EP0241636B1 - Process for the separation of phenols and bases from coal tar oils by extraction - Google Patents
Process for the separation of phenols and bases from coal tar oils by extraction Download PDFInfo
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- EP0241636B1 EP0241636B1 EP87100269A EP87100269A EP0241636B1 EP 0241636 B1 EP0241636 B1 EP 0241636B1 EP 87100269 A EP87100269 A EP 87100269A EP 87100269 A EP87100269 A EP 87100269A EP 0241636 B1 EP0241636 B1 EP 0241636B1
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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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/003—Solvent de-asphalting
Definitions
- the carbol oil boiling between 180 and 210 ° C and obtained in an amount of 2 to 3% of the coal tar during the primary distillation contains, apart from benzene homologues, naphthalene and bases, up to 35% phenols, which consist of a mixture of phenol, cresols and xylenols (Franck , Collin: Coal Tar, page 74).
- phenols consist of a mixture of phenol, cresols and xylenols
- the filtered naphthalene oil with a phenol content of up to 25% and the light oil containing up to 10% of phenols are mainly used.
- the most important process for extracting phenol from these coal tar oils is sodium hydroxide extraction (Franck, Collin: Coal tar, pages 75 - 77). The process is based on the fact that phenols are weak acids and consequently form water-soluble salts with bases and that they are formed by stronger acids, e.g. B. the carbon
- the phenol-containing tar oil is freed from the phenols in 2 stages with 8-12% sodium hydroxide solution.
- the phenols pass into the sodium hydroxide solution with the formation of phenolate.
- the process is usually carried out at approx. 50 ° C in order to achieve a faster separation of lye and oil.
- the saturated or almost completely saturated phenolate solution is freed of adhering neutral oils by clear steaming.
- the phenols are then precipitated from the clear vaporized phenolate solution by introducing carbon oxide.
- the carbon dioxide required for this is produced in a lime kiln, which is part of the production unit.
- the crude phenol separates out over the aqueous soda solution and can be separated from it.
- the soda solution is causticized with lime, which is produced when limestone is burned, and the calcium carbonate is filtered off from the recovered sodium hydroxide solution.
- the lye is again set to 8-12% alkali content and returns to the cycle.
- the Metasolvan process worked with aqueous methanol; but it could not prevail.
- the phenoraffin method (Franck, Collin: coal tar, pages 77-79) uses a sodium phenolate solution for extraction.
- the supersaturated phenolate liquor is washed with petrol or toluene to remove bases and neutral oils.
- the crude phenol is obtained from the supersaturated phenolate liquor by extraction with diisopropyl ether. This procedure has also not been able to establish itself in the long run.
- the bases contained in the oils are extracted after extraction with 25 - 35% sulfuric acid obtained. Dissolved neutral oils are removed by solvent washing. The bases are then precipitated by neutralizing the base sulfuric acid. Ammonia is mainly used for this. The bases are drawn off and the aqueous solution is worked up by evaporation on ammonium sulfate (Franck, Collin: coal tar, pages 84-85). This process is also very energy-intensive and has a high chemical requirement.
- this is accomplished in two stages by extraction with the aid of supercritical extractants which consist of a supercritical substance and a subcritical entrainer.
- the neutral oil is separated in the first stage; in the second stage the bases.
- a supercritical extractant C0 2 is mixed with a hydrocarbon with a chain length of 3 to 8 carbon atoms, for example 5-80% by weight, preferably 20-60% by weight, based on C0 2 , propane or butane as entrainer Suitable conditions in which pressure and temperature are chosen so that the binary mixture is supercritical, that is, the state point of the system lies above the critical curve in the single-phase area.
- a base or a base mixture can be added in an amount of 2-25% by weight, preferably 5-15% by weight, based on the tar oil, in order to improve the selectivity in the first extraction stage.
- Suitable bases are collidine, pyridine, alkyl derivatives of pyridine or amines of the general structure wherein R 1, R 2 and R 3 can be a hydrogen atom or an alkyl radical having 1 to 12 carbon atoms.
- loads of the extract phase of the volatile can be up to 30% by weight with separation factors (a) between 1,2 and 2 can be obtained.
- the separation factor (a) is defined as follows: where X 1 is the molar fraction of the substance to be extracted and X 2 is the molar fraction of the substance remaining predominantly in the extraction residue, and the indices "ü” and "f” denote the supercritical phase and the liquid phase, respectively.
- a neutral oil is obtained in the first stage as top product, which contains no phenols and bases.
- the bottom product contains the phenols and bases.
- the neutral oils are separated from the gas stream by relaxing to 30-90 bar, preferably 50-70 bar or / and heating to 60-120 ° C., preferably 80-100 ° C., in the separator.
- the mixture of phenols and bases is broken down into bases and phenols by extraction with a mixture of CO 2 and propane as an entrainer.
- the second extraction stage is expediently carried out at a temperature which is 10-50 K, preferably 20-40 K, higher than the first stage.
- An association between phenols and bases is effective in separating the neutral oil. At higher temperatures, the association becomes weaker and separation of bases and phenols is facilitated.
- separation factors suitable for practical separation can be achieved with pure CO 2 as a supercritical extractant
- relatively high separation factors (a) of 1.2-1.5, depending on the pressure, temperature and phenol content can be obtained by adding the entrainer propane.
- the loading is 5-20% by weight.
- the bases go into the top product of the countercurrent extraction and the phenols into the bottom product.
- the bases are separated from the gas stream in the separator by relaxing to 30-90 bar, preferably 50-70 bar, or / and heating to 60-120 ° C., preferably 80-100 ° C.
- Some of the bases withdrawn as top production from the second extraction stage can be returned to the first extraction stage as entrainer. A further part of the bases is removed as a product in accordance with the base proportion present in the input product. The phenols obtained as residues are free of neutral oil and bases.
- the extractant leaving the column at the top contains neutral oil in which only traces of bases and phenols are present.
- the separator (4) downstream of the column the dissolved neutral oil is practically completely separated by relaxing the extract to 70 bar and heating to 130 ° C. Part of the neutral oil is added to the top of the countercurrent column (3) in order to set a reflux ratio of 3. The rest is stored in the tank (10).
- the gas leaving the separator (4) is cooled in the cooler (5) together with the gas from the separator (6) and returned to the gas circuit with the compressor (7) after passing through a preheater (8,13).
- the bottom product from the column (3) (36.2 parts by weight) containing the phenols and bases is fed into the middle part of the countercurrent column (9) of the second stage.
- a countercurrent extraction with carbon dioxide, which contains 30% by weight propane as entrainer takes place at 110 bar and 60 ° C.
- the extraction agent loading achieved is 7 to 8% by weight.
- With a separation factor (a) of over 1.4, the bases are obtained as the top product.
