Methods for producing API group 111, technical white oil from rubber derived pyrolysis oil

Abstract

API Group III Technical White Oils useful for skin contact, cosmetics, food contact and other applications may be produced in a variety of viscosity ranges including 30 SUS to 2000 SUS at 100 deg. F. by pretreating rubber pyrolysis oil via hydroprocessing in the presence of hydrogen and a non-noble metal catalyst, subjecting the pretreated rubber pyrolysis oil to hydrotreatment in the presence of hydrogen and a noble metal catalyst, and fractionating the resulting product into API Group III Technical White Oils. The disclosed method can remove or substantially reduce heteroatoms and aromatic color bodies in the rubber pyrolysis oil and provide a water-white product.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation of International Application No. PCT / US2024 / 056406 filed Nov. 18, 2024 and entitled “METHODS FOR PRODUCING API GROUP III, TECHNICAL WHITE OIL FROM RUBBER DERIVED PYROLYSIS OIL”, which claims priority from U.S. Provisional Application Ser. No. 63 / 599,937 filed Nov. 16, 2023 and entitled “METHODS FOR UPGRADING RUBBER DERIVED PYROLYSIS OIL TO API GROUP III, TECHNICAL WHITE OIL”, the disclosures of which are incorporated herein by reference.TECHNICAL FIELD

[0002] This disclosure relates to the production of technical white oils for use in cosmetics, other skin care applications and for use on or in food-contact products.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 rubber pyrolysis oil. Rubber 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. These cleaner fuels may be further hydrocracked into lower molecular weight molecules that also may be used as fuels. Rather than converting rubber pyrolysis oil into fuels, what is needed in the art are other applications and uses for rubber pyrolysis oils. Such applications and uses are disclosed and claimed herein.SUMMARY

[0004] The present invention provides methods for producing an API Group III, Technical White Oil from pyrolysis oil derived from rubber (e.g., waste tire) pyrolysis. In a first aspect, the method comprises the steps of (i) hydroprocessing a rubber 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, thereby providing a pretreated rubber pyrolysis oil; and (ii) hydrotreating the pretreated rubber pyrolysis oil in the presence of hydrogen and a noble metal catalyst to reduce remaining unsaturation in the pretreated rubber pyrolysis oil, thereby providing the API Group III, Technical White Oil.

[0005] In a second aspect, the disclosed method further comprises iii) blending the API Grade III, Technical White Oil with skin care ingredients to provide a skin care product or food-contact product.

[0006] In a third aspect, the disclosed method also includes steps of:

[0007] atmospheric distilling the pretreated rubber pyrolysis oil to produce one or more pretreated rubber pyrolysis atmospheric gas oils in a first viscosity range and pretreated rubber pyrolysis oil residual bottoms;

[0008] vacuum distilling the pretreated rubber pyrolysis oil residual bottoms to produce one or more pretreated rubber pyrolysis vacuum gas oils in a second viscosity range; and

[0009] blending the rubber pyrolysis atmospheric gas oils and the rubber pyrolysis vacuum gas oils in a feedstock blending and storage unit to provide a further pretreated rubber pyrolysis oil for use in the hydrotreating step.

[0010] The disclosed methods and compositions can employ materials obtained by pyrolyzing waste tires or other post-consumer rubber products to provide technical white oils having much greater utility than the fuels normally produced from rubber pyrolysis oils. The rubber pyrolysis oil production, rubber pyrolysis oil hydroprocessing pretreatment step and noble Metal pretreated rubber pyrolysis oil hydrotreating step may each be performed at separate locations or may be performed at a single location. The hydroprocessing step employs hydrogen and a non-noble metal catalyst to saturate olefins and diolefins and decrease the amount of halide, sulfur and nitrogen moieties that could contaminate the noble metal catalyst employed in the hydrotreating step. The hydrotreating step reduces remaining unsaturation, heteroatoms and aromatic color bodies in the pretreated rubber pyrolysis oil, thereby providing a high-quality API Grade III Technical White Oil. The disclosed methods also enable improved control of the hydrotreating step resulting in improved catalyst life, better control of the Technical White Oil product quality, and greater operational flexibility.BRIEF DESCRIPTION OF THE DRAWING

[0011] FIG. 1 through FIG. 3 are schematic diagrams illustrating the disclosed methods.

[0012] Like reference symbols in the various figures indicate like elements. The elements in the drawing are not to scale.Definitions

[0013] 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.

[0014] 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[1,2-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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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. When used as so-called “process oils” in rubber formulations, 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.

[0019] 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 typically will contain at least about 10% CA content and less than about 90% total Cp plus CN content as measured according to ASTM D2140.

[0020] The term “aromatic concentration” or “CA” when used with respect to a feedstock, process stream or product refers to the weight percent of aromatic molecules in such feedstock, process stream or product. Aromatic concentration can be measured according to ASTM D2140, D7419, or D3238, with the latter method typically being used for heavier petroleum fractions.

[0021] 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.

[0022] 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.

[0023] 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 rubber pyrolysis or another at least partially destructive, incompletely oxygenated thermal conversion technique.

[0024] The terms “char oil” and “rubber 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 rubber pyrolysis or another at least partially destructive, incompletely oxygenated thermal conversion technique.

[0025] The term “clean naphthenic” when used with respect to a process stream or product refers to a liquid material having a VGC of about 0.82 to about 0.86 as determined by ASTM D2501, and which will pass either or both of FDA C part 2 and EN-16143:2013. These materials will contain a lower CA content than typical naphthenic materials and higher CN content than typical paraffinic materials as measured according to ASTM D2140.

[0026] 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.

[0027] 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.

[0028] The term “FDA C part 2” refers to one of 3 sets of criteria / methods set in place by the US Federal Food and Drug Administration in the Code of Federal Regulations Title 21, Section 178 that standardize requirements to safely use a petroleum product that is intended for use in contact with food.

[0029] The term “Group III Base Oil” refers to an API (American Petroleum Institute) Definition for an oil having greater than 90 wt % saturates, less than 0.03 wt % sulfur, and a Viscosity Index above 120.

[0030] 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 (viz., breakup into smaller molecules) and saturate the majority of the aromatic hydrocarbons present and eliminate all or nearly all sulfur-, nitrogen-, and oxygen-containing compounds.

[0031] 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 hydrocracked product.

[0032] 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. Hydroprocessing includes but is not limited to hydrofinishing, hydrotreating and hydrocracking.

[0033] 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 take place in the ranges of 1500-2800 psig and 500-680 deg. F.

