EP0489371B1 - Flüssige Kohlenwasserstoffgemische mit hohen ein- und zweikernigen Aromatenanteilen - Google Patents

Flüssige Kohlenwasserstoffgemische mit hohen ein- und zweikernigen Aromatenanteilen Download PDF

Info

Publication number
EP0489371B1
EP0489371B1 EP91120570A EP91120570A EP0489371B1 EP 0489371 B1 EP0489371 B1 EP 0489371B1 EP 91120570 A EP91120570 A EP 91120570A EP 91120570 A EP91120570 A EP 91120570A EP 0489371 B1 EP0489371 B1 EP 0489371B1
Authority
EP
European Patent Office
Prior art keywords
content
aromatic
pah
hydrocarbon mixtures
extracts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91120570A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0489371A1 (de
Inventor
Nils Hansen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TUDAPETROL MINERALOLERZEUGNISSE NILS HANSEN KG
Original Assignee
TUDAPETROL MINERALOLERZEUGNISSE NILS HANSEN KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TUDAPETROL MINERALOLERZEUGNISSE NILS HANSEN KG filed Critical TUDAPETROL MINERALOLERZEUGNISSE NILS HANSEN KG
Publication of EP0489371A1 publication Critical patent/EP0489371A1/de
Application granted granted Critical
Publication of EP0489371B1 publication Critical patent/EP0489371B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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

Definitions

  • the invention relates to liquid hydrocarbon mixtures, hereinafter abbreviated as KW mixtures, with a high proportion of mono- and dinuclear aromatics.
  • Mixtures with a high proportion of aromatics can be obtained not only in the direct processing of the crude oil, but also as by-products in the catalytic reforming of straightrun gasoline fractions with subsequent aromatics extraction from the reformate and in the production of pyrolysis gasoline and oil gasification gasoline are present as by-products in substantial quantities in the production of ethylene or synthesis gas or town gas from petroleum fractions. Extracts rich in aromatics can also be obtained from the cracker, i.e. a residue of catalytic and thermal cracking.
  • aromatic extracts contain up to 40% aromatic constituents, in which compounds with one or two aromatic rings predominate, but also in which there are multinuclear compounds, in particular those with four to seven or more rings.
  • the aromatic extracts are used, for example, in the printing ink industry as a constituent for printing inks and as a plasticizer in rubber and rubber processing.
  • the high aromatic content is decisive for these applications; with a low aromatics content and too high a paraffin content of such additives, the compatibility in the production of printing inks with the resins and carbon blacks used deteriorates, and in the rubber industry a reduced aromatics content leads to the risk of sweating out of the plasticizer oil from the rubber and rubber mixture during vulcanization.
  • aromatic extracts can also contain a surprisingly high proportion of polycyclic compounds; an average of 3% polycycles can be expected. Depending on the origin of the original material, the content can also increase to 40 to 50%.
  • PAH Polycyclic aromatic hydrocarbons
  • PAH Polycyclic aromatic hydrocarbons
  • PAH is understood to mean polycycles with at least four ring systems and in particular those with four to seven ring systems.
  • PAHs have largely emerged as cancerogens or at least cocancerogens.
  • classic carcinogenic substances are considered Benzo (a) pyrene, benzofluoranthenes (b, j, k) and benzo (a) anthracene.
  • the carcinogenic properties of these compounds appear to be linked to the presence of so-called Bay regions; more detailed studies are available from Lowe et al in "Accounts Chem. Res. 17 (1984)", 362 ff.
  • PAHs are not only carcinogens, but that they can also trigger mutagenic effects and are also partially phototoxic.
  • aromatic extracts Since November 1, 1990, these substances have had to be labeled in the FRG.
  • liquid, predominantly naphthenic aromatic hydrocarbon mixtures are now proposed, which are characterized by a high content of mononuclear and dinuclear aromatics and a PAH content of less than 0.03%.
  • the KW mixtures claimed according to the invention can be produced by extraction of the aromatic extracts usually used by means of supercritical gases.
  • the separation of gases using gases as a solvent is being used to an increasing extent, since the density of gases near the critical temperature at approximately critical pressure assumes values that are comparable to those of liquids. Gases in the supercritical state and liquids in the subcritical range close to the critical temperature therefore have essential properties of a solvent and can be used for material separation. Details of extraction processes with supercritical gases can be found, for example, in the publication by Penninger et al in "Supercritical fluid technology", Elsevier, Amsterdam, 1985.
  • the use of supercritical gases, especially supercritical CO2 has already been introduced in petroleum chemistry; For example, G.
  • Aromatic extracts of various origins are separated into two phases by means of supercritical gases, a PAH-rich phase being formed, the solubility of which is relatively low in the supercritical gases used.
  • the other phase essentially comprises paraffins, naphthenes and aromatics with one or two rings, for which the supercritical gas used is a good selective solvent.
  • pure CO2 can be used as a supercritical gas or a mixture of CO2 and propane in a mixing ratio of 20 to 100 weight percent CO2 and 0 to 80 weight percent propane.
  • the pressure is 100 to 400 bar at a temperature of 50 to 150 ° C.
  • a second stage is preferably connected to the first stage of the separation in order to carry out a further separation of the PAH-containing phase.
  • the supercritical gas consists of 50 to 100 percent by weight carbon dioxide, 0 to 50 percent by weight propane and 1 to 15 percent by weight ethanol, since the addition factors such as ethanol can be used to influence the distribution factors of substances between the phases, as Brunner in " Fluid phase equilibrium "(1983, pp. 289 to 398).
  • the extraction is carried out at a temperature of 30 to 130 ° C. and a pressure of 250 to 350 bar.
  • Aromatic extracts can be obtained by the process according to the invention Process different origins, so that the PAH content in the end product is below 0.005% Pressure, temperature and the composition of the supercritical gas used vary depending on the starting material used Gas mixture is increased because the critical temperature of CO2 propane mix with increasing proportion of propane up to the critical temperature of the Propane itself rises. It is also known that compressed gases also separate substance mixtures according to their molecular weight or the volatility of the substances, or that polar substances are dissolved more poorly with increasing polarity, so that the pressure required for the respective extraction can be varied depending on the composition of the starting material.
  • the aromatic extract that is to say the educt E
  • the supercritical gas mixture GM1 is fed to the first separation stage; in the following phase separation, the product 1 as a PAH-enriched fraction can be taken off as the "bottom" of the first stage and the desired end product can be taken off as PAH-free fraction P at the top.
  • the product P1 is transferred together with the supercritical gas mixture GM2 into a second separation stage, from which, after phase separation, a PAH-reduced product can be taken as fraction P2, which is returned to stage 1 and mixed with the starting material.
  • the fraction P3 enriched in PAH is removed in the second stage and consists of over 90% only PAH.
  • the desired end product P is a fraction which has a high content of mononuclear or dinuclear aromatics, usually 20 to over 40%, and an extremely low PAH content of approximately below 0.03%, determined by the method of Prof. Grümmer , published in "Fresenius, Analytician Chemie", 1983, Volume 314, pp. 29 to 36.
  • the P3 fraction consists almost exclusively of polycyclic aromatics, which are to be regarded as highly carcinogenic. It must therefore be avoided that this product in the Environment. For these reasons, this fraction is disposed of by treatment with supercritical water, with which the polycyclic hydrocarbons are split into carbon dioxide and water at elevated temperature.

