EP4237518A1 - Biodegradable bright stock preparation and a method of manufacturing thereof - Google Patents
Biodegradable bright stock preparation and a method of manufacturing thereofInfo
- Publication number
- EP4237518A1 EP4237518A1 EP21819170.8A EP21819170A EP4237518A1 EP 4237518 A1 EP4237518 A1 EP 4237518A1 EP 21819170 A EP21819170 A EP 21819170A EP 4237518 A1 EP4237518 A1 EP 4237518A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oil
- feed composition
- composition according
- bright stock
- feed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 61
- 239000003921 oil Substances 0.000 claims abstract description 54
- 235000019198 oils Nutrition 0.000 claims abstract description 54
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 35
- 239000008158 vegetable oil Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 25
- 235000019484 Rapeseed oil Nutrition 0.000 claims abstract description 20
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 claims abstract description 19
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims abstract description 14
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims abstract description 14
- 240000002791 Brassica napus Species 0.000 claims abstract description 10
- 235000004977 Brassica sinapistrum Nutrition 0.000 claims abstract description 10
- 239000000944 linseed oil Substances 0.000 claims abstract description 10
- 235000021388 linseed oil Nutrition 0.000 claims abstract description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 10
- 239000002480 mineral oil Substances 0.000 claims abstract description 8
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005642 Oleic acid Substances 0.000 claims abstract description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011630 iodine Substances 0.000 claims abstract description 4
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000007334 copolymerization reaction Methods 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229920005605 branched copolymer Polymers 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 description 20
- 239000000047 product Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000000314 lubricant Substances 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 239000002199 base oil Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- -1 cyclic lactones Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000010727 cylinder oil Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010720 hydraulic oil Substances 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005555 metalworking Methods 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 235000019463 artificial additive Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 239000000828 canola oil Substances 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007156 chain growth polymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000010722 industrial gear oil Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- HOIQWTMREPWSJY-GNOQXXQHSA-K iron(3+);(z)-octadec-9-enoate Chemical compound [Fe+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HOIQWTMREPWSJY-GNOQXXQHSA-K 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004525 petroleum distillation Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M109/00—Lubricating compositions characterised by the base-material being a compound of unknown or incompletely defined constitution
- C10M109/02—Reaction products
Definitions
- the invention to which this application relates is a biodegradable bright stock preparation and a method of manufacturing thereof.
- the term “bright stock” usually refers to heavy petroleum base oil produced from residues of petroleum distillation by refineries producing API Group I base oils. Solvent-extracted bright stock, with a viscosity in the range of 28.0 to 35.0 mm2/ s (cSt) at 100°C, is often used in heavy duty automotive, marine and industrial lubricants such as heavy duty engine oils, slow-speed engine cylinder oils, industrial gear oils, process oils etc.
- Synthetic alternatives for mineral bright stock include polyisobutylene (PIB), high viscosity polyalphaolefin (PAO), polyalkylene glycol (PAG), polyesters, heavy naphthenic oils and ionized vegetable oils.
- PIB polyisobutylene
- PAO high viscosity polyalphaolefin
- PAG polyalkylene glycol
- polyesters heavy naphthenic oils and ionized vegetable oils.
- Vegetable oil-based polymers have a long history of use as oil thickeners and viscosity index improvers in lubricant formulations.
- Vegetable oil-based polymers can be obtained by free radical, cationic, olefin metathesis, and condensation polymerization.
- Blown oil base oils have been developed over many years and include a diverse group of products based on castor oil, rapeseed oil and soyabean oil. Blown oils are also known as oxidized oils and oxidatively polymerised oils. Oxidative polymerization occurs by the interaction of double bonds and oxygen to form peroxides. Conjugation of double bonds occurs to stabilize hydroperoxides. A free radical chain reaction is initiated as hydroperoxides decompose and the subsequent chain-growth polymerization reaction gives high molecular weight, crosslinked products. See Figure 1, which illustrates the mechanism of oxidative polymerization of vegetable oil.
- the rate of oxidative polymerization increases with the extent of conjugation and unsaturation.
