Patent Grant
11332679
This invention relates to rubber process oils and their use.
Process oils are obtained in the refining of petroleum, and are used as plasticizers or extender oils in the manufacture of tires and other rubber products. Process oils may be classified based on their aromatic carbon content (CA), naphthenic carbon content (CN) and paraffinic carbon content (CP), as measured for example according to ASTM D2140. Distillate Aromatic Extract (DAE) process oils contain considerable (e.g., about 35 to 50%) CA content, and have been used as process oils for truck tire tread compounds and other demanding rubber applications. However DAEs also contain benzopyrene and other polycyclic aromatic hydrocarbons (PAH compounds, also known as polycyclic aromatics or PCA) that may be classified as carcinogenic, mutagenic or toxic to reproduction. For example, European Council Directive 69/2005/EEC issued Nov. 16, 2005 prohibited the use after Jan. 1, 2010 of plasticizers with high PAH content.
High viscosity naphthenic oils have been used as DAE process oil substitutes. However, due to the generally lower CA content of naphthenic oils compared to that of DAEs, some rubber compound reformulation may be required to recover or maintain acceptable performance. Also, a variety of test criteria may need to be satisfied following reformulation. For tires, the test criteria may include wet grip (tan delta at 0° C.), rolling resistance (tan delta at 60° C.), skid resistance, dry traction, abrasion resistance and processability. This long list of potential test criteria has made it difficult to find suitable replacements for DAE process oils.
Accordingly, there remains an ongoing need for materials that can replace DAE process oils and thereby reduce or minimize PAH content, without unduly compromising the performance of rubber formulations employing such replacement materials compared to formulations employing a DAE process oil.
The present invention provides, in one aspect, a method for making naphthenic process oils, the method comprising:
The present invention provides, in another aspect, a method for making naphthenic process oils, the method comprising:
In another embodiment the present invention provides a method for making naphthenic process oils, the method comprising:
In a further embodiment the present invention provides a method for making naphthenic process oils, the method comprising:
The present invention provides, in yet another aspect, a method for making naphthenic process oils, the method comprising:
wherein the feedstock and naphthenic process oil each have greater CA content than that of a comparison oil made by similarly hydrotreating the naphthenic vacuum gas oil alone.
The present invention also provides a naphthenic process oil comprising a hydrotreated blend of a) at least one naphthenic vacuum gas oil having a viscosity of at least 60 SUS at 38° C. (100° F.) and b) a feedstock selected from ethylene cracker bottoms, slurry oil, heavy cycle oil and light cycle oil and having greater CA content than that of a comparison oil made by similarly hydrotreating the at least one naphthenic vacuum gas oil alone.
High CA content feedstocks for use in the above method may be obtained as selected process streams or byproducts from other petroleum refining processes. For example, ethylene cracker bottoms may be obtained from a naphtha cracking unit, and slurry oil may be obtained from a fluid catalytic cracking (FCC) unit. The enhanced CA content naphthenic process oils obtained from the above methods have increased aromatic content and improved solvency in rubber compounds compared to conventional naphthenic process oils, and may be used to replace conventional DAE process oils.
Like reference symbols in the various FIGS. of the drawing indicate like elements.
Numerical ranges expressed using endpoints include all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4 and 5). All percentages are weight percentages unless otherwise stated.
The term “8-markers” when used with respect to a feedstock, process stream or product refers to the total quantity of the polycyclic aromatic hydrocarbons benzo(a)pyrene (BaP, CAS No. 50-32-8), benzo(e)pyrene (BeP, CAS No. 192-97-2), benzo(a)anthracene (BaA, CAS No. 56-55-3), chrysene (CHR, CAS No. 218-01-9), benzo(b)fluoranthene (BbFA, CAS No. 205-99-2), benzoG)fluoranthene (BjFA, CAS No. 205-82-3), benzo(k)fluoranthene (BkFA, CAS No. 207-08-9) and dibenzo(a,h)anthracene (DBAhA, CAS No. 53-70-3) in such feedstock, process stream or product. Limits for these aromatics are set forth in European Union Directive 2005/69/EC of the European Parliament and of the Council of 16 Nov. 2005, at 10 ppm for the sum of the 8-markers, and 1 ppm for benzo[a]pyrene. PAH 8-marker levels may also be evaluated using gas chromatography/mass spectrometry (GC/MS) procedures to provide results that will be similar to those obtained using European standard EN 16143:2013.