Landscapes

  • 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)
EP91120570A 1990-12-03 1991-11-29 Flüssige Kohlenwasserstoffgemische mit hohen ein- und zweikernigen Aromatenanteilen Expired - Lifetime EP0489371B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4038458A DE4038458A1 (de) 1990-12-03 1990-12-03 Fluessige kohlenwasserstoffgemische mit hohen ein- und zweikernigen aromatenanteilen
DE4038458 1990-12-03

Publications (2)

Publication Number Publication Date
EP0489371A1 EP0489371A1 (de) 1992-06-10
EP0489371B1 true EP0489371B1 (de) 1995-02-15

Family

ID=6419444

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91120570A Expired - Lifetime EP0489371B1 (de) 1990-12-03 1991-11-29 Flüssige Kohlenwasserstoffgemische mit hohen ein- und zweikernigen Aromatenanteilen

Country Status (5)

Country Link
EP (1) EP0489371B1 (enrdf_load_stackoverflow)
AT (1) ATE118524T1 (enrdf_load_stackoverflow)
DE (2) DE4038458A1 (enrdf_load_stackoverflow)
DK (1) DK0489371T3 (enrdf_load_stackoverflow)
ES (1) ES2069180T3 (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102971400A (zh) * 2010-05-17 2013-03-13 印尼国家石油和天然气公司 生产具有低含量的多环芳烃的加工油的方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6248929B1 (en) 1998-01-22 2001-06-19 Japan Energy Corporation Rubber process oil and production process thereof
JP4037515B2 (ja) * 1998-04-17 2008-01-23 出光興産株式会社 プロセスオイル及びその製造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3350470A (en) * 1961-12-01 1967-10-31 Union Oil Co Solvent extraction
US3927136A (en) * 1974-07-05 1975-12-16 Texaco Inc Treatment of hydrocarbons
CA1207699A (en) * 1982-01-25 1986-07-15 Isao Honzyo Process for the solvent deasphalting of asphaltene- containing hydrocarbons
DE3610369A1 (de) * 1986-03-27 1987-10-01 Ruetgerswerke Ag Verfahren zur abtrennung von phenolen und basen aus steinkohlenteeroelen durch extraktion
DE3813636A1 (de) * 1988-04-22 1989-11-02 Ruetgerswerke Ag Verfahren zur abtrennung von indol, chinolinbasen und hoeheren phenolderivaten aus steinkohlenteeroel durch extraktion mit ueberkritischen gasen
DE3930422A1 (de) * 1989-09-12 1991-03-21 Bp Oiltech Gmbh Verfahren zur herstellung von prozessoelen mit niedrigem gehalt an polycyclischen aromaten
DE3938620C1 (enrdf_load_stackoverflow) * 1989-11-21 1991-04-18 Klaus Dahleke Kg, 2000 Hamburg, De

