EP0168068B1 - Entfernung von primären Aminen aus Überwiegend aromatischen Ölen - Google Patents

Entfernung von primären Aminen aus Überwiegend aromatischen Ölen Download PDF

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Publication number
EP0168068B1
EP0168068B1 EP85200629A EP85200629A EP0168068B1 EP 0168068 B1 EP0168068 B1 EP 0168068B1 EP 85200629 A EP85200629 A EP 85200629A EP 85200629 A EP85200629 A EP 85200629A EP 0168068 B1 EP0168068 B1 EP 0168068B1
Authority
EP
European Patent Office
Prior art keywords
oil
oxidation
primary amines
process according
oils
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
Application number
EP85200629A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0168068A3 (en
EP0168068A2 (de
Inventor
Jürgen Dr. Haase
Günter Biadala
Gabriele Momm
Jürgen Dr. Palm
Jörg Dr. Talbiersky
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.)
Ruetgers Germany GmbH
Original Assignee
Ruetgerswerke AG
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 Ruetgerswerke AG filed Critical Ruetgerswerke AG
Publication of EP0168068A2 publication Critical patent/EP0168068A2/de
Publication of EP0168068A3 publication Critical patent/EP0168068A3/de
Application granted granted Critical
Publication of EP0168068B1 publication Critical patent/EP0168068B1/de
Expired legal-status Critical Current

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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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
    • C10C3/04—Working-up pitch, asphalt, bitumen by chemical means reaction by blowing or oxidising, e.g. air, ozone
    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen

Definitions

  • the invention is concerned with the removal of, in particular, primary amines from predominantly aromatic oils, such as are obtained by hydrogenation or by pyrolysis from coal, oil shale, oil sands, mineral oil fractions and hydrocarbon-rich wastes. It is known that the hydrogenation or pyrolysis of these substances produces primary amines, some of which have a toxic potential.
  • Analytical methods are known for separating aromatic amines from such oils.
  • Analytica Chimica Acta, 134 (1982) 301-311 describes the isolation of ⁇ -naphthylamine from oils by liquid chromatography methods, in which 50 to 80% of the amine present on the ppm scale could be obtained.
  • the task was therefore to develop a simple, effective chemical process for removing primary amines from these oils.
  • the object is achieved in that the amine-containing oil is treated with an oxidizing agent in the temperature range from 50 to 300 ° C. for 0.5 to 48 h.
  • the amines are oxidized or dehydrated under these conditions and partially react with other reactive components of the oil.
  • the oxidation of pure primary and secondary amines is known (H.R. Christen, Fundamentals of Organic Chemistry, Verlag Sauerators, 1970, p. 649).
  • the amines are diluted with a pure solvent, it is found with a strong dilution in the order of 10 to 1000 ppm that the oxidation proceeds very slowly.
  • Mesitylene was gassed with 325 ppm ⁇ -naphthylamine at 150 ° C for 6 h with 10 1 / h air per kg oil. The ⁇ -naphthylamine content only decreased to 309 ppm.
  • Oxygen-containing gases such as air are preferably used as the oxidizing agent.
  • the pressure has little impact. At overpressure, the solubility of the oxygen in the oils increases, which increases the rate of oxidation.
  • the oxidation of the amines is preferably carried out under normal pressure in order not to require pressure-resistant apparatus.
  • oxidation For the oxidation, 1 to 30 l / h of air per kg of oil, preferably about 10 l / h kg, are required, which are dispersed in the oil. Mixing sirens, intensive stirrers and bird bush dispersers, as are customary for the gassing of liquids, are suitable as well as venturi washers. Simple gassing devices such as sintered disks, sieve trays, etc. are less suitable because mostly higher amounts of air are required to achieve sufficient mixing.
  • the reaction temperature is preferably in the range from 100 to 200 ° C. Because of the loading of the exhaust air with aromatic hydrocarbons, it can make sense to carry out the oxidation with liquid (e.g. hydrogen peroxide) or solid oxidizing agents (e.g.
  • dibenzoyl peroxide dibenzoyl peroxide
  • the choice of the suitable oxidizing agent depends, among other things. after further processing of the oils.
  • the breakdown of the primary amines was determined using the example of ⁇ -naphthylamine.
  • the amine contents can be reduced by the claimed method up to the detection limit of 1 ppm (high pressure liquid chromatography with electrochemical detection).
  • the fumigation experiments were carried out in a 1 liter round-bottom flask with a gas inlet tube, stirrer and reflux condenser under normal pressure. 0.75 kg of oil were filled into the flask.
  • Examples 6 to 8 show the influence of the amount of air offered on the breakdown of a defined amount of ⁇ -naphthylamine in a synthetic oil.
  • the experimental setup and implementation correspond to Examples 1 to 5.
  • the results depending on the fumigation time are shown in Table 2:
  • Examples 9 to 12 show the effectiveness of solid oxidizing agents at different temperatures and stirring times in the oxidation of ⁇ -naphthylamine. All the oils used were doped with ⁇ -naphthylamine before the start of the experiment in order to clarify the oxidation effect. Dibenzoyl peroxide is used as the oxidizing agent. The tests are carried out in a 1 liter round bottom flask with stirrer and reflux condenser. The results are shown in Tab. 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP85200629A 1984-07-09 1985-04-24 Entfernung von primären Aminen aus Überwiegend aromatischen Ölen Expired EP0168068B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3425216A DE3425216A1 (de) 1984-07-09 1984-07-09 Entfernung von primaeren aminen aus ueberwiegend aromatischen oelen
DE3425216 1984-07-09