The term “high CA content feedstock” when used with respect to a feedstock, process stream, product, or resulting process oil refers to a liquid material having a viscosity-gravity constant (YGC) close to 1 (e.g., greater than about 0.95) as determined by ASTM D2501. Aromatic feedstocks or process streams typically will contain at least about 10% CA content and less than about 90% total CP plus CN content as measured according to ASTM D2140 or ASTM3238, with the latter method typically being used for heavier petroleum fractions.
The term “ASTM” refers to the American Society for Testing and Materials which develops and publishes international and voluntary consensus standards. Exemplary ASTM test methods are set out below. However, persons having ordinary skill in the art will recognize that standards from other internationally recognized organizations will also be acceptable and may be used in place of or in addition to ASTM standards.
The term “ethylene cracker bottoms” refers to a residual fraction obtained after removal of a desired ethylene production fraction from a cracking unit (e.g., a steam cracking unit) used for ethylene production.
The term “heavy cycle oil” refers to a byproduct obtained from an FCC unit which is heavier (viz., has a higher boiling range) than light cycle oil and lighter (viz., has a lower boiling range) than slurry oil. Heavy cycle oil is commonly used as a base stock for carbon black manufacturing.
The term “enhanced CA content napthenic process oil” refers to an oil having a greater CA content than that of a comparison oil made by similarly hydrotreating at least one naphthenic vacuum gas oil alone without using the method of this disclosure.
The term “hydrocracking” refers to a process in which a feedstock or process stream is reacted with hydrogen in the presence of a catalyst at very high temperatures and pressures, so as to crack and saturate the majority of the aromatic hydrocarbons present and eliminate all or nearly all sulfur-, nitrogen- and oxygen-containing compounds.
The term “hydrofinishing” refers to a process in which a feedstock or process stream is reacted with hydrogen in the presence of a catalyst under less severe conditions than for hydrotreating or hydrocracking, so as to saturate olefins and to some extent aromatic rings, and thus reduce the levels of PAH compounds and stabilize (e.g., reduce the levels of) otherwise unstable molecules. Hydrofinishing may for example be used following hydrocracking to improve the color stability and stability towards oxidation of a hydrocracked product.
The term “hydrogenated” when used with respect to a feedstock, process stream or product refers to a material that has been hydrofinished, hydrotreated, reacted with hydrogen in the presence of a catalyst or otherwise subjected to a treatment process that materially increases the bound hydrogen content of the feedstock, process stream or product.
The term “hydrotreating” refers to a process in which a feedstock or process stream is reacted with hydrogen in the presence of a catalyst under more severe conditions than for hydrofinishing and under less severe conditions than for hydrocracking, so as to reduce unsaturation (e.g., aromatics) and reduce the amounts of sulfur-, nitrogen- or oxygen-containing compounds.
The term “light cycle oil” refers to an aromatic byproduct obtained from an FCC unit and which is heavier than gasoline and lighter than heavy cycle oil. Light cycle oil is commonly used as a blend stock in diesel and heating oil production.
The term “liquid yield” when used with respect to a process stream or product refers to the weight percent of liquid products collected based on the starting liquid material amount.
The term “naphthenic” when used with respect to a feedstock, process stream or product refers to a liquid material having a VGC from about 0.85 to about 0.95 as determined by ASTM D2501. Naphthenic feedstocks typically will contain at least about 30% CN content and less than about 70% total CP plus CA content as measured according to ASTM D2140.
The term “naphthenic blend stock” refers to a naphthenic crude residual bottom, naphthenic crude, naphthenic vacuum gas oil or naphthenic atmospheric gas oil for use in the disclosed method, viz., for use in blending with a disclosed feedstock.
The term “paraffinic” when used with respect to a feedstock, process stream or product refers to a liquid material having a VGC near 0.8 (e.g., less than 0.85) as determined by ASTM D2501. Paraffinic feedstocks typically will contain at least about 60 wt. % CP content and less than about 40 wt. % total CN+ CA content as measured according to ASTM D2140.
