EP3545054A1 - Process for producing an extender process oil - Google Patents
Process for producing an extender process oilInfo
- Publication number
- EP3545054A1 EP3545054A1 EP17804534.0A EP17804534A EP3545054A1 EP 3545054 A1 EP3545054 A1 EP 3545054A1 EP 17804534 A EP17804534 A EP 17804534A EP 3545054 A1 EP3545054 A1 EP 3545054A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- astm
- accordance
- solvent
- determined
- oil
- 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
Links
- 239000010734 process oil Substances 0.000 title claims abstract description 54
- 239000004606 Fillers/Extenders Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 67
- 230000008569 process Effects 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 52
- 239000003921 oil Substances 0.000 claims description 50
- 238000000605 extraction Methods 0.000 claims description 47
- 239000000284 extract Substances 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 43
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 238000000638 solvent extraction Methods 0.000 claims description 19
- 125000003367 polycyclic group Chemical group 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 claims description 10
- 239000005060 rubber Substances 0.000 claims description 10
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 9
- 239000002199 base oil Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000001050 lubricating effect Effects 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012296 anti-solvent Substances 0.000 claims description 5
- -1 molibdenum Chemical compound 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 229920003051 synthetic elastomer Polymers 0.000 claims description 4
- 239000005061 synthetic rubber Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- HBXWYZMULLEJSG-UHFFFAOYSA-N chromium vanadium Chemical compound [V][Cr][V][Cr] HBXWYZMULLEJSG-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- 238000005555 metalworking Methods 0.000 claims description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000004821 distillation Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000000113 differential scanning calorimetry Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229910003294 NiMo Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 201000007902 Primary cutaneous amyloidosis Diseases 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 208000014670 posterior cortical atrophy Diseases 0.000 description 5
- 238000000513 principal component analysis Methods 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000009533 lab test Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 2
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 2
- KHNYNFUTFKJLDD-UHFFFAOYSA-N Benzo[j]fluoranthene Chemical compound C1=CC(C=2C3=CC=CC=C3C=CC=22)=C3C2=CC=CC3=C1 KHNYNFUTFKJLDD-UHFFFAOYSA-N 0.000 description 2
- HAXBIWFMXWRORI-UHFFFAOYSA-N Benzo[k]fluoranthene Chemical compound C1=CC(C2=CC3=CC=CC=C3C=C22)=C3C2=CC=CC3=C1 HAXBIWFMXWRORI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- FTOVXSOBNPWTSH-UHFFFAOYSA-N benzo[b]fluoranthene Chemical compound C12=CC=CC=C1C1=CC3=CC=CC=C3C3=C1C2=CC=C3 FTOVXSOBNPWTSH-UHFFFAOYSA-N 0.000 description 2
- TXVHTIQJNYSSKO-UHFFFAOYSA-N benzo[e]pyrene Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- LHRCREOYAASXPZ-UHFFFAOYSA-N dibenz[a,h]anthracene Chemical compound C1=CC=C2C(C=C3C=CC=4C(C3=C3)=CC=CC=4)=C3C=CC2=C1 LHRCREOYAASXPZ-UHFFFAOYSA-N 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 231100001223 noncarcinogenic Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 210000003625 skull Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting 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
- 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
Definitions
- EP16382554 filed on 24.1 1 .2016.
- the present disclosure is concerned with an improved process for preparing extender process oils and to the extender process oils thus obtained.
- Distillate aromatic extracts are currently used as aromatic process oils for the manufacture of oil extended natural or synthetic rubber and also tire compounds. Nevertheless, these oils contain high levels of polycydic aromatic hydrocarbons (PAH) and polycydic aromatic compounds (PCA). The content on PCA in DAE is found in concentrations very much in excess of 3 %wt determined in accordance with the IP-346 method. Therefore, process oils of the distillate aromatic extract type have consequently been classified as "carcinogenic" according to the European legislation (EU Substance Directive 67/548/EEC). PAHs are organic compounds possessing two or more aromatic rings, of which eight types are identified as carcinogens.
- Treated Distillate Aromatic Extract is a non-carcinogenic mineral oil, used as aromatic process oils for the manufacture of oil extender natural or synthetic rubber and tire compounds.
