US3816302A - Process for the recovery of aromatic hydrocarbons from mixtures containing the same - Google Patents

Process for the recovery of aromatic hydrocarbons from mixtures containing the same Download PDF

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Publication number
US3816302A
US3816302A US00213567A US21356771A US3816302A US 3816302 A US3816302 A US 3816302A US 00213567 A US00213567 A US 00213567A US 21356771 A US21356771 A US 21356771A US 3816302 A US3816302 A US 3816302A
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United States
Prior art keywords
morpholine
solvent
aromatics
column
formyl
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US00213567A
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English (en)
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G Paret
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SnamProgetti SpA
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SnamProgetti SpA
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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
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/20—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
    • C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
    • 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
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/08—Azeotropic or extractive distillation

Definitions

  • ABSTRACT [30] F i A li ti P i it D t A process is disclosed whereby aromatic hydrocarbons Dec 29 1970 Italy 3361 5/70 such as benzene, toluene and xylene are separated with high selectivity from mixtures in which they are [52] U 5 Cl 208/323 208/313 208/326 contained through extraction and/or extractive distil- 6 /67 4 lation with the aid of a solvent mixture including mor- [511 Int Cl Clog 21/06 pholine and another solvent such as an oxygen con- [58] Field 326 taining derivative of morpholine and water, e.g.
  • the present invention relates to a process for the recovery of aromatic hydrocarbons from mixtures containing the same. More particularly the present invention relates to a process for the recovery of benzene, toluene, xylene and aromatics C from mixtures containing the same, obtaining aromatics at the purity levels required by the petrochemical uses.
  • the above mentioned process makes use as means of extraction and/or of extractive distillation, of a solvent constituted by a mixture containing morpholine, the remaining part of the mixture being constituted by one or more than one solvents, comprising among them also water. More particularly the present invention makes use, as means of extraction and/or of extractive distillation, of mixtures of morpholine in the presence of one or more solvents among which mention is made of acetonitrile, furfural, aniline, dimethyl formammide, dimethylacetamide, N-methyl pyrrolidone, ,B-methoxypropionitrile, sulpholane, glycols as diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, singly or in mixtures, dimethylsulfoxide and others among which according to the process of the present invention the oxygenated compounds of morpholine are of particular importance. As oxygenated compounds of morpholine one can advantageously use all the compounds having an oxygen containing group bound to the
  • N-formylmorpholine 2-formyl-morpholine, 3-formylmorpholine, morpholine-acetone and the like.
  • one of the constituents of the solvent mixture can be also water, in addition to morpholine.
  • morpholine-formyl morpholine, morpholine-water and morpholine-formyl morpholine-water mixtures they present very good solvent and selectivity properties; said properties can be possibly improved by a possible addition of one or more than one of the other mentioned solvents in variable amounts.
  • morpholine being a remarkably stable and inert compound, it can be mixed with water without corrosion and decomposition risks. Furthermore it is known that morpholine has very good properties as corrosion inhibitor in corrosion conditions.
  • the very high selectivity of the solvent mixtures easily allows one to recover products of high purity.
  • Another important feature according to the present invention is the fact that with the use of the described solvent mixtures the column and in particular the reboiler, can work at low temperatures. Moreover the high solvent power allows one to maintain low solvent/hydrocarbon ratios, even if a high recovery of aromatics is effected.
  • a further advantage is that of requiring the use only of low pressure steam, reducing in such a way the working costs.
  • compositions of the solvent mixtures used in the process according to the present invention are always present in concentrations higher than 0.5 percent by weight, up to 99 percent by weight.
  • Water can be used in concentrations ranging from 1 to 35 percent, preferably between 1 and 20 percent, the complement to 100 of the whole mixture being constituted by one or more than one of the other mentioned solvents.
  • the concentration may range from 1 to 98.5 percent by weight and preferably between 1 and 50 percent by weight.
  • the solvent mixtures previously described can be preferably but unrestrictively used for recoverying aromatics, in particular benzene, toluene, xylene and aromatic hydrocarbons having a higher number of C atoms, from mixtures containing the same either by extraction or by distillation or by a combination of the two operations.
  • the first step and a part of the second step are effected by liquid-liquid extraction and said extraction operations (production of a raffinate without aromatics and partial purification of the extract) are effected in only one apparatus 1.
  • the feed 2 enters the extraction column at about half height; the solvent 3 is fed to the top of the extraction column.
  • the raffinate 4, poor in aromatics and containing some dissolved solvent is discharged from the top of the extraction column and is fed to a scrubbing column 17 for the recovery of the solvent by means of water 5 thus obtaining a purified raffinate 19.
  • the extract 6 constituted by the solvent containing the aromatics is discharged from the bottom of extraction column 1; the reflux 7 constituted by a mixture of saturated and aromatic hydrocarbons coming from the extractive distillation column 8 and by a part of the water coming from the column 17 for the raffinate scrubbing, enters the bottom (of column 1).
  • the reflux has the purpose of changing the composition of the saturated hydrocarbons present in the solvent rich stream running downwards along the column, removing the heavier hydrocarbons which can hardly be removed in the subsequent extractive distillation. Water has an analogous effect since it lowers in a more emphasized way the solubility of the more heavy saturated hydrocarbons in the solvent running downwards along the column.
  • the extract obtained from the extraction column bottom constituted by a mixture of aqueous solvent, aromatics and relatively light saturated hydrocarbons is fed to the top of the extractive distillation column 8.
  • This column works without external reflux and at atmospheric pressure; the feed is preheated by making use of the sensible heat of the solvent leaving the bottom of the aromatics recovery column 10.
  • the small amount of water which condenses together with the hydrocarbon usually is not separated and is recycled together with the same to the extraction column l.
  • the bottom product 14 of the extractive distillation column is constituted by solvent and pure aromatics and is fed to the column l for the recovery of the aromatics.
  • the feed enters the column some plates below the top plate; the highest plates have the purpose of removing the solvent contained in the vapour phase so that the overhead product 16 would not contain solvent.
  • the overhead product is constituted by water and aromatics 18, the water is of such a purity that it can be used for washing the raffinate in 17 without supplementary manipulations.
  • the temperature of the column bottom is related to the composition of the solvent mixtures and to the pressure; with the formyl morpholine-morpholine-water mixtures usually utilized, the temperature of -the bottom of the stripping column is maintained at such values that it is possible to make use of low pressure steam, working with the condenser at atmospheric pressure.
  • the solvent 9 leaving the column bottom is free from aromatics. It can be cooled, firstly by heat exchange with the water leaving the column top, thus contemporaneously producing steam which is introduced into the bottom of the same column, then by heat exchange with the solvent 6 leaving the extraction column and by heat exchange with cooling water down to the working temperature of extraction column l.
  • the solvent mixtures of the present invention can be advantageously utilized in other processes and in differ.- ent points of the same mixtures, different both in composition and in components, can be used.
  • the distillate was condensed in two steps.
  • the rich solvent 5 leaving the bottom of the extractive distillation column 2 was then fed to the 25th plate of the aromatics separation column 6, having 40 plates and working with atmospheric pressure at the top.
  • the overhead vapours were condensed totally and separated in two phases.
  • the hydrocarbon phase 7 (aromatic extract) leaving the separator had the following composition:
  • the aqueous phase 8 obtained by decantation of the condensate of the vapours leaving the top of the stripping column (0.1 kg/h) was divided in two portions:
  • the aqueous solution 12 coming out from 11 was then fed, as aqueous reflux, to the bottom of the aromatics extraction column 1.
  • the temperature of the lean solvent leaving the bottom of the stripping column 6 was reduced to room temperature before the same was fed to the 60th plate of the aromatics extraction column.
  • a liquid-liquid extraction step wherein said hydrocarbon mixture is contacted with a solvent mixture of from 0.5 to 99 percent by weight of morpholine, from 1 to 98.5 percent by weight of a formyl morpholine and the balance to 100 percent by weight of water, to produce a raffinate substantially free from aromatic hydrocarbons and an extract rich in aromatic hydrocarbons;
  • N-formylmorpholine constitutes from 1 to 50 percent of the solvent mixture.
  • aromatic hydrocarbons are comprised of benzene, toluene, xylene and aromatic hydrocarbons having nine or more carbon atoms.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US00213567A 1970-12-29 1971-12-29 Process for the recovery of aromatic hydrocarbons from mixtures containing the same Expired - Lifetime US3816302A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT3361570 1970-12-29