- the degree of unsaturation is usually characterized by using the iodine value (ASTM D5554) .
- Polymerized vegetable oils are good lubricity additives and perform well in water-based metalworking fluids as well as in neat oils. They are manufactured to a specific viscosity specification ranging from 1 poise @ 25°C up to 1600 poise @ 25°C, depending on the oil type.
- the feedstock containing natural fatty triglycerides of various chain length and degree of unsaturation undergoes electro-ionising treatment that leads to an increase in viscosity index, viscosity and polarity, due to probably partial oligomerisation and isomerisation of fatty triglyceride molecules and the formation of small amounts of free fatty acids and monoglycerides and biglycerides.
- catalyst nor any synthetic additives are used (M. Roegiers, B. Zhmud, Lubrication Science 2011 , 23, pp. 263—278; C. Boelhouwer C, et al., Polymerization of linseed oil in an electric discharge. Journal of the American Oil Chemists’ Society 1960, 37, pp. 373-376) .
- Vegetable oils can also be polymerized by heating them in vacuum or an inert gas atmosphere (see, for instance, US Patent 5229023) .
- Erhan and Bagby carried out polymerization by heating oil at 330C in nitrogen atmosphere under continuous stirring (S.Z. Erhan, M. O. Bagby, Polymerization of vegetable oils and their uses in printing inks, J. Am. Oil Chemists Soc. 71 , 1994, pp. 1223-1226; WO 92/07051), see Figure 2, which illustrates the oil viscosity increase kinetics for thermoinduced polymerization.
- Carboxylates of Ni, Fe, Co, Cu and Sn all were found to be effective polymerization catalysts (V.M. Mello et al., Industrial Crops and Products 2013, 43(1) pp.56—60) .
- the catalytic thermal polymerization process is more economic than the plasma polymerization.
- the formation of intermolecular bonds through in soybean oil under can be activated at 160°C in the presence of metallic catalysts, compared to 300-330°C in their absence.
- One of such problems is that other known bright stock replacements lack utility of one-to-one replacement that would enable their use in the existing product formulations without requiring reformulation.
- the present invention relates to the manufacture of a bio-based bright stock replacement by sonochemical co-polymerization of two oils, one being a vegetable oil and the other, a mineral oil.
- feed composition for manufacturing a biodegradable bright stock comprising: a vegetable oil; and a mineral oil, characterized in that the vegetable oil is formed from one of the following: a) a rapeseed oil containing >2% erucic acid and having a polyunsaturated fatty acid content below 10%; b) high erucic acid rapeseed (>50% erucic acid) oil with low polyunsaturated fatty acid content ( ⁇ 25%); c) high oleic acid rapeseed (>50% oleic acid) oil with low polyunsaturated fatty acid content ( ⁇ 25%); or d) a blend of any of the above rapeseed oils and linseed oil having an iodine value (IV) in the range of 80- 120 gI 2 / 100g, and wherein the mineral oil is a high viscosity hydrotreated naphthenic oil.
- the vegetable oil is formed from one of the following: a) a rape
- said high viscosity hydrotreated naphthenic oil has a mean molecular weight in a range of between 350 to 700 g/mol.
- said high viscosity hydrotreated naphthenic oil has a mean molecular weight in a range of between 400 to 550 g/mol.
- said high viscosity hydrotreated naphthenic oil has a napththenic carbon content in a range of 20% to 60%.
- said high viscosity hydrotreated naphthenic oil has a napththenic carbon content in a range of 30% to 40%.
- said high viscosity hydrotreated naphthenic oil has an aromatic carbon content in a range of 5% to 30%.
- said high viscosity hydrotreated naphthenic oil has an aromatic carbon content in a range of 10% to 20%.
- said composition comprises 50-80% hydrotreated naphthenic oil and 20-50% refined vegetable oil.
- said composition comprises 50% or less hydrotreated naphthenic oil and 50% or more refined vegetable oil.
- said feed composition is formed from sonochemical co-polymerization of the constituent components.