The term “slurry oil” refers to a heavy aromatic byproduct containing fine particles of catalyst from the operation of an FCC unit, and may include both unclarified slurry oils and slurry oils that have been clarified to remove or reduce their fine particle content. Slurry oils are sometimes referred to as carbon black oils, decant oils or FCC bottom oils.
The terms “Viscosity-Gravity Constant” or “VGC” refer to an index for the approximate characterization of the viscous fractions of petroleum. VGC formerly was defined as the general relation between specific gravity and Saybolt Universal viscosity. VGC may be determined based on density and viscosity measurements according to ASTM D2501. VGC is relatively insensitive to molecular weight.
The term “viscosity” when used with respect to a feedstock, process stream or product refers to the kinematic viscosity of a liquid. Kinematic viscosities typically are expressed in units of mm2/s or centistokes (cSt), and may be determined according to ASTM D445. Historically the petroleum industry has measured kinematic viscosities in units of Saybolt Universal Seconds (SUS). Viscosities at different temperatures may be calculated according to ASTM D341 and converted from cSt to SUS according to ASTM D2161.
Several embodiments of the disclosed method are schematically illustrated in
Blending can be carried out using a variety of devices and procedures including mixing valves, static mixers, mixing tanks and other techniques that will be familiar to persons having skill in the art. Source unit 130 may for example be a naphtha cracking unit, in which case high CA feedstock 132 will contain ethylene cracker bottoms. Source unit 130 may instead be an FCC unit, in which case high CA feedstock 132 will contain slurry oil, heavy cycle oil or light cycle oil. Although not shown in
Hydrotreatment unit 140 is employed to hydrotreat at least the above-mentioned blend of vacuum gas oil 122 and high CA feedstock 132, and desirably also to hydrotreat some or all of the remaining lower viscosity vacuum gas oils obtained from unit 112, or to hydrotreat blends of such lower viscosity vacuum gas oils with high CA feedstock 132. The resulting naphthenic process oils 146, 148, 150 and 152 have respective nominal viscosities of approximately 60, 100, 500 and 2000 SUS at 38° C. (100° F.), and if hydrotreated also have reduced unsaturation and reduced amounts of sulfur-, nitrogen- or oxygen-containing compounds. The resulting modified oils (for example, 500 SUS or 2000 SUS viscosity naphthenic process oil 152) may be used as a replacement for DAE process oils.
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Additional processing steps may optionally be employed before or after the steps mentioned above. Exemplary such steps include solvent extraction, catalytic dewaxing, solvent dewaxing, hydrofinishing and hydrocracking. In some embodiments no additional processing steps are employed, and in other embodiments additional processing steps such as any or all of deasphalting, solvent extraction, catalytic dewaxing, solvent dewaxing, hydrofinishing and hydrocracking are not required or are not employed.
A variety of naphthenic crude residual bottoms and naphthenic crudes may be employed as naphthenic blend stocks in the disclosed method. When naphthenic crude residual bottoms are employed, they typically will be obtained from an atmospheric distillation unit for naphthenic crudes operated in accordance with procedures that will be familiar to persons having ordinary skill in the art, and normally will have a boiling point above about 370 to 380° C. When naphthenic crudes are employed in the disclosed method, they may be obtained from a variety of sources. Exemplary naphthenic crudes include Brazilian, North Sea, West African, Australian, Canadian and Venezuelan naphthenic crudes from petroleum suppliers including BHP Billiton Ltd., BP p.l.c., Chevron Corp., ExxonMobil Corp., Mitsui & Co., Ltd., Royal Dutch Shell p.l.c., Petrobras, Total S.A., Woodside Petroleum Ltd. and other suppliers that will be familiar to persons having ordinary skill in the art. The chosen naphthenic crude may for example have a VGC of at least about 0.85, 0.855, 0.86 or 0.865, and a VGC less than about 1, 0.95. 0.9 or 0.895, as determined by ASTM D2501. Preferred naphthenic crudes will provide a vacuum gas oil having a VGC from about 0.855 to 0.895. The chosen crude may also contain at least about 30%, at least about 35% or at least about 40% CN content, and less than about 70%, less than about 65% or less than about 60 total CP plus CA content as measured according to ASTM D2140.
