EP2557143A1 - Method for manufacturing high naphthenic process oils through hydration - Google Patents

Method for manufacturing high naphthenic process oils through hydration Download PDF

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Publication number
EP2557143A1
EP2557143A1 EP11006606A EP11006606A EP2557143A1 EP 2557143 A1 EP2557143 A1 EP 2557143A1 EP 11006606 A EP11006606 A EP 11006606A EP 11006606 A EP11006606 A EP 11006606A EP 2557143 A1 EP2557143 A1 EP 2557143A1
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Prior art keywords
weight
oils
oil
naphthenic
content
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EP11006606A
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German (de)
French (fr)
Inventor
Nils Hansen
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Klaus Dahleke GmbH and Co KG
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Klaus Dahleke GmbH and Co KG
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Priority to EP11006606A priority Critical patent/EP2557143A1/en
Priority to PCT/EP2012/003426 priority patent/WO2013020711A1/en
Publication of EP2557143A1 publication Critical patent/EP2557143A1/en
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0409—Extraction of unsaturated hydrocarbons
    • C10G67/0436—The hydrotreatment being an aromatic saturation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106—Naphthenic fractions
    • C10M2203/1065—Naphthenic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/065—Saturated Compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/067—Unsaturated Compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/36—Release agents or mold release agents