- the feed composition may be used in voltolization or thermal polymerization processes.
- Sonochemical co-polymerization processes are preferred in the present invention since they have been demonstrated to be more cost- and energy efficient than other processes mentioned.
- the conventional thermoinduced polymerization process consumes on average 200-300 kWh energy per ton of finished product, while the sonochemical process of the present invention halves the energy demand, consuming only 100- 150 kWh per ton.
- the polyunsaturated fatty acid (PUFA) content is less than 5%.
- An ultra-low ( ⁇ 5%) PUFA content is preferable because it has been shown that such a low content can greatly increase the thermal stability of rapeseed oil, and the final composition.
- the feed composition may further include an amount of linseed oil. Typically said amount is provided as less than 10% of the total weight of the composition.
- the provision of an increased amount of linseed oil increases the formation of branched copolymers in the composition.
- a biodegradable bright stock formed from a feed composition as described above.
- a bright stock composition which is inherently biodegradeable in accordance with OECD Test No. 301B, obtained by sonochemical co-polymerization of a feed containing 50-80% hydrotreated naphthenic oil and 20-50% refined vegetable oil.
- a readily biodegradable bright stock composition obtained by sonochemical co-polymerization of a feed containing less than 50% hydrotreated naphthenic oil and more than 50% refined vegetable oil.
- a method of making a bright stock / feed composition for a bright stock including the steps of: a) premixing raw materials and loading the feed into the reactor, said raw materials including a feed composition as described above; b) triggering polymerization using sonic activation or cavity blending; and c) controlling the blend temperature and viscosity using suitable control devices such as a thermocouple and a vibrating viscometer, or the like.
- Figure 1 illustrates the mechanism of oxidative polymerization of vegetable oil
- Figure 2 illustrates the oil viscosity increase kinetics for thermoinduced polymerization.
- the proper reaction feed, treatment conditions and eventual deployment of a catalyst are all important for the sonochemical polymerization process and affect the characteristics of the final product. It was found that, by using a reaction feed comprised of high oleic or high erucic rapeseed oil and a hydrotreated high viscosity mineral oil, with eventual inclusion of a small percent o f Im seed oil as polymerization seeds, the sonochemical reaction yield and the product homogeneity unexpectedly increase, leading to significant energy savings compared to thermal or plasma polymerization processes described in the Previous Art section. The said process enables production of biodegradable bright stock of API Group V category that can be used as one- to-one replacement for mineral bright stock in lubricant formulations.
- Preferred mineral base oils suitable for use in the reaction feed in the said sonochemical process are high viscosity hydrotreated naphthenic oils with a mean molecular weight in a range between 350 to 700 g/mol, and more preferably, in a range 400 to 550 g/mol, a naphthenic carbon content in a range 20% to 60%, and more preferably, in a range 30% to 40%, and an aromatic carbon content in a range 5 to 30%, and more preferably, in a range 10 to 20%, where the carbon content is determined according to ASTM D 2140 , or as an alternative, by using the FTIR method as described in G.W. Stachowiak, A.W. Bachelor, Engineering Tribology, 3d ed., Cha p . 3: Lubricants and their composition, Elsevier, 2006. Examples of suitable base oils for use in the said process are given in TABLE 1.
- the preferred vegetable oil choice for the said sonochemical process is a blended feed containing 90 to 100% refined rapeseed oil and 0 to 10% linseed oil.
- the presence of linseed oil favours the formation of branched copolymers.
- Iron carboxylate salts, such as iron oleate, can be added to the reactive mixture at a treat rate ca 100 ppm to reduce the polymerization temperature and to speed up the polymerization process.
- the preferred reaction temperature is between 100 and 300 °C, and process duration 8 to 24 hours under gentle stirring in an inert atmosphere.
- Another object of the invention is using rapeseed oil from the class of rapeseed varieties with ultra-low polunasturated fatty acid content such as high oleic and low PUFA (HOLP) or high erucic and low PUFA (HELP) and optionally from the seeds of standard high erucic acid rape varieties (HEAR) or low erucic (’00) rapeseed varieties with fatty acid profile as presented in Table 5 or that falls outside the regulated limit of 2% maximum erucic acid for specification as edible.