- the phenols are drawn off and fed to the phenol preparation via the tank (11).
- the extractant containing the bases leaves the countercurrent column (9) at the top and is freed from the dissolved bases in the separator (6) by relaxing to 70 bar and heating to 130 ° C.
- the separated bases contain only traces of neutral oils and. Phenols. Some of the bases are added to the top of column (9) to set a reflux ratio of 4. The rest is temporarily stored in the tank (2) in order to be used for base processing or to serve as an additional entrainer for the first extraction stage.
- Losses of extractants are made up of the mixture of carbon dioxide and propane located in the pressure vessel (12).
- Carbol oil and collidine from tank (1) and tank (2) are fed into the counterflow column (3) approximately in the middle.
- the amount of collidine is measured so that a mixture with a content of about 10% of bases is formed.
- the countercurrent column (3) is flowed through from bottom to top by carbon dioxide which contains 63% by weight of propane.
- the pressure in the column is 110 bar and the temperature is 40 ° C.
- the column contains a wire mesh (Sulzer packing) as packing material.
- the loading of the mixture of CO 2 and propane with low volatile compounds is 20% by weight.
- the extractant leaving the column at the top contains neutral oil, in which only traces of bases and phenols are present.
- the separator (4) downstream of the column the dissolved neutral oil is virtually completely separated by relaxing the extract to 70 bar and heating to 130 ° C. Part of the neutral oil is fed as reflux to the top of the countercurrent column.
- the gas leaving the separator (4) is cooled in the cooler (5) together with the gas from the separator (6) and returned to the gas circuit with the compressor (7) after passing through a preheater (8, 13).
- the bottom product from the column (3) containing the phenols and bases is fed into the middle part of the countercurrent column (9) of the second stage as feed.
- a counter-current extraction with carbon dioxide which contains 63% by weight propane as entrainer, takes place at 110 bar and 40 ° C.
- the extraction agent loading achieved here is about 15% by weight.
- a separation factor a> 1.3 the bases are obtained as the top product.
- the phenols are withdrawn as bottom product.
- the extractant containing the bases leaves the countercurrent column (9) at the top and is freed from the dissolved bases in the separator (6) by relaxing to 70 bar and heating to 130 ° C.
- the separated bases are divided into three sub-streams, the first of which is fed to the carbol oil as entrainer of the first stage and the second as the reflux of the extraction column (9), while the third as product stream removes the bases supplied with the carbol oil.
- Carbol oil and diethylamine are pumped into the middle part of the counterflow column (3) of the first process stage.
- the amount of diethylamine is measured so that a mixture with a diethylamine content of 10% by weight, based on carbolic oil, is formed.
- the countercurrent column (3) was flowed through from bottom to top of carbon dioxide.
- the pressure in the column is 135 bar, the temperature is 40 ° C.
- the column contains a wire mesh (Sulzer packing) as packing material.
- the loading of the C0 2 with low volatile compounds is 20 wt .-%.
- the extracting agent leaving the column (3) at the top contains neutral oil, in which only traces of bases and phenols are present.
- the separator (4) downstream of the column the dissolved neutral oil is virtually completely separated off by expanding to 70 bar and heating to 130 ° C. Part of the neutral oil is fed as reflux to the top of the countercurrent column (3).
- the gas leaving the separator (4) is cooled in the cooler (5) together with the gas from the separator (6) and returned to the gas circuit with the compressor (7) after passing through a preheater (8, 13).
- the bottom product from the column (3) containing the phenols and bases is fed into the middle part of the counterflow column (9) of the second process stage as feed.
- a counter-current extraction with carbon dioxide takes place here at 135 bar and 70 ° C.
- the extraction agent loading achieved is about 3% by weight.
- the bases are obtained as the top product.
- the phenols are withdrawn as bottom product.
- the extractant containing the bases leaves the countercurrent column (9) at the top and is freed from the dissolved bases in the separator (6) by relaxing to 70 bar and heating to 130 ° C.
- the separated bases are divided into three partial streams, the first of which is fed to the carbol oil as entrainer of the first stage, the second as reflux to the extraction column (9) and the third is withdrawn as the product stream.
- the diethylamine can be recovered from the base mixture by distillation.
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Description
Das zwischen 180 und 210 °C siedende, in einer Menge von 2 bis 3 % des Steinkohlenteers bei der Primärdestillation erhaltene Carbolöl enthält außer Benzolhomologen, Naphthalin und Basen bis zu 35 % Phenole, die aus einem Gemisch von Phenol, Kresolen und Xylenolen bestehen (Franck, Collin: Steinkohlenteer, Seite 74). Zur Gewinnung von Phenolen werden außerdem vor allem das bei der Naphthalin-Kristallisation anfallende filtrierte Naphthalinöl mit einem Phenolgehalt bis zu 25 % und das bis zu 10 % Phenole enthaltende Leichtöl herangezogen. Das bedeutendste Verfahren zur Phenolgewinnung aus diesen Steinkohlenteerölen ist die Natronlauge-Extraktion (Franck, Collin: Steinkohlenteer, Seiten 75 - 77). Das Verfahren beruht darauf, daß Phenole schwache Säuren sind und folglich mit Basen wasserlösliche Salze bilden und daß sie durch stärkere Säuren, z. B. der Kohlensäure, wieder ausgefällt werden können.The carbol oil boiling between 180 and 210 ° C and obtained in an amount of 2 to 3% of the coal tar during the primary distillation contains, apart from benzene homologues, naphthalene and bases, up to 35% phenols, which consist of a mixture of phenol, cresols and xylenols (Franck , Collin: Coal Tar, page 74). To obtain phenols, the filtered naphthalene oil with a phenol content of up to 25% and the light oil containing up to 10% of phenols are mainly used. The most important process for extracting phenol from these coal tar oils is sodium hydroxide extraction (Franck, Collin: Coal tar, pages 75 - 77). The process is based on the fact that phenols are weak acids and consequently form water-soluble salts with bases and that they are formed by stronger acids, e.g. B. the carbonic acid can be precipitated again.
Das phenolhaltige Teeröl wird in 2 Stufen mit 8 - 12%iger Natronlauge von den Phenolen befreit. Die Phenole gehen dabei unter Phenolatbildung in die Natronlauge über. Das Verfahren wird meistens bei ca. 50 °C durchgeführt, um eine schnellere Trennung von Lauge und Öl zu erreichen.The phenol-containing tar oil is freed from the phenols in 2 stages with 8-12% sodium hydroxide solution. The phenols pass into the sodium hydroxide solution with the formation of phenolate. The process is usually carried out at approx. 50 ° C in order to achieve a faster separation of lye and oil.