Definitions

  • the invention relates to a process for the preparation of naphthenic process oils with a very high content of naphthenic hydrocarbons and a content of polycyclic aromatics of less than 3 wt .-% according to IP 346 and the use of these process oils for adhesives and for the production of fat.
  • Process oils are generally understood to mean hydrocarbon mixtures which boil in the lubricating oil range, but are usually not used as and also not in conjunction with lubricating oils.
  • the process oils are extracted from petroleum refining.
  • the crude oil is subjected to atmospheric distillation to remove any products which boil under normal pressure to about 350 ° C.
  • the residue after distilling off gives a mixture of bitumen, asphaltenes, waxes and heavy oils.
  • the heavy oils are processed into various products, in addition to lubricating oils also to the process oils, which are preferably used as a plasticizer.
  • the process oils are differentiated according to their content of aromatic carbon atoms (C A ), naphthenic carbon atoms (C N ) and paraffinic carbon atoms (C P ) measured according to ASTM D 2140.
  • Aromatic process oils sometimes have undesirably large amounts of polycyclic aromatics (PCA).
  • PCA polycyclic aromatics
  • Polycyclic aromatics are understood as meaning compounds having more than 2 condensed aromatic nuclei. Since the polycyclic aromatics, such as benzo [a] pyrene, are suspected of being carcinogenic, process oils with high PCA content have been used only to a limited extent in the past.
  • the naphthenic oils are characterized by a high degree of cycloalkanes, but may have a higher proportion of aromatic hydrocarbon compounds than paraffinic oils. Accordingly, naphthenic oils have better release properties compared to rubber than paraffinic oils and can be processed better. Naphthenic process oils for medical products usually have no or only a small proportion of aromatics.
  • One way to obtain process oils with a low content of polycyclic aromatics is to re-extract a primary extract obtained by extracting a mineral oil-derived lube distillate. Such a method is in the EP 0 417 980 B1 described.
  • the process oil obtained, eg TDAE has a content of polycyclic aromatics which is less than 3% by weight according to IP 346.
  • Disadvantage of this method is that as a secondary extract, ie as "lower phase", which is tapped from the second extraction column, a product having a high concentration of polycyclic aromatic compounds of up to 15 or even over 20 wt .-% is obtained.
  • the process should allow for environmentally friendly use of the DUE, secondary extracts and extraction residues from the extraction of other process oils.
  • the process oils obtained should be of high quality so as to meet the standard requirements of common process oils, e.g. as part of fat production, i. the production of greases or as part of adhesives.
  • the object is achieved according to the invention by a process for producing naphthenic process oils which have a carbon distribution C A to C N to C p of from 0 to 30% by weight to 20 to 80% by weight to 20 to 55% by weight, preferably has a C N of> 65% by weight, particularly preferably between 65 and 80% by weight, determined according to ASTM D 2140, and a content of polycyclic aromatics (PCA) of less than 3% by weight according to IP 346 .
  • C A to C N to C p of from 0 to 30% by weight to 20 to 80% by weight to 20 to 55% by weight, preferably has a C N of> 65% by weight, particularly preferably between 65 and 80% by weight, determined according to ASTM D 2140, and a content of polycyclic aromatics (PCA) of less than 3% by weight according to IP 346 .
  • the invention further relates to the use of a process oil according to the invention as a plasticizer or extender oil for rubbers or rubber mixtures, based on natural and synthetic rubbers, or thermoplastic elastomers, as a raw material for technical or medical white oils, as printing ink oils, as a release agent in building protection, for Industriefetther ein Transformer oils or special metalworking oils, as well as the use as an ingredient in the production of fat and as an ingredient, such as plasticizer or extender oil, of adhesives.
  • a process oil according to the invention as a plasticizer or extender oil for rubbers or rubber mixtures, based on natural and synthetic rubbers, or thermoplastic elastomers, as a raw material for technical or medical white oils, as printing ink oils, as a release agent in building protection, for Industriefetther ein Transformer oils or special metalworking oils, as well as the use as an ingredient in the production of fat and as an ingredient, such as plasticizer or extender oil, of adhesives.
  • a process oil is passed with hydrogen under the conditions mentioned above a metal catalyst.
  • transition metal catalysts are preferably used on a support.
  • Preferred metal catalysts are cobalt, nickel, molybdenum, chromium, vanadium, nickel-molybdenum catalysts, chromium-vanadium catalysts, metal oxides, metal sulfides or combinations thereof.
  • carrier substances the usual in the art substances such. Alumina or zeolites proven. In principle, conventional hydrogenation catalysts can be used for the hydrogenation.
  • the hydrogenation is preferably carried out at temperatures of from 250 to 400.degree. C., more preferably from 300 to 375.degree.
  • the reactor is preferably operated at a pressure of 80 to 200 bar.
  • the hydrogenation is preferably carried out with a mean residence time of 6 to 60 minutes.
  • process oils are obtained which have a proportion of naphthenic hydrocarbon atoms of C N 30 to 65% by weight, preferably between 65 and 80% by weight, particularly preferably between 65 and 75% by weight, determined in accordance with ASTM D 2140 , exhibit.
  • the process according to the invention can be used to obtain process oils whose C N content is> 65 or> 70% by weight according to ASTM D 2140.
  • ASTM D 2140 According to prevailing opinion and according to ASTM D 2140, a maximum content of 45 in process oils Wt .-% naphthenic hydrocarbon atoms possible.
  • the process oils obtained also have a content of less than 3 wt .-% polycyclic aromatic (PCA), determined according to IP 346, on.
  • PCA polycyclic aromatic
  • Starting materials used for the hydrogenation are process oil components which have a content of polycyclic aromatics of> 3% by weight, determined to IP 346, preferably a content of polycyclic aromatics of from 10 to 30% by weight.
  • suitable processing components are, for example, the secondary extracts resulting from the production of TDAE or MES. Such a method is from the EP 0 417 980 B1 known.
  • the secondary extract obtained there can be used as starting material for the process according to the invention. By selecting the reactant and optionally mixing different starting extracts, certain hydrocarbon distributions of the products can be achieved in a targeted manner.
  • DAE stillate Aromatic Extract
  • a conventional TDAE crude oil is usually subjected to atmospheric distillation to separate off gas, naphtha and kerosene fractions.
  • the atmospheric residue is separated in a vacuum distillation into a vacuum residue and one or more distillates.
  • the distillate is then separated in an extraction with a suitable solvent into a raffinate and an extract (primary extract), the DAE.
  • a process oil can be obtained which has a content of polycyclic aromatics ⁇ 3 wt .-%.
  • another extract the secondary extract, is obtained.
  • This secondary extract may be used alone or in admixture, e.g. be used with other extracts or process oils, as starting material for the process according to the invention and is hydrogenated in a further process step accordingly.
  • DAE stillate Aromatic Extract
  • the naphthenic process oils can be obtained in high yields by the process according to the invention. For example, in the hydrogenation of DAE, high yields of up to 100% could be obtained. If the appropriate procedure is followed, no environmentally harmful process oils subject to labeling are required more. Rather, naphthenic, non-marking process oils can be obtained by the process according to the invention from the hazardous and environmentally hazardous DAE.
  • process oil other substances can also be used as process oil, provided that the sum of C A and C N in the process oil is higher than the sum of the desired C N content plus the residual content of aromatics and / or if it has a polycyclic aromatic content of> 3 wt .-%, measured according to IP 346, have.
  • process oil components such extracts, mineral oil fractions or process oils are used whose sum is C A plus C N 55.
  • a starting material mixture of DAE and secondary extract is used. It has been found that the glass transition point T g of the process oils can be adjusted by selecting the educt mixture. Surprisingly, process oils prepared according to the invention from a DAE / secondary extract mixture have different Tg depending on the starting mixture for the same C A content. The Tg can be varied between -52 ° C - + 45 ° C. Preference is given to using mixtures of 75% to 25% to 25% to 75% secondary extract to DAE. By choosing a process oil with a certain glass transition temperature, it is possible to control the dynamic properties of the later rubber product.
  • the process according to the invention thus makes it possible to convert a process oil, which has a high content of polycyclic aromatic compounds and thus can no longer be marketed according to the new EU directive and is in any case questionable from a health and environmental point of view, to a high-quality product.
  • the starting materials can be used in a different way and no longer have to be added to the fuel oil. By avoiding heating oil, therefore, the CO 2 emission is reduced.
  • the resulting naphthenic process oil despite the low content of PCA, depending on the reaction conditions still a high content of aromatic hydrocarbon atoms C A , preferably between 0 and 30 wt .-%, determined according to ASTM D 2140, is.
  • the sum of C A and C N between 50 and 70.
  • a high content of aromatic hydrocarbon compounds in the process oil improves the wet skid resistance of a car tire and cornering on dry roads
  • a high C N content of the process oil improves the rolling resistance of a car tire.
  • the process oil produced according to the invention is used as a plasticizer or extender oil for rubbers and rubber mixtures based on natural and synthetic rubbers or thermoplastic elastomers. It may also be used as a raw material for medical or engineering white oils, as printing ink oil, e.g. for colored and black in newspaper printing, transformer oil, release agents in building protection or special metalworking oil can be used, also in the Industriefetther too it is used.
  • the process oil produced according to the invention is particularly preferably used as plasticizer in tires or technical rubber goods, as white oil or as a metalworking oil, e.g. when pulling copper wire, used.
  • the plasticizers continue to be used for adhesives or as a component of greases in the production of grease.
  • the process oil of the invention is preferably incorporated in the resin of the adhesive.
  • the process oils can be used in particular to give hard adhesives a certain elasticity or, in the case of brittle products, also to give them improved elasticity.
  • FIG. 1 shows the second extraction step of conventional extraction for the preparation of TDAE or MES.
  • An extraction column 1 is the primary extract 2 supplied.
  • the primary extract is a mixture of various hydrocarbon compounds, including aromatic hydrocarbon compounds and polycyclic aromatics.
  • solvent 3 is added to the extraction column via line 3.
  • the raffinate 4, such as a TDAE or MES is removed.
  • a secondary extract 5 is removed from the bottom of the column, which contains a high proportion of polycyclic aromatic compounds.
  • FIG. 2 the sequence of the method according to the invention can be seen.
  • a process oil 5 with a high proportion of polycyclic aromatics, as for example from the in FIG. 1 is obtained, is fed to a hydrogenation reactor 6 and hydrogenated there with hydrogen.
  • the hydrogenation reactor 6 is taken from a naphthenic process oil 7 and a stripping oil 8.
  • the naphthenic process oil 7 has a PCA content of less than 3 wt .-%.
  • the process can also be carried out in such a way that end products with a relatively high residual aromatics content, whose PCA content according to IP 346 can be> 3% by weight, are obtained.
  • These relatively highly aromatic fractions can be added via line 9 to the primary extract 2 or alternatively added to the extraction column 1 and are suitable as a feedstock for the production of labeling-free process oils both alone and in admixture with primary extract.
  • FIG. 3 shows the recovery of a naphthenic process oil 7 by direct hydrogenation of a primary extract 2 in a hydrogenation reactor 6.
  • a stripping oil 8 accumulates.
  • a crude oil 10 is subjected to atmospheric distillation 11.
  • the resulting atmospheric residue 12 is further treated exclusively in a vacuum distillation 13.
  • a distillate 14 and a vacuum residue 15 are obtained.
  • the distillate 14 is separated in an extraction column 16 into the primary extract 2 and a raffinate 17.
  • a secondary extract with a content of polycyclic aromatics of 45% by weight according to IP 346 and C N content of 22% by weight and a C P content of 23% by weight was added at a temperature of 340 ° C and a pressure of 200 bar with hydrogen in a hydrogenation reactor.
  • the reactor contained a nickel-molybdenum catalyst (Axens HR548 from Evonik).
  • the hydrogenation was carried out with an average residence time of 25 minutes. 94% naphthenic process oil and 6% stripping oil were obtained.
  • the obtained naphthenic process oil had the properties given in Table 1.
  • Table 1 Properties of the obtained naphthenic process oil from Example 1 Properties of the process oil according to example Benz [a] pyrene [ppm] ⁇ 1 Sum of PAH [ppm] acc. RL 2005/69 EC ⁇ 10 Viscosity at 40 ° C [mm 2 / s] 612 Viscosity at 100 ° C [mm 2 / s] 39 C A according to ASTM D 2140 [% by weight] 3 C N according to ASTM D 2140 [% by weight] 57 C P according to ASTM D 2140 [% by weight] 40 Aniline point [° C] 93
  • Table 2 shows a comparison of the various production conditions and data of three products according to the invention (hydrogenation products) compared to a TDAE.
  • the hydrogenation products were prepared analogously to the example described above.
  • the mixture of primary extract to secondary extract was 50:50.
  • Table 2 Production conditions and properties of the process oils produced according to the invention and of a comparison process oil Determination method Vivatec ® 500 (TDAE) Hydrogenation products from primary extract (DAE) Hydrogenation products from primary secondary extract mixture Hydrogenation products from secondary extract catalyst Axens HR 548 A1024 Axens HR 548 A1024 Axens HR 548 A1024 Reactor temperature [° C] 310 330 350 Pressure [bar] 200 200 200 Residence time [min.] 18 18 16 DMSO extract [% ] IP 346 2.6 2.8 2.9 2.8 Benzo (a) -pyrene [ppm] GC-MS 0.4 0.3 0.1 0.5 Sum of PAH [ppm] GC-MS 5.7 2.5 3.1 4.2 Viscosity 100 ° C [mm 2 / s] DIN 51562 T.

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  • 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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Producing naphthenic process oils (7) with an aromatic carbon atom (C a) to naphthenic carbon atom (C n) to paraffinic carbon atom (C p) of 0-30 wt.% to 20-80 wt.% to 20-55 wt.%, preferably C nof 65-80 wt.% according to ASTM D 2140, and less than 3 wt.% of polycyclic aromatic compound, according to IP 346, comprises hydrogenation of a process oil educt (5) containing at least 3 wt.% of polycyclic aromatic compounds according to IP 346 and = 23 wt.% of naphthenic hydrocarbon atoms using a metal catalyst with hydrogen at 200-400[deg] C and 80-250 bar.