A variety of naphthenic vacuum gas oils may be used as naphthenic blend stocks in the disclosed method. The vacuum gas oil may be used in a non-hydrotreated form, blended with the chosen feedstock, and then the resulting blended liquid may be hydrotreated. Alternatively, a hydrotreated naphthenic vacuum gas oil may be employed as the naphthenic blend stock, blended with the chosen feedstock, and then the resulting blended liquid may be further hydrotreated. Before it is hydrotreated, the chosen naphthenic vacuum gas oil may for example contain at least about 10%, at least about 12%, at least about 14%, at least about 16% or at least about 18% CA content, and may also or instead contain less than about 24%, less than about 22%, less than about 21% or less than about 20% CA content. Before hydrotreating, the chosen naphthenic vacuum gas oil may for example also or instead contain at least about 40% or at least about 45% CA plus CN content.
Preferred hydrotreated naphthenic 60 SUS vacuum gas oils may for example have the following desirable characteristics separately or in combination: an aniline point (ASTM D611) of about 64° C. to about 85° C. or about 72° C. to about 77° C.; a flash point (Cleveland Open Cup, ASTM D92) of at least about 80° C. to about 230° C., or of at least about 136° C. to about 176° C.; a viscosity (SUS at 37.8° C.) of about 35 to about 85 or about 54 to about 72; a pour point (° C., ASTM D5949) of about −90° C. to about −20° C. or about −75° C. to about −35° C.; and yields that are greater than 85 vol. %, e.g., greater than about 90%, greater than about 97%, or about 97% to about 99% of total lube yield based on feedstock.
Preferred hydrotreated naphthenic 100 SUS vacuum gas oils may for example have the following desirable characteristics separately or in combination: an aniline point (ASTM D611) of about 64° C. to about 85° C. or about 72° C. to about 77° C.; a flash point (Cleveland Open Cup, ASTM D92) of at least about 90° C. to about 260° C., or of at least about 154° C. to about 196° C.; a viscosity (SUS at 37.8° C.) of about 85 to about 135 or about 102 to about 113; a pour point (° C., ASTM D5949) of about −90° C. to about −12° C. or about −70° C. to about −30° C.; and yields that are greater than 85 vol. %, e.g., greater than about 90%, greater than about 97%, or about 97% to about 99% of total lube yield based on feedstock.
Preferred hydrotreated naphthenic 500 SUS vacuum gas oils may for example have the following desirable characteristics separately or in combination: an aniline point (ASTM D611) of about 77° C. to about 98° C. or about 82° C. to about 92° C.; a flash point (Cleveland Open Cup, ASTM D92) of at least about 111° C. to about 333° C., or of at least about 167° C. to about 278° C.; a viscosity (SUS at 37.8° C.) of about 450 to about 600 or about 500 to about 550; a pour point (° C., ASTM D5949) of about −73° C. to about −17° C. or about −51° C. to about −6° C.; and yields that are greater than 85 vol. %, e.g., greater than about 90%, greater than about 97%, or about 97% to about 99%, of total lube yield based on feedstock.
Preferred naphthenic 2000 vacuum gas oils may for example have the following desirable characteristics separately or in combination: an aniline point (ASTM D611) of about 90° C. to about 110° C. or about 93° C. to about 103° C.; a flash point (Cleveland Open Cup, ASTM D92) of at least about 168° C. to about 363° C., or of at least about 217° C. to about 314° C.; a viscosity (SUS at 37.8° C.) of about 1700 to about 2500 or about 1900 to about 2300; a pour point (° C., ASTM D5949) of about −53° C. to about 24° C. or about −33° C. to about 6° C.; and yields that are greater than 85 vol. %, e.g., greater than about 90%, greater than about 97%, or about 97% to about 99%, of total lube yield based on feedstock.
Other desirable characteristics for the disclosed hydrotreated naphthenic vacuum gas oils may include compliance with environmental standards such as EU Directive 2005/69/EC, IP346 and Modified AMES testing ASTM E1687, to evaluate whether the finished product may be carcinogenic. These tests correlate with the concentration of polycyclic aromatic hydrocarbons. Desirably, the disclosed hydrotreated naphthenic vacuum gas oils have less than about 8 ppm, more desirably less than about 2 ppm and most desirably less than about 1 ppm of the sum of the 8-markers when evaluated according to European standard EN 16143:2013. The latter values represent especially noteworthy 8-markers scores, and represent up to an order of magnitude improvement beyond the EU regulatory requirement.