Eine höher konzentrierte Lauge zu verwenden, ist nicht ratsam, weil mit zunehmendem Gehalt an Phenolen in der Phenolatlauge auch Neutralöle durch Lösungsvermittlung in der wäßrigen Phase gelöst werden.It is not advisable to use a more concentrated lye, because with increasing phenol content in the phenolate lye, neutral oils are also dissolved in the aqueous phase by means of a solution.
Die gesättigte bzw. fast vollständig gesättigte Phenolatlauge wird durch Klardampfen von anhaftenden Neutralölen befreit. Anschließend werden die Phenole aus der klargedampften Phenolatlauge durch Einleiten von Kohlenoxid gefällt. Die dazu erforderliche Kohlensäure wird in einem Kalkofen erzeugt, der einen Anlageteil der Produktionseinheit darstellt.The saturated or almost completely saturated phenolate solution is freed of adhering neutral oils by clear steaming. The phenols are then precipitated from the clear vaporized phenolate solution by introducing carbon oxide. The carbon dioxide required for this is produced in a lime kiln, which is part of the production unit.
Nach der Fällung scheidet sich das Rohphenol über der wäßrigen Sodalösung ab und kann von dieser getrennt werden.After the precipitation, the crude phenol separates out over the aqueous soda solution and can be separated from it.
Die Sodalösung wird mit Kalk, der beim Brennen von Kalkstein entsteht, kaustifiziert und das dabei anfallende Calciumcarbonat von der zurückgewonnenen Natronlauge abfiltriert. Die Lauge wird erneut auf 8 - 12 % Alkaligehalt eingestellt und kehrt in den Kreislauf wieder zurück.The soda solution is causticized with lime, which is produced when limestone is burned, and the calcium carbonate is filtered off from the recovered sodium hydroxide solution. The lye is again set to 8-12% alkali content and returns to the cycle.
Dieser Prozeß ist durch den Vorgang des Klardampfens sowie durch das Betreiben eines Kalkofens sehr energieaufwendig und enthält eine Reihe von Nachteilen:
- 1.) Nach der Extraktion des Carbolöls mit NaOH verbleibt ein wirtschaftlich nicht gewinnbarer Restphenolgehalt von 0,5 % im Öl.
- 2.) Durch den nachfolgenden Klardampfprozeß werden die ca. 0,5 % organischen, nicht phenolischen Bestandteile aus der Phenolatlauge entfernt. Dieses ist notwendig, um reine Phenolprodukte zu erhalten, die auch den strengen Lieferspezifikationen entsprechen. Der Wärmebedarf wird zwar durch Verwendung von mit Füllkörpern versehenen Austauschkolonnen und mehrstufige Verdampfungssysteme vermindert, doch entstehen durch diesen Prozeß trotzdem noch erhebliche Kosten.
- 3.) Außerdem fällt als Destillat ein Gemisch aus Neutralöl, Teerbasen und Wasser an. Durch die Wasserdampfdestillation wird auch ein geringer Teil des in der Lauge gelösten Phenols mit abgetrieben, geht einerseits der Produktion verloren und verunreinigt zudem das Abwasser erheblich. Ein Teil der Basen geht ebenfalls verloren, obwohl das Destillatwasser mit Benzol oder einem ähnlichen Lösungsmittel extrahiert wird.
- 4.) Das Rohphenol enthält nach der Trennung von der Sodalauge noch Sodalösung, die durch nochmaliges Waschen mit Wasser weitgehend entfernt wird. Zum Schluß enthält das Rohphenol noch ca. 2 % Alkali bei 10 - 20 % Wasser.
Vor der Fraktionierung des Rohphenols muß dieses entwässert werden. Das dabei anfallende Destillatwasser wird aber wegen seines sehr hohen Phenolgehaltes nicht in das Abwasser gegeben, sondern kehrt in den Kreislauf zurück. - 5.) Der beim Kaustifizieren der Sodalauge anfallende Kalkschlamm ist sehr feinkörnig und enthält auch noch in stichfester Form ca. 50 % Wasser. Trotz mehrfachen Waschens mit Wasser auf dem Vakuumfilter verbleibt ein restlicher Alkaligehalt von 0,5 %.
- 6.) Die Rückgewinnung des Alkali beträgt maximal nur 95 %.
- 1.) After extraction of the carbolic oil with NaOH, an economically unrecoverable residual phenol content of 0.5% remains in the oil.
- 2.) The approx. 0.5% organic, non-phenolic constituents are removed from the phenolate liquor by the subsequent clear steam process. This is necessary to obtain pure phenol products that also meet the strict delivery specifications. The heat requirement is reduced by the use of packed columns and multi-stage evaporation systems, but this process still incurs considerable costs.
- 3.) In addition, a mixture of neutral oil, tar bases and water is obtained as the distillate. The steam distillation also removes a small part of the phenol dissolved in the lye, on the one hand it is lost in production and it also contaminates the wastewater considerably. Some of the bases are also lost, although the distillate water is extracted with benzene or a similar solvent.
- 4.) After separation from the soda lye, the raw phenol still contains soda solution, which is largely removed by washing again with water. Finally, the raw phenol contains about 2% alkali with 10-20% water.
The raw phenol must be dewatered before it is fractionated. The resulting distillate water is not released into the wastewater due to its very high phenol content, but rather returns to the cycle. - 5.) The lime sludge obtained when causticizing the soda lye is very fine-grained and also contains approx. 50% water in a puncture-proof form. Despite repeated washing with water on the vacuum filter, a residual alkali content of 0.5% remains.
- 6.) The recovery of the alkali is a maximum of only 95%.
Der Gesamtchemikalienbedarf pro 1 t Rohphenol beträgt durchschnittlich
- 625 kg Kalkstein
- 68 kg Koks
- 65 kg Natriumhydroxid
- 625 kg limestone
- 68 kg of coke
- 65 kg sodium hydroxide
Man hat versucht, den Verlust an Chemikalien oder die Phenolverluste durch den Fällkalk abzusenken bzw. den Fällkalk in Zementwerken o. ä. wieder zu verwenden, um die bei der Aufhaldung des Fällkalkes durch Regenauswaschung entstehende Umweltverunreinigung zu vermeiden.Attempts have been made to reduce the loss of chemicals or the loss of phenol due to the lime lime or to reuse the lime lime in cement works or the like in order to avoid environmental pollution caused by washing out the lime lime by washing out rain.
Es hat auch nicht an Versuchen gefehlt, das Verfahren zu ändern und wenigstens den Betrieb des Kalkofens überflüssig zu machen.There has been no lack of attempts to change the process and at least to make the lime kiln superfluous.
