EP0078951A1 - Procédé pour préparation d'huiles blanches techniques par hydrogénation - Google Patents
Procédé pour préparation d'huiles blanches techniques par hydrogénation Download PDFInfo
- Publication number
- EP0078951A1 EP0078951A1 EP82109747A EP82109747A EP0078951A1 EP 0078951 A1 EP0078951 A1 EP 0078951A1 EP 82109747 A EP82109747 A EP 82109747A EP 82109747 A EP82109747 A EP 82109747A EP 0078951 A1 EP0078951 A1 EP 0078951A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oil
- hydrogenation
- technical white
- catalyst
- boiling
- 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.)
- Granted
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/14—White oil, eating oil
Definitions
- the present invention relates to a method for producing technical white oils.
- unrefined or raw mineral oils for the production of technical white oils are catalytically hydrogenated in one step without the usual use of noble metal catalysts.
- Technical white oils are highly refined petroleum fractions that are largely free of oxygen, nitrogen and sulfur compounds and, depending on the intended use, contain only small amounts of aromatics.
- Technical white oils are widely used as carrier oils for insecticides and herbicides and as components for printing inks for textiles or textile fibers.
- Older processes for the production of white oils are based on suitable petroleum fractions which are refined either directly or after prior partial dearomatization by solvent extraction, for example with furfural, SO 2 , phenol or with highly concentrated sulfuric acid or oleum.
- Multi-stage catalytic refining processes for the production of white oils are also known in order to avoid the sulfuric acid treatment which was customary in the past.
- the published German application 16 45 791 describes a two-stage catalytic process in which a low-aromatic petroleum fraction is hydrogenated in a first catalytic process stage on a sulfur-resistant hydrogenation catalyst and in a second hydrogenation stage on a catalyst containing noble metal.
- the object was therefore to develop a process for the catalytic refining of white oil precursors to technical white oils, in which the disadvantages described do not occur.
- the present invention is based on a process for the production of industrial white oils from petroleum fractions containing aromatics, nitrogen, oxygen and sulfur compounds with a boiling range from 200 to 580 ° C., which have optionally been subjected to solvent extraction and solvent dewaxing, by catalytic hydrogenation in Presence of a sulfurized catalyst containing nickel and molybdenum.
- the advantage of the process according to the invention is that, in addition to the light stripping oil, an additional fraction with the properties of technical white oil is obtained from the distillation of the more volatile hydrogenation constituents by separating off the parts boiling from approx. 150 ° C. when stripping in the distillation column after the hydrogenation reactor .
- Sulfurized catalysts which contain nickel and molybdenum and advantageously also phosphoric acid and which have been prepared by impregnating a support with a phosphoric acid nickel molybdate solution are used as hydrogenation catalysts.
- a sulfidic catalyst which, in the oxidic state, based on the catalyst weight, contains 3 to 6% nickel oxide, 10 to 15% molybdenum oxide and 3 to 6% o-phosphoric acid on a support consisting in particular of ⁇ -aluminum oxide.
- the carrier consists, for example, of 100 to 95% by weight ⁇ -aluminum oxide and up to 5% by weight Si0 2 .
- the preparation of the catalyst differs from the usual production methods for, for example, cobalt / molybdenum, nickel / molybdenum and nickel / tungsten-containing catalysts by the impregnation with a phosphoric acid nickel molybdate solution.
- This special catalyst containing nickel, molybdenum and phosphoric acid is expediently used under the following conditions: pressure range 140 to 160 at, preferably 150 at; Temperature range 250 to 370 ° C, preferably 300 to 350 ° C; Gas: oil ratio greater than 1.0 Nm 3 , advantageously 1.2 Nm 3 hydrogen per kg of oil; Catalyst load 0.15 to 1.0 kg of oil per liter of catalyst per hour.
- Active diluents are used to reduce the nickel-molybdenum content of the catalyst.
- “Active diluents” are to be understood as meaning large-area aluminum oxides or aluminum oxide / silicon dioxide mixtures which, because of their surface properties, are themselves catalytically active and further increase the activity of the catalyst.
- the activity of the catalyst can additionally be changed in a known manner by introducing MgO, C aO, ZnO, B 2 0 3 and TiO 2 in amounts of 1 to 10% by weight.
- Particularly suitable surface-rich aluminum oxides are obtained by precipitation of aluminum oxide hydrates from aqueous solutions containing aluminum salts.
- Suitable starting products for the production of white oils of technical quality are oils with a boiling range between 200 and 550 ° C, e.g. Gas oil fractions with a boiling range of 220 to 340 ° C, spindle oil or lubricating oil fractions. Higher boiling starting products generally require stricter refining conditions.
- the aromatic content of the raw materials is not particularly critical since the aromatics can be largely reduced by the hydrogenation. Only in particularly stored cases when the aromatic content of the raw material has considerable values, e.g. over 30%, it may be appropriate to remove some of the aromatics beforehand by extraction.
- FIG. 1 shows a diagram for the implementation of the method according to the invention.
- a hydrocarbon feed which boils in the range of 200 to 550 ° C, is led from line (1) together with fresh hydrogen from line (2) and the circulating hydrogen from line (3) into the reaction and there over a sulfur-resistant hydrogenation catalyst, the nickel and Contains molybdenum, implemented.
- the hydrocarbons are hydrogenated in (4) at 360 ° C and at 140 bar.
- the stream coming from the reactor (4) is passed through line (5) into the separation zone (6), in which the gas phase is separated from the liquid phase.
- the liquid phase is then passed through line (7) into the separation zone (8), which can be a distillation zone and there into a light stripping oil fraction which is loaded with gaseous components and which is removed through line (9) and a heavy product which Line (11) is withdrawn, separated.
