Methods for using pyrolysis oil as a feedstock for making naphthenic process and LUBE oils

Abstract

Low polynuclear aromatic hydrocarbon (low-PAH) naphthenic lube or process oils are produced in viscosity ranges including, but not limited to, 30 SUS to 6000 SUS at 100 deg. F by pretreating pyrolysis oil to reduce the amount(s) of one or more of minerals, metals, halides, alkenes or olefins (e.g., through hydroprocessing), blending the treated or untreated pyrolysis oil with a naphthenic oil in a feedstock blending and storage unit to produce at least one blended feedstock, and subjecting the blended feedstock to hydrotreatment to produce low-PAH naphthenic lube or process oils. The hydroprocessing step may include reacting the pyrolysis oil with hydrogen in the presence of a non-noble metal catalyst, and the hydrotreatment step may include reacting the blended feedstock with hydrogen in the presence of a non-noble metal catalyst to produce naphthenic lube or process oils.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation of International Application No. PCT / US2024 / 056404 filed Nov. 18, 2024, which claims priority from U.S. Provisional Application Ser. No. 63 / 599,933 filed Nov. 16, 2023, both entitled “METHODS FOR USING PYROLYSIS OIL AS A FEEDSTOCK FOR MAKING NAPHTHENIC PROCESS AND LUBE OILS”, and the disclosures of which are both incorporated herein by reference.TECHNICAL FIELD

[0002] This invention relates to using pyrolysis oil as a feedstock in the production of naphthenic process and lube oils.BACKGROUND

[0003] Passenger cars and trucks on U.S. highways wear out millions of tires each year, making disposal of used tires a major environmental challenge. Reclaimed rubber from waste tires may be pyrolyzed to produce a highly aromatic and olefinic oil stream known as pyrolysis oil. Pyrolysis oil normally is burned as a fuel, but is sometimes also treated to remove contaminants, saturate olefins, and fractionally separate lighter naphtha and diesel compounds, resulting in cleaner fuels containing little to no sulfur or nitrogen compounds (see e.g., Budhwani, Removal of PAHs Present in Tyre Pyrolytic Oil Using Low Cost natural Adsorbents, International Scholarly and Scientific Research & Innovation 9(2), pp. 186-190 (2015); Campuzano et al., On the distillation of waste tire pyrolysis oil, Fuel 290, 120041 pp. 1-15 (2021); Roy et al, The vacuum pyrolysis of used tires end-uses for oil and carbon black products, Journal of Analytical and Applied Pyrolysis, 51, pp. 201-221 (1999); Roy et al, Conversion of Used Tires to Carbon Black and Oil by Pyrolysis, in De et al., Rubber Recycling, pp. 429-467 (2005) and Williams et al., Sulfur-Polycyclic Aromatic Hydrocarbons in Tyre Pyrolysis Oil, Fuel 74(5), pp. 736-742 (1994). These cleaner fuels may be further hydrocracked into lower molecular weight molecules that also may be used as fuels. Rather than converting pyrolysis oil into fuels, what is needed in the art are other applications and uses for pyrolysis oils. Such applications and uses are disclosed and claimed herein.SUMMARY OF THE INVENTION

[0004] The present invention provides methods for using pyrolysis oil as a feedstock in the production of naphthenic process and lube oils. In a first aspect, the method comprises the steps of (i) blending one or more naphthenic atmospheric gas oils or naphthenic vacuum gas oils with a pyrolysis oil that has been pretreated to reduce the amount(s) of one or more of minerals, metals, halides, alkenes or olefins in such pyrolysis oil, in a feedstock blending and storage unit to produce at least one blended feedstock; and (ii) hydrotreating the at least one blended feedstock in the presence of hydrogen and a non-noble metal catalyst to produce a naphthenic process or lube oil.

[0005] In a second embodiment, the disclosed method comprises the steps of (i) blending residual bottoms from a naphthenic crude atmospheric distillation unit with the pretreated pyrolysis oil in a feedstock blending and storage unit to provide a blended feedstock; (ii) vacuum distilling the blended feedstock to provide one or more blended vacuum gas oils in one or more viscosity ranges; and (iii) hydrotreating the one or more blended vacuum gas oils in the presence of hydrogen and a non-noble metal catalyst to provide the naphthenic process or lube oil.

[0006] In a third embodiment, the disclosed method comprises the steps of (i) blending naphthenic crude with pyrolysis oil in a feedstock blending and storage unit to provide a blended feedstock; (ii) atmospheric distilling the blended feedstock to provide one or more blended atmospheric gas oils in one or more viscosity ranges and residual bottoms; (iii) vacuum distilling the residual bottoms to provide one or more blended vacuum gas oils in one or more viscosity ranges; and (iv) hydrotreating, in combination or separately, the one or more blended atmospheric gas oils and the one or more blended vacuum gas oils to provide the naphthenic process or lube oil.

[0007] The disclosed methods and compositions can employ pyrolysis oil obtained by pyrolyzing waste tires or other post-consumer rubber products. Prior to being blended with naphthenic oil, the pyrolysis oil may undergo a variety of forms of pretreatment to reduce (e.g., to modify or remove) the amount(s) of one or more, two or more, three or more or even all of minerals, metals, halides, alkenes or olefins. In one instance, the pyrolysis oil may be pretreated by subjecting the pyrolysis oil to hydroprocessing in the presence of hydrogen and a non-noble metal catalyst to saturate olefins and diolefins and decrease the halide, sulfur, and nitrogen contents within the pyrolysis oil and produce a pretreated pyrolysis oil. The pretreated pyrolysis oil may then be blended with a crude or fractionated naphthenic oil prior to undergoing hydrotreatment to produce a refined naphthenic process or lube oil. The production and hydroprocessing of the pyrolysis oil and subsequent blending with naphthenic oil may be performed at separate locations or a single location. Additionally, it is to be understood that naphthenic crude, untreated pyrolysis oil or pretreated pyrolysis oil may be blended with naphthenic oils at different stages of naphthenic processing. For example, untreated or pretreated pyrolysis oil may be blended with naphthenic crude, residual bottoms or separated fractions prior to undergoing hydrotreatment to produce the disclosed naphthenic process and lube oils.BRIEF DESCRIPTION OF THE DRAWING

[0008] FIG. 1 through FIG. 8 are schematic diagrams illustrating embodiments of the disclosed methods. Like reference numbers in the various figures indicate like elements.DEFINITIONS

[0009] In this specification, the following terms have the following meanings unless clearly otherwise specified. Further, 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, 3.8, 4, and 5). All percentages are weight percentage unless otherwise stated.

[0010] The term “30-markers” when used with respect to a feedstock, process stream or product refers to the total quantity of the PAH compounds acenaphthene (ACE, CAS No. 83-32-9), acenaphthylene (ACY, CAS No. 208-96-8), anthanthrene (ANT, CAS No. 191-26-4), anthracene (ANTH, CAS No. 120-12-7), benzo(a)anthracene (BaA, CAS No. 56-55-3), benzo(a)pyrene (BaP, CAS No. 50-32-8), benzo(b)fluoranthene (BbFA, CAS No. 205-99-2), benzo(b)naphtho[l,2-d]thiophene (BNT, CAS No. 205-43-6), benzo(e)pyrene (BeP, CAS No. 192-97-2), benzo(ghi)fluoranthene (BghiF, CAS No. 203-12-3), benzo(ghi)perylene (BGI, CAS No. 191-24-2), benzo(j)fluoranthene (BjFA, CAS No. 205-82-3), benzo(k)fluoranthene (BkFA, CAS No. 207-08-9), benzo[c]phenanthrene (BeP, CAS No. 195-19-7), chrysene (CHR, CAS No. 218-01-9), coronene (COR, CAS No. 191-07-1), cyclopenta(c,d)pyrene (CPP, CAS No. 27208-37-3), dibenzo(a,e)pyrene (DBaeP, CAS No. 192-65-4), dibenzo(a,h)anthracene (DBAhA, CAS No. 53-70-3), dibenzo(a,h)pyrene (DBahP, CAS No. 189-64-0), dibenzo(a,i)pyrene (DBaiP, CAS No. 189-55-9), dibenzo(a,l)pyrene (DBalP, CAS No. 191-30-0), fluoranthene (FLA, CAS No. 206-44-0), fluorene (FLU, CAS No. 86-73-7), indeno[123-cd]pyrene (IP, CAS No. 193-39-5), naphthalene (NAP, CAS No. 91-20-3), perylene (PERY, CAS No. 198-55-0), phenanthrene (PHN, CAS No. 85-01-8), pyrene (PYR, CAS No. 129-00-0) and triphenylene (TRIP, CAS No. 217-59-4) in such feedstock, process stream or product.

[0011] The term “22-markers” refers to a subset of the 30-markers PAH compounds, namely the PAH compounds acenaphthene, acenaphthylene, anthracene, benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(e)pyrene, benzo(ghi)perylene, benzo(j)fluoranthene, benzo(k)fluoranthene, chrysene, dibenzo(a,e)pyrene, dibenzo(a,h)anthracene, dibenzo(a,h)pyrene, dibenzo(a,i)pyrene, dibenzo(a,l)pyrene, fluoranthene, fluorene, indeno[123-cd]pyrene, naphthalene, phenanthrene and pyrene.

[0012] The term “18-markers” refers to another subset of the 30-markers PAH compounds, namely the PAH compounds acenaphthene, acenaphthylene, anthracene, benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(e)pyrene, benzo(ghi)perylene, benzo(j)fluoranthene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthracene, fluoranthene, fluorene, indeno[123-cd]pyrene, naphthalene, phenanthrene and pyrene.

[0013] The term “16-markers” refers to yet another subset of the 30-markers PAH compounds, namely the PAH compounds acenaphthene, acenaphthylene, anthracene, benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(ghi)perylene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthracene, fluoranthene, fluorene, indeno[123-cd]pyrene, naphthalene, phenanthrene and pyrene.

[0014] The term “8-markers” refers to a further subset of the 30-markers PAH compounds, namely the compounds benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(e)pyrene, benzo(j)fluoranthene, benzo(k)fluoranthene, chrysene, and dibenzo(a,h)anthracene. Limits of 10 ppm for the sum of the 8-markers, and 1 ppm for benzo[a]pyrene are set forth in European Union Directive 2005 / 69 / EC of the European Parliament and of the Council of 16 Nov. 2005. Industry and regulators have not yet set limits for 16-markers, 18-markers, 22-markers or 30 markers.

[0015] The term “aromatic” when used with respect to a feedstock, process stream or product refers to a liquid material having a viscosity-gravity constant (VGC) close to 1 (e.g., greater than about 0.95) as determined by ASTM D2501. Aromatic feedstocks or process streams may be classified according to their aromatic carbon content (CA), naphthenic carbon content (CN) and paraffinic carbon content (CP), as measured for example according to ASTM D2140, and typically will contain at least about 10% CA content and less than about 90% total CP plus CN content.

[0016] The term “aromatic concentration” or “CA” is the weight percent of aromatic molecules in the composite oil or stream. Aromatic concentration can be measured according to ASTM D2140, D7419, or D3238, the latter method typically being used for heavier petroleum fractions.

[0017] 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.

[0018] The term “blended feedstock” refers to any feedstock that has been synthesized through the combining and mixing of two categorically distinctive feedstocks in a storage system. Blended feedstocks are charged to processing units through a common feedstock collection, storage, and charge system.