[0034] The phrases “low concentrations of PAHs” or “low PAH” refer to the total polycyclic aromatic content (PAH) of the technical white oil or the pretreated rubber pyrolysis oil. In some embodiments, this includes a total PAH content of less than 100 ppm for the given material. IN other embodiments, this may include a PAH content of less than 100 ppm for any or all of the 30, 22, 18, 16, or 8 markers. For example, a low PAH may correspond to a PAH of less than 100 ppm, less than 50 ppm, less than 30 ppm, less than 20 ppm, or less than 10 ppm for any or all of the 30, 22, 18, 16, and 8 markers. In additional embodiments, this may include a total sum of 30 markers less than 5 ppm by method EN-16143:2013 employed by the Southwestern Research Institute (SwRI).

[0035] 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.

[0036] The term “noble metal” refers to those metals that substantially resist oxidation at high temperatures. While not uniformly defined, for purposes of this disclosure noble metals will be deemed to include rhenium, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold.

[0037] 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 among a variety of other metals.

[0038] 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 C+CA content as measured according to ASTM D2140.

[0039] The term “polycyclic” refers to organic compounds having at least two closed, connected rings of atoms.

[0040] 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.

[0041] The term “pyrolysis” refers to actual pyrolysis or any other incompletely oxygenated thermal conversion technique that at least partially decomposes or otherwise degrades an organic material and enables the separation or recovery of one or more organic components present in or useful in making such organic material.

[0042] 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.

[0043] The term “rubber pyrolysis” refers to the pyrolysis of elastomeric materials that are contained in whole or in part in waste tires, gaskets, seals, roofing and waterproofing membranes, or any other rubber sources capable of yielding rubber pyrolysis oil.

[0044] The term “rubber pyrolysis oil source” refers to waste tires, gaskets, seals, roofing and waterproofing membranes, or any other rubber sources that in whole or in part are capable of yielding rubber pyrolysis oil via pyrolysis.

[0045] The term “technical white oil” refers to a refined petroleum oil stream containing a mixture of hydrocarbons that has undergone a high degree of saturation in which most, if not all, aromatics, olefins, and polar compounds are removed such that it is suitable for applications requiring conformance to US FDA Regulation 21 CFR 178.3620(B). Due to the high degree of saturation, technical white oils are typically colorless, odorless, non-toxic, chemically stable, and insoluble in water.

[0046] 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.

[0047] 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 SUS viscosity. VGC may be determined according to ASTM D2501. VGC is relatively insensitive to molecular weight. VGC also provides an indirect measure of oil solvency. At a given viscosity and boiling range; VGC is highest for aromatic chemistry, followed by naphthenic chemistry, and lowest for paraffinic chemistry oils.DETAILED DESCRIPTION

[0048] FIG. 1 illustratively shows one method 100 of producing an API Group III, Technical White Oil from rubber pyrolysis oil in accordance with an embodiment of the present invention. Method 100 includes receiving crude rubber pyrolysis oil 101, pre-treating crude rubber pyrolysis oil 102 in the presence of hydrogen and a non-noble metal catalyst, collecting pretreated rubber pyrolysis oil 103, and hydrotreating the pretreated rubber pyrolysis oil 104 in the presence of hydrogen and a noble metal catalyst, to produce API Group III, Technical White Oils 105. The API Group III, Technical White Oils 105 may then be blended with skin care ingredients to provide skin care products.

[0049] In step 101, crude rubber pyrolysis oil is initially provided through the pyrolysis of one or more rubber pyrolysis oil sources. For example, reclaimed tire rubber may undergo mechanical shearing / grinding and pyrolysis to produce crude rubber pyrolysis oil 101. 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 101, 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.

[0050] The rubber pyrolysis reactor may operate at various temperatures and pressures 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 101 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 101, syngas, carbon solids, and ash are continuously discharged or consumed.

[0051] 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 101. 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 101 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 an atmospheric pressure, to provide increased crude rubber pyrolysis oil 101 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 101.

[0052] In step 102, crude rubber pyrolysis oil 101 is subjected to pretreatment 102. Pretreatment 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 saturating olefins and diolefins and decreasing the halide, sulfur and nitrogen contents 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.

[0053] In some embodiments, pretreatment 102 includes hydroprocessing crude rubber pyrolysis oil 101 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 101. Hydroprocessing serves to clean or reduce the impurities within crude rubber pyrolysis oil 101 to allow for further downstream hydrotreatment 104 without running the risk of poisoning or negatively affecting a metal catalyst employed in such downstream hydrotreatment 104. 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.

[0054] 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.

[0055] 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 are contemplated as well 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 101.

[0056] Additional pretreatment steps 102 may be employed as well. 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 a desired viscosity range. The pretreated rubber pyrolysis atmospheric and vacuum gas oils may then be blended or individually supplied for downstream processing to produce API Grade III, Technical White Oils 105. In operation, atmospheric and vacuum distillation may be undertaken in atmospheric and vacuum distillation units operated in accordance with standard industry practices that will be familiar to persons having ordinary skill in the art. While rubber pyrolysis pretreatment 102 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 pretreated rubber pyrolysis oil 103.

[0057] Next, after pretreatment 102, pretreated rubber pyrolysis oil 103 undergoes hydrotreatment 104 to produce API Group III, Technical White Oil 105. Hydrotreatment 104 saturates the remaining olefins and diolefins and removes or reduces aromatic color bodies and heteroatoms to produce API Group III, Technical White Oils 105. API Group III, Technical White Oils 105 may then be combined with skin care ingredients and used in producing skin care products, or may be used on or in food-contact products. In some embodiments, API Group III, Technical White Oil 105 has a sulfur content less than 0.03 wt %, a saturation content greater than 90 wt %, a viscosity index greater than 120, and a viscosity gravity constant (VGC) of less than 0.807. Further, at 40 degrees Celsius, API Group III, Technical White Oil 105, in some embodiments, has a viscosity range of 4 to 600 centistokes (cSt).

[0058] Hydrotreatment 104 may be carried out in a hydrotreater containing a noble metal catalyst and a hydrogen source. In operation, pretreated rubber pyrolysis oil 103 contacts the noble metal catalyst in the presence of hydrogen under suitable hydrotreating conditions to facilitate saturation and removal or reduction of aromatic color bodies and heteroatoms. The hydrotreater may include a fixed catalyst bed, fluidized catalyst bed, moving bed, slurry bed, counter current bed or transfer flow catalyst bed.

[0059] Noble metal catalysts may include, in addition to the 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 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 noble metal 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 will be selected to produce an API Group III, Technical White Oil 105.

[0061] As shown in FIG. 2, API Group III, Technical White Oil 105 may undergo further fractionation 201 to isolate the API Group III, Technical White Oil 105 into a plurality of kinematic viscosity ranges, including, but not limited to, 40 VIS 202, 60 VIS 203, 100 VIS 204, 600 VIS 205, and 2000 VIS 206. Fractionation 201 may include atmospheric distillation, vacuum distillation, solvent extraction, centrifugation, wipe film evaporation, or any other fractionation technique suitable for separating API Group III, Technical White Oil 105 into the desired fractions. In some embodiments, the kinematic viscosity ranges are greater than or equal to 4 centistokes (cSt) and less than or equal to 600 cSt at 40 degrees Celsius. Other kinematic viscosity ranges may be obtained by varying the fractionation method or conditions using techniques familiar to those skilled in the art.