Description

Gegenstand der Erfindung ist ein Verfahren zur Herstellung von naphthenischen Prozessölen mit einem sehr hohen Anteil an naphthenischen Kohlenwasserstoffen und einem Gehalt an polycyclischen Aromaten von weniger als 3 Gew.-% nach IP 346 sowie die Verwendung dieser Prozessöle für Klebstoffe und für die Fettproduktion.The invention relates to a process for the preparation of naphthenic process oils with a very high content of naphthenic hydrocarbons and a content of polycyclic aromatics of less than 3 wt .-% according to IP 346 and the use of these process oils for adhesives and for the production of fat.

Unter Prozessölen werden allgemein Kohlenwasserstoffgemische verstanden, die im Schmierölbereich sieden, jedoch üblicherweise nicht als und auch nicht in Verbindung mit Schmierölen eingesetzt werden. Die Prozessöle werden bei der Raffination von Erdöl gewonnen. Das Rohöl wird einer atmosphärischen Destillation unterzogen, wobei alle Produkte abgetrennt werden, welche unter Normaldruck bis etwa 350°C sieden. Als Rückstand nach dem Abdestillieren erhält man ein Gemisch aus Bitumen, Asphaltenen, Wachsen und Schwerölen. Die Schweröle werden zu verschiedenen Produkten weiterverarbeitet, neben Schmierölen auch zu den Prozessölen, die vorzugsweise als Weichmacher verwendet werden.Process oils are generally understood to mean hydrocarbon mixtures which boil in the lubricating oil range, but are usually not used as and also not in conjunction with lubricating oils. The process oils are extracted from petroleum refining. The crude oil is subjected to atmospheric distillation to remove any products which boil under normal pressure to about 350 ° C. The residue after distilling off gives a mixture of bitumen, asphaltenes, waxes and heavy oils. The heavy oils are processed into various products, in addition to lubricating oils also to the process oils, which are preferably used as a plasticizer.

Die Prozessöle werden dabei je nach ihrem Gehalt an aromatischen Kohlenstoffatomen (CA), naphthenischen Kohlenstoffatomen (CN) und paraffinischen Kohlenstoffatomen (CP), gemessen nach ASTM D 2140, unterschieden. Aromatische Prozessöle weisen teilweise unerwünscht große Mengen von polycyclischen Aromaten (PCA) auf. Unter polycyclischen Aromaten werden Verbindungen mit mehr als 2 kondensierten Aromatenkernen verstanden. Da die polycyclischen Aromaten, wie dass Benzo[a]pyren, in Verdacht stehen, krebserregend zu sein, sind bereits in der Vergangenheit Prozessöle mit hohem PCA-Gehalt nur noch eingeschränkt verwendet worden.The process oils are differentiated according to their content of aromatic carbon atoms (C A ), naphthenic carbon atoms (C N ) and paraffinic carbon atoms (C P ) measured according to ASTM D 2140. Aromatic process oils sometimes have undesirably large amounts of polycyclic aromatics (PCA). Polycyclic aromatics are understood as meaning compounds having more than 2 condensed aromatic nuclei. Since the polycyclic aromatics, such as benzo [a] pyrene, are suspected of being carcinogenic, process oils with high PCA content have been used only to a limited extent in the past.

Gemäß der europäischen Richtlinie 769/76, ergänzt durch die Richtlinie 69/2005 vom 16. November 2005, ist nun eine Verwendung von Prozessölen nur noch zulässig, sofern diese einen Gehalt an polycyclischen Aromaten von weniger als 3 Gew.-%, gemessen nach der Methode IP 346, aufweisen.In accordance with European Directive 769/76, supplemented by Directive 69/2005 of 16 November 2005, the use of process oils is now only permitted if it has a polycyclic aromatic content of less than 3% by weight as measured by Method IP 346, exhibit.

Neben den Prozessölen mit hohen aromatischen Gehalten gibt es eine weitere Gruppe der häufig angewendeten Prozessöle, die naphthenischen Öle. Die naphthenischen Öle zeichnen sich durch einen hohen Grad an Cycloalkanen aus, können jedoch einen höheren Anteil an aromatischen Kohlenwasserstoffverbindungen als paraffinische Öle aufweisen. Entsprechend zeigen naphthenische Öle bessere Löseeigenschaften gegenüber Kautschuk als paraffinische Öle und lassen sich besser verarbeiten. Naphthenische Prozessöle für medizinische Produkte weisen üblicherweise keinen oder nur einen geringen Anteil Aromaten auf.In addition to the process oils with high aromatic contents, there is another group of commonly used process oils, the naphthenic oils. The naphthenic oils are characterized by a high degree of cycloalkanes, but may have a higher proportion of aromatic hydrocarbon compounds than paraffinic oils. Accordingly, naphthenic oils have better release properties compared to rubber than paraffinic oils and can be processed better. Naphthenic process oils for medical products usually have no or only a small proportion of aromatics.

Die entsprechenden Prozessöle, die noch einen Gehalt an polycyclischen Aromaten von mehr als 3 Gew.-% nach IP 346 aufweisen, müssen künftig entweder als Sondermüll entsorgt werden oder können allenfalls dem Heizöl zugeschlagen werden, wobei die Verbrennung von dem Nachteil begleitet ist, dass bei Verbrennung des Heizöls höhere Schwefelemissionen entstehen. Auf Grund der geänderten Gesetzgebung dürfen daher solche Produkte zur Verringerung des Schwefelausstoßes künftig nicht mehr dem Heizöl zugeschlagen werden. Eine Verbrennung ist allenfalls noch in Anlagen mit speziellen Filtern zulässig. Zudem fallen auch bei der Produktion von Prozessölen mit einem niedrigen Gehalt an polycyclischen Aromaten, wie beispielsweise den Prozessölen TDAE und MES, Extraktionsrückstände mit einem hohen Gehalt an PCA an. Auch diese müssen künftig entsorgt werden bzw. dem Heizöl zugeschlagen werden.The corresponding process oils, which still have a content of polycyclic aromatics of more than 3 wt .-% according to IP 346, must either be disposed of as hazardous waste or may be added to the fuel oil, the combustion is accompanied by the disadvantage that at Combustion of fuel oil, higher sulfur emissions arise. Due to the amended legislation, such products may no longer be added to fuel oil to reduce sulfur emissions. Combustion is still permitted in systems with special filters. In addition, in the production of process oils with a low content of polycyclic aromatics, such as the process oils TDAE and MES, extraction residues with a high content of PCA are also incurred. These must also be disposed of in the future or be added to the fuel oil.

Eine Möglichkeit, Prozessöle mit einem niedrigen Gehalt an polycyclischen Aromaten zu gewinnen, ist es, einen Primär-Extrakt, der durch Extraktion eines aus Mineralöl stammenden Schmieröldestillates gewonnen wird, erneut zu extrahieren. Ein solches Verfahren ist in der EP 0 417 980 B1 beschrieben. Das dabei erhaltene Prozessöl, z.B. TDAE, weist einen Gehalt von polycyclischen Aromaten auf, der geringer als 3 Gew.-% nach IP 346 ist. Nachteil dieses Verfahrens ist jedoch, dass als Sekundärextrakt, d.h. als "untere Phase", die aus der zweiten Extraktionskolonne abgegriffen wird, ein Produkt mit einer hohen Konzentration an polycyclischen Aromaten von bis zu 15 oder sogar über 20 Gew.-% erhalten wird.One way to obtain process oils with a low content of polycyclic aromatics is to re-extract a primary extract obtained by extracting a mineral oil-derived lube distillate. Such a method is in the EP 0 417 980 B1 described. The process oil obtained, eg TDAE, has a content of polycyclic aromatics which is less than 3% by weight according to IP 346. Disadvantage of this method, however, is that as a secondary extract, ie as "lower phase", which is tapped from the second extraction column, a product having a high concentration of polycyclic aromatic compounds of up to 15 or even over 20 wt .-% is obtained.