[0019] The term “char” refers to a combustible solid organic residue remaining after thermal conversion of a rubber product (e.g., whole tires, ground tire rubber or other whole or comminuted rubber product) using pyrolysis or another at least partially destructive, incompletely oxygenated thermal conversion technique.

[0020] The terms “char oil” and “pyrolysis oil” are used interchangeably and refer to a combustible liquid organic residue remaining after thermal conversion of a rubber product (e.g., whole tires, ground tire rubber or other whole or comminuted rubber product) using pyrolysis or another at least partially destructive, incompletely oxygenated thermal conversion technique.

[0021] The term “clean naphthenic” when used with respect to process stream or product refers to liquid material as determined by ASTM D2501. These materials will contain lower CA content than typical naphthenic material and higher CN content than paraffinic material as measured according to ASTM D2140. These materials will pass FDA C part 2 as well as exhibit low concentrations of PAHs according to EN-16143:2013M.

[0022] The term “co-feed” refers to any feedstock that is charged into a processing unit alongside another categorically distinctive feedstock, and can be contrasted with processing a blended feedstock.

[0023] The term “co-processing” refers to the act of feeding two or more categorically distinct feedstocks to a processing unit at the same time from separate storage and charge systems, and can be contrasted with feeding a blended feedstock into such processing unit.

[0024] The terms “hydrocracking” and “hydrocracker” refer 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.

[0025] The terms “hydrofinishing” and “hydrofinisher” refer 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 or following hydrotreating to improve the color stability and stability towards oxidation of a hydrotreated product.

[0026] The terms “hydroprocessing” and “hydroprocesser” refer to a process in which a feedstock or process stream is reacted with hydrogen in the presence of a catalyst.

[0027] The terms “hydrotreating” and “hydrotreater” refer 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. Mild hydrotreating conditions may for example be in the ranges of 1500-2800 psig and 500-680 deg. F.

[0028] The phrases “low concentrations of PAHs” or “low PAHs” refer to the total polycyclic aromatic hydrocarbon (PAH) content of a desired material, e.g., an untreated or pretreated pyrolysis oil, a process oil or a lube oil. In some embodiments, this may represent a total PAH content of less than 100 ppm for the given material. In other embodiments, this may represent a ppm of less than 100 for any of the 30, 22, 18, 16, or 8 markers. For example, a low PAH may correspond to a PAH of less than 100 ppm, 50 ppm, 30 ppm, 20 ppm, or 10 ppm for any, or all, of the 30, 22, 18, 16, and 8 markers. In additional embodiments, this may represent a total 30 markers sum of less than 5 ppm by method EN-16143:2013M employed by the Southwestern Research Institute (SwRI).

[0029] The term “lube oil” refers to a liquid material with lubricating properties (viz., imparting a reduction in friction between two opposed sliding surfaces) obtained from a petroleum source.

[0030] 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+CA content as measured according to ASTM D2140.

[0031] The term “noble metal” refers to those metals that substantially resist oxidation at high temperatures. While not uniformly defined, such metals typically include rhenium, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold.

[0032] The term “non-noble metal,” while not uniformly defined, generally refers to those metals not considered to be “noble metals.” Such non-noble metals may include tungsten, cobalt, nickel, zinc, manganese, molybdenum, iron, or copper and a variety of other metals.

[0033] The term “paraffinic” when used with respect to a feedstock, process stream or product refers to 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.

[0034] The term “polycyclic” refers to organic compounds having at least two closed, connected rings of atoms.

[0035] The term “pretreated” when used in connection with pyrolysis oil means that the pyrolysis oil has been reacted or separated to reduce or modify undesirable molecular species that may interfere with subsequent steps in the disclosed methods, and especially steps that employ a catalyst susceptible to poisoning by such molecular species.

[0036] The term “process oil” refers to a plasticizer or extender oil useful in the manufacture of tires and other rubber products.

[0037] The term “processing unit” refers to any non-storage unit or subunit within a facility where one or more process operations are performed. Processing operations can include separating, heating, cooling, pressuring, depressuring, pumping or compressing with the intent of movement, subjecting to a chemical reaction, or causing a phase change.

[0038] The term “pyrolysis” refers to actual pyrolysis or any other incompletely oxygenated thermal conversion technique that at least partially destroys an organic material and enables the separation or recovery of one or more organic components present in or useful in making such organic material.

[0039] The term “pyrolysis oil source” refers to, in whole or in part, waste tires, gaskets, seals, roofing membranes, waterproofing membranes, and any other rubber sources capable of yielding pyrolysis oil.

[0040] The term “reactive olefin” when used with respect to a rubber pyrolysis oil refers to unsaturated hydrocarbons that may be present in such rubber pyrolysis oil and contain at least one reactive carbon-carbon double bond which when combined with a heavy crude to form a blended feedstock and fed to a processing unit may cause precipitation of asphaltenes, heat exchanger fouling or objectionable sludge accumulation in the processing unit.

[0041] 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.

[0042] The terms “Viscosity-Gravity Constant” or “VGC” refer to an index for the approximate characterization of the viscous fractions of petroleum. VGC is defined as the general relation between specific gravity and Saybolt Universal viscosity. VGC may be determined according to ASTM D2501. It should be noted that VGC is relatively insensitive to molecular weight.DETAILED DESCRIPTION

[0043] FIG. 1 illustratively shows one method for producing a low-PAH naphthenic lube or process oil(s) from pyrolysis and naphthenic crude feedstocks in accordance with an embodiment of the present invention. To summarize this embodiment, pyrolysis oil is pretreated as discussed in more detail below, fractionated into narrow boiling range treated pyrolysis oils, blended with appropriate viscosity (VIS) grades of naphthenic atmospheric oils and vacuum gas oils in a feedstock blending and storage unit, e.g., tankage, and then subjected to hydrotreatment to produce low-PAH naphthenic lube or process oils. For example, method 100 may include receiving naphthenic crude 110; atmospheric distilling 111 naphthenic crude 110 into atmospheric residual bottoms 112 and naphthenic atmospheric gas oils 114 (40 VIS) and 115 (60 VIS); vacuum distilling 113 atmospheric residual bottoms 112 into naphthenic vacuum gas oils 116 (100 VIS), 117 (600 VIS), and 118 (2000 VIS); solvent deasphalting 119 the vacuum distillation residue to make deasphalted oil 120 (5000 VIS); blending naphthenic atmospheric and vacuum gas oils 114, 115, 116, 117, and 118 with the corresponding viscosity grade treated pyrolysis oils 130, 131, 132, 133, and 134 to form blended feedstocks in feedstock blending and storage unit(s) 135; and hydrotreating 121 the blended feedstocks to produce low-PAH naphthenic lube or process oils 122, 123, 124, 125, 126, and 127. The FIG. 1 method provides good control over quality and good protection of equipment integrity even at high charge rates.

[0044] A variety of naphthenic crude residual bottoms and naphthenic crudes may be employed as naphthenic crude in the disclosed method. Exemplary naphthenic crudes may be obtained from a variety of sources, including Brazilian, North Sea, West African, Australian, Canadian, Venezuelan, and North American 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, at least about 0.855, at least about 0.86 or at least about 0.865, and a VGC less than about 1, less than about 0.95, less than about 0.9 or less than about 0.895, as determined by ASTM D2501. Preferred naphthenic crudes will provide atmospheric and vacuum gas oils 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+CA content as measured according to ASTM D2140.

[0045] Turning to step 111, atmospheric distillation 111 of naphthenic crude 110 may be performed in an atmospheric distillation unit operated in accordance with standard industry practices that will be familiar to persons having ordinary skill in the art. In the FIG. 1 embodiment, atmospheric distillation 111 produces atmospheric gas oils 114 and 115 with viscosity grades of 40 VIS and 60 VIS and atmospheric residual bottoms 112, but atmospheric gas oils with other viscosity grades and initial boiling points may be produced if desired. The remaining atmospheric residual bottoms are subjected to vacuum distillation 113. Vacuum distillation 113 may be performed in a vacuum distillation unit operated in accordance with standard industry practices that will be familiar to persons having ordinary skill in the art. In the FIG. 1 embodiment, distillation 113 produces vacuum gas oils 116, 117, and 118 with viscosity grades of 100 VIS, 600 VIS, and 2000 VIS, but vacuum gas oils with other viscosity grades and initial boiling points may be produced if desired. The remaining vacuum distillation residue is subjected to solvent deasphalting 119 to produce 5000 VIS oil 120, but oils with other viscosity grades and initial boiling points may be produced if desired.

[0046] Turning to pyrolysis oil 128 and pretreatment step 129, crude pyrolysis oil 128 is initially provided via pyrolysis of one or more rubber pyrolysis oil sources. For example, reclaimed tire rubber may undergo mechanical shearing / grinding and pyrolysis to produce crude pyrolysis oil 128. Mechanical shearing / grinding is however optional, and whole waste tires may be used by themselves, or in combination with, other rubber pyrolysis oil sources. Rubber pyrolysis commonly takes place in a pyrolysis reactor and necessitates heating the rubber pyrolysis oil source in an absence of oxygen to produce crude rubber pyrolysis oil 128, typically, “liquified rubber” or “LR,” along with syngas, carbon solids, and ash. The carbon solids fraction may be referred to as “char,”“carbon char,”“tired derived char” or “tire derived carbon char,” and typically includes a substantial amount of carbon black which may be used in the manufacture of new tires or other rubber products. Syngas may be incinerated, flared, or compressed to provide fuel which may be employed in the pyrolysis reaction or in any other process that uses thermal energy.

[0047] The rubber pyrolysis reactor may operate at temperatures and pressures that will be familiar to persons having ordinary skill in the art, and may utilize either batch feed or continuous feed rubber pyrolysis oil source loading. Batch feed systems process a single charge of rubber pyrolysis oil source at a given time to produce crude rubber pyrolysis oil 128 for downstream processing together with syngas, carbon solids, and ash. In continuous feed systems, a rubber pyrolysis oil source feedstock is continuously conveyed through a rubber pyrolysis reactor, and crude rubber pyrolysis oil 128, syngas, carbon solids, and ash are continuously discharged or consumed.

[0048] Operating temperatures and pressures of the rubber pyrolysis reactor may be chosen to break up desired chemical bonds, including carbon-carbon, sulfur-carbon and sulfur-sulfur bonds within the rubber pyrolysis oil source to produce crude rubber pyrolysis oil 128. Typical operating temperatures may be about 480 to 1740° C. Above 750° C., and depending on the particular process employed, the yield of crude rubber pyrolysis oil 128 and char may decrease relative to gas production. In other embodiments, rubber pyrolysis may be carried out at a reduced pressure, e.g., under vacuum or at atmospheric pressure, to provide increased crude rubber pyrolysis oil 128 yields. However, such yields may be impacted by the type of rubber pyrolysis oil source (e.g., passenger, truck, all-season or snow tires). Operating temperatures and pressures may be adjusted to produce an optimized yield of crude rubber pyrolysis oil 128.