- HEAR high erucic acid rape varieties
- ’00 low erucic
- Use of novel rapeseed oils with ultra-low (below 5%) polyunsaturated fatty acid content is specially preferred in the context of the present invention thank to its outstanding oxidation stability, see Table 4 and Table 6.
- oleic acid is represented by C18:1; and erucic acid is represented by C22:1.
- the polyunsaturated fatty acids are C18:2 and C18:3.
- a variety of commercially available sonic processors in connection with standard accessories, can be used to run the aforesaid sonochemical polymerization process, for instance, the ultrasonic processors UIP500hdT, UIP1000hdT, UIP1500hdT, UIP2000hdT and UIP4000hdT supplied by Hielscher. Nitrogen or another inert gas blanketing is recommended to minimize oil oxidation. Alternatively, hydrogen gas can be used to induce controlled hydrogenation of conjugated double bonds, which further enhances the oxidation stability of the product.
- the same feed composition is also suitable for use in the classical voltolization and thermal polymerization processes, but the sonochemical process offers improved cost- and energy- efficiency.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The present invention provides feed composition for manufacturing a biodegradable bright stock. The composition comprises a vegetable oil and a mineral oil. The vegetable oil is formed from one of the following: a) a rapeseed oil containing >2% erucic acid and having a polyunsaturated fatty acid content below 10%; b) high erucic acid rapeseed (>50% erucic acid) oil with low polyunsaturated fatty acid content (≤25%); c) high oleic acid rapeseed (>50% oleic acid) oil with low polyunsaturated fatty acid content (≤25%); or d) a blend of any of the above rapeseed oils and linseed oil having an iodine value (IV) in the range of 80-120 gI2/100g. The mineral oil is a high viscosity hydrotreated naphthenic oil. Also provided are bright stock compositions utilizing the feed composition defined herein, and a method for making a bright stock or feed composition for a bright stock.
Description
Biodegradable Bright Stock Preparation and a method of manufacturing thereof
The invention to which this application relates is a biodegradable bright stock preparation and a method of manufacturing thereof.
In the lubricant industry, the term “bright stock” usually refers to heavy petroleum base oil produced from residues of petroleum distillation by refineries producing API Group I base oils. Solvent-extracted bright stock, with a viscosity in the range of 28.0 to 35.0 mm2/ s (cSt) at 100°C, is often used in heavy duty automotive, marine and industrial lubricants such as heavy duty engine oils, slow-speed engine cylinder oils, industrial gear oils, process oils etc.
As the base oil market shifts away from API Group I production, less bright stocks are being produced globally. By 2025, the global deficit is expected to be around 300 metric tonnes per year. The applications that rely on bright stock are faced with two options: continue to use bright stocks, which are getting pricier because of declining availability, or consider alternatives.
Synthetic alternatives for mineral bright stock include polyisobutylene (PIB), high viscosity polyalphaolefin (PAO), polyalkylene glycol (PAG), polyesters, heavy naphthenic oils and ionized vegetable oils. However, such alternatives tend to be much pricier than mineral bright stocks and require reformulation and re-approval of finished lubricants. Hence, it would be highly advantageous to have a one-to-one bright stock replacement that can be used in the existing product formulations without requiring costly re-approvals.
Vegetable oil-based polymers have a long history of use as oil thickeners and viscosity index improvers in lubricant formulations. Vegetable oil-based polymers can be obtained by free radical, cationic, olefin metathesis, and condensation polymerization. Blown oil base oils have been developed over many years and include a diverse group of products based on castor oil, rapeseed oil and soyabean oil. Blown oils are also known as oxidized oils and oxidatively polymerised oils. Oxidative polymerization occurs by the interaction of double bonds and oxygen to form peroxides. Conjugation of double bonds occurs to stabilize hydroperoxides. A free radical chain reaction is initiated as hydroperoxides decompose and the subsequent chain-growth polymerization reaction gives high molecular weight, crosslinked products. See Figure 1, which illustrates the mechanism of oxidative polymerization of vegetable oil.