[0062] The product oil viscosity will be impacted by the type, structure, and size of the component molecules in the oil. During saturation reactions, as the aromatic rings are opened and saturated with hydrogen atoms, the oil molecules become collectively more paraffinic in structure. Consequently there is an inherent chemistry and viscosity shift as the severity or extent of the hydrotreatment reaction is increased. For heavier, aromatic molecules, the viscosity is generally higher for a given boiling range, while for lighter, paraffinic molecules the viscosity is generally lower. For this reason, as the chemistry shifts from more aromatic to more paraffinic, the viscosity will be reduced. If a more naphthenic chemistry is present at a desired cleanliness level, then the product will also have a greater native viscosity at a specific boiling range when compared to a more paraffinic product.

[0063] Referring to FIG. 3, another method for producing API Group III, Technical White Oils 105 is shown. Method 300 includes fractionating naphthenic crude, through atmospheric 302 and vacuum distillation 304, into one or more atmospheric and vacuum gas oils 305, 306, 307, 308, 309, 310, and 311 with respective nominal viscosities of approximately 40, 60, 100, 600, 2000, and 5000 VIS. The respective naphthenic atmospheric and vacuum gas oils are then blended with pretreated, fractionated rubber pyrolysis oils 313, 314, 315, 316, and 317 in feedstock blending and storage unit(s) 106 and subjected to hydrotreatment 104 to produce API Group III, Technical White Oils 318, 319, 320, 321, and 322 and 5000 VIS naphthenic lube oil 323.

[0064] For example, naphthenic crude 301 may be collected and subjected to atmospheric distillation 302 to produce one or more naphthenic atmospheric gas oils with a viscosity of 40 VIS 305 and 60 VIS 306 and residual bottoms 303. Residual bottoms 303 may then undergo vacuum distillation 304 to produce naphthenic vacuum gas oils of 100 VIS 307, 600 VIS 308, and 2000 VIS 309 and residuals for solvent deasphalting 310. While fractionating of naphthenic crude is shown, it is expressly contemplated that other processing techniques may be implemented before or after such fractionation. For example, crude naphthenic oil 301, before or after fractionation, may undergo hydroprocessing to remove or eliminate any one or more of the 30-, 22-, 16-, or 8-markers and provide a lowered or low PAH level as well as sulfur, halide, and nitrogen compounds to produce clean naphthenic oil.

[0065] In FIG. 3, crude rubber pyrolysis oil 101 from a rubber pyrolysis oil source is subjected to pretreatment 312 which may be similar to, or different from, pretreatment 102. In some embodiments, as shown, pretreatment 312 includes hydroprocessing and fractionation to provide one or more treated rubber pyrolysis oils 313, 314, 315, 316, and 317 with respective nominal viscosities of approximately, 2000 VIS, 600 VIS, 100 VIS, 60 VIS, and 40 VIS. Treated rubber pyrolysis oils 313-317 are then blended with naphthenic atmospheric and vacuum gas oils 305-309 in a feedstock blending and storage unit 106 prior to undergoing hydrotreatment 104. Blending may occur in a feedstock storage unit 106, and the resulting blended feedstock fed to a hydrotreater of hydrotreatment 104.

[0066] 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 101. Generally, a blended feedstock of treated pyrolysis oils 313-317, e.g., tire pyrolysis oils, 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.

[0067] 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.

[0068] 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 tire 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. Upon undergoing hydrotreatment 104, API Group III, Technical White Oils may be produced with 40 VIS 318, 60 VIS 319, 100 VIS 320, 600 VIS 321, and 2000 VIS 322.

[0069] A variety of naphthenic crude residual bottoms and naphthenic crudes may be employed as naphthenic blend stocks in the disclosed method. When naphthenic crudes are employed in the disclosed method, they may be obtained from a variety of sources. Exemplary naphthenic crudes include Brazilian, North Sea, West African, Australian, Canadian, 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, 0.855, 0.86, 0.865, and a VGC less than about 1, 0.95, 0.9, or 0.895, as determined by ASTM D2501. Preferred naphthenic crudes will provide atmospheric and vacuum gas oils having a VGC from about 0.855 to 0.895. The chosen crude may also contain at least 30%, at least 35% or at least about 40% CN content, and less than about 70%, less than 65% or less than about 60% total CP+CA content as measured according to ASTM D2140.

[0070] 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.

[0071] Exemplary VGC's at 100° F. for a naphthenic feedstock, naphthenic base oil, clean naphthenic base oil, and technical white oil are shown below in Table 1:TABLE 1Viscosity Gravity Constant Ranges by Viscosity Grades at 100° F.CleanViscosityNaphthenicNaphthenicNaphthenicTechnicalGradeFeedstockBase OilBase OilWhite Oil 60 SUS>0.8660.849-0.8660.831-0.849<0.831 100 SUS>0.8770.853-0.8770.817-0.853<0.817 500 SUS>0.8690.853-0.8690.837-0.853<0.8372000 SUS>0.8590.842-0.8590.826-0.842<0.826

[0072] The above-described methods provide a highly efficient route to production of an API Group III Technical White Oil.Example 1Rubber Pyrolysis Oil Pretreatment