- This environment friendly extender process oil is used as a softening additive in the process of vulcanization of natural rubber and as a component of rubber compounds.
- VOC viscosity gravity constant
- TDAEs are obtained in a process which comprises atmospheric distillation of crude oil to separate gas, naphta, kerosene and diesel fractions. The atmospheric residue is separated into a vacuum residue and one or more distillates in a vacuum distillation.
- the distillate is then separated into a raffinate and a extract (primary extract or DAE) in a extraction unit using a polar extraction solvent.
- Lubricating base oils and waxes are obtained from the raffinate.
- a second extraction of the primary extract affords the TDAE and a high-PCAs content residue (secondary extract).
- WO0071643 it is disclosed a process of preparation of a process oil having a PCAs content lower than 3 %wt. and an aniline point between 80 °C to 120 °C, the method comprising hydrotreating naphthenic distillates under specific conditions.
- Inventors have found a method for producing an extender process oil which meets various technical specifications simultaneously. Particularly, the inventors have found a method for producing an extender process oil having a kinematic viscosity at 100 °C from 16 to 30 cSt determined in accordance with ASTM D-445, an aniline point from 55 to 80 °C determined in accordance with ASTM D-61 1 , a content of polycyclic aromatics of less than 3 %wt.
- Tg minimum of -56 °C (preferably between -56°C ⁇ Tg ⁇ -47°C) determined in accordance with Differential Scanning Calorimetry (DSC), and an aromatic content higher or equal to 24 %wt. deternnined in accordance with ASTM D-2140.
- Tg value is comprised between -56°C ⁇ Tg ⁇ -47°C, more preferably between -55°C ⁇ Tg ⁇ -49°C; particularly preferred between -54°C ⁇ Tg ⁇ -50°C.
- Tg values are comprised between - 53.5°C ⁇ Tg ⁇ -50.5°C; more preferably between -53°C ⁇ Tg ⁇ -51 °C.
- gap refers to the difference between the 5% of the heavy cut and the 95% of the light cut
- the heavy cut is the cut with higher TBP (true boiling point) and the light cut is the one with lower TBP being both contiguous cuts.
- anti-solvent refers to a solvent that is mixed with the main one in order to change the mixture polarity and so, its selectivity and extraction power.
- counter-solvent refers to a solvent that is mixed with the feed and present an opposite polarity from the main solvent. Its use changes the extraction equilibrium and so, the process selectivity. In this process, the counter-solvent is a not polar component.
- a method for producing an extender process oil comprises a hydrotreating step under particular conditions of a process oil educt; vacuum fractionating the hydrotreated oil, and finally, performing a liquid-liquid extraction process with a polar extraction solvent in order to obtain an extender process oil which meets simultaneously the following technical specifications: kinematic viscosity at 100 °C from 16 to 30 cSt determined in accordance with ASTM D-445, an aniline point from 55 to 80 °C determined in accordance with ASTM D-61 1 , a content of polycyclic aromatics of less than 3 %wt determined in accordance with the IP-346 method, a Tg minimum of -56 °C (preferably between -56°C ⁇ Tg ⁇ -47°C) determined in accordance with DSC, and an aromatic content higher or equal to 24 %wt determined in accordance with ASTM D-2140.
- the present disclosure provides a process for producing an extender process oil having a kinematic viscosity at 100 °C from 16 to 30 cSt determined in accordance with ASTM D-445, an aniline point from 55 to 80 °C determined in accordance with ASTM D-61 1 , a content of polycyclic aromatics of less than 3 %wt determined in accordance with IP-346 method, a Tg minimum of -56 °C (preferably between -56°C ⁇ Tg ⁇ -47°C) determined in accordance with DSC, and an aromatic content higher or equal to 24 % wt. determined in accordance with ASTM D-2140; the process comprising:
- step b) contacting the vacuum fractionated hydrotreated oil stream obtained in step b) with a solvent or a mixture of solvents, where at least one solvent is a polar extraction solvent, in an extraction unit and performing a liquid-liquid extraction process; obtaining the extender process oil which meets
- an extender process oil obtainable by the process herein disclosed.