[0049] After crude pyrolysis oil 128 is produced, pretreatment 129 of the crude pyrolysis oil 128 is performed to reduce (e.g., to modify or remove) undesirable molecular species that may interfere with subsequent steps in the disclosed method, such as reducing one or more of minerals, metals, halides, alkenes or olefins in such pyrolysis oil. For example, pretreatment may be carried out by modifying the feedstocks and processing steps employed in published patent applications US 2021 / 371753 A1, US 2023 / 020918 A1, GB2605002 A, WO 2011 / 077419 A1, WO 2016 / 030460 A1, WO 2022 / 084238 A1, WO 2022 / 084433 A1, WO 2023 / 017250 A1 and WO 2023 / 094629 A1, the disclosures of which are incorporated by reference in their entirety, including replacing the plastic feedstocks employed in these applications with rubber pyrolysis oil sources.

[0050] In some embodiments, pretreatment 129 includes hydroprocessing crude rubber pyrolysis oil 128 in the presence of hydrogen and a non-noble metal catalyst to saturate the olefins and diolefins and decrease the halide, sulfur, and nitrogen content of crude rubber pyrolysis oil 128. Hydroprocessing serves to clean or reduce the impurities within crude rubber pyrolysis oil 128 to allow for further downstream hydrotreatment 121 without running the risk of poisoning or negatively affecting a metal catalyst employed in such downstream hydrotreatment 121. Further, hydroprocessing may also allow for significant reduction or elimination of any existing 30-, 22-, 18-, 16-, or 8-markers to achieve a reduced or even low PAH level.

[0051] Non-noble metal catalysts suitable for hydroprocessing include any combination of non-noble metals, e.g., tungsten, cobalt, nickel, zinc, manganese, molybdenum, iron, or copper. Within the hydroprocessor, the non-noble metal catalyst may be coupled to a catalyst support structure. The support may be a refractory metal oxide, for example, alumina, silica or silica-alumina. Exemplary commercially available hydroprocessing catalysts are available from companies including Advanced Refining Technologies, Albemarle, Axens, Criterion and Haldor Topsoe.

[0052] In operation, hydroprocessing may be performed at operating conditions of about 10,342 kPa (1500 psig) to about 19,305 kPa (2800 psig) and about 260° C. (500° F.) to about 360° C. to about 680° F. However, other operating conditions may be employed so long as desired impurities are sufficiently removed and a suitable level of saturation is achieved. The quantity of hydrogen used to contact a feedstock may for example be about 17.8 to about 1,780 m / m (about 100 to about 10,000 standard cubic feet per barrel (scf / B)) of the feedstock stream. Reaction times between the hydroprocessing catalyst and the feedstock may be chosen to provide a liquid hourly space velocity (LHSV) of about 0.25 to about 5 cc of oil per cc of catalyst per hour. However, it is to be understood that other operating conditions may be used as well based on downstream processing needs or the innate characteristics of crude rubber pyrolysis oil 128.

[0053] Additional pretreatment steps may be employed as a part of pretreatment 129. For example, before or after hydroprocessing, the pretreated rubber pyrolysis oil may undergo atmospheric and vacuum distillation to produce one or more pretreated rubber pyrolysis atmospheric gas oils and pretreated rubber pyrolysis vacuum gas oils in desired VIS grades. The pretreated rubber pyrolysis atmospheric and vacuum gas oils may then be subjected to hydroprocessing. While rubber pyrolysis pretreatment 129 includes hydroprocessing and, in some embodiments, atmospheric and vacuum distillation, it is to be understood that further additional or alternative steps may be used to produce treated rubber pyrolysis oils 130-134.

[0054] Blending of treated pyrolysis oils 130-134 with naphthenic atmospheric and vacuum gas oils 114-118 may occur in a variety of ways. For example, treated pyrolysis oils 130-134 may be blended with appropriate e.g., matching or overlapping VIS grades of naphthenic atmospheric and vacuum gas oils 114-118 in a feedstock storage unit 135, and then later supplied as a blended feedstock, to the hydrotreater of hydrotreatment 121. However, it is expressly contemplated that the pyrolysis oils 130-134 may be blended with naphthenic atmospheric and vacuum gas oils in other ways that will be familiar to those skilled in the art. After blending, the resulting blended feedstock(s) may be subjected to hydrotreatment 121 or other types of downstream processing.

[0055] During formation of a blended feedstock, it may be advantageous to avoid asphaltene instability, resulting in sludge formation or gum formation due to highly reactive olefins in pyrolysis oil 128, e.g., tire pyrolysis oil. Generally, a blended feedstock of treated pyrolysis oils 130-134 should include a reactive olefin content under 2,000 ppm, preferably under 1,000 ppm, and, most preferably, under 750 ppm. To assist in the prevention of gum formation, additives may be used as well. Such additives may include antioxidants, e.g., RPS-828 from Halliburton, and polymerization inhibitors, e.g., Trident 290 from Innospec Inc.

[0056] A blending envelope, or blending conditions, may vary as a resulting blended feedstock is stored or otherwise charged to downstream processing units through a common feedstock collection, storage, and charge system. For example, a much larger amount of treated pyrolysis oil may be blended into crude oil located in a tank, e.g., up to 20 wt. %, as compared to downstream processing units, e.g., up to 1 wt. %. Specifically, for tank blending with heavy crude oil, blending of up to 20 wt. %, 10 wt. %, and, most desirably, 5 wt. % of pyrolysis oil may occur without causing significant asphaltene precipitation. However, factors influencing or altering such blending ratio with crude oil may include asphaltene content, resin content, aromatic content, saturated compound content, condensate content (C5, C6, and C7 compounds), and API gravity.

[0057] For downstream unit processing, blended feedstocks desirably include up to 1 wt. % and, in exemplary embodiments, up to 0.5 wt. % of pyrolysis oil. If greater pyrolysis oil amounts are used, reactive olefins in the pyrolysis oil may react on heat exchanger surfaces causing gum formation, plugging, generalized fouling, and loss of heat transfer. However, depending on a reactive olefin content and processing unit, other amounts of pyrolysis oil may be used as well. In accordance with the present disclosure, a reactive olefin content of pyrolysis oil should be kept as low as possible to prevent asphaltene instability and sludge formation.

[0058] Hydrotreatment 121 may be carried out in a hydrotreater containing a non-noble metal catalyst and a hydrogen source. In operation, the blended oils contact the non-noble metal catalyst in the presence of hydrogen under suitable hydrotreating conditions to facilitate the production of naphthenic lube or process oils through the saturation and removal or reduction of heteroatoms, and if desired the removal or reduction of aromatic color bodies. The hydrotreater may include a fixed catalyst bed, fluidized catalyst bed, moving bed, slurry bed, counter current bed or transfer flow catalyst bed.

[0059] Non-noble metal catalysts for hydrotreating may include, in addition to the non-noble metal, at least one other 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 other metal will generally be present in the catalyst composition in the form of an oxide or sulfide. Exemplary other metals include iron, cobalt, nickel, tungsten, molybdenum and chromium. Particularly desirable other metals are cobalt, nickel, molybdenum and tungsten. Within the hydrotreater, the non-noble metal catalyst may be coupled to a catalyst support structure. 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 from Criterion. Companies such as Albemarle, Axens, Haldor Topsoe, and Advanced Refining Technologies also market suitable non-noble metal hydrotreating catalysts.

[0060] Operating conditions of the hydrotreater may 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. It will be understood by those skilled in the art that such operation conditions may be selected to produce naphthenic lube or process oils 122, 123, 124, 125, 126, and 127 with 40 VIS, 60 VIS, 100 VIS, 600 VIS, 2000 VIS, and 5000 VIS respectively, or to produce naphthenic lube or process oils having other viscosity grades.

[0061] Referring to FIG. 2, a method for producing low-PAH naphthenic lube or process oils is shown. To summarize this embodiment, crude pyrolysis oil is pretreated and fractionated into narrow boiling ranges as in the FIG. 1 method, but the resulting treated pyrolysis oils are blended with appropriate VIS grades of naphthenic vacuum gas oils and solvent deasphalted oil in a feedstock blending and storage unit to form blended feedstocks, but are not blended with naphthenic atmospheric gas oils. In turn, the blended feedstocks are subjected to hydrotreatment to produce naphthenic lube or process oils. For example, method 200 may include vacuum distilling 113 atmospheric residual bottoms 212 to produce naphthenic gas oils 216, 217, and 218 with viscosity grades of 100 VIS, 600 VIS, and 2000 VIS respectively. Residue from vacuum distillation 113 is subjected to solvent deasphalting 219 to produce deasphalted oil 220 with a 5000 VIS. The naphthenic vacuum gas oils 216, 217, and 218 and deasphalted oil 220 are appropriately blended with treated pyrolysis oils 130, 131, 132, 133, and 134 in feedstock blending and storage unit 135 to form blended feedstocks prior to undergoing hydrotreatment 121 to produce low-PAH naphthenic lube or process oils 224, 225, 226, and 227 with viscosity grades of 100 VIS, 600 VIS, 2000 VIS, and 5000 VIS. It will be understood by those skilled in the art that the operation conditions may be selected to produce naphthenic lube or process oils having other viscosity grades.

[0062] Turning to FIG. 3, another method for producing low-PAH naphthenic lube or process oils is shown. Here, treated pyrolysis oil may be blended with atmospheric residue residual bottoms in a feedstock blending and storage unit. In turn, the blended feedstock may be subjected to vacuum distillation and hydrotreatment to produce naphthenic lube or process oils. For example, in method 300, crude pyrolysis oil 128 is subjected to pretreatment 129 to produce treated pyrolysis oil 330. Treated pyrolysis oil 330 is blended with atmospheric residue residual bottoms 112 in feedstock blending and storage unit 135. The blended feedstock is processed in a vacuum distillation column 113 to produce vacuum gas oils 316, 317, and 318 with viscosity grades of 100 VIS, 500 VIS, and 2000 VIS. Residue from vacuum distillation 113 is subjected to solvent deasphalting 119 to produce deasphalted oil 320 with a viscosity grade of 5000 VIS. The resulting vacuum gas oils 316, 317, 318 and deasphalted oil 320 are then subjected to hydrotreatment 121 to produce naphthenic lube or process oils 324, 325, 326, and 327 with viscosity grades of 100 VIS, 500 VIS, 2000 VIS, and 5000 VIS. It will be understood by those skilled in the art that the operation conditions may be selected to produce naphthenic lube or process oils having other viscosity grades.

[0063] Although not shown in FIG. 3, pyrolysis pretreatment 129 of crude pyrolysis oil 128 may include hydroprocessing pyrolysis oil 128 in the presence of hydrogen and a non-noble metal catalyst to saturate the olefins and diolefins and decrease the halide, sulfur, and nitrogen content of the crude rubber pyrolysis oil 128 as well as fractionating the pretreated pyrolysis oil into a series of vacuum gas oil boiling range treated pyrolysis oils rather than the single treated pyrolysis oil 330. However, it is expressly contemplated that other processing techniques may be used as well to produce or modify treated pyrolysis oil 330.