[0073] Commercially produced rubber pyrolysis oil was obtained by pyrolyzing ground tires. The resulting crude rubber pyrolysis oil had the properties shown below in Table 2. The oil was subjected to a pretreatment performed by modifying the Plastic Energy / Axens “Rewind Mix” process to use rubber pyrolysis oil rather than plastic pyrolysis oil, and by using a nickel, molybdenum and copper catalyst. The product was subjected to vacuum distillation to provide a pretreated rubber pyrolysis oil having the properties shown below in Table 3. The pretreated oil had significantly reduced unsaturation (Diene Value) and significantly reduced sulfur, nitrogen, oxygen, chlorine, silicon and total metal content, as well as a narrower boiling point range. In particular, the reduction in sulfur and nitrogen content enables the pretreated rubber pyrolysis vacuum gas oil to be fed to a hydrotreater unit equipped with a noble metal catalyst and operated under severe hydrotreating conditions without poisoning active sites on the noble metal catalyst.TABLE 2Tire / Rubber Pyrolysis OilRubberUnit ofPyrolysisPropertyMethodMeasureOilSpecific GravityASTM D40520.9412Oxygen ContentASTM D5599ppm wt12500Total SulfurASTM D5453ppm wt10027Total NitrogenASTM D5762ppm wt2900Total ChlorineASTM D7359ppm wt16.9Fluorine ContentASTM D7359ppm wt<1Bromine ContentASTM D7359ppm wt<1ConradsonNF EN ISOwt %1.19Carbon10370Silicon ContentASTM D5185ppm wt10.9Arsenic ContentASTM D5185ppb wt200Mercury ContentASTM D5185ppb wt50Total MetalsASTM D5185ppm wt13.1Bromine NumberASTM D1159g-Br2 / 100 g65Diene ValueUOP 326g-I2 / 100 g12AromaticIFPEN 9409wt %64.1ContentDistillationASTM D2887CurveIBPDeg. F.211.7 5%Deg. F.322.710%Deg. F.35230%Deg. F.520.950%Deg. F.662.870%Deg. F.785.990%Deg. F.927.595%Deg. F.983.7FBPDeg. F.1087.2TABLE 3Pretreated Pyrolysis Oil Vacuum Gas OilPretreated Unit ofPyrolysisPropertyMeasureOil VGOFlowrateBPSD1430Specific Gravity0.99Bromine Numberg-Br2 / 100 g<0.5Diene Valueg-I2 / 100 g<0.1Sulfurppm wt<50Nitrogenppm wt<100Oxygenppm wt<200Chlorineppm wt<1Siliconppm wt<1Total Metalsppm wt<1Flash PointDeg. F.340Pour PointDeg. F.36D2887 DistillationCurveIBPDeg. F.640 5%Deg. F.67710%Deg. F.70030%Deg. F.77350%Deg. F.83370%Deg. F.90190%Deg. F.100095%Deg. F.1041FBPDeg. F.1073Example 2Rubber Pyrolysis Oil HydrotreatmentThe pretreated rubber pyrolysis oil was sent through a hydrotreater unit equipped with a feed surge drum, charge metering pump, hydrogen gas compressor, reactor, high pressure separator and gas recovery vessel, low pressure separator and gas recovery vessel, product stripper, product vacuum fractionator and temperature-controlled radial heat blocks to regulate temperature profiles across the reactor. The hydrotreater unit used a platinum metal catalyst, and was operated under sufficiently severe conditions to saturate aromatics and naphthenes (including PAHs) to provide an API Group III Technical White Oil with the properties shown below in Table 4:TABLE 4Technical White OilPretreated Unit of Pyrolysis PropertyMeasureOil VGOSaturates Contentwt %>90Viscosity Index>120Sulfurwt %<0.03VGC<0.837The oil was water white and odorless. The oil may be combined with skin care ingredients to produce skin care products, or used on or in food-contact products.

[0076] The oil had greater VGCs at given viscosity values than a typical highly saturated / low CA paraffinic Technical White Oil Material having the properties shown below in Table 5:TABLE 5Typical Low CA White Oil PropertiesViscosity-Grade-Vis atSG Gravity100 F., SUS(60 F.)Constant1000.87-.890.784-0.807 350.85-.880.776-0.805

[0077] 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

example 1

Rubber Pyrolysis Oil Pretreatment

[0073]Commercially produced rubber pyrolysis oil was obtained by pyrolyzing ground tires. The resulting crude rubber pyrolysis oil had the properties shown below in Table 2. The oil was subjected to a pretreatment performed by modifying the Plastic Energy / Axens “Rewind Mix” process to use rubber pyrolysis oil rather than plastic pyrolysis oil, and by using a nickel, molybdenum and copper catalyst. The product was subjected to vacuum distillation to provide a pretreated rubber pyrolysis oil having the properties shown below in Table 3. The pretreated oil had significantly reduced unsaturation (Diene Value) and significantly reduced sulfur, nitrogen, oxygen, chlorine, silicon and total metal content, as well as a narrower boiling point range. In particular, the reduction in sulfur and nitrogen content enables the pretreated rubber pyrolysis vacuum gas oil to be fed to a hydrotreater unit equipped with a noble metal catalyst and operated under severe hy...

example 2

Rubber Pyrolysis Oil Hydrotreatment

The pretreated rubber pyrolysis oil was sent through a hydrotreater unit equipped with a feed surge drum, charge metering pump, hydrogen gas compressor, reactor, high pressure separator and gas recovery vessel, low pressure separator and gas recovery vessel, product stripper, product vacuum fractionator and temperature-controlled radial heat blocks to regulate temperature profiles across the reactor. The hydrotreater unit used a platinum metal catalyst, and was operated under sufficiently severe conditions to saturate aromatics and naphthenes (including PAHs) to provide an API Group III Technical White Oil with the properties shown below in Table 4:

TABLE 4Technical White OilPretreated Unit of Pyrolysis PropertyMeasureOil VGOSaturates Contentwt %>90Viscosity Index>120Sulfurwt %VGC

The oil was water white and odorless. The oil may be combined with skin care ingredients to produce skin care products, or used on or in food-contact products.

[0076]The oil...

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation of International Application No. PCT / US2024 / 056406 filed Nov. 18, 2024 and entitled “METHODS FOR PRODUCING API GROUP III, TECHNICAL WHITE OIL FROM RUBBER DERIVED PYROLYSIS OIL”, which claims priority from U.S. Provisional Application Ser. No. 63 / 599,937 filed Nov. 16, 2023 and entitled “METHODS FOR UPGRADING RUBBER DERIVED PYROLYSIS OIL TO API GROUP III, TECHNICAL WHITE OIL”, the disclosures of which are incorporated herein by reference.TECHNICAL FIELD

[0002] This disclosure relates to the production of technical white oils for use in cosmetics, other skin care applications and for use on or in food-contact products.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 rubber pyrolysis oil. Rubber 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. These cleaner fuels may be further hydrocracked into lower molecular weight molecules that also may be used as fuels. Rather than converting rubber pyrolysis oil into fuels, what is needed in the art are other applications and uses for rubber pyrolysis oils. Such applications and uses are disclosed and claimed herein.SUMMARY

[0004] The present invention provides methods for producing an API Group III, Technical White Oil from pyrolysis oil derived from rubber (e.g., waste tire) pyrolysis. In a first aspect, the method comprises the steps of (i) hydroprocessing a rubber 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, thereby providing a pretreated rubber pyrolysis oil; and (ii) hydrotreating the pretreated rubber pyrolysis oil in the presence of hydrogen and a noble metal catalyst to reduce remaining unsaturation in the pretreated rubber pyrolysis oil, thereby providing the API Group III, Technical White Oil.

[0005] In a second aspect, the disclosed method further comprises iii) blending the API Grade III, Technical White Oil with skin care ingredients to provide a skin care product or food-contact product.

[0006] In a third aspect, the disclosed method also includes steps of:

[0007] atmospheric distilling the pretreated rubber pyrolysis oil to produce one or more pretreated rubber pyrolysis atmospheric gas oils in a first viscosity range and pretreated rubber pyrolysis oil residual bottoms;

[0008] vacuum distilling the pretreated rubber pyrolysis oil residual bottoms to produce one or more pretreated rubber pyrolysis vacuum gas oils in a second viscosity range; and

[0009] blending the rubber pyrolysis atmospheric gas oils and the rubber pyrolysis vacuum gas oils in a feedstock blending and storage unit to provide a further pretreated rubber pyrolysis oil for use in the hydrotreating step.