So arbeitete das Metasolvan-Verfahren mit wäßrigem Methanol; es hat sich aber nicht durchsetzten können. Das Phenoraffin-Verfahren (Franck, Collin: Steinkohlenteer, Seiten 77 - 79) benutzt eine Natriumphenolatlösung zur Extraktion. Die übersättigte Phenolatlauge wird zur Entfernung von Basen und Neutralölen mit Benzin oder Toluol gewaschen. Die Gewinnung des Rohphenols aus der übersättigten Phenolatlauge erfolgt durch Extraktion mit Diisopropyläther. Auch dieses Verfahren hat sich nicht auf Dauer durchsetzen können.So the Metasolvan process worked with aqueous methanol; but it could not prevail. The phenoraffin method (Franck, Collin: coal tar, pages 77-79) uses a sodium phenolate solution for extraction. The supersaturated phenolate liquor is washed with petrol or toluene to remove bases and neutral oils. The crude phenol is obtained from the supersaturated phenolate liquor by extraction with diisopropyl ether. This procedure has also not been able to establish itself in the long run.
Das zwischen 70 und 200 °C siedende, in einer Menge von 0,5 - 3 % des Rohteers bei der Primärdestillation anfallende Leichtöl enthält 2 - 7 % Basen (Franck, Collin: Steinkohlenteer, Seite 84). Zur Gewinnung von Basen wird außerdem Carbolöl eingesetzt.The light oil boiling between 70 and 200 ° C, in an amount of 0.5 - 3% of the raw tar during primary distillation, contains 2 - 7% bases (Franck, Collin: Coal tar, page 84). Carbolic oil is also used to obtain bases.
Die in den Ölen enthaltenen Basen werden nach der Entphenolung durch Extrahieren mit 25 - 35%iger Schwefelsäure gewonnen. Mitgelöste Neutralöle werden durch Lösungsmittelwäsche entfernt. Danach werden die Basen durch Neutralisation der Basen-Schwefelsäure gefällt. Hierzu wird hauptsächlich Ammoniak verwendet. Die Basen werden abgezogen und die wäßrige Lösung durch Eindampfen auf Ammonsulfat aufgearbeitet (Franck, Collin: Steinkohlenteer, Seiten 84 - 85). Auch dieser Verfahrensgang ist sehr energieaufwendig und hat einen hohen Chemikalienbedarf.The bases contained in the oils are extracted after extraction with 25 - 35% sulfuric acid obtained. Dissolved neutral oils are removed by solvent washing. The bases are then precipitated by neutralizing the base sulfuric acid. Ammonia is mainly used for this. The bases are drawn off and the aqueous solution is worked up by evaporation on ammonium sulfate (Franck, Collin: coal tar, pages 84-85). This process is also very energy-intensive and has a high chemical requirement.
Zusammenfassend kann festgestellt werden, daß die Gewinnung von Phenolen und Basen aus Teerölen einen hohen Wärmeenergiebedarf und einen starken Chemikalienverbrauch hat.In summary, it can be stated that the extraction of phenols and bases from tar oils has a high thermal energy requirement and a high consumption of chemicals.
Es besteht daher die Aufgabe, ein Extraktionsverfahren zur Abtrennung von Phenolen und Basen aus Steinkohlenteerölen zu entwickeln, das die geschilderten Nachteile vermeidet und besonders energiesparend und umweltfreundlich ist.It is therefore the task of developing an extraction process for the separation of phenols and bases from coal tar oils which avoids the disadvantages described and is particularly energy-saving and environmentally friendly.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß die Teeröle mit einem überkritischen Extraktionsmittel unter Zusatz eines Schleppmittels in zwei Stufen extrahiert werden, wobei in der ersten Stufe die Neutralöle und in der zweiten Stufe die Basen von den Phenolen abgetrennt werden.This object is achieved in that the tar oils are extracted with a supercritical extractant with the addition of an entrainer in two stages, the neutral oils being separated from the phenols in the first stage and the bases in the second stage.
Nach dem Verfahren dieser Erfindung gelingt das durch Extraktion mit Hilfe überkritischer Extraktionsmittel, die aus einem überkritischen Stoff und einem unterkritischen Schleppmittel bestehen, in zwei Stufen. In der ersten Stufe wird das Neutralöl abgetrennt; in der zweiten Stufe die Basen. Als überkritisches Extraktionsmittel ist C02 im Gemisch mit einem Kohlenwasserstoff mit einer Kettenlänge von 3 bis 8 Kohlenstoffatomen, beispielsweise mit 5 - 80 Gew.-%, vorzugsweise 20 - 60 Gew.-%, bezogen auf C02, Propan oder Butan als Schleppmittel unter Bedingungen geeignet, bei denen Druck und Temperatur so gewählt werden, daß das binäre Gemisch überkritisch ist, das heißt, der Zustandspunkt des Systems liegt oberhalb der kritischen Kurve im Einphasengebiet. Als weiteres Schleppmittel kann zur Verbesserung der Selektivität in der ersten Extraktionsstufe eine Base oder ein Basengemisch in einer Menge von 2 - 25 Gew.-%, vorzugsweise von 5 - 15 Gew.-%, bezogen auf das Teeröl, zugesetzt werden. Geeignete Basen sind Collidin, Pyridin, Alkylderivate des Pyridins oder Amine der allgemeinen Struktur
Bei Drücken von 80 - 200 bar, vorzugsweise 100 - 120 bar, können im Temperaturbereich von 30 bis 100 °C, vorzugsweise von 40 - 60 °C, Beladungen der Extraktphase an Schwerflüchtigem bis zu 30 Gew.-% bei Trennfaktoren (a) zwischen 1,2 und 2 erhalten werden.At pressures of 80-200 bar, preferably 100-120 bar, in the temperature range from 30 to 100 ° C, preferably 40-60 ° C, loads of the extract phase of the volatile can be up to 30% by weight with separation factors (a) between 1,2 and 2 can be obtained.
Der Trennfaktor (a) ist, wie folgt, definiert:
In einer Gegenstromkolonne mit teilweiser Produktrückführung wird in der ersten Stufe als Kopfprodukt ein Neutralöl erhalten, das keine Phenole und Basen enthält. Das Sumpfprodukt enthält die Phenole und Basen. Die Abtrennung der Neutralöle aus dem Gasstrom erfolgt durch Entspannen auf 30 - 90 bar, vorzugsweise 50 - 70 bar oder/und Erhitzen auf 60 - 120 °C, vorzugsweise 80 - 100 °C, im Abscheider.In a countercurrent column with partial product recirculation, a neutral oil is obtained in the first stage as top product, which contains no phenols and bases. The bottom product contains the phenols and bases. The neutral oils are separated from the gas stream by relaxing to 30-90 bar, preferably 50-70 bar or / and heating to 60-120 ° C., preferably 80-100 ° C., in the separator.
