US3200165A - Recovery of aromatic and olefinic hydrocarbons - Google Patents

Recovery of aromatic and olefinic hydrocarbons Download PDF

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Publication number
US3200165A
US3200165A US207515A US20751562A US3200165A US 3200165 A US3200165 A US 3200165A US 207515 A US207515 A US 207515A US 20751562 A US20751562 A US 20751562A US 3200165 A US3200165 A US 3200165A
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Prior art keywords
aromatics
solvent
mixture
pure
extraction
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US207515A
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English (en)
Inventor
Eiseulohr Karl-Heinz
Offenbach Kreis
Wirth Hans
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GEA Group AG
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Metallgesellschaft AG
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30Aromatics

Definitions

  • the present invention relates to a process for recovering pure aromatics, such as benzene, toluene and xylene, from hydrocarbon mixtures, especially gasolines, which contain a considerable proportion of unsaturated compounds by partially hydrogenating the mixture and then extracting the desired components.
  • the invention comprises a process for recovering pure aromatics from cracked gasolines (benzines), gasolines obtained by pressure gasification processes, gasolines recovered from low temperature carbonizations and generally hydrocarbon mixtures which contain a high content of unsaturated compounds besides aromatics.
  • benzines cracked gasolines
  • gasolines obtained by pressure gasification processes gasolines recovered from low temperature carbonizations
  • hydrocarbon mixtures which contain a high content of unsaturated compounds besides aromatics.
  • hydrocarhon mixtures are not introduced since they are passed through a pretreatment in order to make them suitable for the extraction.
  • the pretreatment depends on the properties and source of the starting materials. When products from reforming of petroleum hydrocarbons are employed, it is sufiicient merely to produce the corresponding boiling point out.
  • a very important source for recovering aromatics are liquid hydrocarbon mixtures which are obtained as byproducts in the pyrolysis of petroleum hydrocarbons in the production of heating gas or lower oiefins.
  • By-products or similar composition also result under certain conditions in the pyrolysis of solid fuels, that is, by low temperature carbonization or gasification under pressure.
  • These hydrocarbon mixtures are distinguished from coke plant benzine which has an aromatic content of 97 to 98% by a lower content of aromatics and a larger proportion of non-aromatic unsaturated constituents.
  • Aromatic and olefinic hydrocarbons can be recovered according to the invention from hydrocarbon fractions having a high content of unsaturated compounds, especial- 1y from cracked gasolines and low temperature carbonization gasolines by first removing the polyunsaturated components in a known Way, while to a great extent retaining the olefins, and subsequently extracting the aromatics with a solvent containing a pyrrolidone compound.
  • the pyrrolidones expediently are employed as a mixture with small amounts of water for the extraction according to the invention.
  • a mixture of N-methylpyrrolidone with 15 to 30% water is especially well suited.
  • the selective solvent mixture is added preferably in such amounts that the volume ratio of the aromatics present in the starting mixture to the solvent amounts to 0.2 to 0.005.
  • the extraction of the aromatics is preferably carried out in a multi-stage counterilow apparatus in which the mixture to be separated is introduced into one of the central stages.
  • the selective solvent is introduced into one end of the counterflow apparatus.
  • the saturated and unsaturated non-aromatics, which flow countercurrent to the selective solvent, leave the extraction apparatus at the same end.
  • the aromatics contained in the starting material are dissolved in the selective solvent and leave the extraction apparatus with this solvent.
  • a non-aromatic anti-solvent is introduced at the same end as that where the aromatics and selective solvent leave the extractor, so as to flow through the apparatus countercurrent to the selective solvent.
  • the non-aromatic anti-solvent must be easily separable from the aromatics to be recovered through distillation, and it should only slightly dissolve in the selective solvent.
  • a hydrocarbon fraction boiling below 60 C. is employed as the anti-solvent and the volume ratio of aromatics to anti-solvent should be between 1.2 and 0.5.
  • a part of the recovered aromatics can be introduced in the form of an extract recycle together with the antisolvent or in place of it.
  • the selective solvent is separated from the aromatics by distillation and recycled back into the extraction apparatus for reuse.
  • the anti-solvent when used, is also separated from the non-aromatics in a separating column and recycled into the extraction process.
  • the solubility of the aromatic mixture in the solvent in the presence of the anti-solvent should be about to 70%.
  • the extraction can take place at room temperature or also at elevated temperatures as Well as under pressure.
  • the bromine number of such a mixture is about 80 g./100 g.
  • To refine these products by hydrogenation more than 110 normal cubic meters of hydrogen per 1000 kilograms of charge are used up and it is necessary to employ temperatures of 300 to 400 C. at high pressures, that is, reaction conditions are required which make a hydrogenation apparatus that is very costly necessary. The great heat of the reaction and other phenomena also cause considerable technical difficulties.
  • the starting mixture was fed to a stage extraction column 1 by means of inlet 2.
  • the solvent was supplied at 3.
  • the solvent left the column 1 at 4 together with the aromatics contained in the starting mixture.
  • the Bennettane flowed countercurrent to the solvent and carried the non-aromatics with it, with which it left the extraction at 6.
  • the solvent enriched with aromatics coming from 4 was carried by way of 7 into the stripper column 8, in which the dissolved aromatics were separated from the solvent which was recycled by way of 9 and 3 into the extraction column 1.
  • the column 8 was heated if necessary with steam supplied at 31.
  • Example 1 A hydrocarbon mixture, resulting as a by-product from the thermal cracking of petroleum to gaseous olefins, of the following composition served as the starting material for the recovery of benzene:
  • Such fraction was extracted in the system schematically illustrated in the drawing employing four times the amount of solvent consisting of 85% N-methylpyrrolidone (NMP) and 15% water. 30 parts validationane were supplied as the anti-solvent per parts of the fraction introduced. A benzene with a crystallization point of 5.5 C. was recovered in 99.5% yield.
  • NMP N-methylpyrrolidone
  • Example 2 The same cracked hydrocarbon mixture that was used in Example 1 was employed for recovery of benzene, toluene and xylene. For this purpose it was first hydrogenated with the aid of a nickel catalyst that contained 15% nickel and had been reduced at 350 C. using 98% hydrogen at 50 atmospheres and 70 C. The amount of cracked hydrocarbon passed over the catalyst amounted to 1 kg. per liter of catalyst per hour. The hydrogenation caused the bromine number to decrease to a value of 41 g./ 100 g. By fractionation the constituents boiling below C. were separated and the distillate extracted in a similar system as employed in Example 1 with the same solvent. The amount of solvent was 3.5 times the amount of starting material and the amount of prostateane employed was half as large as the mixture introduced.
  • the recovered extract contained small amounts of polyunsaturated hydrocarbons. These were removed by treatment with bleaching earth at 200 C. under pressure. A pure benzene with a crystallization point of 5.5 C. in approximately quantitative yield was obtained from the thus treated extract. The recovered toluene and xylene were 99.8 to 99.9% pure and thus very highly pure.
  • said selective solvent comprises a mixture of N-methyl pyrrolidone and to 30% by weight water.
  • benzene which is at least 99.8% pure and has a crystallization point of 5.5 C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US207515A 1961-07-08 1962-07-05 Recovery of aromatic and olefinic hydrocarbons Expired - Lifetime US3200165A (en)