Exemplary commercially available naphthenic vacuum gas oils, some of which may already have been hydrotreated, include HYDROCAL™, HYDROSOL™ and HR TUFFLO™ oils from Calumet Specialty Products Partners, LP; CORSO™ RPO, CORSOL 1200, CORSOL 2000 and CORSOL 2400 oils from Cross Oil and Refining Co., Inc.; HYPRENE™ L2000 oil from Ergon, Inc; NYTEX™ 230, NYTEX 810, NYTEX 820, NYTEX 832, NYTEX 840, NYTEX 8150, NYFLEX™ 220, NYFLEX 223, NYFLEX 820 and NYFLEX 3100 oils from Nynas AB; and RAFFENE™ 1200L, RAFFENE 2000L, HYNAP™ 500, HYNAP 2000 and HYNAP 4000 oils from San Joaquin Refining Co., Inc.
The above-mentioned HYPRENE L2000 oil is a severely hydrotreated base oil having the following typical test values:
Another exemplary hydrotreated naphthenic vacuum gas oil for use in the disclosed method is available as TUFFLO™ 2000 from Calumet Specialty Products Partners, LP with the following typical test values:
The above-mentioned HYPRENE L2000 and TUFFLO 2000 oils may be used as is in process oil applications. However, the disclosed method may be used to improve such oils further by for example-increasing their CA content and improving their solubility in rubber formulations.
The vacuum distillation unit (and if used, the atmospheric distillation unit) may be operated in accordance with standard industry practices that will be familiar to persons having ordinary skill in the art. Vacuum gas oils and atmospheric gas oils having desired viscosity ranges can be obtained from such distillation units. Exemplary viscosity ranges include oils having a viscosity from about 60 to about 3,500, about 500 to about 3,000 or about 1,000 to about 2,500 SUS at 38° C., and properties like or unlike (e.g., between) those listed above for naphthenic 600 and naphthenic 2000 vacuum gas oils.
When ethylene cracker bottoms are employed in the disclosed method, they typically will be obtained from a naphtha cracking unit operated in accordance with procedures that will be familiar to persons having ordinary skill in the art. Ethylene cracker bottoms represent a preferred high CA feedstock for use in the disclosed method. The chosen ethylene cracker bottoms may for example contain at least about 20%, at least about 25% or at least about 30% CA content, and may be as high as 90% or more CA content. Exemplary ethylene cracker bottoms are typically sold into the fuel oil market and may be obtained from suppliers including Royal Dutch Shell p.l.c., Dow Chemical Co. and Braskem.
When slurry oils are employed in the disclosed method, they typically will be obtained from an FCC unit operated in accordance with procedures that will be familiar to persons having ordinary skill in the art. FCC units that process paraffinic feedstocks represent a preferred slurry oil source. As noted above, slurry oil feedstocks preferably also are treated to remove solid particles. The chosen slurry oil may for example contain at least about 20%, at least about 25% or at least about 30% CA content, and may be as high as 90% or more CA content. Exemplary slurry oils typically will be produced as a byproduct from fuel refineries equipped with a catalytic cracking unit, and may be obtained from suppliers including BP p.l.c., Chevron Corp., CountryMark Refining and Logistics, LLC, ExxonMobil Corp., Royal Dutch Shell p.l.c. and WRB Refining.
The above-mentioned high CA feedstocks may each have a different influence on the properties of the disclosed naphthenic process oils. However, as a generalization, addition of the feedstock may increase CA, reduce the aniline point, increase UV absorption and refractive index, increase the VGC value compared to the starting naphthenic blend stock or vacuum gas oil, and increase the solvency of the process oil in rubber compounds. Use of an ethylene cracker bottom or slurry oil high CA feedstock may also increase CN while reducing CP, due for example to conversion of CA from the feedstock to saturated naphthenes (CN) during the hydrotreating step. Increasing the CN content may also increase solvency of the process oil in rubber compounds, although to a lesser degree than may be observed for increased CA content.