The rate of oxidative polymerization increases with the extent of conjugation and unsaturation. The degree of unsaturation is usually characterized by using the iodine value (ASTM D5554) . Polymerized vegetable oils are good lubricity additives and perform well in water-based metalworking fluids as well as in neat oils. They are manufactured to a specific viscosity specification ranging from 1 poise @ 25°C up to 1600 poise @ 25°C, depending on the oil type. There are numerous producers of oxidatively polymerized vegetable oils: Afton, Croda, Oleon to name a few. Due to their excellent lubricity and a benign health safety profile, blown vegetable oils are successfully used in industrial lubricants and metalworking fluid formulations.
As an alternative to oxidative polymerization, plasma treatment has been used, see for instance WO2018/002329. The basic process is similar to the legacy Elektrion process developed by
Alexandre de Hemptinne in Belgium in the beginning of the 20th century (M. Roegiers, The Elektrion process: its history, its mechanism, its action on lubricating oils. Elektrion s.a., Ghent, 1952) and the Voltolization process developed by Standard Oil Development Company in USA (US 2,071,551; 2,274,636; GB 488026) . The Elektrion process uses silent electric discharges to trigger the polymerization. The feedstock containing natural fatty triglycerides of various chain length and degree of unsaturation undergoes electro-ionising treatment that leads to an increase in viscosity index, viscosity and polarity, due to probably partial oligomerisation and isomerisation of fatty triglyceride molecules and the formation of small amounts of free fatty acids and monoglycerides and biglycerides. Neither catalyst nor any synthetic additives are used (M. Roegiers, B. Zhmud, Lubrication Science 2011 , 23, pp. 263—278; C. Boelhouwer C, et al., Polymerization of linseed oil in an electric discharge. Journal of the American Oil Chemists’ Society 1960, 37, pp. 373-376) .
Vegetable oils can also be polymerized by heating them in vacuum or an inert gas atmosphere (see, for instance, US Patent 5229023) . Erhan and Bagby carried out polymerization by heating oil at 330C in nitrogen atmosphere under continuous stirring (S.Z. Erhan, M. O. Bagby, Polymerization of vegetable oils and their uses in printing inks, J. Am. Oil Chemists Soc. 71 , 1994, pp. 1223-1226; WO 92/07051), see Figure 2, which illustrates the oil viscosity increase kinetics for thermoinduced polymerization.
Carboxylates of Ni, Fe, Co, Cu and Sn all were found to be effective polymerization catalysts (V.M. Mello et al., Industrial Crops and Products 2013, 43(1) pp.56—60) . The catalytic thermal polymerization process is more economic than the plasma polymerization. Thus, the formation of intermolecular bonds
through in soybean oil under can be activated at 160°C in the presence of metallic catalysts, compared to 300-330°C in their absence.
Multiple hardware configurations are possible to run the process and different feedstock compositions can be used to achieve specific product properties.
In general, it is known that high intensity ultrasound can be used to activate various chemical reactions, including polymerization, due to cavitation energy. Thus, ring-opening polymerization of cyclic lactones to polyesters can be triggered by 20 kHz ultrasound. Sonication was also applied to the preparation of polyurethanes from a number of diisocyanates and diols. In all cases, the sonochemical reactions proceeded faster in the early stages and led to higher molecular weight polymers, but in other cases, sonication can lead to depolymerization and a reduction in molecular weight (G.J. Price, Recent developments in sonochemical polymerization, Ultrasonics Sonochemistry 10 (2003) 277; Price G.J. Polymer Sonochemistry: Controlling the Structure and Properties of Macromolecules. In: Crum L.A., Mason T.J., Reisse J .L., Suslick K.S. (eds) Sonochemistry and Sonoluminescence. NATO ASI Series (Series C: Mathematical and Physical Sciences), vol 524. Springer, Dordrecht, 1999).