[0064] Referring to FIG. 4, another method for producing low-PAH naphthenic lube or process oil is shown. To summarize this embodiment, a full boiling point range treated pyrolysis oil and a full boiling point range naphthenic vacuum gas oil undergo blending in a feedstock blending and storage unit to form a blended feedstock. In turn, the blended feedstock undergoes processing in a hydrotreater to produce a wide boiling point range naphthenic lube or process oil. For example, in method 400, crude pyrolysis oil 128 undergoes pyrolysis pretreatment 129 via hydroprocessing in the presence of hydrogen and a non-noble metal catalyst to saturate the olefins and diolefins and decrease the halide, sulfur, and nitrogen content of the crude rubber pyrolysis oil 128. Without fractionation, the resulting treated pyrolysis oil 330 encompasses a full boiling point range and is blended with a full boiling point range naphthenic vacuum gas oil 412 in a feedstock blending and storage unit 135 to form a blended feedstock prior to undergoing hydrotreatment 121. Naphthenic vacuum gas oil 412 may be provided using vacuum distillation 113 or any other fractionation technique that yields a desired (e.g., full) boiling point range naphthenic vacuum gas oil. Both the naphthenic vacuum gas oil 412 and treated pyrolysis oil 330 may be blended to form a blended feedstock and subjected to hydrotreatment 121 to produce low-PAH naphthenic lube or process oil 417 with a wide boiling point range.

[0065] FIG. 5 shows another method for producing low-PAH naphthenic lube or process oils. In this embodiment treated pyrolysis oil and naphthenic crude oil are blended in a feedstock blending and storage unit to form a blended feedstock which, in turn, undergoes processing g in an atmospheric distillation unit. Processing the blended feedstock in an atmospheric distillation unit may allow a greater overall volume of pyrolysis oil to be processed. For example, in method 500, crude pyrolysis oil 128 is subjected to pretreatment 129 in the form of hydroprocessing in the presence of hydrogen and a non-noble metal catalyst. The resulting treated pyrolysis oil 330 and naphthenic crude 110 are then blended in feedstock blending and storage unit 135 and subjected to processing in atmospheric distillation column 111. Naphthenic and pyrolysis atmospheric gas oils 514 and 515 are produced with viscosity grades of 40 VIS and 60 VIS. Atmospheric residual bottoms 512 are subjected to vacuum distillation 113. Vacuum distillation 113 produces naphthenic and pyrolysis vacuum gas oils 516, 517, and 518 with viscosity grades of 100 VIS, 500 VIS, and 2000 VIS. Additionally, vacuum residue is produced and may be subjected to solvent deasphalting 119 to produce deasphalted oil 520 with a viscosity grade of 5000 VIS. Naphthenic and pyrolysis atmospheric and vacuum gas oils 514, 515, 516, 517, and 518 and deasphalted oil 520 then undergo hydrotreatment 121 to produce low-PAH naphthenic lube or process oils 522, 523, 524, 525, and 526 with viscosity grades of 40 VIS, 60 VIS, 100 VIS, 500 VIS, 2000 VIS, and 5000 VIS. In the FIG. 5 method, pretreatment 129 allows for the removal of contaminants prior to charging to the crude unit, and may reduce changes in the bulk properties of the atmospheric and vacuum gas oils before hydrotreatment as well as changes in the bulk properties of the naphthenic lube or process oils obtained after hydrotreatment.

[0066] Turning to FIG. 6, another method for producing low-PAH naphthenic lube or process oils is shown. To summarize this method, a controlled percentage of untreated or treated pyrolysis oil is blended with naphthenic crude to form a blended feedstock in a feedstock blending and storage unit prior to being introduced into an atmospheric distillation unit. The pyrolysis oil dose preferably is sufficiently low so as to not change the bulk properties of the resulting atmospheric and vacuum gas oils and the product low-PAH naphthenic lube or process oils. For example, when using pretreated pyrolysis oil, then the pyrolysis oil amount may be greater than zero %, e.g., at least 2 wt. %, and up to about 50 wt. %, of the combined weight of pyrolysis oil and naphthenic crude. When using untreated pyrolysis oil, the pyrolysis oil dose may be lower so as to avoid asphaltene instability, sludge formation, and poisoning the downstream hydrotreatment catalyst. Additionally, as noted above, a blended feedstock may include greater than 0% and up to 20% pyrolysis oil components based on the weight of the blended liquid. In FIG. 6, untreated pyrolysis oil 128 is blended with naphthenic crude 110 in a feedstock blending and storage unit 135 prior to being introduced to atmospheric distillation unit 111. Blending may use known techniques that will be familiar to persons of ordinary skill in the art. Once provided to unit 111, naphthenic and pyrolysis atmospheric gas oils 614 and 615 are produced with viscosity grades of 40 VIS and 60 VIS. Additionally, unit 111 produces atmospheric residual bottoms 612 that are provided to vacuum distillation 113 unit to produce naphthenic and pyrolysis vacuum gas oils 616, 617, and 618 and a vacuum distillation residue. The vacuum distillation residue is subjected to solvent deasphalting 119 to produce deasphalted oil 620 with a viscosity grade of 5000 VIS. As shown, naphthenic and pyrolysis vacuum gas oils 616, 617, and 618 have viscosity grades of 100 VIS, 600 VIS, and 2000 VIS. Naphthenic and pyrolysis atmospheric and vacuum gas oils 614-618 may then undergo hydrotreatment 121 to produce low-PAH naphthenic lube or process oils 622-627 with viscosity grades of 40 VIS, 60 VIS, 100 VIS, 600 VIS, 2000 VIS, and 5000 VIS.

[0067] FIG. 7 shows another method for producing low-PAH lube or process oils that will meet naphthenic specifications but which are made without using native naphthenic components (e.g., without prior blending with naphthenic oil). In method 700, crude pyrolysis oil 128 is subjected to pretreatment 129 by hydroprocessing pyrolysis oil 128 in the presence of hydrogen and a non-noble metal catalyst. Treated pyrolysis oil 330 undergoes hydrotreatment 121 in the presence of hydrogen and a non-noble metal catalyst to produce a wide boiling point range low-PAH lube or process oil 717. The hydroprocessing and hydrotreating conditions are adjusted so that oil 717 will meet naphthenic specifications (e.g., VGC, CN content and CP+CA content).

[0068] FIG. 8 shows another method for producing low-PAH lube or process oils that will meet naphthenic specifications but which are made without using native naphthenic components. In this method, crude pyrolysis oil is pretreated by itself using hydroprocessing and fractionation, followed by hydrotreatment to produce low-PAH lube or process oils. For example, in method 800, crude pyrolysis oil 128 undergoes pretreatment 129 in the form of hydroprocessing in the presence of hydrogen and a non-noble metal catalyst followed by fractionation to produce treated pyrolysis oils 130, 131, 132, 133, and 134 with viscosity grades of 40 VIS, 60 VIS, 100 VIS, 600 VIS, and 2000 VIS. Treated pyrolysis oils 130-134 are not blended with naphthenic crude, and instead are subjected to hydrotreatment 121 in the presence of hydrogen and a non-noble metal catalyst to produce low-PAH lube or process oils 822, 823, 824, 825, 826, and 827 with viscosity grades of 40 VIS, 60 VIS, 100 VIS, 600 VIS, 2000 VIS, and 5000 VIS. As in method 700, the hydroprocessing and hydrotreating conditions are adjusted so that oils 822-827 will meet naphthenic specifications.

[0069] Additional processing steps may optionally be employed before or after the steps mentioned above. Examples of such steps include solvent deasphalting, solvent extraction, catalytic dewaxing, solvent dewaxing, hydrofinishing, and hydrocracking. In some embodiments, 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.

[0070] Furthermore, while particular viscosity grades and ranges are referred to above and in the figures, it is expressly contemplated that other viscosity grades and ranges may be produced as well in accordance with the present invention.

[0071] The above description is directed to the disclosed methods 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.

Examples

Embodiment Construction

[0043]FIG. 1 illustratively shows one method for producing a low-PAH naphthenic lube or process oil(s) from pyrolysis and naphthenic crude feedstocks in accordance with an embodiment of the present invention. To summarize this embodiment, pyrolysis oil is pretreated as discussed in more detail below, fractionated into narrow boiling range treated pyrolysis oils, blended with appropriate viscosity (VIS) grades of naphthenic atmospheric oils and vacuum gas oils in a feedstock blending and storage unit, e.g., tankage, and then subjected to hydrotreatment to produce low-PAH naphthenic lube or process oils. For example, method 100 may include receiving naphthenic crude 110; atmospheric distilling 111 naphthenic crude 110 into atmospheric residual bottoms 112 and naphthenic atmospheric gas oils 114 (40 VIS) and 115 (60 VIS); vacuum distilling 113 atmospheric residual bottoms 112 into naphthenic vacuum gas oils 116 (100 VIS), 117 (600 VIS), and 118 (2000 VIS); solvent deasphalting 119 the ...

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation of International Application No. PCT / US2024 / 056404 filed Nov. 18, 2024, which claims priority from U.S. Provisional Application Ser. No. 63 / 599,933 filed Nov. 16, 2023, both entitled “METHODS FOR USING PYROLYSIS OIL AS A FEEDSTOCK FOR MAKING NAPHTHENIC PROCESS AND LUBE OILS”, and the disclosures of which are both incorporated herein by reference.TECHNICAL FIELD

[0002] This invention relates to using pyrolysis oil as a feedstock in the production of naphthenic process and lube oils.BACKGROUND

[0003] Passenger cars and trucks on U.S. highways wear out millions of tires each year, making disposal of used tires a major environmental challenge. Reclaimed rubber from waste tires may be pyrolyzed to produce a highly aromatic and olefinic oil stream known as pyrolysis oil. Pyrolysis oil normally is burned as a fuel, but is sometimes also treated to remove contaminants, saturate olefins, and fractionally separate lighter naphtha and diesel compounds, resulting in cleaner fuels containing little to no sulfur or nitrogen compounds (see e.g., Budhwani, Removal of PAHs Present in Tyre Pyrolytic Oil Using Low Cost natural Adsorbents, International Scholarly and Scientific Research & Innovation 9(2), pp. 186-190 (2015); Campuzano et al., On the distillation of waste tire pyrolysis oil, Fuel 290, 120041 pp. 1-15 (2021); Roy et al, The vacuum pyrolysis of used tires end-uses for oil and carbon black products, Journal of Analytical and Applied Pyrolysis, 51, pp. 201-221 (1999); Roy et al, Conversion of Used Tires to Carbon Black and Oil by Pyrolysis, in De et al., Rubber Recycling, pp. 429-467 (2005) and Williams et al., Sulfur-Polycyclic Aromatic Hydrocarbons in Tyre Pyrolysis Oil, Fuel 74(5), pp. 736-742 (1994). These cleaner fuels may be further hydrocracked into lower molecular weight molecules that also may be used as fuels. Rather than converting pyrolysis oil into fuels, what is needed in the art are other applications and uses for pyrolysis oils. Such applications and uses are disclosed and claimed herein.SUMMARY OF THE INVENTION

[0004] The present invention provides methods for using pyrolysis oil as a feedstock in the production of naphthenic process and lube oils. In a first aspect, the method comprises the steps of (i) blending one or more naphthenic atmospheric gas oils or naphthenic vacuum gas oils with a pyrolysis oil that has been pretreated to reduce the amount(s) of one or more of minerals, metals, halides, alkenes or olefins in such pyrolysis oil, in a feedstock blending and storage unit to produce at least one blended feedstock; and (ii) hydrotreating the at least one blended feedstock in the presence of hydrogen and a non-noble metal catalyst to produce a naphthenic process or lube oil.

[0005] In a second embodiment, the disclosed method comprises the steps of (i) blending residual bottoms from a naphthenic crude atmospheric distillation unit with the pretreated pyrolysis oil in a feedstock blending and storage unit to provide a blended feedstock; (ii) vacuum distilling the blended feedstock to provide one or more blended vacuum gas oils in one or more viscosity ranges; and (iii) hydrotreating the one or more blended vacuum gas oils in the presence of hydrogen and a non-noble metal catalyst to provide the naphthenic process or lube oil.