- the extender process oil obtainable by the process meets simultaneously all the following technical specifications: a kinematic viscosity at 100 °C from 16 to 30 cSt determined in accordance with ASTM D-445, an aniline point from 55 to 80 °C determined in accordance with ASTM D-61 1 , a content of polycyclic aromatics of less than 3 %wt determined in accordance with IP-346 method, a Tg comprised between -56°C ⁇ Tg ⁇ -47°C determined in accordance with DSC, and an aromatic content higher or equal to 24 %wt determined in accordance with ASTM D-2140.
- the extended process oil obtainable by the process of the invention shows a Tg value between -55°C ⁇ Tg ⁇ -49°C; more preferably between -54°C ⁇ Tg ⁇ -50°C; being particularly preferably Tg values comprised between -53.5°C ⁇ Tg ⁇ -50.5°C; and even more preferably between -53°C ⁇ Tg ⁇ -51 °C.
- an object of the present disclosure is the use of a extender process oil that is obtainable by the process of the present disclosure as a plasticizer or extender oil for rubbers or rubber mixtures that are based on natural and synthetic rubbers, or for thermoplastic elastomers, as a raw material for technical or medicinal white oils, as printing ink oils, as a release agent for architectural coatings, or industrial fat production, transformer oils, or special metalworking oils.
- a pneumatic tyre comprising a rubber composition, wherein the rubber composition comprises the extender process oil as described herein.
- the process of the present disclosure produces an extender process oil which meets simultaneously all the technical features above mentioned, independently of the properties of the feedstock used. Flexibility of the new process regarding fluctuation of feedstock quality is higher than current state of the art. Furthermore, the extender process oil may be obtained at yields up to 80 %wt versus up to 50 %wt yield which may be obtained in the
- any ranges given include both the lower and the upper end-points of the range. Ranges given, such as temperatures, times, and the like, should be considered approximate, unless specifically stated.
- the viscosity indicates the ability of an oil to flow. If viscosity is high, molecular weight is generally high and compatibility with the rubber is less, so more mixing time is required for the full dispersion of additives.
- the high viscosity oil needs to be heated to reduce its viscosity before being added to the rubber compound.
- Dynamic viscosity is a measure of a liquid's resistance to movement and is measured in centipoise (cP).
- the aniline point is measured according to ASTM D-61 1 and is based on a measurement of the temperature at w hich aniline dissolves in the oil.
- the aniline point is a measure of the solvency of the oil.
- Low aniline points indicate a high solvency of the oil, and also high aromaticity.
- IP-346 an analytical method essentially measuring the level of certain polyaromatic compounds through selective extraction with a solvent.
- EU European Community
- DMSO dimethyl Sulfoxide
- steps b) and c) may be modified, thus the hydrotreated oil obtained in step a) is extracted first and vacuum fractionated later.
- a feedstock comprising a process oil educt (VI) having a PCAs concentration from 3 % wt to 55 % wt, preferably from 5-52% wt, more preferably from 10-35 % wt; particularly preferred from 13-25 % wt; and a kinematic viscosity from 16 to 250 cSt, preferably from 17 to 200 cSt; is fed via line 1 to a hydrotreating unit A where it is treated in a single process oil educt (VI) having a PCAs concentration from 3 % wt to 55 % wt, preferably from 5-52% wt, more preferably from 10-35 % wt; particularly preferred from 13-25 % wt; and a kinematic viscosity from 16 to 250 cSt, preferably from 17 to 200 cSt; is fed via line 1 to a hydrotreating unit A where it is treated in a single
- Hydrotreating stage is operated within a temperature from 300 to 380 °C, a pressure from 40 to 200 bar and a liquid space velocity from 0.1 to 1 .5 h "1 , to provide a hydrotreated oil.
- the hydrotreated oil is fed via line 2 to a vacuum fractionation tower B, obtaining a heavier fraction where the 5% according to ASTM D-2887 is at a temperature from 400 to 465 °C and a gap value equal or higher than -35 °C, preferably equal or higher than -30 °C, more preferably equal or higher than -27 °C; being the gap defined as the difference between the 5% of the heavier fraction and the 95% of lights, the temperatures measured according to ASTM D-2887.
