EP0241636B1 - Verfahren zur Abtrennung von Phenolen und Basen aus Steinkohlenteerölen durch Extraktion - Google Patents

Verfahren zur Abtrennung von Phenolen und Basen aus Steinkohlenteerölen durch Extraktion Download PDF

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Publication number
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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EP
European Patent Office
Prior art keywords
bases
process according
stage
extraction
phenols
Prior art date
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Expired - Lifetime
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EP87100269A
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German (de)
English (en)
French (fr)
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EP0241636A2 (de
EP0241636A3 (en
Inventor
Siegfried Prof. Dr. Peter
Marc Seekamp
Herbert Dr. Beneke
Jürgen Dr. Stadelhofer
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Rain Carbon Germany GmbH
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Ruetgerswerke AG
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Publication of EP0241636A3 publication Critical patent/EP0241636A3/de
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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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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Working-Up Tar And Pitch (AREA)
EP87100269A 1986-03-27 1987-01-12 Verfahren zur Abtrennung von Phenolen und Basen aus Steinkohlenteerölen durch Extraktion Expired - Lifetime EP0241636B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863610369 DE3610369A1 (de) 1986-03-27 1986-03-27 Verfahren zur abtrennung von phenolen und basen aus steinkohlenteeroelen durch extraktion
DE3610369 1986-12-10

Publications (3)

Publication Number Publication Date
EP0241636A2 EP0241636A2 (de) 1987-10-21
EP0241636A3 EP0241636A3 (en) 1989-01-25
EP0241636B1 true EP0241636B1 (de) 1990-09-26

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EP87100269A Expired - Lifetime EP0241636B1 (de) 1986-03-27 1987-01-12 Verfahren zur Abtrennung von Phenolen und Basen aus Steinkohlenteerölen durch Extraktion

Country Status (7)

Country Link
US (1) US4827050A (cs)
EP (1) EP0241636B1 (cs)
JP (1) JPS62238224A (cs)
CS (1) CS265236B2 (cs)
DE (2) DE3610369A1 (cs)
PL (1) PL149884B1 (cs)
ZA (1) ZA871918B (cs)

Cited By (1)

* Cited by examiner, † Cited by third party
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

Families Citing this family (16)

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DE3743058A1 (de) * 1987-12-18 1989-06-29 Krupp Gmbh Verfahren zur kontinuierlichen extraktion von hoch- bzw. nichtsiedenden aber schmelzenden organischen stoffgemischen
DE4038458A1 (de) * 1990-12-03 1992-06-04 Tudapetrol Mineraloelerzeugnis Fluessige kohlenwasserstoffgemische mit hohen ein- und zweikernigen aromatenanteilen
US5672774A (en) * 1995-10-24 1997-09-30 General Electric Company Phenol tar processing method
CN103289717B (zh) * 2013-06-21 2015-05-13 西北大学 一种溶剂萃取-柱层析分离煤焦油的方法及装置
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 (zh) * 2015-04-27 2017-12-15 陕西煤业化工集团神木天元化工有限公司 一种煤焦油提取吡啶类化合物的方法
CN106566571A (zh) * 2016-11-07 2017-04-19 山东科技大学 一种煤焦油络合法脱酚装置
DE102019209844A1 (de) 2018-07-10 2020-01-16 Research Triangle Institute Verfahren zum selektiven gewinnen einer phenolischen verbindung aus einer charge, die rohe bio-rohöl und/oder bio-öl umfasst
CN110559684B (zh) * 2019-09-16 2021-11-02 西南石油大学 一种采用超临界二氧化碳连续萃取含油固体废物中油基成分的两级撬装分离装置
CN112050654B (zh) * 2020-09-25 2025-03-07 济南尚德瑞化工科技有限公司 粗酚提取工艺的废水处理系统及处理方法
US20250051253A1 (en) * 2021-12-22 2025-02-13 Research Triangle Institute Supercritical ethylene extraction process for selectively recovering phenolic compounds from bio-crude and/or bio-oil
CN114832436A (zh) * 2022-06-20 2022-08-02 运城市盐湖区禾呈信息技术有限公司 一种复合萃取剂二次萃取自酚油提取粗酚的工艺
CN115569409A (zh) * 2022-09-30 2023-01-06 西北大学 一种煤焦油中酚类化合物的分离装置及工艺
CN115504608A (zh) * 2022-11-04 2022-12-23 河南龙成煤高效技术应用有限公司 含油煤化工废水处理方法和设备
CN116459554B (zh) * 2023-04-26 2024-01-09 邢台旭阳煤化工有限公司 一种回收酚渣中轻质组分的方法

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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 (de) * 1942-01-23 1954-11-11 Metallgesellschaft Ag Verfahren und Vorrichtung zur Aufarbeitung von Teeren, Kohleextrakten, Hydrierprodukten od. dgl. mit Hilfe von selektiven Loesungsmitteln
US2997477A (en) * 1958-08-16 1961-08-22 Metallgesellschaft Ag Extraction and recovery of phenols and pyridines from phenol containing oils
DE2340566C2 (de) * 1973-08-10 1985-11-07 Peter, Siegfried, Prof.Dr., 8520 Erlangen Verfahren zur Trennung von Komponenten von Stoffgemischen mit niedrigem Dampfdruck mit Hilfe eines komprimierten Gases unter überkritischen Bedingungen und einer weiteren, den Trenneffekt beeinflussenden Substanz
DE3017876A1 (de) * 1980-05-09 1982-05-19 Peter, Siegfried, Prof.Dr., 8520 Erlangen Verfahren zur abtrennung von feststoffen aus oelen
DE3539432A1 (de) * 1984-11-09 1986-06-05 Instytut Chemii Przemysłowej, Warschau/Warszawa Verfahren zur trennung von kohlenteeren

Cited By (1)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
PL149884B1 (en) 1990-03-31
EP0241636A2 (de) 1987-10-21
DE3765158D1 (de) 1990-10-31
CS180487A2 (en) 1989-01-12
DE3610369A1 (de) 1987-10-01
CS265236B2 (en) 1989-10-13
ZA871918B (en) 1987-09-08
JPS62238224A (ja) 1987-10-19
EP0241636A3 (en) 1989-01-25
PL264838A1 (en) 1988-05-12
US4827050A (en) 1989-05-02

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