Publications (3)

Publication Number Publication Date
EP0168068A2 EP0168068A2 (de) 1986-01-15
EP0168068A3 EP0168068A3 (en) 1987-05-06
EP0168068B1 true EP0168068B1 (de) 1988-11-02

Family

ID=6240177

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85200629A Expired EP0168068B1 (de) 1984-07-09 1985-04-24 Entfernung von primären Aminen aus Überwiegend aromatischen Ölen

Country Status (4)

Country Link
EP (1) EP0168068B1 (da)
DE (2) DE3425216A1 (da)
DK (1) DK164921C (da)
ES (1) ES8603931A1 (da)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3630789A1 (de) * 1986-09-10 1987-01-29 Al Douri Amad Dipl Ing Verfahren zur herstellung von oxidationsbitumen durch reaktion mit luft in gegenwart von radikalbildnern

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE60833C (de) * TH. LEES, R. LEES und W. LEES JR. in Hollinwood bei Manchester, England Vom Regulator verstellbare Expansionsvorrichtung
DE30786C (de) * Dr. C. ROTH, gerichtlich vereidigter Chemiker in Berlin N-, Strafsburgerstr. 18 Verfahren zur Herstellung reiner unverharzbarer Maschinenschmier- und Einfettungsöle aus Erdölen oder deren hochsiedenden Bestandteilen
CH41272A (fr) * 1907-12-09 1908-10-01 Attilio Fama Procédé pour l'épuration de l'ensemble des essences minérales d'une densité de 0,7-0,75
US2767204A (en) * 1953-08-05 1956-10-16 Sun Oil Co Preventing discoloration of partially oxidized petroleum
US3162598A (en) * 1962-03-12 1964-12-22 Sinelair Res Inc Removing nitrogen compounds by oxidation

Also Published As

Publication number Publication date
EP0168068A3 (en) 1987-05-06
DK224285D0 (da) 1985-05-21
DK164921C (da) 1993-01-25
DE3565995D1 (en) 1988-12-08
DK164921B (da) 1992-09-07
DK224285A (da) 1986-01-10
EP0168068A2 (de) 1986-01-15
ES543955A0 (es) 1986-01-16
DE3425216A1 (de) 1986-02-06
ES8603931A1 (es) 1986-01-16

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