[0010] The disclosed methods and compositions can employ materials obtained by pyrolyzing waste tires or other post-consumer rubber products to provide technical white oils having much greater utility than the fuels normally produced from rubber pyrolysis oils. The rubber pyrolysis oil production, rubber pyrolysis oil hydroprocessing pretreatment step and noble Metal pretreated rubber pyrolysis oil hydrotreating step may each be performed at separate locations or may be performed at a single location. The hydroprocessing step employs hydrogen and a non-noble metal catalyst to saturate olefins and diolefins and decrease the amount of halide, sulfur and nitrogen moieties that could contaminate the noble metal catalyst employed in the hydrotreating step. The hydrotreating step reduces remaining unsaturation, heteroatoms and aromatic color bodies in the pretreated rubber pyrolysis oil, thereby providing a high-quality API Grade III Technical White Oil. The disclosed methods also enable improved control of the hydrotreating step resulting in improved catalyst life, better control of the Technical White Oil product quality, and greater operational flexibility.BRIEF DESCRIPTION OF THE DRAWING

[0011] FIG. 1 through FIG. 3 are schematic diagrams illustrating the disclosed methods.

[0012] Like reference symbols in the various figures indicate like elements. The elements in the drawing are not to scale.Definitions

[0013] 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.

[0014] 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[1,2-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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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. When used as so-called “process oils” in rubber formulations, 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.

[0019] 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 typically will contain at least about 10% CA content and less than about 90% total Cp plus CN content as measured according to ASTM D2140.

[0020] The term “aromatic concentration” or “CA” when used with respect to a feedstock, process stream or product refers to the weight percent of aromatic molecules in such feedstock, process stream or product. Aromatic concentration can be measured according to ASTM D2140, D7419, or D3238, with the latter method typically being used for heavier petroleum fractions.

[0021] 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.

[0022] 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.

[0023] 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 rubber pyrolysis or another at least partially destructive, incompletely oxygenated thermal conversion technique.

[0024] The terms “char oil” and “rubber 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 rubber pyrolysis or another at least partially destructive, incompletely oxygenated thermal conversion technique.

[0025] The term “clean naphthenic” when used with respect to a process stream or product refers to a liquid material having a VGC of about 0.82 to about 0.86 as determined by ASTM D2501, and which will pass either or both of FDA C part 2 and EN-16143:2013. These materials will contain a lower CA content than typical naphthenic materials and higher CN content than typical paraffinic materials as measured according to ASTM D2140.

[0026] 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.

[0027] 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.

[0028] The term “FDA C part 2” refers to one of 3 sets of criteria / methods set in place by the US Federal Food and Drug Administration in the Code of Federal Regulations Title 21, Section 178 that standardize requirements to safely use a petroleum product that is intended for use in contact with food.

[0029] The term “Group III Base Oil” refers to an API (American Petroleum Institute) Definition for an oil having greater than 90 wt % saturates, less than 0.03 wt % sulfur, and a Viscosity Index above 120.

[0030] 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 (viz., breakup into smaller molecules) and saturate the majority of the aromatic hydrocarbons present and eliminate all or nearly all sulfur-, nitrogen-, and oxygen-containing compounds.

[0031] 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 hydrocracked product.

[0032] 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. Hydroprocessing includes but is not limited to hydrofinishing, hydrotreating and hydrocracking.

[0033] 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 take place in the ranges of 1500-2800 psig and 500-680 deg. F.

[0034] The phrases “low concentrations of PAHs” or “low PAH” refer to the total polycyclic aromatic content (PAH) of the technical white oil or the pretreated rubber pyrolysis oil. In some embodiments, this includes a total PAH content of less than 100 ppm for the given material. IN other embodiments, this may include a PAH content of less than 100 ppm for any or all of the 30, 22, 18, 16, or 8 markers. For example, a low PAH may correspond to a PAH of less than 100 ppm, less than 50 ppm, less than 30 ppm, less than 20 ppm, or less than 10 ppm for any or all of the 30, 22, 18, 16, and 8 markers. In additional embodiments, this may include a total sum of 30 markers less than 5 ppm by method EN-16143:2013 employed by the Southwestern Research Institute (SwRI).

[0035] 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.

[0036] The term “noble metal” refers to those metals that substantially resist oxidation at high temperatures. While not uniformly defined, for purposes of this disclosure noble metals will be deemed to include rhenium, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold.

[0037] 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 among a variety of other metals.

[0038] 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 C+CA content as measured according to ASTM D2140.

[0039] The term “polycyclic” refers to organic compounds having at least two closed, connected rings of atoms.

[0040] 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.

[0041] The term “pyrolysis” refers to actual pyrolysis or any other incompletely oxygenated thermal conversion technique that at least partially decomposes or otherwise degrades an organic material and enables the separation or recovery of one or more organic components present in or useful in making such organic material.

[0042] 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.

[0043] The term “rubber pyrolysis” refers to the pyrolysis of elastomeric materials that are contained in whole or in part in waste tires, gaskets, seals, roofing and waterproofing membranes, or any other rubber sources capable of yielding rubber pyrolysis oil.

[0044] The term “rubber pyrolysis oil source” refers to waste tires, gaskets, seals, roofing and waterproofing membranes, or any other rubber sources that in whole or in part are capable of yielding rubber pyrolysis oil via pyrolysis.

[0045] The term “technical white oil” refers to a refined petroleum oil stream containing a mixture of hydrocarbons that has undergone a high degree of saturation in which most, if not all, aromatics, olefins, and polar compounds are removed such that it is suitable for applications requiring conformance to US FDA Regulation 21 CFR 178.3620(B). Due to the high degree of saturation, technical white oils are typically colorless, odorless, non-toxic, chemically stable, and insoluble in water.

[0046] 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.

[0047] 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 SUS viscosity. VGC may be determined according to ASTM D2501. VGC is relatively insensitive to molecular weight. VGC also provides an indirect measure of oil solvency. At a given viscosity and boiling range; VGC is highest for aromatic chemistry, followed by naphthenic chemistry, and lowest for paraffinic chemistry oils.DETAILED DESCRIPTION

[0048] FIG. 1 illustratively shows one method 100 of producing an API Group III, Technical White Oil from rubber pyrolysis oil in accordance with an embodiment of the present invention. Method 100 includes receiving crude rubber pyrolysis oil 101, pre-treating crude rubber pyrolysis oil 102 in the presence of hydrogen and a non-noble metal catalyst, collecting pretreated rubber pyrolysis oil 103, and hydrotreating the pretreated rubber pyrolysis oil 104 in the presence of hydrogen and a noble metal catalyst, to produce API Group III, Technical White Oils 105. The API Group III, Technical White Oils 105 may then be blended with skin care ingredients to provide skin care products.