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DEM0049611 1961-07-08

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US (1) US3200165A (it)
BE (1) BE619846A (it)
FR (1) FR1325444A (it)
GB (1) GB964152A (it)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3347948A (en) * 1963-05-01 1967-10-17 Ici Ltd Hydrocarbon separation process
US3422163A (en) * 1965-10-21 1969-01-14 Universal Oil Prod Co Recovery of aromatics from multiple hydrocarbon streams
US3434936A (en) * 1966-12-19 1969-03-25 Koppers Gmbh Heinrich Method of separating aromatic compounds from hydrocarbon mixtures containing the same by extractive distillation with an n-substituted morpholine
US3437585A (en) * 1967-12-28 1969-04-08 Universal Oil Prod Co Olefin production and subsequent recovery
DE1645809C3 (de) * 1966-12-23 1973-07-12 Texaco Development Corp Verfahren zum Raffinieren von Schmieroel
US4571442A (en) * 1983-09-19 1986-02-18 Institut Francais Du Petrole Process for selectively hydrogenating acetylene in a mixture of acetylene and ethylene
FR2847260A1 (fr) * 2002-11-14 2004-05-21 Inst Francais Du Petrole Procede de desulfuration comprenant une etape d'hydrogenation selective des diolefines et une etape d'extraction des composes soufres