- One of the objectives of this step is to have in the heavy product a kinematic viscosity at 100 °C from 16-60 cSt. Vacuum fractionated
- hydrotreated oil thus obtained is fed via line 3 to an extraction unit C, and at least a polar extraction solvent or a mixture of solvents (being at least one of them a polar solvent) is fed via line 4 to the extraction unit C.
- a liquid-liquid extraction process is thus performed under conditions sufficient to provide an extract (VII) and an extender process oil (VIII), the extender process oil (VIII) having a viscosity at 100 °C from 16 to 30 est determined in accordance with ASTM D-445, an aniline point from 55 to 80 determined in accordance with ASTM D-61 1 , a content of polycyclic aromatics (PCA) of less than 3 % w determined in accordance with IP-346 method, a Tg minimum of -56 °C (preferably between -56°C ⁇ Tg ⁇ -47°C) determined in accordance with DSC, and an aromatic content higher or equal to 24%w determined in accordance with ASTM D-2140.
- the process oil educt having a viscosity at
- the primary extract is obtainable by solvent extraction of vacuum distillates in the lubricating base oil preparation
- the secondary extract is obtainable by solvent extraction of a primary extract with a solvent or a mixture of solvents, where at least one solvent is a polar extraction solvent, the secondary extract.
- This process oil educt which is used as feed to the hydrotreating step have a content in polycyclic aromatics from 3% wt to 55% wt, determined in accordance with IP-346 method.
- a primary extract (II) (Distillate Aromatic Extract) obtainable by solvent extraction of vacuum distillates (III) in the lubricating base oil (I) preparation, is fed via line 10 to an extraction unit D, wherein at least a polar extraction solvent is fed via line 1 1 to the extraction unit D to produce a Treated Distillate Aromatic Extract (IV) and a secondary extract (V).
- the secondary extract is obtainable by solvent extraction of a primary extract with a solvent or a mixture of solvents, where at least one solvent is a polar extraction solvent.
- Process oil educt (VI) which is fed via line 1 to the hydrotreating unit A, may comprise at least one of the secondary extract or the primary extract.
- extraction unit D may be the same as extraction unit C.
- primary extract (II) is fed via line 7 to an extraction unit C, and extract obtained (VII) is fed to the hydrotreating unit A via line 8.
- primaray extract (II) is obtainable by solvent extraction of vacuum distillates (III) in the lubricating base oil (I) preparation; vacuum distillates (III) are obtainable by vacuum distillation in a vacuum distillation unit F of the atmospheric residue resulting of the atmospheric distillation of crude oil (X) in an atmospheric distillation unit G.
- the process oil educt which is used as feed to the hydrotreating unit A comprises a mixture of a secondary extract and a primary extract in a ratio from 25 %wt to 75 %wt up to 75 %wt to 25 %wt.
- the process oil educt comprises a mixture of a secondary extract and a primary extract in a ratio from 40 %wt to 60 %wt up to 85 %wt to 15 %wt; more preferably, 50 %wt to 50 %wt up to 95 %wt to 5 %wt.
- the process oil educt comprises at least 95 %wt of secondary extract; more preferably the process oil educt comprises at least 99 %wt of secondary extract.
- the extract (VII) obtained in step c) may be recirculated to the
- step a) hydrotreatment step a) to maximize the yield of TDAE. Therefore, referring to Figure 2, at least a portion of extract (VII) obtained in step c) may be recirculated via line 8 and combined with the process oil educt (VI) which is fed via line 1 to the hydrotreating unit A.
- the extract (VII) obtained in step c) is recirculated to the hydrotreatment step a).
- At least a portion of a primary extract (II) obtainable by solvent extraction of vacuum distillates (III) in the lubricating base oil (I) preparation may be mixed with the vacuum fractionated hydrotreated oil stream obtained in step b) previously to the liquid-liquid extraction step c).
- a primary extract (II) is passed through line 7 and combined with the vacuum fractionated hydrotreated oil stream obtained in the vacuum distillation unit B, and the mixture is fed via line 3 to the extraction unit C.
- the hydrotreating step is carried out at temperatures from 320 to 370 °C, preferably from 330 to 360 °C.