The naphthenic blend stock and feedstock may be mixed in any convenient fashion, for example by adding the feedstock to the naphthenic blend stock or vice-versa. The naphthenic blend stock and feedstock may be mixed in a variety of ratios. The chosen mixing ratio can readily be selected by persons skilled in the art, and may depend in part on the chosen materials and their viscosities, CA contents and PAH 8-marker values. Preferably the resulting blended liquid will contain at least about 2, at least about 5 or at least about 10 wt. % feedstock based on the weight of the blended liquid. Also, the blended liquid preferably will contain up to about 40, up to about 20 or up to about 15 wt. % feedstock based on the weight of the blended liquid. Extenders and rubber additives that will be familiar to those skilled in the art may also be added to the blended liquid if desired.
The blended liquid is hydrotreated. The primary purpose of hydrotreating is to remove sulfur, nitrogen and polar compounds and to saturate some aromatic compounds. The hydrotreating step thus produces a first stage effluent or hydrotreated effluent having at least a portion of the aromatics present in the blended liquid saturated, and the concentration of sulfur- or nitrogen-containing heteroatom compounds decreased. The hydrotreating step may be carried out by contacting the blended liquid with a hydrotreating catalyst in the presence of hydrogen under suitable hydrotreating conditions, using any suitable reactor configuration. Exemplary reactor configurations include a fixed catalyst bed, fluidized catalyst bed, moving bed, slurry bed, counter current, and transfer flow catalyst bed.
The hydrotreating catalyst is used in the hydrotreating step to remove sulfur and nitrogen and typically includes a hydrogenation metal on a suitable catalyst support. The hydrogenation metal may include at least one metal selected from Group 6 and Groups 8-10 of the Periodic Table (based on the IUPAC Periodic Table format having Groups from 1 to 18). The metal will generally be present in the catalyst composition in the form of an oxide or sulfide. Exemplary metals include iron, cobalt, nickel, tungsten, molybdenum, chromium and platinum. Particularly desirable metals are cobalt, nickel, molybdenum and tungsten. The support may be a refractory metal oxide, for example, alumina, silica or silica-alumina. Exemplary commercially available hydrotreating catalysts include LH-23, DN-200, DN-3330, and DN-3620/3621 from Criterion. Companies such as Albemarle, Axens, Haldor Topsoe, and Advanced Refining Technologies also market suitable catalysts.
The temperature in the hydrotreating step typically may be about 260° C. (500° F.) to about 399° C. (750° F.), about 287° C. (550° F.) to about 385° C. (725° F.), or about 307° C. (585° F.) to about 351° C. (665° F.). Exemplary hydrogen pressures that may be used in the hydrotreating stage typically may be about 5,515 kPa (800 psig) to about 27,579 kPa (4,000 psig), about 8,273 kPa (1,200 psig) to about 22,063 kPa (3,200 psig), or about 11,721 kPa (1700 psig) to about 20,684 kPa (3,000 psig). The quantity of hydrogen used to contact the feedstock may typically be about 17.8 to about 1,780 m3/m3 (about 100 to about 10,000 standard cubic feet per barrel (scf/B)) of the feedstock stream, about 53.4 to about 890.5 m3/m3 (about 300 to about 5,000 scf/B) or about 89.1 to about 623.4 m3/m3 (500 to about 3,500 scf/B). Exemplary reaction times between the hydrotreating catalyst and the feedstock may be chosen so as to provide a liquid hourly space velocity (LHSV) of about 0.25 to about 5 cc of oil per cc of catalyst per hour (hr−1), about 0.35 to about 1.5 hr−1, or about 0.5 to about 0.75 hr−1.
The resulting modified naphthenic process oil may for example have the following desirable characteristics separately or in combination: a flash point (Cleveland Open Cup, ASTM D92) of at least about 240° C.; a boiling point (corrected to atmospheric pressure) of about 320° to about 650° C. or about 350° to about 600° C.; a kinematic viscosity of about 15 to about 30 or about 18 to about 25 cSt @ 100° C.; a viscosity index of about 5 to about 30; a pour point (ASTM D5949) of about −6° to about 4° C.; an aromatic content (Clay Gel Analysis ASTM D2007) of about 30 to about 55 weight percent, about 30 to about 50 weight percent or about 35 to about 48 weight percent; a saturates content (Clay Gel Analysis ASTM D2007) of about 40 to about 65, about 40 to about 55 or about 42 to about 52 weight percent; a polar compounds content (Clay Gel Analysis ASTM D2007) of about 0.4 to about 1, about 0.4 to about 0.9 or about 0.5 to about 0.8 weight percent; a VGC of about 0.86 to about 0.89; a PCA extract content less than 3 weight percent, e.g. from 1 to 3 or 1 to 2 weight percent, based on the total weight of hydrocarbons contained in the oil composition as determined according to IP 346; and a PAH 8-markers content less than 10 ppm when evaluated according to European standard EN 16143:2013.