[0049] In step 101, crude rubber pyrolysis oil is initially provided through the pyrolysis of one or more rubber pyrolysis oil sources. For example, reclaimed tire rubber may undergo mechanical shearing / grinding and pyrolysis to produce crude rubber pyrolysis oil 101. 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 101, 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.

[0050] The rubber pyrolysis reactor may operate at various temperatures and pressures 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 101 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 101, syngas, carbon solids, and ash are continuously discharged or consumed.

[0051] 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 101. 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 101 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 an atmospheric pressure, to provide increased crude rubber pyrolysis oil 101 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 101.

[0052] In step 102, crude rubber pyrolysis oil 101 is subjected to pretreatment 102. Pretreatment 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 saturating olefins and diolefins and decreasing the halide, sulfur and nitrogen contents 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.

[0053] In some embodiments, pretreatment 102 includes hydroprocessing crude rubber pyrolysis oil 101 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 101. Hydroprocessing serves to clean or reduce the impurities within crude rubber pyrolysis oil 101 to allow for further downstream hydrotreatment 104 without running the risk of poisoning or negatively affecting a metal catalyst employed in such downstream hydrotreatment 104. 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.

[0054] 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.

[0055] 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 are contemplated as well 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 101.

[0056] Additional pretreatment steps 102 may be employed as well. 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 a desired viscosity range. The pretreated rubber pyrolysis atmospheric and vacuum gas oils may then be blended or individually supplied for downstream processing to produce API Grade III, Technical White Oils 105. In operation, atmospheric and vacuum distillation may be undertaken in atmospheric and vacuum distillation units operated in accordance with standard industry practices that will be familiar to persons having ordinary skill in the art. While rubber pyrolysis pretreatment 102 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 pretreated rubber pyrolysis oil 103.

[0057] Next, after pretreatment 102, pretreated rubber pyrolysis oil 103 undergoes hydrotreatment 104 to produce API Group III, Technical White Oil 105. Hydrotreatment 104 saturates the remaining olefins and diolefins and removes or reduces aromatic color bodies and heteroatoms to produce API Group III, Technical White Oils 105. API Group III, Technical White Oils 105 may then be combined with skin care ingredients and used in producing skin care products, or may be used on or in food-contact products. In some embodiments, API Group III, Technical White Oil 105 has a sulfur content less than 0.03 wt %, a saturation content greater than 90 wt %, a viscosity index greater than 120, and a viscosity gravity constant (VGC) of less than 0.807. Further, at 40 degrees Celsius, API Group III, Technical White Oil 105, in some embodiments, has a viscosity range of 4 to 600 centistokes (cSt).

[0058] Hydrotreatment 104 may be carried out in a hydrotreater containing a noble metal catalyst and a hydrogen source. In operation, pretreated rubber pyrolysis oil 103 contacts the noble metal catalyst in the presence of hydrogen under suitable hydrotreating conditions to facilitate saturation and removal or reduction of aromatic color bodies and heteroatoms. The hydrotreater may include a fixed catalyst bed, fluidized catalyst bed, moving bed, slurry bed, counter current bed or transfer flow catalyst bed.

[0059] Noble metal catalysts may include, in addition to the 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 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 noble metal 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 will be selected to produce an API Group III, Technical White Oil 105.

[0061] As shown in FIG. 2, API Group III, Technical White Oil 105 may undergo further fractionation 201 to isolate the API Group III, Technical White Oil 105 into a plurality of kinematic viscosity ranges, including, but not limited to, 40 VIS 202, 60 VIS 203, 100 VIS 204, 600 VIS 205, and 2000 VIS 206. Fractionation 201 may include atmospheric distillation, vacuum distillation, solvent extraction, centrifugation, wipe film evaporation, or any other fractionation technique suitable for separating API Group III, Technical White Oil 105 into the desired fractions. In some embodiments, the kinematic viscosity ranges are greater than or equal to 4 centistokes (cSt) and less than or equal to 600 cSt at 40 degrees Celsius. Other kinematic viscosity ranges may be obtained by varying the fractionation method or conditions using techniques familiar to those skilled in the art.

[0062] The product oil viscosity will be impacted by the type, structure, and size of the component molecules in the oil. During saturation reactions, as the aromatic rings are opened and saturated with hydrogen atoms, the oil molecules become collectively more paraffinic in structure. Consequently there is an inherent chemistry and viscosity shift as the severity or extent of the hydrotreatment reaction is increased. For heavier, aromatic molecules, the viscosity is generally higher for a given boiling range, while for lighter, paraffinic molecules the viscosity is generally lower. For this reason, as the chemistry shifts from more aromatic to more paraffinic, the viscosity will be reduced. If a more naphthenic chemistry is present at a desired cleanliness level, then the product will also have a greater native viscosity at a specific boiling range when compared to a more paraffinic product.

[0063] Referring to FIG. 3, another method for producing API Group III, Technical White Oils 105 is shown. Method 300 includes fractionating naphthenic crude, through atmospheric 302 and vacuum distillation 304, into one or more atmospheric and vacuum gas oils 305, 306, 307, 308, 309, 310, and 311 with respective nominal viscosities of approximately 40, 60, 100, 600, 2000, and 5000 VIS. The respective naphthenic atmospheric and vacuum gas oils are then blended with pretreated, fractionated rubber pyrolysis oils 313, 314, 315, 316, and 317 in feedstock blending and storage unit(s) 106 and subjected to hydrotreatment 104 to produce API Group III, Technical White Oils 318, 319, 320, 321, and 322 and 5000 VIS naphthenic lube oil 323.

[0064] For example, naphthenic crude 301 may be collected and subjected to atmospheric distillation 302 to produce one or more naphthenic atmospheric gas oils with a viscosity of 40 VIS 305 and 60 VIS 306 and residual bottoms 303. Residual bottoms 303 may then undergo vacuum distillation 304 to produce naphthenic vacuum gas oils of 100 VIS 307, 600 VIS 308, and 2000 VIS 309 and residuals for solvent deasphalting 310. While fractionating of naphthenic crude is shown, it is expressly contemplated that other processing techniques may be implemented before or after such fractionation. For example, crude naphthenic oil 301, before or after fractionation, may undergo hydroprocessing to remove or eliminate any one or more of the 30-, 22-, 16-, or 8-markers and provide a lowered or low PAH level as well as sulfur, halide, and nitrogen compounds to produce clean naphthenic oil.