In der zweiten Stufe wird das Gemisch aus Phenolen und Basen durch Extraktion mit einem Gemisch aus C02 und Propan als Schleppmittel in Basen und Phenolen zerlegt. Die zweite Extraktionsstufe wird zweckmäßigerweise bei einer um 10 - 50 K, vorzugsweise 20 - 40 K, höheren Temperatur als die erste Stufe durchgeführt. Bei der Abtrennung des Neutralöls ist eine Assoziation zwischen Phenolen und Basen wirksam. Bei höherer Temperatur wird die Assoziation schwächer und eine Trennung von Basen und Phenolen erleichtert. Während mit reinem C02 als überkritisches Extraktionsmittel keine für eine praktische Trennung geeignete Trennfaktoren erreichbar sind, können überraschenderweise durch die Zugabe des Schleppmittels Propan relativ hohe Trennfaktoren (a) von 1,2 - 1,5 je nach Druck, Temperatur und Phenolgehalt erhalten werden. Die Beladung beträgt 5 - 20 Gew.-%. Dabei gehen die Basen in das Kopfprodukt der Gegenstromextraktion und die Phenole in das Sumpfprodukt. Die Basen werden aus dem Gasstrom durch Entspannen auf 30 - 90 bar, vorzugsweise 50 - 70 bar, oder/und Erwärmen auf 60 - 120 °C, vorzugsweise 80 - 100 °C, im Abscheider abgetrennt.In the second stage, the mixture of phenols and bases is broken down into bases and phenols by extraction with a mixture of CO 2 and propane as an entrainer. The second extraction stage is expediently carried out at a temperature which is 10-50 K, preferably 20-40 K, higher than the first stage. An association between phenols and bases is effective in separating the neutral oil. At higher temperatures, the association becomes weaker and separation of bases and phenols is facilitated. While no separation factors suitable for practical separation can be achieved with pure CO 2 as a supercritical extractant, surprisingly, relatively high separation factors (a) of 1.2-1.5, depending on the pressure, temperature and phenol content, can be obtained by adding the entrainer propane. The loading is 5-20% by weight. The bases go into the top product of the countercurrent extraction and the phenols into the bottom product. The bases are separated from the gas stream in the separator by relaxing to 30-90 bar, preferably 50-70 bar, or / and heating to 60-120 ° C., preferably 80-100 ° C.
Die als Kopfproduktion der zweiten Extraktionsstufe abgezogenen Basen können teilweise als Schleppmittel in die erste Extraktionsstufe zurückgeführt werden. Den im Eingangsprodukt vorhandenen Basenanteil entsprechend, wird ein weiterer Teil der Basen als Produkt entnommen. Die als Rückstand anfallenden Phenole sind frei von Neutralöl und Basen.Some of the bases withdrawn as top production from the second extraction stage can be returned to the first extraction stage as entrainer. A further part of the bases is removed as a product in accordance with the base proportion present in the input product. The phenols obtained as residues are free of neutral oil and bases.
Eisenbach und Niemann (Erdöl und Kohle-Erdgas, Petrochemie, Bd. 34, (1981), 296 - 300) berichten über Versuche zur Aufbereitung von Braunkohlenteeren mit Hilfe von überkritischem Kohlendioxid, überkritischem Ethan und Propan. Danach , werden bei 55 °C und 200 bar die Kreosote selektiv mit C02 und die Paraffine selektiv mit Ethan extrahiert.Eisenbach and Niemann (Petroleum and Coal-Natural Gas, Petrochemicals, Vol. 34, (1981), 296-300) report on attempts to process lignite tars with the help of supercritical carbon dioxide, supercritical ethane and propane. Then, at 55 ° C and 200 bar, the creosote is selectively extracted with CO 2 and the paraffins are selectively extracted with ethane.
Im Steinkohlenteeröl sind die Begleitstoffe der Phenole aber keine Aliphaten, sondern Benzol-Homologe, Naphthalin und Teerbasen. Die Benzol-Homologen mit Naphthalin ergeben das sogenannte Neutralöl. Wird z. B. Carbolöl mit überkritischem C02 oder Ethan extrahiert, so ist innerhalb der analytischen Fehlergrenze keine selektive Trennung von Neutralöl und Phenolen zu beobachten. Auch die Extraktion von entbastem Carbolöl mit Gemischen aus C02 und Propan läßt keine selektive Löslichkeit in Hinsicht auf eine Trennung der Neutralöle von den Phenolen erkennen. Erst die Zugabe eines Basengemisches als weiterem Schleppmittel führt zu einer merklichen Selektivität. Das Neutralöl wird dann bevorzugt gelöst. Die Menge an Basen sollte aber die zur Neutralisation notwendige stöchiometrische Menge nicht überschreiten. Gute Ergebnisse werden erzielt, wenn gerade soviel Basen zugesetzt werden, daß ihr Gehalt etwa dem halben Gehalt an Phenolen in dem jeweiligen Teeröl entspricht.In coal tar oil, however, the accompanying substances of the phenols are not aliphatics, but benzene homolo ge, naphthalene and tar bases. The benzene homologues with naphthalene give the so-called neutral oil. Is z. B. Carbol oil extracted with supercritical C0 2 or ethane, no selective separation of neutral oil and phenols can be observed within the analytical error limit. The extraction of degassed carbolic oil with mixtures of C0 2 and propane shows no selective solubility with regard to the separation of the neutral oils from the phenols. Only the addition of a base mixture as an additional entrainer leads to a noticeable selectivity. The neutral oil is then preferably dissolved. However, the amount of bases should not exceed the stoichiometric amount necessary for neutralization. Good results are achieved if just enough bases are added that their content corresponds to approximately half the phenol content in the respective tar oil.
Die nachstehenden Beispiele sollen den Prozeß anhand der Fig. 1 näher erläutern, ohne die Erfindung darauf zu beschränken.The examples below are intended to explain the process in more detail with reference to FIG. 1, without restricting the invention thereto.
100 Gew.-Teile Carbolöl mit 24,0 Gew.-% Phenolen, 3,2 Gew.-% Teerbasen und 72,8 Gew.-% Neutralölen aus Tank (1) werden mit 9,0 Gew.-Teilen Teerbasen aus Tank (2) in die Mitte der Gegenstromkolonne (3) eingespeist. Die Gegenstromkolonne (3) wird von unten nach oben von Kohlendioxid, das 30 Gew.-%, bezogen auf C02, Propan enthält, unter einem Druck von 110 bar bei einer Temperatur von 40 °C durchströmt. Als Packungsmaterial enthält die Kolonne eine Drahtgewebepackung (Sulzer). Die Beladung des Gemisches aus C02 und Propan mit schwerflüchtigen Verbindungen beträgt 20 Gew.-%.100 parts by weight of carbolic oil with 24.0% by weight of phenols, 3.2% by weight of tar bases and 72.8% by weight of neutral oils from tank (1) are mixed with 9.0 parts by weight of tar bases from tank (2) fed into the center of the counterflow column (3). The counter-current column (3) is flowed through from bottom to top of carbon dioxide containing 30 wt .-%, based on C0 2, propane under a pressure of 110 bar at a temperature of 40 ° C. The column contains a wire mesh packing (Sulzer) as packing material. The loading of the mixture of CO 2 and propane with low volatile compounds is 20% by weight.
