EP0168068B1 - Removal of primary amines from substantially aromatic oils - Google Patents
Removal of primary amines from substantially aromatic oils Download PDFInfo
- 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
Links
- 150000003141 primary amines Chemical class 0.000 title claims description 9
- 239000010692 aromatic oil Substances 0.000 title claims description 6
- 239000003921 oil Substances 0.000 claims description 29
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 239000004058 oil shale Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 239000011269 tar Substances 0.000 claims 1
- 150000001412 amines Chemical class 0.000 description 11
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003958 fumigation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000269400 Sirenidae Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000721 toxic potential Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (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)
Description
Die Erfindung befaßt sich mit der Entfernung von insbesondere primären Aminen aus überwiegend aromatischen Ö1en, wie sie durch Hydrieren oder durch Pyrolyse aus Kohle, Ölschiefer, Ölsanden, Mineralölfraktionen und kohlenwasserstoffreichen Abfällen gewonnen werden. Es ist bekannt, daß bei der Hydrierung oder Pyrolyse dieser Stoffe primäre Amine entstehen, von denen einige ein toxisches Potential besitzen.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.
Es sind analytische Methoden bekannt, aromatische Amine aus derartigen Ölen abzutrennen. So wird beispielsweise in der Analytica Chimica Acta, 134 (1982) 301 - 311 die Isolierung von β-Naphthylamin aus Ölen durch flüssigkeitschromatographische Methoden beschrieben, bei denen 50 bis 80 % des im ppm-Maßstab vorhandenen Amins gewonnen werden konnten.Analytical methods are known for separating aromatic amines from such oils. For example, Analytica Chimica Acta, 134 (1982) 301-311 describes the isolation of β-naphthylamine from oils by liquid chromatography methods, in which 50 to 80% of the amine present on the ppm scale could be obtained.
Auch gaschromatographische Trennmethoden sind bekannt (Analytical Chemistry, Vol 54 (1982), No.1, 119). Diese Verfahren sind jedoch für eine technische Anwendung ungeeignet. Andere physikalische Trennverfahren scheitern an der geringen Konzentration der Amine in den Ölen.Gas chromatographic separation methods are also known (Analytical Chemistry, Vol 54 (1982), No.1, 119). However, these methods are unsuitable for industrial use. Other physical separation processes fail due to the low concentration of the amines in the oils.
Es ist weiterhin bekannt, Amine durch eine Wäsche mit Schwefelsäure aus Ölen zu entfernen. Bei geringen Amin-Konzentrationen ist dieses Verfahren jedoch nicht geeignet.It is also known to remove amines from oils by washing with sulfuric acid. However, this method is not suitable for low amine concentrations.
Es bestand daher die Aufgabe, ein einfaches, effektives chemisches Verfahren zur Entfernung von primären Aminen aus diesen Ölen zu entwickeln. Die Aufgabe wird dadurch gelöst, daß das aminhaltige Öl im Temperaturbereich von 50 bis 300°C 0,5 bis 48 h mit einem Oxidationsmittel behandelt wird.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.