[0065] In FIG. 3, crude rubber pyrolysis oil 101 from a rubber pyrolysis oil source is subjected to pretreatment 312 which may be similar to, or different from, pretreatment 102. In some embodiments, as shown, pretreatment 312 includes hydroprocessing and fractionation to provide one or more treated rubber pyrolysis oils 313, 314, 315, 316, and 317 with respective nominal viscosities of approximately, 2000 VIS, 600 VIS, 100 VIS, 60 VIS, and 40 VIS. Treated rubber pyrolysis oils 313-317 are then blended with naphthenic atmospheric and vacuum gas oils 305-309 in a feedstock blending and storage unit 106 prior to undergoing hydrotreatment 104. Blending may occur in a feedstock storage unit 106, and the resulting blended feedstock fed to a hydrotreater of hydrotreatment 104.

[0066] 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 101. Generally, a blended feedstock of treated pyrolysis oils 313-317, e.g., tire pyrolysis oils, 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.

[0067] 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.

[0068] 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 tire 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. Upon undergoing hydrotreatment 104, API Group III, Technical White Oils may be produced with 40 VIS 318, 60 VIS 319, 100 VIS 320, 600 VIS 321, and 2000 VIS 322.

[0069] A variety of naphthenic crude residual bottoms and naphthenic crudes may be employed as naphthenic blend stocks in the disclosed method. When naphthenic crudes are employed in the disclosed method, they may be obtained from a variety of sources. Exemplary naphthenic crudes include Brazilian, North Sea, West African, Australian, Canadian, 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, 0.855, 0.86, 0.865, and a VGC less than about 1, 0.95, 0.9, or 0.895, as determined by ASTM D2501. Preferred naphthenic crudes will provide atmospheric and vacuum gas oils having a VGC from about 0.855 to 0.895. The chosen crude may also contain at least 30%, at least 35% or at least about 40% CN content, and less than about 70%, less than 65% or less than about 60% total CP+CA content as measured according to ASTM D2140.

[0070] 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.

[0071] Exemplary VGC's at 100° F. for a naphthenic feedstock, naphthenic base oil, clean naphthenic base oil, and technical white oil are shown below in Table 1:TABLE 1Viscosity Gravity Constant Ranges by Viscosity Grades at 100° F.CleanViscosityNaphthenicNaphthenicNaphthenicTechnicalGradeFeedstockBase OilBase OilWhite Oil 60 SUS>0.8660.849-0.8660.831-0.849<0.831 100 SUS>0.8770.853-0.8770.817-0.853<0.817 500 SUS>0.8690.853-0.8690.837-0.853<0.8372000 SUS>0.8590.842-0.8590.826-0.842<0.826

[0072] The above-described methods provide a highly efficient route to production of an API Group III Technical White Oil.Example 1Rubber Pyrolysis Oil Pretreatment

[0073] Commercially produced rubber pyrolysis oil was obtained by pyrolyzing ground tires. The resulting crude rubber pyrolysis oil had the properties shown below in Table 2. The oil was subjected to a pretreatment performed by modifying the Plastic Energy / Axens “Rewind Mix” process to use rubber pyrolysis oil rather than plastic pyrolysis oil, and by using a nickel, molybdenum and copper catalyst. The product was subjected to vacuum distillation to provide a pretreated rubber pyrolysis oil having the properties shown below in Table 3. The pretreated oil had significantly reduced unsaturation (Diene Value) and significantly reduced sulfur, nitrogen, oxygen, chlorine, silicon and total metal content, as well as a narrower boiling point range. In particular, the reduction in sulfur and nitrogen content enables the pretreated rubber pyrolysis vacuum gas oil to be fed to a hydrotreater unit equipped with a noble metal catalyst and operated under severe hydrotreating conditions without poisoning active sites on the noble metal catalyst.TABLE 2Tire / Rubber Pyrolysis OilRubberUnit ofPyrolysisPropertyMethodMeasureOilSpecific GravityASTM D40520.9412Oxygen ContentASTM D5599ppm wt12500Total SulfurASTM D5453ppm wt10027Total NitrogenASTM D5762ppm wt2900Total ChlorineASTM D7359ppm wt16.9Fluorine ContentASTM D7359ppm wt<1Bromine ContentASTM D7359ppm wt<1ConradsonNF EN ISOwt %1.19Carbon10370Silicon ContentASTM D5185ppm wt10.9Arsenic ContentASTM D5185ppb wt200Mercury ContentASTM D5185ppb wt50Total MetalsASTM D5185ppm wt13.1Bromine NumberASTM D1159g-Br2 / 100 g65Diene ValueUOP 326g-I2 / 100 g12AromaticIFPEN 9409wt %64.1ContentDistillationASTM D2887CurveIBPDeg. F.211.7 5%Deg. F.322.710%Deg. F.35230%Deg. F.520.950%Deg. F.662.870%Deg. F.785.990%Deg. F.927.595%Deg. F.983.7FBPDeg. F.1087.2TABLE 3Pretreated Pyrolysis Oil Vacuum Gas OilPretreated Unit ofPyrolysisPropertyMeasureOil VGOFlowrateBPSD1430Specific Gravity0.99Bromine Numberg-Br2 / 100 g<0.5Diene Valueg-I2 / 100 g<0.1Sulfurppm wt<50Nitrogenppm wt<100Oxygenppm wt<200Chlorineppm wt<1Siliconppm wt<1Total Metalsppm wt<1Flash PointDeg. F.340Pour PointDeg. F.36D2887 DistillationCurveIBPDeg. F.640 5%Deg. F.67710%Deg. F.70030%Deg. F.77350%Deg. F.83370%Deg. F.90190%Deg. F.100095%Deg. F.1041FBPDeg. F.1073Example 2Rubber Pyrolysis Oil HydrotreatmentThe pretreated rubber pyrolysis oil was sent through a hydrotreater unit equipped with a feed surge drum, charge metering pump, hydrogen gas compressor, reactor, high pressure separator and gas recovery vessel, low pressure separator and gas recovery vessel, product stripper, product vacuum fractionator and temperature-controlled radial heat blocks to regulate temperature profiles across the reactor. The hydrotreater unit used a platinum metal catalyst, and was operated under sufficiently severe conditions to saturate aromatics and naphthenes (including PAHs) to provide an API Group III Technical White Oil with the properties shown below in Table 4:TABLE 4Technical White OilPretreated Unit of Pyrolysis PropertyMeasureOil VGOSaturates Contentwt %>90Viscosity Index>120Sulfurwt %<0.03VGC<0.837The oil was water white and odorless. The oil may be combined with skin care ingredients to produce skin care products, or used on or in food-contact products.