Das die Kolonne am Kopf verlassende Extraktionsmittel enthält Neutralöl, in welchem nur noch Spuren von Basen und Phenolen vorhanden sind. In dem der Kolonne nachgeschalteten Abscheider (4) wird durch Entspannung des Extraktes auf 70 bar und Erwärmung auf 130 °C das gelöste Neutralöl praktisch vollständig abgetrennt. Ein Teil des Neutralöls wird auf den Kopf der Gegenstromkolonne (3) aufgegeben, um ein Rücklaufverhältnis von 3 einzustellen. Der Rest wird im Tank (10) zwischengelagert. Das den Abscheider (4) verlassende Gas wird im Kühler (5) gemeinsam mit dem Gas aus dem Abscheider (6) abgekühlt und mit dem Kompressor (7) in den Gaskreislauf nach Passieren eines Vorwärmers (8,13) zurückgegeben.The extractant leaving the column at the top contains neutral oil in which only traces of bases and phenols are present. In the separator (4) downstream of the column, the dissolved neutral oil is practically completely separated by relaxing the extract to 70 bar and heating to 130 ° C. Part of the neutral oil is added to the top of the countercurrent column (3) in order to set a reflux ratio of 3. The rest is stored in the tank (10). The gas leaving the separator (4) is cooled in the cooler (5) together with the gas from the separator (6) and returned to the gas circuit with the compressor (7) after passing through a preheater (8,13).
Das die Phenole und Basen enthaltende Sumpfprodukt aus Kolonne (3) (36,2 Gew.-Teile) wird in den mittleren Teil der Gegenstromkolonne (9) der zweiten Stufe eingespeist. Hier findet bei 110 bar und 60 °C eine Gegenstromextraktion mit Kohlendioxid, das 30 Gew.-% Propan als Schleppmittel enthält, statt. Die erzielte Beladung des Extraktionsmittels beträgt 7 bis 8 Gew.-%. Bei einem Trennfaktor (a) von über 1,4 fallen als Kopfprodukt die Basen an. Als Sumpfprodukt werden die Phenole abgezogen und über den Tank (11) der Phenolaufbereitung zugeführt. Das die Basen enthaltende Extraktionsmittel verläßt die Gegenstromkolonne (9) am Kopf und wird im Abscheider (6) von den gelösten Basen durch Entspannung auf 70 bar und Erwärmung auf 130 °C befreit.The bottom product from the column (3) (36.2 parts by weight) containing the phenols and bases is fed into the middle part of the countercurrent column (9) of the second stage. Here a countercurrent extraction with carbon dioxide, which contains 30% by weight propane as entrainer, takes place at 110 bar and 60 ° C. The extraction agent loading achieved is 7 to 8% by weight. With a separation factor (a) of over 1.4, the bases are obtained as the top product. As the bottom product, the phenols are drawn off and fed to the phenol preparation via the tank (11). The extractant containing the bases leaves the countercurrent column (9) at the top and is freed from the dissolved bases in the separator (6) by relaxing to 70 bar and heating to 130 ° C.
Die abgetrennten Basen enthalten nur Spuren von Neutralölen und. Phenolen. Ein Teil der Basen wird am Kopf der Kolonne (9) zur Einstellung eines Rücklaufverhältnisses von 4 aufgegeben. Der Rest wird im Tank (2) zwischengelagert, um der Basenaufarbeitung zugeführt zu werden oder als zusätzliches Schleppmittel für die erste Extraktionsstufe zu dienen.The separated bases contain only traces of neutral oils and. Phenols. Some of the bases are added to the top of column (9) to set a reflux ratio of 4. The rest is temporarily stored in the tank (2) in order to be used for base processing or to serve as an additional entrainer for the first extraction stage.
Verluste an Extraktionsmitteln werden aus dem im Druckbehälter (12) befindlichen Gemische aus Kohlendioxid und Propan ergänzt.Losses of extractants are made up of the mixture of carbon dioxide and propane located in the pressure vessel (12).
In die Gegenstromkolonne (3) werden Carbolöl und Collidin aus Tank (1) und Tank (2) etwa in der Mitte eingespeist. Dabei wird die Collidinmenge so bemessen, daß ein Gemisch mit einem Gehalt von etwa 10 % an Basen entsteht. Die Gegenstromkolonne (3) wird von unten nach oben von Kohlendioxid, das 63 Gew.-% Propan enthält, durchströmt. Der Druck in der Kolonne beträgt 110 bar, die Temperatur 40 °C. Als Packungsmaterial enthält die Kolonne ein Drahtgewebe (Sulzerpackung). Die Beladung des Gemisches aus C02 und Propan mit schwerflüchtigen Verbindungen beträgt 20 Gew.-%.Carbol oil and collidine from tank (1) and tank (2) are fed into the counterflow column (3) approximately in the middle. The amount of collidine is measured so that a mixture with a content of about 10% of bases is formed. The countercurrent column (3) is flowed through from bottom to top by carbon dioxide which contains 63% by weight of propane. The pressure in the column is 110 bar and the temperature is 40 ° C. The column contains a wire mesh (Sulzer packing) as packing material. The loading of the mixture of CO 2 and propane with low volatile compounds is 20% by weight.
Das die Kolonne am Kopf verlassende Extraktionsmittel enthält Neutralöl, in welchem nur noch Spuren von Basen und Phenolen vorhanden sind. In dem der Kolonne nachgeschalteten Abscheider (4) wird durch Entspannung des Extraktes auf 70 bar und Erwärmung auf 130 °C das gelöste Neutralöl praktisch vollständig abgetrennt. Ein Teil des Neutralöls wird als Rücklauf auf den Kopf der Gegenstromkolonne aufgegeben. Das den Abscheider (4) verlassende Gas wird im Kühler (5) gemeinsam mit dem Gas aus dem Abscheider (6) abgekühlt und mit dem Kompressor (7) in den Gaskreislauf nach Passieren eines Vorwärmers (8, 13) zurückgegeben.The extractant leaving the column at the top contains neutral oil, in which only traces of bases and phenols are present. In the separator (4) downstream of the column, the dissolved neutral oil is virtually completely separated by relaxing the extract to 70 bar and heating to 130 ° C. Part of the neutral oil is fed as reflux to the top of the countercurrent column. The gas leaving the separator (4) is cooled in the cooler (5) together with the gas from the separator (6) and returned to the gas circuit with the compressor (7) after passing through a preheater (8, 13).