- the separation zone (8) can be operated so that in addition to the heavy product with white oil quality from line (11) from line (10) as a further product only heavy stripping oil can be removed, which also has the quality of a technical white oil.
- the catalyst is prepared as follows and sulfurized before use.
- An aluminum oxide hydrate is precipitated from an Al 2 (SO 4 ) 3 solution (7.5% A12 0 3 ) with 25% NH 4 OH at a pH of 6.5 and a temperature of 85 ° C. 0.25% (NH 4 ) 2 CO 3 solution washed sulfate-free and dried at 120 ° C.
- extrudates with a diameter of 1.5 mm are produced from the aluminum oxide which has been calcined at 500.degree. 1,000 g of catalyst are sprayed with 755 g of a solution which contains the equivalent of 22.1% Mo03, 8.5% NiO and 6.8% by weight phosphoric acid.
- Mo03 sublimate is digested by heating with the calculated amount of an o-phosphoric acid solution.
- the required amount of Ni (NO 3 ) 2 .6 H 2 0 is then added to this solution, a clear solution being obtained.
- the impregnated extrusions are dried at 120 ° C. for 12 hours and then calcined at 350 ° C. for 2 hours.
- the finished catalyst contains 5% NiO, 13% Mo03 and 4% H 3 PO 4 .
- Table 1 compares the properties of the starting material with those of the raffinates.
- Hydrogenation stage can be used for the production of medical white oil.
- the process also makes it possible to adjust the viscosity and flash point of the end products by varying the process conditions.
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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19813143869 DE3143869A1 (de) | 1981-11-05 | 1981-11-05 | Verfahren zur herstellung von technischen weissoelen durch hydrierung |
DE3143869 | 1981-11-05 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0078951A1 true EP0078951A1 (fr) | 1983-05-18 |
EP0078951B1 EP0078951B1 (fr) | 1986-03-05 |
Family
ID=6145643
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82109747A Expired EP0078951B1 (fr) | 1981-11-05 | 1982-10-22 | Procédé pour préparation d'huiles blanches techniques par hydrogénation |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0078951B1 (fr) |
DE (2) | DE3143869A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5976353A (en) * | 1996-06-28 | 1999-11-02 | Exxon Research And Engineering Co | Raffinate hydroconversion process (JHT-9601) |
US6096189A (en) * | 1996-12-17 | 2000-08-01 | Exxon Research And Engineering Co. | Hydroconversion process for making lubricating oil basestocks |
US6099719A (en) * | 1996-12-17 | 2000-08-08 | Exxon Research And Engineering Company | Hydroconversion process for making lubicating oil basestocks |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1645791A1 (de) * | 1966-08-16 | 1970-05-21 | Sinclair Research Inc | Verfahren zur Herstellung eines weissen Mineraloeles |
DE2300038A1 (de) * | 1973-01-02 | 1974-07-04 | Basf Ag | Verfahren zur herstellung von technischen bzw. medizinischen weissoelen |
FR2235997A1 (fr) * | 1973-07-03 | 1975-01-31 | Shell Int Research | |
US3959122A (en) * | 1972-02-24 | 1976-05-25 | Sun Oil Company Of Pennsylvania | Making a white oil by hydrogenation with a sulfided nickel and molybdenum catalyst |
DE2813571A1 (de) * | 1977-03-30 | 1978-10-05 | Exxon France | Weissoele und verfahren zu ihrer herstellung |
-
1981
- 1981-11-05 DE DE19813143869 patent/DE3143869A1/de not_active Withdrawn
-
1982
- 1982-10-22 DE DE8282109747T patent/DE3269677D1/de not_active Expired
- 1982-10-22 EP EP82109747A patent/EP0078951B1/fr not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1645791A1 (de) * | 1966-08-16 | 1970-05-21 | Sinclair Research Inc | Verfahren zur Herstellung eines weissen Mineraloeles |
US3959122A (en) * | 1972-02-24 | 1976-05-25 | Sun Oil Company Of Pennsylvania | Making a white oil by hydrogenation with a sulfided nickel and molybdenum catalyst |
DE2300038A1 (de) * | 1973-01-02 | 1974-07-04 | Basf Ag | Verfahren zur herstellung von technischen bzw. medizinischen weissoelen |
FR2235997A1 (fr) * | 1973-07-03 | 1975-01-31 | Shell Int Research | |
DE2813571A1 (de) * | 1977-03-30 | 1978-10-05 | Exxon France | Weissoele und verfahren zu ihrer herstellung |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5976353A (en) * | 1996-06-28 | 1999-11-02 | Exxon Research And Engineering Co | Raffinate hydroconversion process (JHT-9601) |
US6096189A (en) * | 1996-12-17 | 2000-08-01 | Exxon Research And Engineering Co. | Hydroconversion process for making lubricating oil basestocks |
US6099719A (en) * | 1996-12-17 | 2000-08-08 | Exxon Research And Engineering Company | Hydroconversion process for making lubicating oil basestocks |
Also Published As
Publication number | Publication date |
---|---|
EP0078951B1 (fr) | 1986-03-05 |
DE3269677D1 (en) | 1986-04-10 |
DE3143869A1 (de) | 1983-05-11 |
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Inventor name: WIRTZ, GERHARD Inventor name: SCHORR, VICTOR, DR. Inventor name: SCHWARZMANN, MATTHIAS, DR. Inventor name: ANSTOCK, THOMAS, DR. Inventor name: GALLEI, EWALD, DR. Inventor name: DUROCHER, ALAIN, DR. |
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