[0006] In a third embodiment, the disclosed method comprises the steps of (i) blending naphthenic crude with pyrolysis oil in a feedstock blending and storage unit to provide a blended feedstock; (ii) atmospheric distilling the blended feedstock to provide one or more blended atmospheric gas oils in one or more viscosity ranges and residual bottoms; (iii) vacuum distilling the residual bottoms to provide one or more blended vacuum gas oils in one or more viscosity ranges; and (iv) hydrotreating, in combination or separately, the one or more blended atmospheric gas oils and the one or more blended vacuum gas oils to provide the naphthenic process or lube oil.

[0007] The disclosed methods and compositions can employ pyrolysis oil obtained by pyrolyzing waste tires or other post-consumer rubber products. Prior to being blended with naphthenic oil, the pyrolysis oil may undergo a variety of forms of pretreatment to reduce (e.g., to modify or remove) the amount(s) of one or more, two or more, three or more or even all of minerals, metals, halides, alkenes or olefins. In one instance, the pyrolysis oil may be pretreated by subjecting the pyrolysis oil to hydroprocessing in the presence of hydrogen and a non-noble metal catalyst to saturate olefins and diolefins and decrease the halide, sulfur, and nitrogen contents within the pyrolysis oil and produce a pretreated pyrolysis oil. The pretreated pyrolysis oil may then be blended with a crude or fractionated naphthenic oil prior to undergoing hydrotreatment to produce a refined naphthenic process or lube oil. The production and hydroprocessing of the pyrolysis oil and subsequent blending with naphthenic oil may be performed at separate locations or a single location. Additionally, it is to be understood that naphthenic crude, untreated pyrolysis oil or pretreated pyrolysis oil may be blended with naphthenic oils at different stages of naphthenic processing. For example, untreated or pretreated pyrolysis oil may be blended with naphthenic crude, residual bottoms or separated fractions prior to undergoing hydrotreatment to produce the disclosed naphthenic process and lube oils.BRIEF DESCRIPTION OF THE DRAWING

[0008] FIG. 1 through FIG. 8 are schematic diagrams illustrating embodiments of the disclosed methods. Like reference numbers in the various figures indicate like elements.DEFINITIONS

[0009] In this specification, the following terms have the following meanings unless clearly otherwise specified. Further, 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, 3.8, 4, and 5). All percentages are weight percentage unless otherwise stated.

[0010] The term “30-markers” when used with respect to a feedstock, process stream or product refers to the total quantity of the PAH compounds acenaphthene (ACE, CAS No. 83-32-9), acenaphthylene (ACY, CAS No. 208-96-8), anthanthrene (ANT, CAS No. 191-26-4), anthracene (ANTH, CAS No. 120-12-7), benzo(a)anthracene (BaA, CAS No. 56-55-3), benzo(a)pyrene (BaP, CAS No. 50-32-8), benzo(b)fluoranthene (BbFA, CAS No. 205-99-2), benzo(b)naphtho[l,2-d]thiophene (BNT, CAS No. 205-43-6), benzo(e)pyrene (BeP, CAS No. 192-97-2), benzo(ghi)fluoranthene (BghiF, CAS No. 203-12-3), benzo(ghi)perylene (BGI, CAS No. 191-24-2), benzo(j)fluoranthene (BjFA, CAS No. 205-82-3), benzo(k)fluoranthene (BkFA, CAS No. 207-08-9), benzo[c]phenanthrene (BeP, CAS No. 195-19-7), chrysene (CHR, CAS No. 218-01-9), coronene (COR, CAS No. 191-07-1), cyclopenta(c,d)pyrene (CPP, CAS No. 27208-37-3), dibenzo(a,e)pyrene (DBaeP, CAS No. 192-65-4), dibenzo(a,h)anthracene (DBAhA, CAS No. 53-70-3), dibenzo(a,h)pyrene (DBahP, CAS No. 189-64-0), dibenzo(a,i)pyrene (DBaiP, CAS No. 189-55-9), dibenzo(a,l)pyrene (DBalP, CAS No. 191-30-0), fluoranthene (FLA, CAS No. 206-44-0), fluorene (FLU, CAS No. 86-73-7), indeno[123-cd]pyrene (IP, CAS No. 193-39-5), naphthalene (NAP, CAS No. 91-20-3), perylene (PERY, CAS No. 198-55-0), phenanthrene (PHN, CAS No. 85-01-8), pyrene (PYR, CAS No. 129-00-0) and triphenylene (TRIP, CAS No. 217-59-4) in such feedstock, process stream or product.

[0011] The term “22-markers” refers to a subset of the 30-markers PAH compounds, namely the PAH compounds acenaphthene, acenaphthylene, anthracene, benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(e)pyrene, benzo(ghi)perylene, benzo(j)fluoranthene, benzo(k)fluoranthene, chrysene, dibenzo(a,e)pyrene, dibenzo(a,h)anthracene, dibenzo(a,h)pyrene, dibenzo(a,i)pyrene, dibenzo(a,l)pyrene, fluoranthene, fluorene, indeno[123-cd]pyrene, naphthalene, phenanthrene and pyrene.

[0012] The term “18-markers” refers to another subset of the 30-markers PAH compounds, namely the PAH compounds acenaphthene, acenaphthylene, anthracene, benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(e)pyrene, benzo(ghi)perylene, benzo(j)fluoranthene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthracene, fluoranthene, fluorene, indeno[123-cd]pyrene, naphthalene, phenanthrene and pyrene.

[0013] The term “16-markers” refers to yet another subset of the 30-markers PAH compounds, namely the PAH compounds acenaphthene, acenaphthylene, anthracene, benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(ghi)perylene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthracene, fluoranthene, fluorene, indeno[123-cd]pyrene, naphthalene, phenanthrene and pyrene.

[0014] The term “8-markers” refers to a further subset of the 30-markers PAH compounds, namely the compounds benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(e)pyrene, benzo(j)fluoranthene, benzo(k)fluoranthene, chrysene, and dibenzo(a,h)anthracene. Limits of 10 ppm for the sum of the 8-markers, and 1 ppm for benzo[a]pyrene are set forth in European Union Directive 2005 / 69 / EC of the European Parliament and of the Council of 16 Nov. 2005. Industry and regulators have not yet set limits for 16-markers, 18-markers, 22-markers or 30 markers.

[0015] The term “aromatic” when used with respect to a feedstock, process stream or product refers to a liquid material having a viscosity-gravity constant (VGC) close to 1 (e.g., greater than about 0.95) as determined by ASTM D2501. Aromatic feedstocks or process streams may be classified according to their aromatic carbon content (CA), naphthenic carbon content (CN) and paraffinic carbon content (CP), as measured for example according to ASTM D2140, and typically will contain at least about 10% CA content and less than about 90% total CP plus CN content.

[0016] The term “aromatic concentration” or “CA” is the weight percent of aromatic molecules in the composite oil or stream. Aromatic concentration can be measured according to ASTM D2140, D7419, or D3238, the latter method typically being used for heavier petroleum fractions.

[0017] 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.

[0018] The term “blended feedstock” refers to any feedstock that has been synthesized through the combining and mixing of two categorically distinctive feedstocks in a storage system. Blended feedstocks are charged to processing units through a common feedstock collection, storage, and charge system.

[0019] The term “char” refers to a combustible solid organic residue remaining after thermal conversion of a rubber product (e.g., whole tires, ground tire rubber or other whole or comminuted rubber product) using pyrolysis or another at least partially destructive, incompletely oxygenated thermal conversion technique.

[0020] The terms “char oil” and “pyrolysis oil” are used interchangeably and refer to a combustible liquid organic residue remaining after thermal conversion of a rubber product (e.g., whole tires, ground tire rubber or other whole or comminuted rubber product) using pyrolysis or another at least partially destructive, incompletely oxygenated thermal conversion technique.

[0021] The term “clean naphthenic” when used with respect to process stream or product refers to liquid material as determined by ASTM D2501. These materials will contain lower CA content than typical naphthenic material and higher CN content than paraffinic material as measured according to ASTM D2140. These materials will pass FDA C part 2 as well as exhibit low concentrations of PAHs according to EN-16143:2013M.

[0022] The term “co-feed” refers to any feedstock that is charged into a processing unit alongside another categorically distinctive feedstock, and can be contrasted with processing a blended feedstock.

[0023] The term “co-processing” refers to the act of feeding two or more categorically distinct feedstocks to a processing unit at the same time from separate storage and charge systems, and can be contrasted with feeding a blended feedstock into such processing unit.

[0024] The terms “hydrocracking” and “hydrocracker” refer 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.

[0025] The terms “hydrofinishing” and “hydrofinisher” refer 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 or following hydrotreating to improve the color stability and stability towards oxidation of a hydrotreated product.

[0026] The terms “hydroprocessing” and “hydroprocesser” refer to a process in which a feedstock or process stream is reacted with hydrogen in the presence of a catalyst.

[0027] The terms “hydrotreating” and “hydrotreater” refer 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. Mild hydrotreating conditions may for example be in the ranges of 1500-2800 psig and 500-680 deg. F.

[0028] The phrases “low concentrations of PAHs” or “low PAHs” refer to the total polycyclic aromatic hydrocarbon (PAH) content of a desired material, e.g., an untreated or pretreated pyrolysis oil, a process oil or a lube oil. In some embodiments, this may represent a total PAH content of less than 100 ppm for the given material. In other embodiments, this may represent a ppm of less than 100 for any of the 30, 22, 18, 16, or 8 markers. For example, a low PAH may correspond to a PAH of less than 100 ppm, 50 ppm, 30 ppm, 20 ppm, or 10 ppm for any, or all, of the 30, 22, 18, 16, and 8 markers. In additional embodiments, this may represent a total 30 markers sum of less than 5 ppm by method EN-16143:2013M employed by the Southwestern Research Institute (SwRI).

[0029] The term “lube oil” refers to a liquid material with lubricating properties (viz., imparting a reduction in friction between two opposed sliding surfaces) obtained from a petroleum source.

[0030] 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+CA content as measured according to ASTM D2140.

[0031] The term “noble metal” refers to those metals that substantially resist oxidation at high temperatures. While not uniformly defined, such metals typically include rhenium, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold.

[0032] The term “non-noble metal,” while not uniformly defined, generally refers to those metals not considered to be “noble metals.” Such non-noble metals may include tungsten, cobalt, nickel, zinc, manganese, molybdenum, iron, or copper and a variety of other metals.

[0033] The term “paraffinic” when used with respect to a feedstock, process stream or product refers to 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.

[0034] The term “polycyclic” refers to organic compounds having at least two closed, connected rings of atoms.

[0035] The term “pretreated” when used in connection with pyrolysis oil means that the pyrolysis oil has been reacted or separated to reduce or modify undesirable molecular species that may interfere with subsequent steps in the disclosed methods, and especially steps that employ a catalyst susceptible to poisoning by such molecular species.

[0036] The term “process oil” refers to a plasticizer or extender oil useful in the manufacture of tires and other rubber products.

[0037] The term “processing unit” refers to any non-storage unit or subunit within a facility where one or more process operations are performed. Processing operations can include separating, heating, cooling, pressuring, depressuring, pumping or compressing with the intent of movement, subjecting to a chemical reaction, or causing a phase change.