Aufgabe der vorliegenden Erfindung ist es daher, ein Verfahren bereitzustellen, das eine Aufarbeitung der Prozessrückstände mit hohem PCA-Anteil erlaubt, wobei die erhaltenen Prozessöle kennzeichnungsfrei sein sollen, d.h. einen PCA-Gehalt von geringer als 3 Gew.-%, bestimmt nach IP 346, aufweisen sollen. Das Verfahren soll eine umweltfreundliche Nutzung , des kennzeichnungspflichtigen DAE, der Sekundärextrakte und der Extraktionsrückstände aus der Gewinnung anderer Prozessöle erlauben. Zudem sollen die erhaltenen Prozessöle qualitativ so hochwertig sein, dass sie den Standardanforderungen der gängigen Prozessöle, z.B. als Bestandteil der Fettproduktion, d.h. der Herstellung von Schmierfetten oder als Bestandteil von Klebstoffen genügen.It is therefore an object of the present invention to provide a process which allows processing of the process residues with a high proportion of PCA, whereby the process oils obtained should be free of labeling, ie. a PCA content of less than 3 wt .-%, determined according to IP 346, should have. The process should allow for environmentally friendly use of the DUE, secondary extracts and extraction residues from the extraction of other process oils. In addition, the process oils obtained should be of high quality so as to meet the standard requirements of common process oils, e.g. as part of fat production, i. the production of greases or as part of adhesives.

Die Aufgabe wird erfindungsgemäß gelöst durch ein Verfahren zur Herstellung von naphthenischen Prozessölen, die eine Kohlenstoffverteilung CA zu CN zu CP von 0 bis 30 Gew.-% zu 20 bis 80 Gew.-% zu 20 bis 55 Gew.-%, bevorzugt einem CN von > 65 Gew.-%, besonders bevorzugt zwischen 65 und 80 Gew.-%, bestimmt nach ASTM D 2140, und einen Gehalt an polycyclischen Aromaten (PCA) von weniger als 3 Gew.-% nach IP 346 aufweisen,
dadurch gekennzeichnet, dass
ein Prozessöledukt, das einen Gehalt an polycyclischen Aromaten von mindestens 3 Gew.-%, bestimmt nach IP 346, und einen Anteil von naphthenischen Kohlenwasserstoffatomen CN ≤ 25 Gew.-% aufweist,
unter Verwendung eines Metallkatalysators mit Wasserstoff hydriert wird bei Temperaturen von 200 bis 400°C und Drücken von 80 bis 250 bar.The object is achieved according to the invention by a process for producing naphthenic process oils which have a carbon distribution C A to C N to C p of from 0 to 30% by weight to 20 to 80% by weight to 20 to 55% by weight, preferably has a C N of> 65% by weight, particularly preferably between 65 and 80% by weight, determined according to ASTM D 2140, and a content of polycyclic aromatics (PCA) of less than 3% by weight according to IP 346 .
characterized in that
a process oil having a polycyclic aromatic content of at least 3% by weight, determined according to IP 346, and a content of naphthenic hydrocarbon atoms C N ≦ 25% by weight,
hydrogenated using a metal catalyst with hydrogen at temperatures of 200 to 400 ° C and pressures of 80 to 250 bar.

Gegenstand der Erfindung ist weiterhin die Verwendung eines erfindungsgemäß hergestellten Prozessöls als Weichmacher oder Extenderöl für Kautschuke oder Kautschukmischungen, basierend auf natürlichen und synthetischen Kautschuken, oder für thermoplastische Elastomere, als Rohstoff für technische oder medizinische Weißöle, als Druckfarbenöle, als Trennmittel im Bautenschutz, zur Industriefettherstellung Transformatorenöle oder spezielle Metallbearbeitungsöle, sowie die Verwendung als Bestandteil bei der Fettproduktion und als Bestandteil, z.B. Weichmacher oder Extenderöl, von Klebstoffen.The invention further relates to the use of a process oil according to the invention as a plasticizer or extender oil for rubbers or rubber mixtures, based on natural and synthetic rubbers, or thermoplastic elastomers, as a raw material for technical or medical white oils, as printing ink oils, as a release agent in building protection, for Industriefettherstellung Transformer oils or special metalworking oils, as well as the use as an ingredient in the production of fat and as an ingredient, such as plasticizer or extender oil, of adhesives.

Weitere Ausführungsformen sind Gegenstand der Unteransprüche oder nachfolgend beschrieben.Further embodiments are the subject matter of the subclaims or described below.

Zur Durchführung des erfindungsgemäßen Verfahrens wird ein Prozessöledukt mit Wasserstoff unter den genannten Bedingungen über einen Metallkatalysator geleitet. Als Katalysator werden bevorzugt Übergangsmetallkatalysatoren auf einem Träger verwendet. Bevorzugte Metallkatalysatoren sind Kobalt-, Nickel-, Molybdän-, Chrom-, Vanadium-, Nickel-Molybdän-Katalysatoren, Chrom-Vanadium-Katalysatoren, Metalloxide, Metallsulfide oder Kombinationen daraus. Als Trägersubstanzen haben sich die in der Technik üblichen Substanzen wie z.B. Aluminiumoxid oder Zeolithe bewährt. Grundsätzlich können übliche Hydrierkatalysatoren für die Hydrierung eingesetzt werden.To carry out the process according to the invention, a process oil is passed with hydrogen under the conditions mentioned above a metal catalyst. As the catalyst, transition metal catalysts are preferably used on a support. Preferred metal catalysts are cobalt, nickel, molybdenum, chromium, vanadium, nickel-molybdenum catalysts, chromium-vanadium catalysts, metal oxides, metal sulfides or combinations thereof. As carrier substances, the usual in the art substances such. Alumina or zeolites proven. In principle, conventional hydrogenation catalysts can be used for the hydrogenation.

Die Hydrierung wird bevorzugt bei Temperaturen von 250 bis 400 °C, besonders bevorzugt 300 bis 375 °C, durchgeführt. Der Reaktor wird bevorzugt mit einem Druck von 80 bis 200 bar betrieben. Die Hydrierung wird bevorzugt mit einer mittleren Verweilzeit von 6 bis 60 min durchgeführt.The hydrogenation is preferably carried out at temperatures of from 250 to 400.degree. C., more preferably from 300 to 375.degree. The reactor is preferably operated at a pressure of 80 to 200 bar. The hydrogenation is preferably carried out with a mean residence time of 6 to 60 minutes.

Bei Durchführung des erfindungsgemäßen Verfahrens werden Prozessöle erhalten, die einen Anteil an naphthenischen Kohlenwasserstoffatomen von CN 30 bis 65 Gew.-%, bevorzugt zwischen 65 und 80 Gew%, besonders bevorzugt zwischen 65 und 75 Gew.-%, bestimmt nach ASTM D 2140, aufweisen. Überraschenderweise lassen sich mit dem erfindungsgemäßen Verfahren Prozessöle gewinnen, deren CN-Gehalt > 65 bzw. > 70 Gew.-% ist nach ASTM D 2140. Nach der bisherigen herrschenden Meinung und entsprechend der ASTM D 2140 ist in Prozessölen maximal ein Gehalt von 45 Gew.-% naphthenischen Kohlenwasserstoffatomen möglich. Die erhaltenen Prozessöle weisen zudem einen Gehalt von weniger als 3 Gew.-% polycyclischen Aromaten (PCA), bestimmt nach IP 346, auf.When carrying out the process according to the invention, process oils are obtained which have a proportion of naphthenic hydrocarbon atoms of C N 30 to 65% by weight, preferably between 65 and 80% by weight, particularly preferably between 65 and 75% by weight, determined in accordance with ASTM D 2140 , exhibit. Surprisingly, the process according to the invention can be used to obtain process oils whose C N content is> 65 or> 70% by weight according to ASTM D 2140. According to prevailing opinion and according to ASTM D 2140, a maximum content of 45 in process oils Wt .-% naphthenic hydrocarbon atoms possible. The process oils obtained also have a content of less than 3 wt .-% polycyclic aromatic (PCA), determined according to IP 346, on.