Die Amine werden unter diesen Bedingungen oxidiert bzw. dehydriert und reagieren teilweise mit anderen reaktiven Komponenten des Öls. Die Oxidation von reinen primären und sekundären Aminen ist bekannt (H.R. Christen, Grundlagen der organischen Chemie, Verlag Sauerländer, 1970, S. 649). Werden die Amine jedoch mit einem reinen Lösungsmittel verdünnt, so zeigt es sich bei starker Verdünnung in der Größenordnung von 10 bis 1000 ppm, daß die Oxidation nur noch sehr langsam verläuft. So wurde Mesitylen mit 325 ppm β-Naphthylamin bei 150°C über 6 h mit 10 1/h Luft pro kg Öl begast. Dabei verringerte sich der β-Naphthylamin-Gehalt nur auf 309 ppm. Überraschenderweise wurde nun gefunden, daß die Oxidation von primären Aminen auch in starker Verdünnung möglich ist, wenn die Amine in Ölen aus der Hydrierung oder Pyrolyse von Kohle, Ölschiefer, Ölsanden, Mineralölfraktionen oder kohlenwasserstoffreichen Abfällen wie z. B. Altreifen gelöst sind. Die beobachteten Amin-Oxidationsgeschwindigkeiten sind in den verschiedenen Ölen bei gleicher Temperatur unterschiedlich. Daraus wird geschlossen, daß Komponenten der Öle in nicht geklärter Weise an der Oxidation beteiligt sind.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 Sauerländer, 1970, p. 649). However, if 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 β-naphthylamine at 150 ° C for 6 h with 10 1 / h air per kg oil. The β-naphthylamine content only decreased to 309 ppm. Surprisingly, it has now been found that the oxidation of primary amines is also possible in strong dilution if the amines in oils from the hydrogenation or pyrolysis of coal, oil shale, oil sands, mineral oil fractions or hydrocarbon-rich wastes such as, for. B. old tires are released. The observed amine oxidation rates are different in the different oils at the same temperature. It is concluded from this that components of the oils are involved in the oxidation in an unexplained manner.
Als Oxidationsmittel werden vorzugsweise sauerstoffhaltige Gase verwendet wie beispielsweise Luft. Der Druck hat nur einen geringen Einfluß. Bei Überdruck erhöht sich die Löslichkeit des Sauerstoffs in den Ölen, wodurch die Oxidationsgeschwindigkeit ansteigt. Vorzugsweise wird die Oxidation der Amine jedoch unter Normaldruck durchgeführt, um keine druckfesten Apparate zu benötigen.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. However, the oxidation of the amines is preferably carried out under normal pressure in order not to require pressure-resistant apparatus.
Für die Oxidation werden 1 bis 30 1/h Luft je kg Öl, vorzugsweise etwa 10 1/h kg, benötigt, die in dem Öl dispergiert werden Hierzu eignen sich Mischsirene, Intensivrührer und Vogelbuschdispergator, wie sie für die Begasung von Flüssigkeiten üblich sind, ebenso wie Venturiwäscher. Einfache Begasungsvorrichtungen wie Sinterscheiben, Siebböden usw. sind weniger geeignet, da meist höhere Luftmengen erforderlich sind, um eine ausreichende Durchmischung zu erreichen. Die Reaktionstemperatur liegt vorzugsweise im Bereich von 100 bis 200°C. Wegen der Beladung der Abluft mit aromatischen Kohlenwasserstoffen kann es sinnvoll sein, die Oxidation mit flüssigen (z. B. Wasserstoffperoxid) oder festen Oxidationsmitteln (z. B. Dibenzoylperoxid) durchzuführen. Die Wahl des geeigneten Oxidationsmittels richtet sich dabei u.a. nach der weiteren Aufarbeitung der Öle. Der Abbau der primären Amine wurde am Beispiel β-Naphthylamin bestimmt. Die Absenkung der Amingehalte durch das beanspruchte Verfahren gelingt bis in die Nachweisgrenze von 1 ppm (Hochdruckflüssigkeitschromatographie mit elektrochemischer Detektion). Die Begasungsversuche wurden in einem 1 I-Rundkolben mit Gaseinleitungsrohr, Rührer und Rückflußkühler unter Normaldruck durchgeführt. In den Kolben wurden jeweils 0,75 kg Öl eingefüllt.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). 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 β-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.
In den Beispielen 1 bis 7 wird β-Naphthylamin in verschiedenen Ölen bei 150°C und einem Luftdurchsatz von 10 1/h je kg Öl oxidiert. Als aromatisches Öl werden verwendet:
- Kohlehydrieröl A, Siedebereich 188 - 320° C;
- Kohlehydrieröl B, Siedebereich 78 - 314° C;
- Kohlehydrieröl C, Siedebereich 75 - 375° C;
- Pyrolyseöl aus Gasölspaltung, Siedebereich 280 - 370° C
- Steinkohlenteeröl Siedebereich 300 - 450° C.
- Die Ergebnisse sind in Tabelle 1 wiedergegeben.