It is an aim of the present invention to provide a bio-based bright stock replacement which overcomes the problems associated with the prior art.
It is a further aim of the present invention to provide a method of manufacture of a bio-based bright stock replacement, which overcomes the problems associated with the prior art.
One of such problems is that other known bright stock replacements lack utility of one-to-one replacement that would enable their use in the existing product formulations without requiring reformulation.
The present invention relates to the manufacture of a bio-based bright stock replacement by sonochemical co-polymerization of two oils, one being a vegetable oil and the other, a mineral oil.
According to a first aspect of the invention there is provided feed composition for manufacturing a biodegradable bright stock, said composition comprising: a vegetable oil; and a mineral oil, characterized in that the vegetable oil is formed from one of the following: a) a rapeseed oil containing >2% erucic acid and having a polyunsaturated fatty acid content below 10%; b) high erucic acid rapeseed (>50% erucic acid) oil with low polyunsaturated fatty acid content (≤25%); c) high oleic acid rapeseed (>50% oleic acid) oil with low polyunsaturated fatty acid content (≤25%); or d) a blend of any of the above rapeseed oils and linseed oil having an iodine value (IV) in the range of 80- 120 gI2/ 100g, and wherein the mineral oil is a high viscosity hydrotreated naphthenic oil.
The aforesaid limits exclude competition with food-grade rapeseed oil (also known as canola oil, rapeseed '00 oil, low erucic acid rapeseed oil, LEAR oil, and rapeseed canola- equivalent oil) that is allowed to contain a maximum of 2% erucic acid by weight in the USA and 5% in the EU.
In one embodiment, said high viscosity hydrotreated naphthenic oil has a mean molecular weight in a range of between 350 to 700 g/mol. Preferably, said high viscosity hydrotreated naphthenic oil has a mean molecular weight in a range of between 400 to 550 g/mol.
In one embodiment, said high viscosity hydrotreated naphthenic oil has a napththenic carbon content in a range of 20% to 60%. Preferably, said high viscosity hydrotreated naphthenic oil has a napththenic carbon content in a range of 30% to 40%.
In one embodiment, said high viscosity hydrotreated naphthenic oil has an aromatic carbon content in a range of 5% to 30%. Preferably, said high viscosity hydrotreated naphthenic oil has an aromatic carbon content in a range of 10% to 20%.
In one embodiment, said composition comprises 50-80% hydrotreated naphthenic oil and 20-50% refined vegetable oil.
In another embodiment, said composition comprises 50% or less hydrotreated naphthenic oil and 50% or more refined vegetable oil.
Typically, said feed composition is formed from sonochemical co-polymerization of the constituent components. In other embodiments of the invention, the feed composition may be used in voltolization or thermal polymerization processes. Sonochemical co-polymerization processes are preferred in the present invention since they have been demonstrated to be more cost- and energy efficient than other processes mentioned. Thus, the conventional thermoinduced polymerization process consumes on average 200-300 kWh energy per ton of finished product, while the sonochemical process of the present
invention halves the energy demand, consuming only 100- 150 kWh per ton.
In one embodiment, for vegetable oil compounds a)-c), the polyunsaturated fatty acid (PUFA) content is less than 5%. An ultra-low (<5%) PUFA content is preferable because it has been shown that such a low content can greatly increase the thermal stability of rapeseed oil, and the final composition.
In one embodiment, for vegetable oil compounds a)-c), the feed composition may further include an amount of linseed oil. Typically said amount is provided as less than 10% of the total weight of the composition.
Typically, the provision of an increased amount of linseed oil increases the formation of branched copolymers in the composition.
According to another aspect of the present invention, there is provided a biodegradable bright stock formed from a feed composition as described above.
In another aspect of the present invention, there is provided a bright stock composition, which is inherently biodegradeable in accordance with OECD Test No. 301B, obtained by sonochemical co-polymerization of a feed containing 50-80% hydrotreated naphthenic oil and 20-50% refined vegetable oil.