Als Edukt für die Hydrierung werden Prozessöledukte eingesetzt, die einen Gehalt an polycyclischen Aromaten von > 3 Gew.-%, bestimmt nach IP 346, aufweisen, bevorzugt einen Gehalt an polycyclischen Aromaten von 10 bis 30 Gew.-%. Solche geeigneten Prozessöledukte sind beispielsweise die bei der TDAE- oder MES-Herstellung anfallenden Sekundärextrakte. Ein solches Verfahren ist aus der EP 0 417 980 B1 bekannt. Der dort erhaltene Sekundärextrakt kann als Einsatzstoff für das erfindungsgemäße Verfahren genutzt werden. Durch Wahl des Eduktes und ggf. Mischung verschiedener Ausgangsextrakte können bestimmte Kohlenwasserstoffverteilungen der Produkte gezielt erreicht werden. Ebenso ist DAE (Destillate Aromatic Extract) ein geeignetes Edukt für das erfindungsgemäße Verfahren.Starting materials used for the hydrogenation are process oil components which have a content of polycyclic aromatics of> 3% by weight, determined to IP 346, preferably a content of polycyclic aromatics of from 10 to 30% by weight. Such suitable processing components are, for example, the secondary extracts resulting from the production of TDAE or MES. Such a method is from the EP 0 417 980 B1 known. The secondary extract obtained there can be used as starting material for the process according to the invention. By selecting the reactant and optionally mixing different starting extracts, certain hydrocarbon distributions of the products can be achieved in a targeted manner. Likewise, DAE (Distillate Aromatic Extract) is a suitable educt for the process according to the invention.

Zur Gewinnung eines herkömmlichen TDAEs wird üblicherweise Rohöl einer atmosphärischen Destillation zur Abtrennung von Gas, Naphtha und Kerosinfraktionen unterzogen. Der atmosphärische Rückstand wird in einer Vakuumdestillation in einen Vakuumrückstand und ein oder mehrere Destillate aufgetrennt. Das Destillat wird anschließend in einer Extraktion mit einem geeigneten Lösungsmittel in ein Raffinat und einen Extrakt (Primärextrakt), das DAE, aufgetrennt. Aus dem Raffinat werden Grundöl und Wachse erhalten. Eine zweite Extraktion des Primärextrakts liefert das TDAE, wobei bei geeigneter Wahl der Reaktionsbedingungen ein Prozessöl erhalten werden kann, das einen Gehalt an polycyclischen Aromaten ≤ 3 Gew.-% aufweist. Außerdem fällt bei der zweiten Extraktion ein weiterer Extrakt, der Sekundärextrakt an. Dieser Sekundärextrakt kann alleine oder in Mischung, z.B. mit anderen Extrakten oder Prozessölen, als Edukt für das erfindungsgemäße Verfahren genutzt werden und wird entsprechend in einem weiteren Prozessschritt hydriert.To obtain a conventional TDAE, crude oil is usually subjected to atmospheric distillation to separate off gas, naphtha and kerosene fractions. The atmospheric residue is separated in a vacuum distillation into a vacuum residue and one or more distillates. The distillate is then separated in an extraction with a suitable solvent into a raffinate and an extract (primary extract), the DAE. From the raffinate base oil and waxes are obtained. A second extraction of the primary extract provides the TDAE, whereby with a suitable choice of the reaction conditions, a process oil can be obtained which has a content of polycyclic aromatics ≤ 3 wt .-%. In addition, during the second extraction, another extract, the secondary extract, is obtained. This secondary extract may be used alone or in admixture, e.g. be used with other extracts or process oils, as starting material for the process according to the invention and is hydrogenated in a further process step accordingly.

Als Edukt für das erfindungsgemäße Herstellungsverfahren Herstellung von Prozessölen ist auch DAE (Destillate Aromatic Extract) geeignet. Bei DAE handelt es sich um hocharomatische Prozessöle. Beispiele für DAE sind die bei der Klaus Dahleke KG erhältlichen ProdukteAs starting material for the production process according to the invention production of process oils also DAE (Distillate Aromatic Extract) is suitable. DAE are highly aromatic process oils. Examples of DAE are the products available from Klaus Dahleke KG

Tudalen®65 (CA = 40 Gew.-%, CN = 25 Gew.-%, CP = 35 Gew.-%; PCA nach IP346 > 15 Gew.-%)
Tudalen®81 (CA = 43 Gew.-%, CN = 24 Gew.-%, CP = 33 Gew.-%; PCA nach IP346 > 15 Gew.-%)TUDALEN ® 65 (C A = 40 wt .-%, C N = 25 wt .-%, C P = 35 wt .-%; PCA by IP346> 15 wt .-%)
TUDALEN ® 81 (C A = 43 wt .-%, C N = 24 wt .-%, C P = 33 wt .-%; PCA by IP346> 15 wt .-%)

Die naphthenischen Prozessöle lassen sich durch das erfindungsgemäße Verfahren in hohen Ausbeuten erhalten. Beispielsweise konnte bei der Hydrierung von DAEhohe Ausbeuten von bis zu 100 % erhalten werden. Es fallen bei entsprechender Verfahrensführung keine kennzeichnungspflichtigen, umweltschädlichen Prozessöle mehr an. Vielmehr können über das erfindungsgemäße Verfahren aus dem kennzeichnungspflichtigen und umwelttechnisch bedenklichen DAE naphthenische, kennzeichnungsfreien Prozessöle erhalten werden.The naphthenic process oils can be obtained in high yields by the process according to the invention. For example, in the hydrogenation of DAE, high yields of up to 100% could be obtained. If the appropriate procedure is followed, no environmentally harmful process oils subject to labeling are required more. Rather, naphthenic, non-marking process oils can be obtained by the process according to the invention from the hazardous and environmentally hazardous DAE.

Erfindungsgemäß können ebenso andere Substanzen als Prozessöledukt eingesetzt werden, sofern die Summe CA und CN in dem Prozessöledukt höher als die Summe des angestrebten CN-Gehalts plus dem Restgehalt an Aromaten ist und/oder diese einen Gehalt an polycyclischen Aromaten von > 3 Gew.-%, gemessen nach IP 346, aufweisen. Beispielsweise werden als Prozessöledukte solche Extrakte, Mineralölfraktionen oder Prozessöle eingesetzt, deren Summe CA plus CN 55 beträgt.According to the invention, other substances can also be used as process oil, provided that the sum of C A and C N in the process oil is higher than the sum of the desired C N content plus the residual content of aromatics and / or if it has a polycyclic aromatic content of> 3 wt .-%, measured according to IP 346, have. For example, as process oil components such extracts, mineral oil fractions or process oils are used whose sum is C A plus C N 55.