Das die Phenole und Basen enthaltende Sumpfprodukt aus Kolonne (3) wird in den mittleren Teil der Gegenstromkolonne (9) der zweiten Stufe als Zulauf eingespeist. Hier findet bei 110 bar und 40 °C eine Gegenstromextraktion mit Kohlendioxid, das 63 Gew.-% Propan als Schleppmittel enthält, statt. Die hier erzielte Beladung des Extraktionsmittels beträgt etwa 15 Gew.-%. Bei einem Trennfaktor a > 1,3 fallen als Kopfprodukt die Basen an. Als Sumpfprodukt werden die Phenole abgezogen. Das die Basen enthaltende Extraktionsmittel verläßt die Gegenstromkolonne (9) am Kopf und wird im Abscheider (6) von den gelösten Basen durch Entspannung auf 70 bar und Erwärmung auf 130 °C befreit. Die abgetrennten Basen werden in drei Teilströme aufgeteilt, von denen der erste dem Carbolöl als Schleppmittel der ersten Stufe und der zweiten als Rücklauf der Extraktionskolonne (9) zugeführt werden, während der dritte als Produktstrom die mit dem Carbolöl zugeführten Basen abführt.The bottom product from the column (3) containing the phenols and bases is fed into the middle part of the countercurrent column (9) of the second stage as feed. Here a counter-current extraction with carbon dioxide, which contains 63% by weight propane as entrainer, takes place at 110 bar and 40 ° C. The extraction agent loading achieved here is about 15% by weight. With a separation factor a> 1.3, the bases are obtained as the top product. The phenols are withdrawn as bottom product. The extractant containing the bases leaves the countercurrent column (9) at the top and is freed from the dissolved bases in the separator (6) by relaxing to 70 bar and heating to 130 ° C. The separated bases are divided into three sub-streams, the first of which is fed to the carbol oil as entrainer of the first stage and the second as the reflux of the extraction column (9), while the third as product stream removes the bases supplied with the carbol oil.
In den mittleren Teil der Gegenstromkolonne (3) der ersten Verfahrensstufe werden Carbolöl und Diethylamin zugepumpt. Dabei wird die Menge an Diethylamin so bemessen, daß ein Gemisch mit einem Gehalt an Diethylamin von 10 Gew.-%, bezogen auf Carbolöl, entsteht. Die Gegenstromkolonne (3) wurde von unten nach oben von Kohlendioxid durchströmt. Der Druck in der Kolonne beträgt 135 bar, die Temperatur 40 °C. Als Packungsmaterial enthält die Kolonne ein Drahtgewebe (Sulzerpackung). Die Beladung des C02 mit schwerflüchtigen Verbindungen beträgt 20 Gew.-%.Carbol oil and diethylamine are pumped into the middle part of the counterflow column (3) of the first process stage. The amount of diethylamine is measured so that a mixture with a diethylamine content of 10% by weight, based on carbolic oil, is formed. The countercurrent column (3) was flowed through from bottom to top of carbon dioxide. The pressure in the column is 135 bar, the temperature is 40 ° C. The column contains a wire mesh (Sulzer packing) as packing material. The loading of the C0 2 with low volatile compounds is 20 wt .-%.
Das die Kolonne (3) am Kopf verlassende Extraktionsmittel enthält Neutralöl, in welchem nur noch Spuren von Basen und Phenolen vorhanden sind. In dem der Kolonne nachgeschalteten Abscheider (4) wird durch Entspannung auf 70 bar und Erwärmung auf 130 °C das gelöste Neutralöl praktisch vollständig abgetrennt. Ein Teil des Neutralöls wird als Rücklauf auf den Kopf der Gegenstromkolonne (3) aufgegeben. Das den Abscheider (4) verlassende Gas wird im Kühler (5) gemeinsam mit dem Gas aus dem Abscheider (6) abgekühlt und mit dem Kompressor (7) in den Gaskreislauf nach Passieren eines Vorwärmers (8, 13) zurückgegeben.The extracting agent leaving the column (3) at the top contains neutral oil, in which only traces of bases and phenols are present. In the separator (4) downstream of the column, the dissolved neutral oil is virtually completely separated off by expanding to 70 bar and heating to 130 ° C. Part of the neutral oil is fed as reflux to the top of the countercurrent column (3). The gas leaving the separator (4) is cooled in the cooler (5) together with the gas from the separator (6) and returned to the gas circuit with the compressor (7) after passing through a preheater (8, 13).
Das die Phenole und Basen enthaltende Sumpfprodukt aus Kolonne (3) wird in den mittleren Teil der Gegenstromkolonne (9) der zweiten Verfahrensstufe als Zulauf eingespeist. Hier findet bei 135 bar und 70 °C eine Gegenstromextraktion mit Kohlendioxid statt. Die erzielte Beladung des Extraktionsmittels beträgt etwa 3 Gew.-%. Bei einem Trennfaktor von etwa 0,85 fallen als Kopfprodukt die Basen an. Als Sumpfprodukt werden die Phenole abgezogen. Das die Basen enthaltende Extraktionsmittel verläßt die Gegenstromkolonne (9) am Kopf und wird im Abscheider (6) von den gelösten Basen durch Entspannung auf 70 bar und Erwärmung auf 130 °C befreit. Die abgetrennten Basen werden in drei Teilströme aufgeteilt, von denen der erste dem Carbolöl als Schleppmittel der ersten Stufe, der zweite als Rücklauf der Extraktionskolonne (9) zugeführt und der dritte als Produktstrom abgezogen werden. Aus dem Basengemisch kann das Diethylamin durch Destillation zurückgewonnen werden.The bottom product from the column (3) containing the phenols and bases is fed into the middle part of the counterflow column (9) of the second process stage as feed. A counter-current extraction with carbon dioxide takes place here at 135 bar and 70 ° C. The extraction agent loading achieved is about 3% by weight. With a separation factor of around 0.85, the bases are obtained as the top product. The phenols are withdrawn as bottom product. The extractant containing the bases leaves the countercurrent column (9) at the top and is freed from the dissolved bases in the separator (6) by relaxing to 70 bar and heating to 130 ° C. The separated bases are divided into three partial streams, the first of which is fed to the carbol oil as entrainer of the first stage, the second as reflux to the extraction column (9) and the third is withdrawn as the product stream. The diethylamine can be recovered from the base mixture by distillation.
Nach dem erfindungsgemäßen und umweltfreundlichen Verfahren ist eine quantitative Auftrennung von Phenolen, Basen und Neutralölen, wie sie in den Fraktionen des Steinkohlenteers vorhanden sind, bei geringem Energieverbrauch möglich, ohne daß dabei Rückstände entstehen.According to the inventive and environmentally friendly process, quantitative separation of phenols, bases and neutral oils, such as those present in the fractions of coal tar, is possible with low energy consumption, without any residues being formed.