In another aspect of the present invention, there is provided a readily biodegradable bright stock composition obtained by sonochemical co-polymerization of a feed containing less than 50% hydrotreated naphthenic oil and more than 50% refined vegetable oil.
In another aspect of the present invention, there is provided a method of making a bright stock / feed composition for a bright stock, said method including the steps of: a) premixing raw materials and loading the feed into the reactor, said raw materials including a feed composition as described above; b) triggering polymerization using sonic activation or cavity blending; and c) controlling the blend temperature and viscosity using suitable control devices such as a thermocouple and a vibrating viscometer, or the like.
Embodiments of the present invention will now be described with reference to the accompanying figures, wherein:
Figure 1 illustrates the mechanism of oxidative polymerization of vegetable oil; and
Figure 2 illustrates the oil viscosity increase kinetics for thermoinduced polymerization.
The proper reaction feed, treatment conditions and eventual deployment of a catalyst are all important for the sonochemical polymerization process and affect the characteristics of the final product. It was found that, by using a reaction feed comprised of high oleic or high erucic rapeseed oil and a hydrotreated high viscosity mineral oil, with eventual inclusion of a small percent o f Im seed oil as polymerization seeds, the sonochemical reaction yield and the product homogeneity unexpectedly increase, leading to significant energy savings compared to thermal or plasma polymerization processes described in the Previous Art section. The said process enables production of biodegradable bright stock of API Group V category that can be used as one-
to-one replacement for mineral bright stock in lubricant formulations.
Preferred mineral base oils suitable for use in the reaction feed in the said sonochemical process are high viscosity hydrotreated naphthenic oils with a mean molecular weight in a range between 350 to 700 g/mol, and more preferably, in a range 400 to 550 g/mol, a naphthenic carbon content in a range 20% to 60%, and more preferably, in a range 30% to 40%, and an aromatic carbon content in a range 5 to 30%, and more preferably, in a range 10 to 20%, where the carbon content is determined according to ASTM D 2140
, or
as an alternative, by using the FTIR method as described in G.W. Stachowiak, A.W. Bachelor, Engineering Tribology, 3d ed.,
Cha
p
. 3: Lubricants and their composition, Elsevier, 2006. Examples of suitable base oils for use in the said process are given in TABLE 1.
TABLE 1 : The typical physicochemical properties of mineral base oil used in the reaction feed
The typical physicochemical properties of mineral bright stocks are shown in TABLE 2.
TABLE 2: The typical physicochemical properties of mineral bright stocks
The preferred vegetable oil choice for the said sonochemical process is a blended feed containing 90 to 100% refined rapeseed oil and 0 to 10% linseed oil. The presence of linseed oil favours the formation of branched copolymers. Iron carboxylate salts, such as iron oleate, can be added to the reactive mixture at a treat rate ca 100 ppm to reduce the polymerization temperature and to speed up the polymerization process. The preferred reaction temperature is between 100 and 300 °C, and process duration 8 to 24 hours under gentle stirring in an inert atmosphere.
The typical physicochemical properties of refined rapeseed oil suitable for use as a feedstock in the said process are shown in TABLE 3.
TABLE 3: The typical physicochemical properties of rapeseed oil used as the reaction feed
Another object of the invention is using rapeseed oil from the class of rapeseed varieties with ultra-low polunasturated fatty acid content such as high oleic and low PUFA (HOLP) or high erucic and low PUFA (HELP) and optionally from the seeds of standard high erucic acid rape varieties (HEAR) or low erucic (’00) rapeseed varieties with fatty acid profile as presented in Table 5 or that falls outside the regulated limit of 2% maximum erucic acid for specification as edible. Use of novel rapeseed oils with ultra-low (below 5%) polyunsaturated fatty acid content is specially preferred in the context of the present invention thank to its outstanding oxidation stability, see Table 4 and Table 6. It has been demonstrated that low content of polyunsaturated fatty acids can increase thermal stability of the rapeseed oil 4-fold as shown in Table 4 (Kaur et. al., Plant Biotechnology Journal 18 (2020) 983—991) and in the finished product 5-fold (Table 6).