The modified naphthenic process oil may be used in a variety of rubber formulations. Exemplary rubber formulations typically will contain a high proportion of aromatic groups, and include styrene-butadiene rubber (SBR), butadiene rubber (BR), ethylene-propylene-diene monomer rubber (EPDM) and natural rubber. Rubber formulations containing the modified naphthenic process oil may contain vulcanizing agents (e.g., sulfur compounds), fillers or extenders (e.g., carbon black and silica) and other ingredients that will be familiar to persons having ordinary skill in the art. The rubber formulations may be cured to form a variety of rubber-containing articles that will be familiar to persons having ordinary skill in the art, including tires, belts, hoses, gaskets and seals. The effect of the modified process oil may be assessed using a variety of tests that will be familiar to persons having ordinary skill in the art. For example, rubber formulations used to make tires may be evaluated by measuring wet grip (tan delta at 0° C.), rolling resistance (tan delta at 60° C.), skid resistance, abrasion resistance, dry traction and processability.
The invention is further illustrated in the following non-limiting examples, in which all parts and percentages are by weight unless otherwise indicated.
A wide-boiling naphthenic blend stock (identified below as “WBNBS”) containing non-hydrotreated 60 SUS naphthenic atmospheric gas oil and non-hydrotreated 100, 500 and 2000 SUS naphthenic vacuum gas oils was formed by combining the oils in the same volume ratios at which such oils were produced in a refinery crude distillation unit. Portions of the WSNBS were hydrotreated using a catalyst containing nickel-molybdenum (Ni—Mo) on alumina (hydrotreating catalyst LH-23, commercially available from Criterion Catalyst Company) under four separate sets of hydrotreating conditions. Set out below in Table 3 are the hydrogen charge rate, LHSV and WRAT (weighted reactor average temperature) conditions employed when hydrotreating the WBNBS, together with measured physical properties of the WBNBS before hydrotreating and of the hydrotreated naphthenic blend stocks (respectively identified below as “WBNBS HT1”, “WBNBS HT2”, “WBNBS HT3” and “WBNBS HT4”) obtained using the four hydrotreating conditions.
An ethylene cracker bottom feedstock (identified below as “ECB”) was obtained from a naphtha cracking unit and fractionated to isolate a wide-boiling feedstock (identified below as “WBECB”) whose boiling range of 274 to 547° C. (525 to 1017° F.) generally matched that of the WBNBS. Properties for the ECB and WBECB are shown below in Table 4.
A blend (identified below as “ECB Blend”) was formed from a 92:8 volume ratio WBNBS:WBECB mixture. Portions of the ECB Blend were hydrotreated using four sets of hydrotreating conditions that were each very similar to the conditions used to hydrotreat the WBNBS. Set out below in Table 5 are the hydrogen charge rate, LHSV and WRAT conditions employed when hydrotreating the ECB Blend, together with measured physical properties of the ECB Blend before hydrotreating and the hydrotreated ECB Blends (identified below as “ECB Blend HT1”, “ECB Blend HT2”, “ECB Blend HT3” and “ECB Blend HT4”) obtained using the four hydrotreating conditions:
The results in Tables 3 through 5 show that reduced PAH levels and useful reductions in aniline point (by approximately 5° C., and corresponding to greater aromatic content) were obtained by hydrotreating the ECB Blend. Other properties including refractive index, VGC, ASTM D7419 aromatic content and ASTM D2140 CA content also exhibited favorable changes compared to the hydrotreated naphthenic blend stocks. The CA contents of the hydrotreated ECB blends were greater than those of the corresponding hydrotreated WBNBS samples.
Using a procedure like that shown in
The results in Table 8 show that significantly reduced PAH 8-marker levels were obtained from high PAH 8-marker blend feedstocks. Properties including aniline point, refractive index, VGC and Tg all exhibited favorable changes compared to the hydrotreated L2000HT oil. The CA contents of the hydrotreated blends were greater than that of the hydrotreated L2000HT oil.