In einer Ausführungsform des Verfahrens wird ein Eduktgemisch aus DAE und Sekundärextrakt eingesetzt. Es hat sich gezeigt, dass durch Wahl des Eduktgemisch der Glasübergangspunkt Tg der Prozessöle eingestellt werden kann. Überraschenderweise weisen erfindungsgemäß aus einen DAE/Sekundärextraktgemisch hergestellte Prozeßöle, bei gleichem CA-Gehalt unterschiedliche Tg abhängig vom Ausgangsgemisch auf. Der Tg lässt sich dabei z.B. zwischen -52°C - +45°C varieren. Bevorzugt werden Mischungen von 75 % zu 25 % bis 25 % zu 75 % Sekundärextrakt zu DAE eingesetzt. Durch die Wahl eines Prozessöls mit einer bestimmten Glasübergangstemperatur ist eine Steuerung der dynamischen Eigenschaften des späteren Kautschukprodukts möglich.In one embodiment of the method, a starting material mixture of DAE and secondary extract is used. It has been found that the glass transition point T g of the process oils can be adjusted by selecting the educt mixture. Surprisingly, process oils prepared according to the invention from a DAE / secondary extract mixture have different Tg depending on the starting mixture for the same C A content. The Tg can be varied between -52 ° C - + 45 ° C. Preference is given to using mixtures of 75% to 25% to 25% to 75% secondary extract to DAE. By choosing a process oil with a certain glass transition temperature, it is possible to control the dynamic properties of the later rubber product.

Das erfindungsgemäße Verfahren erlaubt es somit, ein Prozessöledukt, das einen hohen Gehalt an polycyclischen Aromaten hat und somit gemäß der neuen EU-Richtlinie nicht mehr vertrieben werden darf sowie ohnehin aus gesundheitlicher und umweltpolitischer Sicht bedenklich ist, zu einem hochwertigen Produkt umzuwandeln. Zu dem lassen sich die Ausgangsstoffe so einer anderen Verwendung zuführen und müssen nicht mehr dem Heizöl zu gegeben werden. Durch die Vermeidung von Heizöl wird daher auch der CO2-Ausstoß reduziert.The process according to the invention thus makes it possible to convert a process oil, which has a high content of polycyclic aromatic compounds and thus can no longer be marketed according to the new EU directive and is in any case questionable from a health and environmental point of view, to a high-quality product. In addition, the starting materials can be used in a different way and no longer have to be added to the fuel oil. By avoiding heating oil, therefore, the CO 2 emission is reduced.

Überraschenderweise zeigt dabei das erhaltene naphthenische Prozessöl trotz des geringen Gehaltes an PCA je nach Reaktionsbedingungen noch einen hohen Gehalt an aromatischen Kohlenwasserstoffatomen CA, der bevorzugt zwischen 0 und 30 Gew.-%, bestimmt nach ASTM D 2140, liegt. Bevorzugt liegt die Summe aus CA und CN zwischen 50 und 70. Ein hoher Gehalt an aromatischen Kohlenwasserstoffverbindungen im Prozessöl verbessert die Nassrutschfestigkeit eines Autoreifens und das Kurvenfahrverhalten auch auf trockener Straße, ein hoher CN-Gehalt des Prozessöls verbessert den Rollwiderstand eines Autoreifens.Surprisingly, the resulting naphthenic process oil, despite the low content of PCA, depending on the reaction conditions still a high content of aromatic hydrocarbon atoms C A , preferably between 0 and 30 wt .-%, determined according to ASTM D 2140, is. Preferably, the sum of C A and C N between 50 and 70. A high content of aromatic hydrocarbon compounds in the process oil improves the wet skid resistance of a car tire and cornering on dry roads, a high C N content of the process oil improves the rolling resistance of a car tire.

Das erfindungsgemäß hergestellte Prozessöl wird als Weichmacher oder Extenderöl für Kautschuke und Kautschukmischungen, basierend auf natürlichen und synthetischen Kautschuken, oder thermoplastische Elastomere eingesetzt. Ebenso kann es als Rohstoff für medizinische oder technische Weißöle, als Druckfarbenöl, z.B. für Bunt- und Schwarzfarben beim Zeitungsdruck, Transformatorenöl, Trennmittel im Bautenschutz oder spezielles Metallbearbeitungsöl verwendet werden, auch bei der Industriefettherstellung findet es Verwendung. Besonders bevorzugt wird das erfindungsgemäß hergestellte Prozessöl als Weichmacher in Reifen oder technischen Gummiwaren, als Weißöl oder als Metallbearbeitungsöl, z.B. beim Ziehen von Kupferdraht, eingesetzt. Die Weichmacher werden weiterhin für Klebstoffe oder als Bestandteil für Schmierfette bei der Fettproduktion eingesetzt.The process oil produced according to the invention is used as a plasticizer or extender oil for rubbers and rubber mixtures based on natural and synthetic rubbers or thermoplastic elastomers. It may also be used as a raw material for medical or engineering white oils, as printing ink oil, e.g. for colored and black in newspaper printing, transformer oil, release agents in building protection or special metalworking oil can be used, also in the Industriefettherstellung it is used. The process oil produced according to the invention is particularly preferably used as plasticizer in tires or technical rubber goods, as white oil or as a metalworking oil, e.g. when pulling copper wire, used. The plasticizers continue to be used for adhesives or as a component of greases in the production of grease.

Bei der Verwendung in Klebstoffen wird das erfindungsgemäße Prozessöl bevorzugt in das Harz des Klebstoffs eingebracht. Die Prozessöle können insbesondere eingesetzt werden, um harten Klebstoffen eine gewisse Elastizität zu geben bzw. bei spröden Produkten, diesen ebenfalls eine verbesserte Elastizität zu geben.When used in adhesives, the process oil of the invention is preferably incorporated in the resin of the adhesive. The process oils can be used in particular to give hard adhesives a certain elasticity or, in the case of brittle products, also to give them improved elasticity.

Das erfindungsgemäße Verfahren wird anhand der Figuren beispielhaft erläutert. Es zeigt:

Figur 1:
Ein Fließbild des aus dem Stand der Technik bekannten Extraktionsverfahrens zur Herstellung von TDAE und MES.
Figur 2:
Ein Fließbild einer Ausführungsform des erfindungsgemäßen Verfahrens.
Figur 3:
Ein Fließbild einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens.
The method according to the invention will be explained by way of example with reference to the figures. It shows:
FIG. 1:
A flow sheet of the extraction process known from the prior art for the preparation of TDAE and MES.
FIG. 2:
A flow diagram of an embodiment of the method according to the invention.
FIG. 3:
A flow diagram of another embodiment of the method according to the invention.

Figur 1 zeigt den zweiten Extraktionsschritt der herkömmlichen Extraktion zur Herstellung von TDAE oder MES. Einer Extraktionskolonne 1 wird dabei der Primär-Extrakt 2 zugeführt. Der Primär-Extrakt ist eine Mischung verschiedener Kohlenwasserstoffverbindungen, darunter aromatische Kohlenwasserstoffverbindungen und polycyclische Aromaten. Gleichzeitig wird über die Leitung 3 Lösungsmittel in die Extraktionskolonne gegeben. Am Kopf der Kolonne wird das Raffinat 4, z.B. ein TDAE oder MES entnommen. Gleichzeitig wird dem Kolonnensumpf ein Sekundärextrakt 5 entnommen, der einen hohen Anteil polycyclischer Aromaten enthält. FIG. 1 shows the second extraction step of conventional extraction for the preparation of TDAE or MES. An extraction column 1 is the primary extract 2 supplied. The primary extract is a mixture of various hydrocarbon compounds, including aromatic hydrocarbon compounds and polycyclic aromatics. At the same time, solvent 3 is added to the extraction column via line 3. At the top of the column, the raffinate 4, such as a TDAE or MES is removed. At the same time a secondary extract 5 is removed from the bottom of the column, which contains a high proportion of polycyclic aromatic compounds.