[0076] The oil had greater VGCs at given viscosity values than a typical highly saturated / low CA paraffinic Technical White Oil Material having the properties shown below in Table 5:TABLE 5Typical Low CA White Oil PropertiesViscosity-Grade-Vis atSG Gravity100 F., SUS(60 F.)Constant1000.87-.890.784-0.807 350.85-.880.776-0.805

[0077] 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

example 1

Rubber Pyrolysis Oil Pretreatment

[0073]Commercially produced rubber pyrolysis oil was obtained by pyrolyzing ground tires. The resulting crude rubber pyrolysis oil had the properties shown below in Table 2. The oil was subjected to a pretreatment performed by modifying the Plastic Energy / Axens “Rewind Mix” process to use rubber pyrolysis oil rather than plastic pyrolysis oil, and by using a nickel, molybdenum and copper catalyst. The product was subjected to vacuum distillation to provide a pretreated rubber pyrolysis oil having the properties shown below in Table 3. The pretreated oil had significantly reduced unsaturation (Diene Value) and significantly reduced sulfur, nitrogen, oxygen, chlorine, silicon and total metal content, as well as a narrower boiling point range. In particular, the reduction in sulfur and nitrogen content enables the pretreated rubber pyrolysis vacuum gas oil to be fed to a hydrotreater unit equipped with a noble metal catalyst and operated under severe hy...

example 2

Rubber Pyrolysis Oil Hydrotreatment

The pretreated rubber pyrolysis oil was sent through a hydrotreater unit equipped with a feed surge drum, charge metering pump, hydrogen gas compressor, reactor, high pressure separator and gas recovery vessel, low pressure separator and gas recovery vessel, product stripper, product vacuum fractionator and temperature-controlled radial heat blocks to regulate temperature profiles across the reactor. The hydrotreater unit used a platinum metal catalyst, and was operated under sufficiently severe conditions to saturate aromatics and naphthenes (including PAHs) to provide an API Group III Technical White Oil with the properties shown below in Table 4:

TABLE 4Technical White OilPretreated Unit of Pyrolysis PropertyMeasureOil VGOSaturates Contentwt %>90Viscosity Index>120Sulfurwt %VGC

The oil was water white and odorless. The oil may be combined with skin care ingredients to produce skin care products, or used on or in food-contact products.

[0076]The oil...

Claims

1. A method for producing an API Group III Technical White Oil, the method comprising the steps of:hydroprocessing a rubber pyrolysis oil in a presence of hydrogen and a non-noble metal catalyst to saturate olefins and diolefins and decrease the halide, sulfur and nitrogen contents within the rubber pyrolysis oil, thereby providing a pretreated rubber pyrolysis oil; andhydrotreating the pretreated rubber pyrolysis oil in a presence of hydrogen and a noble metal catalyst to reduce remaining unsaturation in the pretreated rubber pyrolysis oil, thereby providing the API Group III Technical White Oil.

2. A method according to claim 1, further comprising steps of:atmospheric distilling the pretreated rubber pyrolysis oil to produce one or more pretreated rubber pyrolysis atmospheric gas oils in a first viscosity range and pretreated rubber pyrolysis oil residual bottoms;vacuum distilling the pretreated rubber pyrolysis oil residual bottoms to produce one or more pretreated rubber pyrolysis vacuum gas oils in a second viscosity range; andblending the one or more rubber pyrolysis atmospheric gas oils and the one or more rubber pyrolysis vacuum gas oils in a feedstock blending and storage unit to provide a further pretreated rubber pyrolysis oil blended feedstock for use in the hydrotreating step.

3. A method according to claim 1, further comprising the step of at least partially pyrolyzing size-reduced rubber particles from a rubber pyrolysis oil source in a presence of heat and an absence of oxygen to produce char, syngas and the rubber pyrolysis oil for use in the hydroprocessing step.

4. A method according to claim 3, wherein the rubber pyrolysis oil source comprises rubber tires, gaskets, seals, roofing membranes, waterproofing membranes, post-consumer rubber products or a combination thereof.

5. A method according to claim 1, wherein the API Group III Technical White Oil is suitable for use in cosmetics or other skin-contact products.

6. A method according to claim 1, wherein the API Group III Technical White Oil is suitable for use on or in food-contact products.

7. A method according to claim 1, wherein the API Group III Technical White Oil has a sulfur content less than 0.03 wt %, a saturates content greater than 90 wt %, and a viscosity index greater than 120.

8. A method according to claim 1, further comprising the step of fractionating the API Group III Technical White Oil after hydrotreating into a plurality of kinematic viscosity ranges.

9. A method according to claim 8, wherein the kinematic viscosity ranges are greater than or equal to 4 centistokes (cSt) and less than or equal to 600 cSt at 40 degrees Celsius.

10. A method according to claim 1, wherein the API Group III Technical White Oil has a viscosity gravity constant (VGC) of less than 0.807.

11. A method according to claim 1, wherein the API Group III Technical White Oil has a viscosity range at 40 degrees Celsius of 4 to 600 centistokes (cSt).

12. A method according to claim 1, wherein the hydrotreating step substantially removes heteroatoms and aromatic color bodies in the pretreated rubber pyrolysis oil.

13. A method according to claim 1, further comprising a step of solvent extraction, catalytic dewaxing or hydrofinishing of the API Group III Technical White Oil.

14. A method according to claim 1, wherein the noble metal catalyst comprises platinum or palladium.

15. A method according to claim 1, wherein the non-noble metal catalyst comprises tungsten, nickel, molybdenum, or cobalt.

16. A method for producing a skin-care product or food-contact product, the method comprising:hydroprocessing a rubber pyrolysis oil in a presence of hydrogen and a non-noble metal catalyst to saturate olefins and diolefins and decrease the halide, sulfur and nitrogen contents within the rubber pyrolysis oil, thereby providing a pretreated rubber pyrolysis oil;hydrotreating the pretreated rubber pyrolysis oil in a presence of hydrogen and a noble metal catalyst to reduce remaining unsaturation in the pretreated rubber pyrolysis oil, thereby providing an API Group III Technical White Oil, andblending the API Group III Technical White Oil with skin care ingredients to provide the skin care product, or combining the API Group III Technical White Oil with food ingredients to provide the food-contact product.

17. An API Group III Technical White Oil made by a process comprising:hydroprocessing a rubber pyrolysis oil in a presence of hydrogen and a non-noble metal catalyst to saturate olefins and diolefins and decrease the halide, sulfur and nitrogen contents within the rubber pyrolysis oil, thereby providing a pretreated rubber pyrolysis oil; andhydrotreating the pretreated rubber pyrolysis oil in a presence of hydrogen and a noble metal catalyst and under sufficiently severe conditions to reduce aromatics and provide an API Group III Technical White Oil having a total polycyclic aromatic (PAH) content of less than 100 ppm (<0.01 wt. %).

18. An API Group III Technical White Oil according to claim 17, wherein the API Group III Technical White Oil has a sulfur content less than 0.03 wt %, a saturates content greater than 90 wt %, and a viscosity index greater than 120.

19. An API Group III Technical White Oil according to claim 17, wherein the API Group III Technical White Oil has a viscosity gravity constant (VGC) of less than 0.807.

20. An API Group III Technical White Oil according to claim 17, wherein the API Group III Technical White Oil has a viscosity range at 40 degrees Celsius of 4 to 600 centistokes (cSt).

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