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102971400A (zh) * 2010-05-17 2013-03-13 印尼国家石油和天然气公司 生产具有低含量的多环芳烃的加工油的方法
CN102971400B (zh) * 2010-05-17 2016-02-10 印尼国家石油和天然气公司 生产具有低含量的多环芳烃的加工油的方法

Also Published As

Publication number Publication date
DE59104605D1 (de) 1995-03-23
DE4038458A1 (de) 1992-06-04
DE4038458C2 (enrdf_load_stackoverflow) 1993-08-26
ES2069180T3 (es) 1995-05-01
DK0489371T3 (da) 1995-07-10
EP0489371A1 (de) 1992-06-10
ATE118524T1 (de) 1995-03-15

Similar Documents

Publication Publication Date Title
DE2953190C2 (enrdf_load_stackoverflow)
DE69132727T2 (de) Verfahren zur kontrolle der herstellung von nicht krebserregenden brightstock extrakten und entasphaltiertem ölen
DE69328029T2 (de) Verfahren zur herstellung von hochreinem benzol durch extraktivdestillation
DE69030970T2 (de) Verfahren zur Herstellung von Produktölen mit niedrigem Polycycloaromatengehalt
DE2051447A1 (de) Verfahren zur Herstellung von Benzin hoher Oktanzahl
DE2454197A1 (de) Verfahren zur herstellung eines synthetischen schmieroels mit hohem viskositaetsindex
EP0232481B1 (de) Verfahren zum Fraktionieren von Steinkohlenteerpech und Verwendung der dabei erhältlichen Fraktionen
EP0009236B1 (de) Verfahren zum Spalten von Kohlenwasserstoffen
EP0489371B1 (de) Flüssige Kohlenwasserstoffgemische mit hohen ein- und zweikernigen Aromatenanteilen
DE2840986C2 (de) Verfahren zur Aufarbeitung der bei der Spaltung von Kohlenwasserstoffen entstehenden über 200 °C siedenden Kohlenwasserstoff-Fraktionen
DE3302938A1 (de) Kohleextraktionsverfahren
DE2344251A1 (de) Verfahren zur umwandlung einer schwefel, asche und asphalten enthaltenden kohlenwasserstoffbeschickung
DE3235127C2 (enrdf_load_stackoverflow)
DE1256221C2 (de) Verfahren zur Aufarbeitung von Steinkohlenteerpech
DE2805721A1 (de) Verfahren zur aufbereitung eines kohlenwasserstoffgemisches
DE1593455A1 (de) Verfahren zum Auftrennen von Mischungen aus organischen Verbindungen unter Verwendung eines selektiven,Furfural enthaltenen Loesungsmittels
DE4041097C1 (en) Prodn. of paraffin oils - comprises extracting solvent raffinate with super-critical gases using carbon di:oxide, propane and butane
DE1936034B2 (de) Verfahren zur gleichzeitigen Doppelextraktion von zwei getrennten Kohlenwasserstoffbeschickungen im Gegenstrom
DE3331756A1 (de) Verfahren zum umwandeln einer kohlenwasserstoffcharge hoher viskositaet in eine weniger viskose kohlenwasserstoffraktion
DE69133121T2 (de) Verwendung von nicht-krebserregenden Brightstock-Extrakte in Drucktinte
DE629762C (de) Verfahren zur Herstellung oxydationsbestaendiger Schmier- und Transformatorenoele
DE69728609T2 (de) Verfahren und Zusatz zur Erhöhung der Ausbeute thermischer Umwandlungen in Petroleumanlagen
DE2149910A1 (de) Verfahren zum Herstellen von Schmieroelen mit hohem Viskositaetsindex
DE2454516A1 (de) Verfahren zur herstellung aromatenreicher und polarer fraktionen aus erdoeldestillaten
DE695329C (de) Verfahren zur Gewinnung von Coronen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19920625

17Q First examination report despatched

Effective date: 19921102

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19950215

REF Corresponds to:

Ref document number: 118524

Country of ref document: AT

Date of ref document: 19950315

Kind code of ref document: T

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 59104605

Country of ref document: DE

Date of ref document: 19950323

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950305

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2069180

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19951001

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19951003

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19951005

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19951012

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19951013

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19951016

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19951019

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19951025

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 19951115

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19951120

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19951130

Year of fee payment: 5

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19961129

Ref country code: GB

Effective date: 19961129

Ref country code: DK

Effective date: 19961129

Ref country code: AT

Effective date: 19961129

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19961130

Ref country code: LI

Effective date: 19961130

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19961130

Ref country code: CH

Effective date: 19961130

Ref country code: BE

Effective date: 19961130

BERE Be: lapsed

Owner name: TUDAPETROL MINERALOLERZEUGNISSE NILS HANSEN K.G.

Effective date: 19961130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19970601

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19961129

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19970731

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19970601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19970801

EUG Se: european patent has lapsed

Ref document number: 91120570.6

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19971213

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20051129