[0038] The term “pyrolysis” refers to actual pyrolysis or any other incompletely oxygenated thermal conversion technique that at least partially destroys an organic material and enables the separation or recovery of one or more organic components present in or useful in making such organic material.

[0039] The term “pyrolysis oil source” refers to, in whole or in part, waste tires, gaskets, seals, roofing membranes, waterproofing membranes, and any other rubber sources capable of yielding pyrolysis oil.

[0040] The term “reactive olefin” when used with respect to a rubber pyrolysis oil refers to unsaturated hydrocarbons that may be present in such rubber pyrolysis oil and contain at least one reactive carbon-carbon double bond which when combined with a heavy crude to form a blended feedstock and fed to a processing unit may cause precipitation of asphaltenes, heat exchanger fouling or objectionable sludge accumulation in the processing unit.

[0041] 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.

[0042] The terms “Viscosity-Gravity Constant” or “VGC” refer to an index for the approximate characterization of the viscous fractions of petroleum. VGC is defined as the general relation between specific gravity and Saybolt Universal viscosity. VGC may be determined according to ASTM D2501. It should be noted that VGC is relatively insensitive to molecular weight.DETAILED DESCRIPTION

[0043] FIG. 1 illustratively shows one method for producing a low-PAH naphthenic lube or process oil(s) from pyrolysis and naphthenic crude feedstocks in accordance with an embodiment of the present invention. To summarize this embodiment, pyrolysis oil is pretreated as discussed in more detail below, fractionated into narrow boiling range treated pyrolysis oils, blended with appropriate viscosity (VIS) grades of naphthenic atmospheric oils and vacuum gas oils in a feedstock blending and storage unit, e.g., tankage, and then subjected to hydrotreatment to produce low-PAH naphthenic lube or process oils. For example, method 100 may include receiving naphthenic crude 110; atmospheric distilling 111 naphthenic crude 110 into atmospheric residual bottoms 112 and naphthenic atmospheric gas oils 114 (40 VIS) and 115 (60 VIS); vacuum distilling 113 atmospheric residual bottoms 112 into naphthenic vacuum gas oils 116 (100 VIS), 117 (600 VIS), and 118 (2000 VIS); solvent deasphalting 119 the vacuum distillation residue to make deasphalted oil 120 (5000 VIS); blending naphthenic atmospheric and vacuum gas oils 114, 115, 116, 117, and 118 with the corresponding viscosity grade treated pyrolysis oils 130, 131, 132, 133, and 134 to form blended feedstocks in feedstock blending and storage unit(s) 135; and hydrotreating 121 the blended feedstocks to produce low-PAH naphthenic lube or process oils 122, 123, 124, 125, 126, and 127. The FIG. 1 method provides good control over quality and good protection of equipment integrity even at high charge rates.

[0044] A variety of naphthenic crude residual bottoms and naphthenic crudes may be employed as naphthenic crude in the disclosed method. Exemplary naphthenic crudes may be obtained from a variety of sources, including Brazilian, North Sea, West African, Australian, Canadian, Venezuelan, and North American 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, at least about 0.855, at least about 0.86 or at least about 0.865, and a VGC less than about 1, less than about 0.95, less than about 0.9 or less than about 0.895, as determined by ASTM D2501. Preferred naphthenic crudes will provide atmospheric and vacuum gas oils 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+CA content as measured according to ASTM D2140.

[0045] Turning to step 111, atmospheric distillation 111 of naphthenic crude 110 may be performed in an atmospheric distillation unit operated in accordance with standard industry practices that will be familiar to persons having ordinary skill in the art. In the FIG. 1 embodiment, atmospheric distillation 111 produces atmospheric gas oils 114 and 115 with viscosity grades of 40 VIS and 60 VIS and atmospheric residual bottoms 112, but atmospheric gas oils with other viscosity grades and initial boiling points may be produced if desired. The remaining atmospheric residual bottoms are subjected to vacuum distillation 113. Vacuum distillation 113 may be performed in a vacuum distillation unit operated in accordance with standard industry practices that will be familiar to persons having ordinary skill in the art. In the FIG. 1 embodiment, distillation 113 produces vacuum gas oils 116, 117, and 118 with viscosity grades of 100 VIS, 600 VIS, and 2000 VIS, but vacuum gas oils with other viscosity grades and initial boiling points may be produced if desired. The remaining vacuum distillation residue is subjected to solvent deasphalting 119 to produce 5000 VIS oil 120, but oils with other viscosity grades and initial boiling points may be produced if desired.

[0046] Turning to pyrolysis oil 128 and pretreatment step 129, crude pyrolysis oil 128 is initially provided via pyrolysis of one or more rubber pyrolysis oil sources. For example, reclaimed tire rubber may undergo mechanical shearing / grinding and pyrolysis to produce crude pyrolysis oil 128. Mechanical shearing / grinding is however optional, and whole waste tires may be used by themselves, or in combination with, other rubber pyrolysis oil sources. Rubber pyrolysis commonly takes place in a pyrolysis reactor and necessitates heating the rubber pyrolysis oil source in an absence of oxygen to produce crude rubber pyrolysis oil 128, typically, “liquified rubber” or “LR,” along with syngas, carbon solids, and ash. The carbon solids fraction may be referred to as “char,”“carbon char,”“tired derived char” or “tire derived carbon char,” and typically includes a substantial amount of carbon black which may be used in the manufacture of new tires or other rubber products. Syngas may be incinerated, flared, or compressed to provide fuel which may be employed in the pyrolysis reaction or in any other process that uses thermal energy.

[0047] The rubber pyrolysis reactor may operate at temperatures and pressures that will be familiar to persons having ordinary skill in the art, and may utilize either batch feed or continuous feed rubber pyrolysis oil source loading. Batch feed systems process a single charge of rubber pyrolysis oil source at a given time to produce crude rubber pyrolysis oil 128 for downstream processing together with syngas, carbon solids, and ash. In continuous feed systems, a rubber pyrolysis oil source feedstock is continuously conveyed through a rubber pyrolysis reactor, and crude rubber pyrolysis oil 128, syngas, carbon solids, and ash are continuously discharged or consumed.

[0048] Operating temperatures and pressures of the rubber pyrolysis reactor may be chosen to break up desired chemical bonds, including carbon-carbon, sulfur-carbon and sulfur-sulfur bonds within the rubber pyrolysis oil source to produce crude rubber pyrolysis oil 128. Typical operating temperatures may be about 480 to 1740° C. Above 750° C., and depending on the particular process employed, the yield of crude rubber pyrolysis oil 128 and char may decrease relative to gas production. In other embodiments, rubber pyrolysis may be carried out at a reduced pressure, e.g., under vacuum or at atmospheric pressure, to provide increased crude rubber pyrolysis oil 128 yields. However, such yields may be impacted by the type of rubber pyrolysis oil source (e.g., passenger, truck, all-season or snow tires). Operating temperatures and pressures may be adjusted to produce an optimized yield of crude rubber pyrolysis oil 128.

[0049] After crude pyrolysis oil 128 is produced, pretreatment 129 of the crude pyrolysis oil 128 is performed to reduce (e.g., to modify or remove) undesirable molecular species that may interfere with subsequent steps in the disclosed method, such as reducing one or more of minerals, metals, halides, alkenes or olefins in such pyrolysis oil. For example, pretreatment may be carried out by modifying the feedstocks and processing steps employed in published patent applications US 2021 / 371753 A1, US 2023 / 020918 A1, GB2605002 A, WO 2011 / 077419 A1, WO 2016 / 030460 A1, WO 2022 / 084238 A1, WO 2022 / 084433 A1, WO 2023 / 017250 A1 and WO 2023 / 094629 A1, the disclosures of which are incorporated by reference in their entirety, including replacing the plastic feedstocks employed in these applications with rubber pyrolysis oil sources.

[0050] In some embodiments, pretreatment 129 includes hydroprocessing crude rubber pyrolysis oil 128 in the presence of hydrogen and a non-noble metal catalyst to saturate the olefins and diolefins and decrease the halide, sulfur, and nitrogen content of crude rubber pyrolysis oil 128. Hydroprocessing serves to clean or reduce the impurities within crude rubber pyrolysis oil 128 to allow for further downstream hydrotreatment 121 without running the risk of poisoning or negatively affecting a metal catalyst employed in such downstream hydrotreatment 121. Further, hydroprocessing may also allow for significant reduction or elimination of any existing 30-, 22-, 18-, 16-, or 8-markers to achieve a reduced or even low PAH level.

[0051] Non-noble metal catalysts suitable for hydroprocessing include any combination of non-noble metals, e.g., tungsten, cobalt, nickel, zinc, manganese, molybdenum, iron, or copper. Within the hydroprocessor, the non-noble metal catalyst may be coupled to a catalyst support structure. The support may be a refractory metal oxide, for example, alumina, silica or silica-alumina. Exemplary commercially available hydroprocessing catalysts are available from companies including Advanced Refining Technologies, Albemarle, Axens, Criterion and Haldor Topsoe.

[0052] In operation, hydroprocessing may be performed at operating conditions of about 10,342 kPa (1500 psig) to about 19,305 kPa (2800 psig) and about 260° C. (500° F.) to about 360° C. to about 680° F. However, other operating conditions may be employed so long as desired impurities are sufficiently removed and a suitable level of saturation is achieved. The quantity of hydrogen used to contact a feedstock may for example be about 17.8 to about 1,780 m / m (about 100 to about 10,000 standard cubic feet per barrel (scf / B)) of the feedstock stream. Reaction times between the hydroprocessing catalyst and the feedstock may be chosen to provide a liquid hourly space velocity (LHSV) of about 0.25 to about 5 cc of oil per cc of catalyst per hour. However, it is to be understood that other operating conditions may be used as well based on downstream processing needs or the innate characteristics of crude rubber pyrolysis oil 128.

[0053] Additional pretreatment steps may be employed as a part of pretreatment 129. For example, before or after hydroprocessing, the pretreated rubber pyrolysis oil may undergo atmospheric and vacuum distillation to produce one or more pretreated rubber pyrolysis atmospheric gas oils and pretreated rubber pyrolysis vacuum gas oils in desired VIS grades. The pretreated rubber pyrolysis atmospheric and vacuum gas oils may then be subjected to hydroprocessing. While rubber pyrolysis pretreatment 129 includes hydroprocessing and, in some embodiments, atmospheric and vacuum distillation, it is to be understood that further additional or alternative steps may be used to produce treated rubber pyrolysis oils 130-134.

[0054] Blending of treated pyrolysis oils 130-134 with naphthenic atmospheric and vacuum gas oils 114-118 may occur in a variety of ways. For example, treated pyrolysis oils 130-134 may be blended with appropriate e.g., matching or overlapping VIS grades of naphthenic atmospheric and vacuum gas oils 114-118 in a feedstock storage unit 135, and then later supplied as a blended feedstock, to the hydrotreater of hydrotreatment 121. However, it is expressly contemplated that the pyrolysis oils 130-134 may be blended with naphthenic atmospheric and vacuum gas oils in other ways that will be familiar to those skilled in the art. After blending, the resulting blended feedstock(s) may be subjected to hydrotreatment 121 or other types of downstream processing.