- the pressure of the hydrotreating step it is preferably from 40 to 200 bar, preferably from 40 to 160 bar; more preferably from 45 to 75 bar, being particularly preferred from 50 to 70 bar. This pressure refers to the total pressure at the reactor exit.
- the hydrotreatment step is preferably carried out at a liquid space velocity from 0.1 to 1 .5 h "1 , preferably from 0.2 to 1 .2 h “1 , more preferably from 0.25 to 0.8 h yet more preferably from 0.35 to 0.75 h "1 .
- the hydrotreating step is carried out at temperatures from 320 to 370 °C, a pressure from 45 to 75 bar, and a space velocity from 0.25-0.8 h "1 . In a another particular embodiment, hydrotreating step is carried out at
- temperatures comprised of from 330 to 360 °C; pressure comprised of from 50 to 70 bar; and space velocity comprised of from 0.35 to 0.75 h "1 .
- hydrogen sulfide and ammonia formed during the hydrotreating may be removed by any known method.
- the hydrotreated material may be passed to a stripping vessel and an inert stream may be used to strip the hydrogen sulfide and ammonia from the hydrotreated material by using techniques well-known in the art.
- the vacuum fractionating step b) is carried out in a vacuum fractionation tower obtaining a heavier fraction where the 5% according to ASTM D-2887 is at a temperature from 400 to 465 °C, preferably from 410 to 455 °C, more preferably from 413 to 445 °C; the gap value being equal or higher than -35 °C, preferably equal or higher than -30
- the kinematic viscosity at 100 °C of the vacuum fractionated hydrotreated oil stream thus obtained is from 16 to 60 cSt, preferably from 17 to 50 cSt.
- the polar solvent of the liquid-liquid extraction step c) is selected from furfural, N-methylpyrrolidone,
- the extraction may be conducted in a counter current type extraction unit.
- an anti-solvent may optionally be added to the flow of the extraction solvent.
- An example of anti-solvent is water. The presence of an anti-solvent allows to increase selectivity.
- a counter-solvent may be added to increase the extraction performance.
- counter-solvents suitable for the process are hydrocarbons with a boiling point of less than 160 °C, preferably less than 140 °C.
- Particularly preferred examples of counter- solvent are C6 and n-heptane.
- the vacuum fractionated hydrotreated oil stream obtained in step b) is extracted with an extraction solvent; the ratio of extraction solvent to extraction unit feed stream is from 0.5 to 4.5, preferably from 0.7 to 4.0, more preferably from 0.9 to 3.7, being particularly preferred from 1 .0 to 3.5.
- the hydrotreating catalyst used in hydrotreating step is important but not critical. It may be used different hydrogenation commercial catalysts , and the skilled person may choose among a huge variety of catalysts.
- the hydrotreating step a) is carried out in presence of a hydrotreating catalyst based on a metal sulfide catalyst where metal could be nickel, cobalt, molibdenum, chromium, vanadium, tungsten, phophorous, nickel-cobalt, nickel-cobalt-molybdenum, nickel- molybdenum, cobalt-molybdenum, nickel-tungsten, chromium-vanadium catalyst, or a mixture thereof.
- metal could be nickel, cobalt, molibdenum, chromium, vanadium, tungsten, phophorous, nickel-cobalt, nickel-cobalt-molybdenum, nickel- molybdenum, cobalt-molybdenum, nickel-tungsten, chromium-vanadium catalyst, or a mixture thereof.
- nickel-molybdenum sulfide catalysts promoted or not with phosphorous.
- the process comprises a) hydrotreating a process oil educt that has a content of polycyclic aromatics from 3%wt to 55 %wt, determined in accordance with IP346, and a viscosity from 16 to 250 cSt; the hydrotreating is carried out at a temperature from 320 to 370 °C, a pressure from 45-75 bar, and a space velocity from 0.25-0.8 h "1 ; to provide a hydrotreated oil;
- step c) contacting the vacuum fractionated hydrotreated oil obtained in step b) with furfural in an extraction unit and performing a liquid-liquid extraction process, obtaining an extender process oil having a viscosity at 100 °C from 16 to 30 cSt determined in accordance with ASTM D-445, an aniline point from 55 to 80 °C determined in accordance with ASTM D-61 1 , a content of polycyclic aromatics of less than 3 %wt determined in accordance with IP-346 method, a Tg minimum of -56 °C (preferably between -56°C ⁇ Tg ⁇ -47°C), and an aromatic content higher or equal to 24 %wt determined in accordance with ASTM D-2140.