In Figur 2 ist der Ablauf des erfindungsgemäßen Verfahrens zu erkennen. Ein Prozessöl 5 mit einem hohen Anteil polycyclischer Aromaten, wie es beispielsweise aus dem in Figur 1 gezeigten Verfahren erhalten wird, wird einem Hydrierungsreaktor 6 zugeführt und dort mit Wasserstoff hydriert. Dem Hydrierungsreaktor 6 werden ein naphthenisches Prozessöl 7 und ein Stripöls 8 entnommen. Das naphthenische Prozessöl 7 hat einen PCA-Gehalt von unter 3 Gew.-%. In einer weniger bevorzugten Ausführungsform kann das Verfahren auch so durchgeführt werden, dass Endprodukte mit einem relativ hohen Restgehalt an Aromaten, deren PCA-Gehalt gemäß IP 346 > 3 Gew.-% sein kann, erhalten werden. Diese relativ hocharomatischen Fraktionen können über Leitung 9 dem Primärextrakt 2 zugegeben oder alternativ in die Extraktionskolonne 1 gegeben werden und sind als Feedstock für die Herstellung kennzeichnungsfreier Prozessöle sowohl alleine als auch im Gemisch mit Primärextrakt geeignet.In FIG. 2 the sequence of the method according to the invention can be seen. A process oil 5 with a high proportion of polycyclic aromatics, as for example from the in FIG. 1 is obtained, is fed to a hydrogenation reactor 6 and hydrogenated there with hydrogen. The hydrogenation reactor 6 is taken from a naphthenic process oil 7 and a stripping oil 8. The naphthenic process oil 7 has a PCA content of less than 3 wt .-%. In a less preferred embodiment, the process can also be carried out in such a way that end products with a relatively high residual aromatics content, whose PCA content according to IP 346 can be> 3% by weight, are obtained. These relatively highly aromatic fractions can be added via line 9 to the primary extract 2 or alternatively added to the extraction column 1 and are suitable as a feedstock for the production of labeling-free process oils both alone and in admixture with primary extract.

Figur 3 zeigt die Gewinnung von einem naphthenischen Prozessöl 7 durch direkte Hydrierung eines Primärextrakts 2 in einem Hydrierreaktor 6. Neben dem naphthenischen Prozessöl 7 fällt ein Strippöl 8 an. Ein Rohöl 10 wird einer atmosphärischen Destillation 11 unterzogen. Der dabei erhaltene atmosphärische Rückstand 12 wird ausschließlich in einer Vakuumdestillation 13 weiterbehandelt. Dabei werden ein Destillat 14 und ein Vakuumrückstand 15 erhalten. Das Destillat 14 wird in einer Extraktionskolonne 16 in den Primärextrakt 2 und ein Raffinat 17 aufgetrennt. FIG. 3 shows the recovery of a naphthenic process oil 7 by direct hydrogenation of a primary extract 2 in a hydrogenation reactor 6. In addition to the naphthenic process oil 7 a stripping oil 8 accumulates. A crude oil 10 is subjected to atmospheric distillation 11. The resulting atmospheric residue 12 is further treated exclusively in a vacuum distillation 13. In this case, a distillate 14 and a vacuum residue 15 are obtained. The distillate 14 is separated in an extraction column 16 into the primary extract 2 and a raffinate 17.

Beispiele:Examples: Beispiel 1example 1

Ein Sekundärextrakt mit einem Gehalt an polycyclischen Aromaten von 45 Gew.% nach IP 346 und CN-Gehalt von 22 Gew.-% und einem CP-Gehalt von 23 Gew.-% wurde bei einer Temperatur von 340°C und einem Druck von 200 bar mit Wasserstoff in einen Hydrierreaktor gegeben. Der Reaktor enthielt einen Nickel-Molybdän Katalysator (Axens HR548 der Evonik). Die Hydrierung wurde durchgeführt bei einer mittleren Verweilzeit von 25 min. Es wurden 94 % naphthenisches Prozessöl und 6 % Stripöl erhalten.A secondary extract with a content of polycyclic aromatics of 45% by weight according to IP 346 and C N content of 22% by weight and a C P content of 23% by weight was added at a temperature of 340 ° C and a pressure of 200 bar with hydrogen in a hydrogenation reactor. The reactor contained a nickel-molybdenum catalyst (Axens HR548 from Evonik). The hydrogenation was carried out with an average residence time of 25 minutes. 94% naphthenic process oil and 6% stripping oil were obtained.

Das erhaltene naphthenische Prozessöl wies die in Tabelle 1 angegebenen Eigenschaften auf. Tabelle 1: Eigenschaften des erhaltenen naphtenischen Prozessöls aus Beispiel 1 Eigenschaften des Prozessöls gemäß Beispiel Benz[a]pyren [ppm] < 1 Summe PAH [ppm] gem. RL 2005/69 EC <10 Viskosität bei 40 °C [mm2/s] 612 Viskosität bei 100 °C [mm2/s] 39 CA nach ASTM D 2140 [Gew.-%] 3 CN nach ASTM D 2140[Gew.-%] 57 CP nach ASTM D 2140[Gew.-%] 40 Anilinpunkt [°C] 93 The obtained naphthenic process oil had the properties given in Table 1. Table 1: Properties of the obtained naphthenic process oil from Example 1 Properties of the process oil according to example Benz [a] pyrene [ppm] <1 Sum of PAH [ppm] acc. RL 2005/69 EC <10 Viscosity at 40 ° C [mm 2 / s] 612 Viscosity at 100 ° C [mm 2 / s] 39 C A according to ASTM D 2140 [% by weight] 3 C N according to ASTM D 2140 [% by weight] 57 C P according to ASTM D 2140 [% by weight] 40 Aniline point [° C] 93

Beispiel 2Example 2

Es wurden zu dem die Eigenschaften verschiedner Produkte, die über das erfindungsgemäße Verfahren erhalten mit denen eines herkömmlichen Prozessöls TDAE verglichen. Tabelle 2 zeigt eine Gegenüberstellung der verschiedenen Herstellungsbedingungen und Daten von drei erfindungsgemäß hergestellten Produkten (Hydrierprodukten) im Vergleich zu einem TDAE. Die Hydrierprodukte wurden analog zum vorbeschriebenen Beispiel hergestellt. Die Mischung aus Primärextrakt zu Sekundarextrakt betrug dabei 50 : 50. Tabelle 2: Herstellungsbedingungen und Eigenschaften der erfindungsgemäß hergestellten Prozessöle und eines Vergleichsprozessöl Bestimmungs-methode Vivatec® 500 (TDAE) Hydrierprodukte aus Primärex-trakt (DAE) Hydrierprodukte aus Primär-Sekundärextrakt-Gemisch Hydrierprodukte aus Sekundärextrakt Katalysator Axens HR 548 A1024 Axens HR 548 A1024 Axens HR 548 A1024 Reaktor-temperatur [°C] 310 330 350 Druck [bar] 200 200 200 Verweilzeit [min.] 18 18 16 DMSO-Extrakt [%] IP 346 2,6 2,8 2,9 2,8 Benzo-(a)-pyren [ppm] GC-MS 0,4 0,3 0,1 0,5 Summe PAH [ppm] GC-MS 5,7 2,5 3,1 4,2 Viskosität 100 °C [mm2/s] DIN 51562 T. 1 21,1 19,1 12,6 20,8 Schwefel [%] DIN EN ISO 14596 1,03 0,15 0,12 0,10 CA [%] DIN 51378 25 24 25 24 CN [%] DIN 51378 30 33 42 48 CP [%] DIN 51378 45 44 33 28 AP [°C] DIN ISO 2977 70 70 64 61 The properties of various products obtained by the process according to the invention were compared with those of a conventional process oil TDAE. Table 2 shows a comparison of the various production conditions and data of three products according to the invention (hydrogenation products) compared to a TDAE. The hydrogenation products were prepared analogously to the example described above. The mixture of primary extract to secondary extract was 50:50. Table 2: Production conditions and properties of the process oils produced according to the invention and of a comparison process oil Determination method Vivatec ® 500 (TDAE) Hydrogenation products from primary extract (DAE) Hydrogenation products from primary secondary extract mixture Hydrogenation products from secondary extract catalyst Axens HR 548 A1024 Axens HR 548 A1024 Axens HR 548 A1024 Reactor temperature [° C] 310 330 350 Pressure [bar] 200 200 200 Residence time [min.] 18 18 16 DMSO extract [% ] IP 346 2.6 2.8 2.9 2.8 Benzo (a) -pyrene [ppm] GC-MS 0.4 0.3 0.1 0.5 Sum of PAH [ppm] GC-MS 5.7 2.5 3.1 4.2 Viscosity 100 ° C [mm 2 / s] DIN 51562 T. 1 21.1 19.1 12.6 20.8 Sulfur [%] DIN EN ISO 14596 1.03 0.15 0.12 0.10 CA [%] DIN 51378 25 24 25 24 CN [%] DIN 51378 30 33 42 48 CP [%] DIN 51378 45 44 33 28 AP [° C] DIN ISO 2977 70 70 64 61