Claims (13)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863610369 DE3610369A1 (en) | 1986-03-27 | 1986-03-27 | METHOD FOR SEPARATING PHENOLES AND BASES FROM CARBON TEOL OILS BY EXTRACTION |
| DE3610369 | 1986-03-27 |
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| EP0241636A2 EP0241636A2 (en) | 1987-10-21 |
| EP0241636A3 EP0241636A3 (en) | 1989-01-25 |
| EP0241636B1 true EP0241636B1 (en) | 1990-09-26 |
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| EP87100269A Expired - Lifetime EP0241636B1 (en) | 1986-03-27 | 1987-01-12 | Process for the separation of phenols and bases from coal tar oils by extraction |
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| US (1) | US4827050A (en) |
| EP (1) | EP0241636B1 (en) |
| JP (1) | JPS62238224A (en) |
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| DE (2) | DE3610369A1 (en) |
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| ZA (1) | ZA871918B (en) |
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| DE4041097C1 (en) * | 1990-12-21 | 1992-06-17 | Tudapetrol Mineraloelerzeugnisse Nils Hansen Kg, 2000 Hamburg, De | Prodn. of paraffin oils - comprises extracting solvent raffinate with super-critical gases using carbon di:oxide, propane and butane |
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| DE3743058A1 (en) * | 1987-12-18 | 1989-06-29 | Krupp Gmbh | PROCESS FOR THE CONTINUOUS EXTRACTION OF HIGH-BZW. NON-REMAINING BUT MELTING ORGANIC FABRIC MIXTURES |
| DE4038458A1 (en) * | 1990-12-03 | 1992-06-04 | Tudapetrol Mineraloelerzeugnis | LIQUID HYDROCARBON MIXTURES WITH HIGH SINGLE AND TWIN-CORE AROMATES |
| US5672774A (en) * | 1995-10-24 | 1997-09-30 | General Electric Company | Phenol tar processing method |
| CN103289717B (en) * | 2013-06-21 | 2015-05-13 | 西北大学 | Method for solvent extraction-column chromatography separation of coal tar, and apparatus thereof |
| US9162952B2 (en) | 2013-11-19 | 2015-10-20 | Uop Llc | Process for purifying products from coal tar |
| US9222034B2 (en) | 2013-11-19 | 2015-12-29 | Uop Llc | Process for removing a product from coal tar |
| CN104893750B (en) * | 2015-04-27 | 2017-12-15 | 陕西煤业化工集团神木天元化工有限公司 | A kind of method of coal tar oil extract pyridine compounds and their |
| CN106566571A (en) * | 2016-11-07 | 2017-04-19 | 山东科技大学 | Coal tar complexation method dephenolization device |
| DE102019209844A1 (en) | 2018-07-10 | 2020-01-16 | Research Triangle Institute | METHOD FOR SELECTIVE OBTAINING A PHENOLIC COMPOUND FROM A BATCH INCLUDING RAW ORGANIC AND / OR ORGANIC OIL |
| CN110559684B (en) * | 2019-09-16 | 2021-11-02 | 西南石油大学 | Two-stage skid-mounted separation device for continuously extracting oil-based components from oil-containing solid waste by adopting supercritical carbon dioxide |
| CN112050654A (en) * | 2020-09-25 | 2020-12-08 | 济南尚德瑞化工科技有限公司 | Wastewater treatment system and method for crude phenol extraction process |
| CA3240291A1 (en) * | 2021-12-22 | 2023-06-29 | Michael Carpenter | Supercritical ethylene extraction process for selectively recovering phenolic compounds from bio-crude and/or bio-oil |
| CN114832436A (en) * | 2022-06-20 | 2022-08-02 | 运城市盐湖区禾呈信息技术有限公司 | Process for extracting crude phenol from phenol oil by secondary extraction of composite extracting agent |
| CN116459554B (en) * | 2023-04-26 | 2024-01-09 | 邢台旭阳煤化工有限公司 | Method for recycling light components in phenol residues |
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| US2321036A (en) * | 1940-08-27 | 1943-06-08 | Shell Dev | Purification of alkyl phenols |
| US2301270A (en) * | 1940-11-09 | 1942-11-10 | Standard Oil Dev Co | Process for the production of petroleum phenols |
| DE920078C (en) * | 1942-01-23 | 1954-11-11 | Metallgesellschaft Ag | Method and device for processing tars, coal extracts, hydrogenation products or the like with the aid of selective solvents |
| US2997477A (en) * | 1958-08-16 | 1961-08-22 | Metallgesellschaft Ag | Extraction and recovery of phenols and pyridines from phenol containing oils |
| DE2340566C2 (en) * | 1973-08-10 | 1985-11-07 | Peter, Siegfried, Prof.Dr., 8520 Erlangen | Process for the separation of components from mixtures of substances with low vapor pressure with the aid of a compressed gas under supercritical conditions and another substance that influences the separation effect |
| DE3017876A1 (en) * | 1980-05-09 | 1982-05-19 | Peter, Siegfried, Prof.Dr., 8520 Erlangen | METHOD FOR SEPARATING SOLIDS FROM OILS |
| DE3539432A1 (en) * | 1984-11-09 | 1986-06-05 | Instytut Chemii Przemysłowej, Warschau/Warszawa | Process for separation of coal tars |
-
1986
- 1986-03-27 DE DE19863610369 patent/DE3610369A1/en not_active Withdrawn
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- 1987-01-12 DE DE8787100269T patent/DE3765158D1/en not_active Expired - Fee Related
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- 1987-03-13 US US07/025,473 patent/US4827050A/en not_active Expired - Fee Related
- 1987-03-16 ZA ZA871918A patent/ZA871918B/en unknown
- 1987-03-17 CS CS871804A patent/CS265236B2/en unknown
- 1987-03-26 PL PL1987264838A patent/PL149884B1/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4041097C1 (en) * | 1990-12-21 | 1992-06-17 | Tudapetrol Mineraloelerzeugnisse Nils Hansen Kg, 2000 Hamburg, De | Prodn. of paraffin oils - comprises extracting solvent raffinate with super-critical gases using carbon di:oxide, propane and butane |
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| Publication number | Publication date |
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| CS265236B2 (en) | 1989-10-13 |
| PL149884B1 (en) | 1990-03-31 |
| EP0241636A2 (en) | 1987-10-21 |
| CS180487A2 (en) | 1989-01-12 |
| ZA871918B (en) | 1987-09-08 |
| PL264838A1 (en) | 1988-05-12 |
| US4827050A (en) | 1989-05-02 |
| EP0241636A3 (en) | 1989-01-25 |
| DE3765158D1 (en) | 1990-10-31 |
| JPS62238224A (en) | 1987-10-19 |
| DE3610369A1 (en) | 1987-10-01 |
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