- an extender process oil having a viscosity at 100 °C from 16 to 30 cSt determined in accordance with ASTM D-445, an aniline point from 55 to 80 °C determined in accordance with ASTM D-61 1 , a content of polycyclic aromatics of less
- the extender process oil obtainable by the process of the present disclosure has a viscosity at 100 °C from 16 to 24 cSt determined in accordance with ASTM D-445, an aniline point from 65 to 75 °C determined in accordance with ASTM D-61 1 , a content of polycyclic aromatics of less than 3 %wt determined in accordance with IP- 346 method, a Tg minimum of -53 °C determined in accordance with DSC, and an aromatic content higher or equal to 26 %wt determined in accordance with ASTM D-2140.
- the extender process oil obtainable by the process of the present disclosure has a viscosity at 100 °C from 16 to 24 cSt determined in accordance with ASTM D-445, an aniline point from 65 to 75 °C determined in accordance with ASTM D-61 1 , a content of polycyclic aromatics of less than 3 %wt determined in accordance with IP- 346 method, a Tg value comprised between -54 °C ⁇ Tg ⁇ -50°C determined in accordance with DSC, and an aromatic content higher or equal to 26 %wt determined in accordance with ASTM D-2140.
- Feedstock 1 Feedstock 2
- Feedstocks 1 and 2 were treated in accordance with the method of the present disclosure in order to obtain a TDAE which meet the technical specifications and with a high yield.
- Feedstock 1 was passed through a hydrotreating stage under the conditions outlined below:
- Catalyst was sulphided according a conventional sulphiding protocol.
- Sulphiding protocol include following stages:
- the product properties were:
- Feedstock 2 was passed through a hydrotreating stage under the conditions outlined below:
- Hydrogenated product was vacuum fractionated in a column with 15 theoretical stages, wherein the heavier fraction has a 5% according to ASTM D-2887 of 413 °C.
- Feedstock 2 was passed through a hydrotreating stage under the conditions outlined below:
- Hydrogenated product was vacuum fractionated in a column with 1 theoretical stage, obtaining two fractions with different distillation curves wherein the heavier fraction has a 5% according to ASTM D-2887 of 461 °C.
- Feedstock 2 was passed through a hydrotreating stage under the conditions outlined below:
- Hydrogenated product was vacuum fractionated in a column with 15 theoretical stages, wherein the heavier fraction has a 5% according to ASTM D-2887 of 413 °C.
- Example 5 following example, another different hydrocarbon stream was used.
- Feedstock 3 was treated in accordance with the method of the present disclosure in order to obtain a TDAE which meet the technical specifications and with a high yield.
- Feedstock 3 was passed through a hydrotreating stage under the conditions outlined below:
- Hydrogenated product was vacuum fractionated in a column with 15 theoretical stages, wherein the heavier fraction has a 5% according to ASTM D-2887 of 436 °C.
- the yield obtained was 27.8 %w related to the feed.
- Example 6 Feedstock 3 was treated in accordance with the method of the present disclosure in order to obtain a TDAE which meet the technical specifications and with a high yield.
- Feedstock 3 was passed through a hydrotreating stage under the conditions outlined below:
- Hydrogenated product was vacuum fractionated in a column with 15 theoretical stages, wherein the heavier fraction has a 5% according to ASTM D-2887 of 436 °C.
- the yield obtained was 27.8 %w related to the feed.
- Fractionated weight product (436°C for the 5% volume according to ASTM D- 2887) was extracted in the laboratory. In this case, the extraction process was carried out in 4 stages and a counter-solvent (nexane) has been used a part from the polar solvent (furfural).
- the conditions of the extraction process are:
- TDAE yield 43 %wt related to the fractionated weight product. TDAE thus obtained showed the following properties:
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Abstract
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PCT/EP2017/080229 WO2018096042A1 (en) | 2016-11-24 | 2017-11-23 | Process for producing an extender process oil |
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