Es zeigt sich, dass durch Hydrierung der genannten Rohstoffe Prozessöle hergestellt werden, die Werte aufweisen, die zu einem TDAE durchaus vergleichbare Werte haben. Dabei ist zu beobachten, dass mit Zunahme des NAP-Gehaltes der Rollwiderstand (Tangens Delta @ 60 °C) besser wird, mit Abnahme des NAP-Gehalts Abrieb und Nassrutschfestigkeit (Tangens Delta @ 0 °C). Dieses versetzt den Anwender, nicht nur bei Reifen, in die Lage, selektiv diese Schlüsseleigenschaft anpassen zu können. Eine solche Anpassung ist bisher bei den herkömmlichen Prozessölen nicht möglich gewesen.It turns out that hydrogenation of the raw materials mentioned produces process oils which have values which are quite comparable to a TDAE. It can be observed that as the NAP content increases, the rolling resistance (tangent delta @ 60 ° C.) improves, with a decrease in the NAP content of abrasion and wet skid resistance (tangent delta @ 0 ° C.). This enables the user, not only in the case of tires, to be able to selectively adapt this key property. Such an adaptation has hitherto not been possible with the conventional process oils.

Claims (11)

Verfahren zur Herstellung von naphthenischen Prozessölen, die eine Kohlenstoffverteilung CA zu CN zu CP von 0 bis 30 Gew.-% zu 20 bis 80 Gew.-% zu 20 bis 55 Gew.-%, bevorzugt einen CN von 65 bis 80 Gew.% bestimmt nach ASTM D 2140, und einen Gehalt an polycyclischen Aromaten (PCA) von weniger als 3 Gew.-% nach IP 346 aufweisen,
dadurch gekennzeichnet, dass
ein Prozessöledukt, das einen Gehalt an polycyclischen Aromaten von mindestens 3 Gew.-%, bestimmt nach IP 346, und einen Anteil von naphthenischen Kohlenwasserstoffatomen CN ≤ 25 Gew.-% aufweist,
unter Verwendung eines Metallkatalysators mit Wasserstoff hydriert wird bei Temperaturen von 200 bis 400°C und Drücken von 80 bis 250 bar.Process for the preparation of naphthenic process oils which has a carbon distribution C A to C N to C p from 0 to 30% by weight to 20 to 80% by weight to 20 to 55% by weight, preferably a C N of 65 to 80% by weight, determined in accordance with ASTM D 2140, and having a polycyclic aromatic (PCA) content of less than 3% by weight according to IP 346,
characterized in that
a process oil having a polycyclic aromatic content of at least 3% by weight, determined according to IP 346, and a content of naphthenic hydrocarbon atoms C N ≦ 25% by weight,
hydrogenated using a metal catalyst with hydrogen at temperatures of 200 to 400 ° C and pressures of 80 to 250 bar. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die Hydrierung bei Temperaturen von 250 bis 400 °C, bevorzugt 300 bis 375°C durchgeführt wird.A method according to claim 1, characterized in that the hydrogenation is carried out at temperatures of 250 to 400 ° C, preferably 300 to 375 ° C. Verfahren gemäß einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass der Metallkatalysator basiert auf einem Nickel-, Kobalt-, Molybdän-, Chrom-, Vanadium-, Nickel-Molybdän, Chrom-Vanadium-Katalysator, einem Metalloxid, einem Metallsulfid oder einer Mischung daraus.Method according to one of claims 1 or 2, characterized in that the metal catalyst is based on a nickel, cobalt, molybdenum, chromium, vanadium, nickel-molybdenum, chromium-vanadium catalyst, a metal oxide, a metal sulfide or a Mix of it. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das hergestellte naphthenische Prozessöl einen Anteil von naphthenischen Kohlenstoffatomen CN von 65 Gew.-% bis 75 Gew.-% aufweist.Method according to one of the preceding claims, characterized in that the naphthenic process oil produced has a content of naphthenic carbon atoms C N of 65 wt .-% to 75 wt .-%. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die mittlere Verweilzeit 6 bis 60 min beträgt.Process according to any one of the preceding claims, characterized in that the average residence time is 6 to 60 minutes. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das eingesetzte Prozessöledukt ein Sekundärextrakt aus der TDAE- oder MES-Herstellung ist.Method according to one of the preceding claims, characterized in that the Prozessöledukt used is a secondary extract from the TDAE or MES production. Verfahren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das eingesetzte Prozessölprodukt ein DAE ist.Method according to one of claims 1 to 5, characterized in that the process oil product used is a DAE. Verfahren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das eingesetzte Prozessöledukt eine Mischung von und DAE ist, bevorzugt eine Mischung von 75 Gew.-% zu 25 Gew.-% bis 25 Gew.-% zu 75 Gew.-% Sekundärextrakt zu DAE.A process according to any one of claims 1 to 5, characterized in that the process oil used is a mixture of and DAE, preferably a mixture of 75% by weight to 25% by weight to 25% by weight to 75% by weight. Secondary extract to DAE. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Anilinpunkt des naphthenischen Prozessöls zwischen 30 und 115°C, bestimmt nach DIN ISO 2977, liegt.Method according to one of the preceding claims, characterized in that the aniline point of the naphthenic process oil is between 30 and 115 ° C, determined according to DIN ISO 2977. Verwendung eines Prozessöls, hergestellt nach einem der vorhergehenden
Ansprüche, als Weichmacher oder Extenderöl für Kautschuke oder Kautschukmischungen, basierend auf natürlichen oder synthetischen Kautschuken, oder für thermoplastische Elastomere, zur Industriefettherstellung, als Rohstoff für technische oder medizinische Weißöle, Druckfarbenöle, Trennmittel im Bautenschutz, Transformatorenöle oder spezielle Metallbearbeitungsöle.Use of a process oil prepared according to one of the preceding
Claims, as a plasticizer or extender oil for rubbers or rubber mixtures, based on natural or synthetic rubbers, or for thermoplastic elastomers, Industriefettherstellung, as a raw material for technical or medical white oils, printing ink oils, release agents in building protection, transformer oils or special metalworking oils. Verwendung eines Prozessöls, hergestellt nach einem der Ansprüche 1 - 9, als Weichmacher oder Extenderöl für Klebstoffe, Bestandteil von Klebstoffen oder Bestandteil bei der Fettprodzuktion.Use of a process oil prepared according to any one of claims 1 to 9, as a plasticizer or extender oil for adhesives, a component of adhesives or an ingredient in fat production.
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EP2357219A1 (en) * 2010-02-17 2011-08-17 Klaus Dahleke KG Method for manufacturing naphthenic process oils through hydrogenation

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EP0214717A1 (en) * 1985-06-21 1987-03-18 Mobil Oil Corporation Hydrocracking process using zeolite beta
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WO1992014779A1 (en) * 1991-02-21 1992-09-03 Exxon Research And Engineering Company Rubber processing oil and rubber products containing it
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EP2357219A1 (en) * 2010-02-17 2011-08-17 Klaus Dahleke KG Method for manufacturing naphthenic process oils through hydrogenation

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