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2737538A (en) * 1952-07-24 1956-03-06 Phillips Petroleum Co 2-pyrrolidone as a selective solvent for aromatic hydrocarbons
US2753381A (en) * 1953-12-18 1956-07-03 Phillips Petroleum Co Nu-acyl pyrrolidines as selective solvents
US2799627A (en) * 1953-08-17 1957-07-16 Universal Oil Prod Co Process for obtaining concentrated aromatic hydrocarbons
US2849396A (en) * 1953-06-29 1958-08-26 Phillips Petroleum Co Selective solvent
CA565312A (en) * 1958-10-28 W. Banes Fred Preparation of olefinic-aromatic feeds for solvent extraction
US2870226A (en) * 1956-03-19 1959-01-20 Universal Oil Prod Co Production and recovery of aromatic hydrocarbons
GB812114A (en) * 1956-11-08 1959-04-15 Esso Engineering And Res Compa Solvent extraction process
US2933448A (en) * 1954-12-06 1960-04-19 Ohio Oil Company Separation of aromatic hydrocarbons from non-aromatic hydrocarbons utilizing a lactam-water solvent
US2943122A (en) * 1957-06-19 1960-06-28 Ohio Oil Company Fractionation of mixtures of aromatic compounds utilizing gamma lactum solvents
US3082271A (en) * 1959-04-11 1963-03-19 Basf Ag N-methyl pyrrolidone for the separation of olefins from hydrocarbon mixtures

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA565312A (en) * 1958-10-28 W. Banes Fred Preparation of olefinic-aromatic feeds for solvent extraction
US2737538A (en) * 1952-07-24 1956-03-06 Phillips Petroleum Co 2-pyrrolidone as a selective solvent for aromatic hydrocarbons
US2849396A (en) * 1953-06-29 1958-08-26 Phillips Petroleum Co Selective solvent
US2799627A (en) * 1953-08-17 1957-07-16 Universal Oil Prod Co Process for obtaining concentrated aromatic hydrocarbons
US2753381A (en) * 1953-12-18 1956-07-03 Phillips Petroleum Co Nu-acyl pyrrolidines as selective solvents
US2933448A (en) * 1954-12-06 1960-04-19 Ohio Oil Company Separation of aromatic hydrocarbons from non-aromatic hydrocarbons utilizing a lactam-water solvent
US2870226A (en) * 1956-03-19 1959-01-20 Universal Oil Prod Co Production and recovery of aromatic hydrocarbons
GB812114A (en) * 1956-11-08 1959-04-15 Esso Engineering And Res Compa Solvent extraction process
US2943122A (en) * 1957-06-19 1960-06-28 Ohio Oil Company Fractionation of mixtures of aromatic compounds utilizing gamma lactum solvents
US3082271A (en) * 1959-04-11 1963-03-19 Basf Ag N-methyl pyrrolidone for the separation of olefins from hydrocarbon mixtures

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3347948A (en) * 1963-05-01 1967-10-17 Ici Ltd Hydrocarbon separation process
US3422163A (en) * 1965-10-21 1969-01-14 Universal Oil Prod Co Recovery of aromatics from multiple hydrocarbon streams
US3434936A (en) * 1966-12-19 1969-03-25 Koppers Gmbh Heinrich Method of separating aromatic compounds from hydrocarbon mixtures containing the same by extractive distillation with an n-substituted morpholine
DE1645809C3 (de) * 1966-12-23 1973-07-12 Texaco Development Corp Verfahren zum Raffinieren von Schmieroel
US3437585A (en) * 1967-12-28 1969-04-08 Universal Oil Prod Co Olefin production and subsequent recovery
US4571442A (en) * 1983-09-19 1986-02-18 Institut Francais Du Petrole Process for selectively hydrogenating acetylene in a mixture of acetylene and ethylene
FR2847260A1 (fr) * 2002-11-14 2004-05-21 Inst Francais Du Petrole Procede de desulfuration comprenant une etape d'hydrogenation selective des diolefines et une etape d'extraction des composes soufres
US7270737B2 (en) 2002-11-14 2007-09-18 Institut Francais Du Petrole Process for desulfurization comprising a stage for selective hydrogenation of diolefins and a stage for extraction of sulfur-containing compounds

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Publication number Publication date
BE619846A (it)
GB964152A (en) 1964-07-15
FR1325444A (fr) 1963-04-26

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