Publications (1)

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US3816302A true US3816302A (en) 1974-06-11

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Country Status (18)

Country Link
US (1) US3816302A (cs)
JP (1) JPS5412456B1 (cs)
AR (1) AR196486A1 (cs)
AT (1) AT313253B (cs)
AU (1) AU462261B2 (cs)
BE (1) BE777249A (cs)
BR (1) BR7108717D0 (cs)
CA (1) CA971906A (cs)
CS (1) CS195662B2 (cs)
DE (1) DE2165455A1 (cs)
DK (1) DK138417B (cs)
ES (1) ES398784A1 (cs)
FR (1) FR2120863A5 (cs)
LU (1) LU64526A1 (cs)
NL (1) NL7118015A (cs)
PL (1) PL82896B1 (cs)
RO (1) RO67158A (cs)
SU (1) SU485588A3 (cs)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4664783A (en) * 1984-03-13 1987-05-12 Krupp-Koppers Gmbh Method for the separation of aromates from hydrocarbon mixtures containing aromatics
US4909927A (en) * 1985-12-31 1990-03-20 Exxon Research And Engineering Company Extraction of hydrocarbon oils using a combination polar extraction solvent-aliphatic-aromatic or polar extraction solvent-polar substituted naphthenes extraction solvent mixture
US5723026A (en) * 1994-10-21 1998-03-03 Krupp Koppers Gmbh Process for recovering pure benzene and pure toluene from aromatic hydrocarbon products
WO1999011740A1 (en) * 1997-09-03 1999-03-11 Hfm International, Inc. Aromatics separation process and method of retrofitting existing equipment for same
US6395141B1 (en) * 1999-01-28 2002-05-28 Izak Nieuwoudt Separation of components from aromatic hydrocarbon mixtures thereof by extractive distillation
US20030042125A1 (en) * 2000-04-28 2003-03-06 Fu-Ming Lee Aromatics purification from petroleum streams
US20030080028A1 (en) * 2001-06-29 2003-05-01 Longsheng Tian Process for separating aromatics by extractive distillation and a composite solvent used therein
US6616831B1 (en) 1997-09-03 2003-09-09 Gtc Technology Inc. Aromatics separation process and method of retrofitting existing equipment for same
US9534174B2 (en) 2012-07-27 2017-01-03 Anellotech, Inc. Fast catalytic pyrolysis with recycle of side products
US9790179B2 (en) 2014-07-01 2017-10-17 Anellotech, Inc. Processes for recovering valuable components from a catalytic fast pyrolysis process