- Carbohydrate oil A, boiling range 188 - 320 ° C;
- Carbohydrate oil B, boiling range 78 - 314 ° C;
- Carbohydrate oil C, boiling range 75 - 375 ° C;
- Pyrolysis oil from gas oil splitting, boiling range 280 - 370 ° C
- Coal tar oil boiling range 300 - 450 ° C.
- The results are shown in Table 1.
In den Beispielen 6 bis 8 wird der Einfluß der angebotenen Luftmenge auf den Abbau einer definierten Menge des β-Naphthylamins in einem Syntheseöl dargelegt. Die Versuchsanordnung und Durchführung entspricht den Beispielen 1 bis 5. Die Ergebnisse in Abhängigkeit von der Begasungszeit sind in der Tabelle 2 wiedergegeben:
In den Beispielen 9 bis 12 wird die Wirksamkeit fester Oxidationsmittel bei unterschiedlichen Temperaturen und Rührzeiten bei der Oxidation von β-Naphthylamin dargelegt. Alle verwendeten Öle wurden vor Versuchsbeginn zwecks Verdeutlichung des Oxidationseffektes mit β-Naphthylamin dotiert. Als Oxidationsmittel wird Dibenzoylperoxid verwendet. Die Versuche werden in einem 1 I-Rundkolben mit Rührer und Rückflußkühler durchgeführt. Die Ergebnisse sind in Tab. 3 wiedergegeben.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3425216A DE3425216A1 (en) | 1984-07-09 | 1984-07-09 | REMOVAL OF PRIMARY AMINES FROM PRIMARY AROMATIC OILS |
| DE3425216 | 1984-07-09 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0168068A2 EP0168068A2 (en) | 1986-01-15 |
| EP0168068A3 EP0168068A3 (en) | 1987-05-06 |
| EP0168068B1 true EP0168068B1 (en) | 1988-11-02 |
Family
ID=6240177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85200629A Expired EP0168068B1 (en) | 1984-07-09 | 1985-04-24 | Removal of primary amines from substantially aromatic oils |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0168068B1 (en) |
| DE (2) | DE3425216A1 (en) |
| DK (1) | DK164921C (en) |
| ES (1) | ES8603931A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3630789A1 (en) * | 1986-09-10 | 1987-01-29 | Al Douri Amad Dipl Ing | Process for producing oxidation bitumen by reaction with air in the presence of free radical-formers |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE30786C (en) * | Dr. C. ROTH, gerichtlich vereidigter Chemiker in Berlin N-, Strafsburgerstr. 18 | Process for the production of pure, non-resinous machine lubricating and greasing oils from petroleum or their high-boiling components | ||
| DE60833C (en) * | TH. LEES, R. LEES und W. LEES JR. in Hollinwood bei Manchester, England | Expansion device adjustable by the regulator | ||
| CH41272A (en) * | 1907-12-09 | 1908-10-01 | Attilio Fama | Process for the purification of all mineral spirits with a density of 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 |
-
1984
- 1984-07-09 DE DE3425216A patent/DE3425216A1/en not_active Withdrawn
-
1985
- 1985-04-24 EP EP85200629A patent/EP0168068B1/en not_active Expired
- 1985-04-24 DE DE8585200629T patent/DE3565995D1/en not_active Expired
- 1985-05-21 DK DK224285A patent/DK164921C/en not_active IP Right Cessation
- 1985-06-05 ES ES543955A patent/ES8603931A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DK224285D0 (en) | 1985-05-21 |
| DE3565995D1 (en) | 1988-12-08 |
| DK164921B (en) | 1992-09-07 |
| DK164921C (en) | 1993-01-25 |
| ES543955A0 (en) | 1986-01-16 |
| EP0168068A3 (en) | 1987-05-06 |
| DE3425216A1 (en) | 1986-02-06 |
| ES8603931A1 (en) | 1986-01-16 |
| EP0168068A2 (en) | 1986-01-15 |
| DK224285A (en) | 1986-01-10 |
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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 |
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