Paraffin erfolgt nach ISO 2908.
Claims (6)
- A process for de-waxing paraffin-containing crude oil products, by means of a solvent, using at least one solvent suitable for de-waxing and a polymer de-waxing adjuvant based on polyacrylate, whereby the products to be de-waxed are mixed with the solvent and the polymer de-waxing adjuvant, the resultant mixture is cooled and the separated wax is removed, and whereby a polymer mixture consisting ofI a polymer P-1 of esters of acrylic acid having C₁₀-C₄₀ alkanols andII a polymer P-2 of esters of methacrylic acid having alkanolsis used as de-waxing adjuvant, with the proviso that the weight ratio of the components I) and II) is 1 : 20 to 20 : 1, characterised in that the alkanols of the polymer P-2 contain branched alkanols in an amount of more than 10 wt.%.
- A process according to claim 1, characterised in that the weight ratio of the components I) and II) is 1 : 10 to 10 : 1.
- A process according to claims 1 and 2,
characterised in that the polymers P-1 are composed of acrylic esters having C₁₈-C₂₄ alkanols. - A process according to claims 1 and 2,
characterised in that the polymers P-2 are composed of esters of methacrylic acid having C₁-C₄₀ alkanols. - A process according to claim 4, characterised in that the polymer P-2 is composed of at least 80 wt.% of esters of methacrylic acid having C₁₀-C₂₄ alkanols.
- A process according to claim 5, characterised in that the polymer P-2 is composed of up to 20 wt.% of esters of methacrylic acid having C₁-C₉ alkanols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT90118450T ATE83001T1 (en) | 1989-10-06 | 1990-09-26 | PROCESS FOR DEWARPING OF WAXY PETROL PRODUCTS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3933376A DE3933376A1 (en) | 1989-10-06 | 1989-10-06 | METHOD FOR DEPARPAINING WAXED PETROLEUM PRODUCTS |
| DE3933376 | 1989-10-06 |
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| Publication Number | Publication Date |
|---|---|
| EP0421256A1 EP0421256A1 (en) | 1991-04-10 |
| EP0421256B1 true EP0421256B1 (en) | 1992-12-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP90118450A Expired - Lifetime EP0421256B1 (en) | 1989-10-06 | 1990-09-26 | Process for dewaxing waxy mineral-oil products |
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| Country | Link |
|---|---|
| US (1) | US5098550A (en) |
| EP (1) | EP0421256B1 (en) |
| CN (1) | CN1023128C (en) |
| AT (1) | ATE83001T1 (en) |
| CA (1) | CA2027201C (en) |
| DE (2) | DE3933376A1 (en) |
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| US5547562A (en) * | 1995-05-25 | 1996-08-20 | Nalco/Exxon Energy Chemicals, L.P. | Oil dewaxing method |
| JP3841404B2 (en) * | 2002-02-22 | 2006-11-01 | 東邦化学工業株式会社 | New dewaxing aid |
| HUE030226T2 (en) * | 2002-03-01 | 2017-04-28 | Evonik Oil Additives Gmbh | Copolymers as dewaxing additives |
| CN1312258C (en) * | 2004-01-19 | 2007-04-25 | 中国石油化工股份有限公司 | Solvent dewaxing method |
| CN1296461C (en) * | 2004-01-19 | 2007-01-24 | 中国石油化工股份有限公司 | Method for directly producing paraffin or micro crystal wax |
| US20060021974A1 (en) * | 2004-01-29 | 2006-02-02 | Applied Materials, Inc. | Method and composition for polishing a substrate |
| CN100448958C (en) * | 2005-10-31 | 2009-01-07 | 中国石油化工股份有限公司 | Device and method for adding solvent, dewaxing auxiliary agent |
| DE102011003855A1 (en) | 2011-02-09 | 2012-08-09 | Evonik Rohmax Additives Gmbh | Process for dewaxing mineral oil compositions |
| CN111378466A (en) * | 2020-04-22 | 2020-07-07 | 中化弘润石油化工有限公司 | Method for preparing asphalt slurry from high-softening-point petroleum asphalt particles |
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| US3458430A (en) * | 1967-05-15 | 1969-07-29 | Exxon Research Engineering Co | Separation of hydrocarbon wax from mineral oil using dewaxing aids |
| US3479278A (en) * | 1967-06-07 | 1969-11-18 | Phillips Petroleum Co | Solvent dewaxing with hydrogenated polymeric dewaxing aids |
| US3773650A (en) * | 1971-03-31 | 1973-11-20 | Exxon Co | Dewaxing process |
| US4191631A (en) * | 1978-02-27 | 1980-03-04 | Shell Oil Company | Dewaxing process |
| US4422924A (en) * | 1981-09-28 | 1983-12-27 | Toa Nenryo Kogyo Kabushiki Kaisha | Solvent dewaxing waxy hydrocarbons using an alpha olefin polymer-olefin vinyl acetate copolymer composite dewaxing aid |
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| US4541917A (en) * | 1983-12-19 | 1985-09-17 | Exxon Research And Engineering Co. | Modified deoiling-dewaxing process |
| US4956492A (en) * | 1984-03-14 | 1990-09-11 | Exxon Research And Engineering Co. | Dialkyl fumarate - vinyl acetate copolymers useful as dewaxing aids |
| US4594142A (en) * | 1985-04-25 | 1986-06-10 | Exxon Research And Engineering Co. | Dewaxing waxy hydrocarbon oils using di-alkyl fumarate-vinyl laurate copolymer dewaxing aids |
| US4564438A (en) * | 1985-05-31 | 1986-01-14 | Nalco Chemical Company | Styrene-dialkyl maleate copolymers as dewaxing agents |
| US4608151A (en) * | 1985-12-06 | 1986-08-26 | Chevron Research Company | Process for producing high quality, high molecular weight microcrystalline wax derived from undewaxed bright stock |
| US4695363A (en) * | 1986-05-27 | 1987-09-22 | Exxon Research And Engineering Company | Wax crystal modification using dewaxing aids under agitated conditions |
| US4728414A (en) * | 1986-11-21 | 1988-03-01 | Exxon Research And Engineering Company | Solvent dewaxing using combination poly (n-C24) alkylmethacrylate-poly (C8 -C20 alkyl (meth-) acrylate dewaxing aid |
-
1989
- 1989-10-06 DE DE3933376A patent/DE3933376A1/en not_active Withdrawn
-
1990
- 1990-09-26 ES ES199090118450T patent/ES2036388T3/en not_active Expired - Lifetime
- 1990-09-26 DE DE9090118450T patent/DE59000545D1/en not_active Expired - Lifetime
- 1990-09-26 EP EP90118450A patent/EP0421256B1/en not_active Expired - Lifetime
- 1990-09-26 AT AT90118450T patent/ATE83001T1/en not_active IP Right Cessation
- 1990-10-03 US US07/592,703 patent/US5098550A/en not_active Expired - Lifetime
- 1990-10-06 CN CN90108164A patent/CN1023128C/en not_active Expired - Lifetime
- 1990-10-09 CA CA002027201A patent/CA2027201C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0421256A1 (en) | 1991-04-10 |
| CA2027201C (en) | 1996-12-10 |
| US5098550A (en) | 1992-03-24 |
| DE3933376A1 (en) | 1991-04-18 |
| DE59000545D1 (en) | 1993-01-14 |
| CN1023128C (en) | 1993-12-15 |
| ES2036388T3 (en) | 1993-05-16 |
| CN1050737A (en) | 1991-04-17 |
| CA2027201A1 (en) | 1991-04-07 |
| ATE83001T1 (en) | 1992-12-15 |
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