Similar results will be obtained by replacing the slurry oil feedstock used in Example 2 with heavy cycle oil or light cycle oil.
The hydrotreated L2000HT oil from Example 2, a commercially available process oil (VIVATEC™ 500 treated distillate aromatic extract (TDAE) from Hansen & Rosenthal) and the hydrotreated Blend 2HT oil from Example 2 were each evaluated as process oils in a silica-filled passenger tire tread formulation containing the ingredients shown below in Table 9. VIVATEC 500 oil provides very good performance in tire tread formulations, and is often used as a control against which other process oils can be evaluated. The tire tread formulation shown below is not that of any particular manufacturer, but instead represents a commonly-used formulation that is often employed in technical papers and other evaluations describing potential new rubber formulation ingredients.
The formulation ingredients were mixed in a Banbury mixer at a batch weight of 3.3 kg using the mixing conditions shown below in Table 10. The rotor speed was adjusted during the Masterbatch stage to prevent the Masterbatch temperature exceeding 155° C. In order to facilitate silane coupling, the batch temperature was held above 140° C. for 3 minutes following addition of the X50S additive. A 3 minute remill stage was employed during which the rotor speed was adjusted to keep the temperature below 155° C. A 2 minute finalization stage was employed during which the rotor speed was adjusted to keep the temperature below 100° C.
Mooney viscosity characteristics of the resulting rubber formulations are shown below in Table 11, and the rheometric characteristics are shown below in Table 12. Mooney viscosity measurements were made at 100° C. using a Mooney rotating disc viscometer equipped with a large rotor. Rheometric measurements were made at 172° C. using a moving die rheometer and a 30 minute plot. The formulations exhibited “marching” cures (normal for this polymer blend when cured at 172° C.), and thus the measured torque rose across the entire measurement period without exhibiting a true maximum. The indicated t95 time is thus somewhat arbitrary as it can vary with the time over which the plot is recorded.
Physical properties for rubbers made from the above rubber formulations are shown below in Table 13. Dynamic properties were measured at 10 Hz and 1% strain over the temperature range −40 to 60° C. The performance of compounds in dynamic property tests can be correlated to tire rolling resistance and wet grip based on the loss angle (or tangent of the loss angle Tan δ) at about 60° and 0° respectively. Tan δ is a measure of rubber hysteresis, viz., energy stored in the rubber that is not recoverable as the rubber is stretched or compressed. For tire formulations normally a low Tan δ at 60° C. is indicative of a low tire tread rolling resistance, and a high Tan δ at 0° C. is indicative of good tread grip in wet conditions.
Skid resistance was measured using a British Pendulum Skid Resistance
apparatus operated according to BS EN 13036-4 (2011) on smooth concrete block that had been wet with room temperature (22° C.) distilled water, and test pieces prepared using 3-micrometer lapping paper. Higher values represent better skid resistance.
As shown above, in most of the conducted tests, the Blend 2HT formulation provided comparable or better results compared to the L2000HT and VIVATEC 500process oil formulations. For tire manufacturing, some test results have greater importance than others. As a generalization, results for processability, abrasion resistance, tan δ at 60° C. and 0° C., and skid resistance may be especially important.
Tensile samples and hardness buttons made from each rubber formulation were also aged in a laboratory fan convection oven at 70° C. for 7 days and evaluated as shown below in Table 14:
Aging usually produces an increase in Modulus (M100, M300) and a reduction in the extension at break. The three formulations exhibited generally similar changes in these properties.
The above description is directed to the disclosed processes and is not intended to limit them. Those of skill in the art will readily appreciate that the teachings found herein may be applied to yet other embodiments within the scope of the attached claims. The complete disclosures of all cited patents, patent documents, and publications are incorporated herein by reference as if individually incorporated. However, in case of any inconsistencies the present disclosure, including any definitions herein, will prevail.
This application is a national stage filing under 35 U.S.C. § 371 of International Application No. PCT/US2016/031844 filed May 11, 2016, which claims priority under 35 U.S.C. § 119 to U.S. Provisional Application No. 62/160,067 filed May 12, 2015, the disclosures of both of which are incorporated herein by reference.
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| WO2016/183195 | 11/17/2016 | WO | A |
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