[0055] During formation of a blended feedstock, it may be advantageous to avoid asphaltene instability, resulting in sludge formation or gum formation due to highly reactive olefins in pyrolysis oil 128, e.g., tire pyrolysis oil. Generally, a blended feedstock of treated pyrolysis oils 130-134 should include a reactive olefin content under 2,000 ppm, preferably under 1,000 ppm, and, most preferably, under 750 ppm. To assist in the prevention of gum formation, additives may be used as well. Such additives may include antioxidants, e.g., RPS-828 from Halliburton, and polymerization inhibitors, e.g., Trident 290 from Innospec Inc.

[0056] A blending envelope, or blending conditions, may vary as a resulting blended feedstock is stored or otherwise charged to downstream processing units through a common feedstock collection, storage, and charge system. For example, a much larger amount of treated pyrolysis oil may be blended into crude oil located in a tank, e.g., up to 20 wt. %, as compared to downstream processing units, e.g., up to 1 wt. %. Specifically, for tank blending with heavy crude oil, blending of up to 20 wt. %, 10 wt. %, and, most desirably, 5 wt. % of pyrolysis oil may occur without causing significant asphaltene precipitation. However, factors influencing or altering such blending ratio with crude oil may include asphaltene content, resin content, aromatic content, saturated compound content, condensate content (C5, C6, and C7 compounds), and API gravity.

[0057] For downstream unit processing, blended feedstocks desirably include up to 1 wt. % and, in exemplary embodiments, up to 0.5 wt. % of pyrolysis oil. If greater pyrolysis oil amounts are used, reactive olefins in the pyrolysis oil may react on heat exchanger surfaces causing gum formation, plugging, generalized fouling, and loss of heat transfer. However, depending on a reactive olefin content and processing unit, other amounts of pyrolysis oil may be used as well. In accordance with the present disclosure, a reactive olefin content of pyrolysis oil should be kept as low as possible to prevent asphaltene instability and sludge formation.

[0058] Hydrotreatment 121 may be carried out in a hydrotreater containing a non-noble metal catalyst and a hydrogen source. In operation, the blended oils contact the non-noble metal catalyst in the presence of hydrogen under suitable hydrotreating conditions to facilitate the production of naphthenic lube or process oils through the saturation and removal or reduction of heteroatoms, and if desired the removal or reduction of aromatic color bodies. The hydrotreater may include a fixed catalyst bed, fluidized catalyst bed, moving bed, slurry bed, counter current bed or transfer flow catalyst bed.

[0059] Non-noble metal catalysts for hydrotreating may include, in addition to the non-noble metal, at least one other 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 other metal will generally be present in the catalyst composition in the form of an oxide or sulfide. Exemplary other metals include iron, cobalt, nickel, tungsten, molybdenum and chromium. Particularly desirable other metals are cobalt, nickel, molybdenum and tungsten. Within the hydrotreater, the non-noble metal catalyst may be coupled to a catalyst support structure. 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 from Criterion. Companies such as Albemarle, Axens, Haldor Topsoe, and Advanced Refining Technologies also market suitable non-noble metal hydrotreating catalysts.

[0060] Operating conditions of the hydrotreater may 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. It will be understood by those skilled in the art that such operation conditions may be selected to produce naphthenic lube or process oils 122, 123, 124, 125, 126, and 127 with 40 VIS, 60 VIS, 100 VIS, 600 VIS, 2000 VIS, and 5000 VIS respectively, or to produce naphthenic lube or process oils having other viscosity grades.

[0061] Referring to FIG. 2, a method for producing low-PAH naphthenic lube or process oils is shown. To summarize this embodiment, crude pyrolysis oil is pretreated and fractionated into narrow boiling ranges as in the FIG. 1 method, but the resulting treated pyrolysis oils are blended with appropriate VIS grades of naphthenic vacuum gas oils and solvent deasphalted oil in a feedstock blending and storage unit to form blended feedstocks, but are not blended with naphthenic atmospheric gas oils. In turn, the blended feedstocks are subjected to hydrotreatment to produce naphthenic lube or process oils. For example, method 200 may include vacuum distilling 113 atmospheric residual bottoms 212 to produce naphthenic gas oils 216, 217, and 218 with viscosity grades of 100 VIS, 600 VIS, and 2000 VIS respectively. Residue from vacuum distillation 113 is subjected to solvent deasphalting 219 to produce deasphalted oil 220 with a 5000 VIS. The naphthenic vacuum gas oils 216, 217, and 218 and deasphalted oil 220 are appropriately blended with treated pyrolysis oils 130, 131, 132, 133, and 134 in feedstock blending and storage unit 135 to form blended feedstocks prior to undergoing hydrotreatment 121 to produce low-PAH naphthenic lube or process oils 224, 225, 226, and 227 with viscosity grades of 100 VIS, 600 VIS, 2000 VIS, and 5000 VIS. It will be understood by those skilled in the art that the operation conditions may be selected to produce naphthenic lube or process oils having other viscosity grades.

[0062] Turning to FIG. 3, another method for producing low-PAH naphthenic lube or process oils is shown. Here, treated pyrolysis oil may be blended with atmospheric residue residual bottoms in a feedstock blending and storage unit. In turn, the blended feedstock may be subjected to vacuum distillation and hydrotreatment to produce naphthenic lube or process oils. For example, in method 300, crude pyrolysis oil 128 is subjected to pretreatment 129 to produce treated pyrolysis oil 330. Treated pyrolysis oil 330 is blended with atmospheric residue residual bottoms 112 in feedstock blending and storage unit 135. The blended feedstock is processed in a vacuum distillation column 113 to produce vacuum gas oils 316, 317, and 318 with viscosity grades of 100 VIS, 500 VIS, and 2000 VIS. Residue from vacuum distillation 113 is subjected to solvent deasphalting 119 to produce deasphalted oil 320 with a viscosity grade of 5000 VIS. The resulting vacuum gas oils 316, 317, 318 and deasphalted oil 320 are then subjected to hydrotreatment 121 to produce naphthenic lube or process oils 324, 325, 326, and 327 with viscosity grades of 100 VIS, 500 VIS, 2000 VIS, and 5000 VIS. It will be understood by those skilled in the art that the operation conditions may be selected to produce naphthenic lube or process oils having other viscosity grades.

[0063] Although not shown in FIG. 3, pyrolysis pretreatment 129 of crude pyrolysis oil 128 may include hydroprocessing pyrolysis oil 128 in the presence of hydrogen and a non-noble metal catalyst to saturate the olefins and diolefins and decrease the halide, sulfur, and nitrogen content of the crude rubber pyrolysis oil 128 as well as fractionating the pretreated pyrolysis oil into a series of vacuum gas oil boiling range treated pyrolysis oils rather than the single treated pyrolysis oil 330. However, it is expressly contemplated that other processing techniques may be used as well to produce or modify treated pyrolysis oil 330.

[0064] Referring to FIG. 4, another method for producing low-PAH naphthenic lube or process oil is shown. To summarize this embodiment, a full boiling point range treated pyrolysis oil and a full boiling point range naphthenic vacuum gas oil undergo blending in a feedstock blending and storage unit to form a blended feedstock. In turn, the blended feedstock undergoes processing in a hydrotreater to produce a wide boiling point range naphthenic lube or process oil. For example, in method 400, crude pyrolysis oil 128 undergoes pyrolysis pretreatment 129 via hydroprocessing in the presence of hydrogen and a non-noble metal catalyst to saturate the olefins and diolefins and decrease the halide, sulfur, and nitrogen content of the crude rubber pyrolysis oil 128. Without fractionation, the resulting treated pyrolysis oil 330 encompasses a full boiling point range and is blended with a full boiling point range naphthenic vacuum gas oil 412 in a feedstock blending and storage unit 135 to form a blended feedstock prior to undergoing hydrotreatment 121. Naphthenic vacuum gas oil 412 may be provided using vacuum distillation 113 or any other fractionation technique that yields a desired (e.g., full) boiling point range naphthenic vacuum gas oil. Both the naphthenic vacuum gas oil 412 and treated pyrolysis oil 330 may be blended to form a blended feedstock and subjected to hydrotreatment 121 to produce low-PAH naphthenic lube or process oil 417 with a wide boiling point range.

[0065] FIG. 5 shows another method for producing low-PAH naphthenic lube or process oils. In this embodiment treated pyrolysis oil and naphthenic crude oil are blended in a feedstock blending and storage unit to form a blended feedstock which, in turn, undergoes processing g in an atmospheric distillation unit. Processing the blended feedstock in an atmospheric distillation unit may allow a greater overall volume of pyrolysis oil to be processed. For example, in method 500, crude pyrolysis oil 128 is subjected to pretreatment 129 in the form of hydroprocessing in the presence of hydrogen and a non-noble metal catalyst. The resulting treated pyrolysis oil 330 and naphthenic crude 110 are then blended in feedstock blending and storage unit 135 and subjected to processing in atmospheric distillation column 111. Naphthenic and pyrolysis atmospheric gas oils 514 and 515 are produced with viscosity grades of 40 VIS and 60 VIS. Atmospheric residual bottoms 512 are subjected to vacuum distillation 113. Vacuum distillation 113 produces naphthenic and pyrolysis vacuum gas oils 516, 517, and 518 with viscosity grades of 100 VIS, 500 VIS, and 2000 VIS. Additionally, vacuum residue is produced and may be subjected to solvent deasphalting 119 to produce deasphalted oil 520 with a viscosity grade of 5000 VIS. Naphthenic and pyrolysis atmospheric and vacuum gas oils 514, 515, 516, 517, and 518 and deasphalted oil 520 then undergo hydrotreatment 121 to produce low-PAH naphthenic lube or process oils 522, 523, 524, 525, and 526 with viscosity grades of 40 VIS, 60 VIS, 100 VIS, 500 VIS, 2000 VIS, and 5000 VIS. In the FIG. 5 method, pretreatment 129 allows for the removal of contaminants prior to charging to the crude unit, and may reduce changes in the bulk properties of the atmospheric and vacuum gas oils before hydrotreatment as well as changes in the bulk properties of the naphthenic lube or process oils obtained after hydrotreatment.

[0066] Turning to FIG. 6, another method for producing low-PAH naphthenic lube or process oils is shown. To summarize this method, a controlled percentage of untreated or treated pyrolysis oil is blended with naphthenic crude to form a blended feedstock in a feedstock blending and storage unit prior to being introduced into an atmospheric distillation unit. The pyrolysis oil dose preferably is sufficiently low so as to not change the bulk properties of the resulting atmospheric and vacuum gas oils and the product low-PAH naphthenic lube or process oils. For example, when using pretreated pyrolysis oil, then the pyrolysis oil amount may be greater than zero %, e.g., at least 2 wt. %, and up to about 50 wt. %, of the combined weight of pyrolysis oil and naphthenic crude. When using untreated pyrolysis oil, the pyrolysis oil dose may be lower so as to avoid asphaltene instability, sludge formation, and poisoning the downstream hydrotreatment catalyst. Additionally, as noted above, a blended feedstock may include greater than 0% and up to 20% pyrolysis oil components based on the weight of the blended liquid. In FIG. 6, untreated pyrolysis oil 128 is blended with naphthenic crude 110 in a feedstock blending and storage unit 135 prior to being introduced to atmospheric distillation unit 111. Blending may use known techniques that will be familiar to persons of ordinary skill in the art. Once provided to unit 111, naphthenic and pyrolysis atmospheric gas oils 614 and 615 are produced with viscosity grades of 40 VIS and 60 VIS. Additionally, unit 111 produces atmospheric residual bottoms 612 that are provided to vacuum distillation 113 unit to produce naphthenic and pyrolysis vacuum gas oils 616, 617, and 618 and a vacuum distillation residue. The vacuum distillation residue is subjected to solvent deasphalting 119 to produce deasphalted oil 620 with a viscosity grade of 5000 VIS. As shown, naphthenic and pyrolysis vacuum gas oils 616, 617, and 618 have viscosity grades of 100 VIS, 600 VIS, and 2000 VIS. Naphthenic and pyrolysis atmospheric and vacuum gas oils 614-618 may then undergo hydrotreatment 121 to produce low-PAH naphthenic lube or process oils 622-627 with viscosity grades of 40 VIS, 60 VIS, 100 VIS, 600 VIS, 2000 VIS, and 5000 VIS.