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5399244A (en) * 1993-12-06 1995-03-21 Glitsch, Inc. Process to recover benzene from mixed hydrocarbons by extractive distillation
KR102358867B1 (ko) * 2014-07-08 2022-02-08 바스프 에스이 선택적인 용매를 사용하여 추출 증류에 의해서 탄화수소 및/또는 탄화수소 유도체의 혼합물을 분리하기 위한 분리 장치를 갖는 컬럼

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4664783A (en) * 1984-03-13 1987-05-12 Krupp-Koppers Gmbh Method for the separation of aromates from hydrocarbon mixtures containing aromatics
US4909927A (en) * 1985-12-31 1990-03-20 Exxon Research And Engineering Company Extraction of hydrocarbon oils using a combination polar extraction solvent-aliphatic-aromatic or polar extraction solvent-polar substituted naphthenes extraction solvent mixture
US5723026A (en) * 1994-10-21 1998-03-03 Krupp Koppers Gmbh Process for recovering pure benzene and pure toluene from aromatic hydrocarbon products
US6565742B1 (en) 1997-09-03 2003-05-20 Gtc Technology Inc. Aromatics separation process and method of retrofitting existing equipment for same
US6616831B1 (en) 1997-09-03 2003-09-09 Gtc Technology Inc. Aromatics separation process and method of retrofitting existing equipment for same
CN100355866C (zh) * 1997-09-03 2007-12-19 Hfm国际公司 芳族化合物分离工艺及为此改装现有设备的方法
US6375802B1 (en) 1997-09-03 2002-04-23 Hfm International, Inc. Method of retrofitting existing equipment for an improved aromatics separation process
WO1999011740A1 (en) * 1997-09-03 1999-03-11 Hfm International, Inc. Aromatics separation process and method of retrofitting existing equipment for same
US6395141B1 (en) * 1999-01-28 2002-05-28 Izak Nieuwoudt Separation of components from aromatic hydrocarbon mixtures thereof by extractive distillation
US6781026B2 (en) 2000-04-28 2004-08-24 Gtc Technology Inc. Aromatics purification from petroleum streams
US20030042125A1 (en) * 2000-04-28 2003-03-06 Fu-Ming Lee Aromatics purification from petroleum streams
US20030080028A1 (en) * 2001-06-29 2003-05-01 Longsheng Tian Process for separating aromatics by extractive distillation and a composite solvent used therein
US7078580B2 (en) 2001-06-29 2006-07-18 China Petroleum & Chemical Corporation Process for separating aromatics by extractive distillation and a composite solvent used therein
DE10242349B4 (de) * 2001-06-29 2007-08-23 China Petroleum And Chemical Corporation Verfahren zur Abtrennung von Aromaten durch extraktive Destillation und dabei verwendetes Verbundlösungsmittel
US9534174B2 (en) 2012-07-27 2017-01-03 Anellotech, Inc. Fast catalytic pyrolysis with recycle of side products
US9790179B2 (en) 2014-07-01 2017-10-17 Anellotech, Inc. Processes for recovering valuable components from a catalytic fast pyrolysis process
US10351783B2 (en) 2014-07-01 2019-07-16 Anellotech, Inc. Processes for recovering valuable components from a catalytic fast pyrolysis process
US10954452B2 (en) 2014-07-01 2021-03-23 Anellotech, Inc. Processes for recovering valuable components from a catalytic fast pyrolysis process

Also Published As

Publication number Publication date
JPS5412456B1 (cs) 1979-05-23
DK138417B (da) 1978-09-04
CA971906A (en) 1975-07-29
LU64526A1 (cs) 1972-06-20
AR196486A1 (es) 1974-02-06
NL7118015A (cs) 1972-07-03
BE777249A (fr) 1972-04-17
AU462261B2 (en) 1975-06-19
AU3667271A (en) 1973-06-14
ES398784A1 (es) 1975-05-16
PL82896B1 (cs) 1975-10-31
RO67158A (ro) 1980-02-15
DE2165455A1 (de) 1972-07-20
DK138417C (cs) 1979-02-12
BR7108717D0 (pt) 1973-03-13
SU485588A3 (ru) 1975-09-25
CS195662B2 (cs) 1980-02-29
AT313253B (de) 1974-02-11
FR2120863A5 (cs) 1972-08-18

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