[0067] FIG. 7 shows another method for producing low-PAH lube or process oils that will meet naphthenic specifications but which are made without using native naphthenic components (e.g., without prior blending with naphthenic oil). In method 700, crude pyrolysis oil 128 is subjected to pretreatment 129 by hydroprocessing pyrolysis oil 128 in the presence of hydrogen and a non-noble metal catalyst. Treated pyrolysis oil 330 undergoes hydrotreatment 121 in the presence of hydrogen and a non-noble metal catalyst to produce a wide boiling point range low-PAH lube or process oil 717. The hydroprocessing and hydrotreating conditions are adjusted so that oil 717 will meet naphthenic specifications (e.g., VGC, CN content and CP+CA content).

[0068] FIG. 8 shows another method for producing low-PAH lube or process oils that will meet naphthenic specifications but which are made without using native naphthenic components. In this method, crude pyrolysis oil is pretreated by itself using hydroprocessing and fractionation, followed by hydrotreatment to produce low-PAH lube or process oils. For example, in method 800, crude pyrolysis oil 128 undergoes pretreatment 129 in the form of hydroprocessing in the presence of hydrogen and a non-noble metal catalyst followed by fractionation to produce treated pyrolysis oils 130, 131, 132, 133, and 134 with viscosity grades of 40 VIS, 60 VIS, 100 VIS, 600 VIS, and 2000 VIS. Treated pyrolysis oils 130-134 are not blended with naphthenic crude, and instead are subjected to hydrotreatment 121 in the presence of hydrogen and a non-noble metal catalyst to produce low-PAH lube or process oils 822, 823, 824, 825, 826, and 827 with viscosity grades of 40 VIS, 60 VIS, 100 VIS, 600 VIS, 2000 VIS, and 5000 VIS. As in method 700, the hydroprocessing and hydrotreating conditions are adjusted so that oils 822-827 will meet naphthenic specifications.

[0069] Additional processing steps may optionally be employed before or after the steps mentioned above. Examples of such steps include solvent deasphalting, solvent extraction, catalytic dewaxing, solvent dewaxing, hydrofinishing, and hydrocracking. In some embodiments, 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.

[0070] Furthermore, while particular viscosity grades and ranges are referred to above and in the figures, it is expressly contemplated that other viscosity grades and ranges may be produced as well in accordance with the present invention.

[0071] The above description is directed to the disclosed methods 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.

Examples

Embodiment Construction

[0043]FIG. 1 illustratively shows one method for producing a low-PAH naphthenic lube or process oil(s) from pyrolysis and naphthenic crude feedstocks in accordance with an embodiment of the present invention. To summarize this embodiment, pyrolysis oil is pretreated as discussed in more detail below, fractionated into narrow boiling range treated pyrolysis oils, blended with appropriate viscosity (VIS) grades of naphthenic atmospheric oils and vacuum gas oils in a feedstock blending and storage unit, e.g., tankage, and then subjected to hydrotreatment to produce low-PAH naphthenic lube or process oils. For example, method 100 may include receiving naphthenic crude 110; atmospheric distilling 111 naphthenic crude 110 into atmospheric residual bottoms 112 and naphthenic atmospheric gas oils 114 (40 VIS) and 115 (60 VIS); vacuum distilling 113 atmospheric residual bottoms 112 into naphthenic vacuum gas oils 116 (100 VIS), 117 (600 VIS), and 118 (2000 VIS); solvent deasphalting 119 the ...

Claims

1. A method for producing a naphthenic process or lube oil, the method comprising the steps of:blending one or more naphthenic atmospheric gas oils or one or more naphthenic vacuum gas oils, in combination or individually, with a pyrolysis oil that has been pretreated to reduce the amount(s) of one or more of minerals, metals, halides, alkenes or olefins in the pretreated pyrolysis oil, in a feedstock blending and storage unit to produce at least one blended feedstock; andhydrotreating the at least one blended feedstock in the presence of hydrogen and a non-noble metal catalyst to produce the naphthenic process or lube oil.

2. A method according to claim 1, wherein the one or more naphthenic atmospheric gas oils and the one or more naphthenic vacuum gas oils are provided by:atmospheric distilling naphthenic crude in an atmospheric distillation unit to produce the one or more naphthenic atmospheric gas oils in one or more viscosity ranges and residual bottoms; andvacuum distilling the residual bottoms from the atmospheric distillation unit to produce the one or more naphthenic vacuum gas oils in one or more viscosity ranges.

3. A method according to claim 2, wherein the pretreated pyrolysis oil is provided by:hydroprocessing pyrolysis oil in the presence of hydrogen and a non-noble metal catalyst to saturate olefins and diolefins and decrease halide, sulfur and nitrogen contents within the pyrolysis oil, thereby providing the pretreated pyrolysis oil.

4. A method according to claim 3, further comprising:atmospheric distilling the pretreated pyrolysis oil to produce one or more pretreated pyrolysis atmospheric gas oils in a first viscosity range and pretreated pyrolysis oil residual bottoms;vacuum distilling the pretreated pyrolysis oil residual bottoms to produce one or more pretreated pyrolysis vacuum gas oils in a second viscosity range; andwherein blending comprises mixing the first and second viscosity ranges with substantially similar viscosity ranges of the one or more naphthenic atmospheric gas oils and the naphthenic vacuum gas oils in the feedstock blending and storage unit to produce the at least one blended feedstock.

5. A method according to claim 3, further comprising:atmospheric distilling the pretreated pyrolysis oil to produce one or more pretreated pyrolysis atmospheric gas oils in a first full boiling range and pretreated pyrolysis oil residual bottoms;vacuum distilling the pretreated pyrolysis oil residual bottoms to produce one or more pretreated pyrolysis vacuum gas oils in a second full boiling range; andwherein blending comprises mixing the first and second full boiling ranges with corresponding full boiling ranges of the one or more naphthenic atmospheric gas oils and the naphthenic vacuum gas oils in the feedstock blending and storage unit to produce the at least one blended feedstock.

6. A method for producing a naphthenic process or lube oil, the method comprising the steps of:blending residual bottoms from a naphthenic crude atmospheric distillation unit with a pyrolysis oil that has been pretreated to reduce the amount(s) of one or more of minerals, metals, halides, alkenes or olefins in the pretreated pyrolysis oil, in a feedstock blending and storage unit to produce a blended feedstock;vacuum distilling the blended feedstock to provide one or more blended vacuum gas oils in one or more viscosity ranges; andhydrotreating the one or more blended vacuum gas oils in the presence of hydrogen and a non-noble metal catalyst to provide the naphthenic process or lube oil.

7. A method according to claim 6, wherein the pretreated pyrolysis oil is provided by:hydroprocessing pyrolysis oil in the presence of hydrogen and a non-noble metal catalyst to saturate olefins and diolefins and decrease a halide, sulfur, and nitrogen content within the pyrolysis oil, thereby providing the pretreated pyrolysis oil.

8. A method for producing a naphthenic process or lube oil, the method comprising the steps of:blending naphthenic crude with pyrolysis oil in a feedstock blending and storage unit to provide a blended feedstock;atmospheric distilling the blended feedstock to provide one or more blended atmospheric gas oils in one or more viscosity ranges and residual bottoms;vacuum distilling the residual bottoms to provide one or more blended vacuum gas oils in one or more viscosity ranges; andhydrotreating, in combination or separately, the one or more blended atmospheric gas oils and the one or more blended vacuum gas oils to provide the naphthenic process or lube oil.

9. A method according to claim 8, wherein the pyrolysis oil comprises pretreated pyrolysis oil provided by:hydroprocessing the pyrolysis oil in the presence of hydrogen and a non-noble metal catalyst to saturate olefins and diolefins and decrease the halide, sulfur, and nitrogen contents within the pyrolysis oil, thereby providing the pretreated pyrolysis oil.

10. A method according to claim 8, wherein the blended feedstock comprises greater than 0% and up to 20% pyrolysis oil components based on the weight of the blended feedstock.

11. A method according to claim 8, wherein the blended feedstock includes a reactive olefin content under 2,000 ppm and the naphthenic process or lube oil comprises less than about 10 ppm PAH 8-markers when evaluated according to European standard EN 16143:2013.

12. A method according to claim 8, wherein the pyrolysis oil is provided by pyrolyzing size-reduced rubber particles from rubber tires, gaskets, seals, roofing membranes, waterproofing membranes, post-consumer rubber products or a combination thereof.

13. A method according to claim 8, further comprising:combining the naphthenic process or lube oil with a rubber formulation.

14. A method according to claim 6, wherein the blended feedstock comprises greater than 0% and up to 20% pyrolysis oil components based on the weight of the blended feedstock.

15. A method according to claim 6, wherein the blended feedstock includes a reactive olefin content under 2,000 ppm and the naphthenic process or lube oil comprises less than about 10 ppm PAH 8-markers when evaluated according to European standard EN 16143:2013.

16. A method according to claim 6, wherein the pyrolysis oil is provided by pyrolyzing size-reduced rubber particles from rubber tires, gaskets, seals, roofing membranes, waterproofing membranes, post-consumer rubber products or a combination thereof.

17. A method according to claim 6, further comprising:combining the naphthenic process or lube oil with a rubber formulation.

18. A method according to claim 1, wherein the blended feedstock comprises greater than 0% and up to 20% pyrolysis oil components based on the weight of the blended feedstock.

19. A method according to claim 1, wherein the blended feedstock includes a reactive olefin content under 2,000 ppm and the naphthenic process or lube oil comprises less than about 10 ppm PAH 8-markers when evaluated according to European standard EN 16143:2013.

20. A method according to claim 1, wherein the pyrolysis oil is provided by pyrolyzing size-reduced rubber particles from rubber tires, gaskets, seals, roofing membranes, waterproofing membranes, post-consumer rubber products or a combination thereof.

21. A method according to claim 1, further comprising:combining the naphthenic process or lube oil with a rubber formulation.

22. A method for producing a process or lube oil meeting naphthenic specifications, the method comprising the steps of:pretreating a rubber pyrolysis oil by hydroprocessing in the presence of hydrogen and a non-noble metal catalyst to provide a pretreated pyrolysis oil having reduced amount(s) of one or more minerals, metals, halides, alkenes or olefins;vacuum distilling or otherwise fractionating the pretreated pyrolysis oil to provide treated oil(s) having one or more viscosity ranges; andhydrotreating the treated oil(s) in the presence of hydrogen and a non-noble metal catalyst to provide process or lube oils, using hydroprocessing and hydrotreating conditions to provide process or lube oils meeting naphthenic specifications.

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