TABLE 4: Oxidation stability of high erucic rapeseed oil and regular rapeseed oil
TABLE 5: Fatty acid profile of various rapeseed oils (%)
It will be understood by those skilled in the art that in the above table oleic acid is represented by C18:1; and erucic acid is represented by C22:1. The polyunsaturated fatty acids are C18:2 and C18:3.
Table 6: Oxidation stability of finished products using the commercial DI packages (Brad-Chem DP3101 or BD351)
TABLE 7: The physicochemical properties of property-matched bio-based bright stock replacements obtained by sonochemical co-polymerization of vegetable oil and heavy naphthenic oil according to present invention
Various vegetable oil/heavy naphthenic oil weight ratios in the feed can be used to attain desired biodegradability rating. Thus, bright stock replacements obtained by sonochemical co- polymerization of a feed containing less than 50% hydrotreated
naphthenic oil and more than 50% refined vegetable oil are readily biodegradable, and those obtained by sonochemical co- polymerization of a feed containing 50-80% hydrotreated naphthenic oil and 20-50% refined vegetable oil are inherently biodegradable according to OECD Test No. 301B (CO2 Evolution Test) . Thus, the conventional thermoinduced polymerization process consumes on average 200-300 kWh energy per ton of finished product, while the sonochemical process of the present invention halves the energy demand, consuming only 100- 150 kWh per ton.
A variety of commercially available sonic processors, in connection with standard accessories, can be used to run the aforesaid sonochemical polymerization process, for instance, the ultrasonic processors UIP500hdT, UIP1000hdT, UIP1500hdT, UIP2000hdT and UIP4000hdT supplied by Hielscher. Nitrogen or another inert gas blanketing is recommended to minimize oil oxidation. Alternatively, hydrogen gas can be used to induce controlled hydrogenation of conjugated double bonds, which further enhances the oxidation stability of the product.
The same feed composition is also suitable for use in the classical voltolization and thermal polymerization processes, but the sonochemical process offers improved cost- and energy- efficiency.
To illustrate some possible applications of the present invention, a few lubricant formulations deploying the biodegradable bright stock replacement in place of conventional mineral bright stock are shown in Tables 8-11, below.
TABLE 8: Hydraulic oil HLP 68
TABLE 9: Hydraulic oil AW 220
TABLE 10: Gear Oil SAE 90 GL-4
TABLE 11: Marine cylinder oil SAE 50 BN40
Claims
1. According to a first aspect of the invention there is provided feed composition for manufacturing a biodegradable bright stock, said composition comprising: a vegetable oil; and a mineral oil, characterized in that the vegetable oil is formed from one of the following: a) a rapeseed oil containing >2% erucic acid and having a polyunsaturated fatty acid content below 10%; b) high erucic acid rapeseed (> 50% erucic acid) oil with low polyunsaturated fatty acid content (≤25%); c) high oleic acid rapeseed (>50% oleic acid) oil with low polyunsaturated fatty acid content (≤25%); or d) a blend of any of the above rapeseed oils and linseed oil having an iodine value (IV) in the range of 80- 120 gI2/100g, and wherein the mineral oil is a high viscosity hydrotreated naphthenic oil.
2. A feed composition according to claim 1, wherein said high viscosity hydrotreated naphthenic oil has a mean molecular weight in a range of between 350 to 700 g/mol.
3. A feed composition according to claim 1, wherein said high viscosity hydrotreated naphthenic oil has a mean molecular weight in a range of between 400 to 550 g/mol.
4. A feed composition according to claim 1, wherein said high viscosity hydrotreated naphthenic oil has a napththenic carbon content in a range of 20% to 60%.
5. A feed composition according to claim 1, wherein said high viscosity hydrotreated naphthenic oil has a napththenic carbon content in a range of 30% to 40%.
6. A feed composition according to claim 1, wherein said high viscosity hydrotreated naphthenic oil has an aromatic carbon content in a range of 5% to 30%.
7. A feed composition according to claim 1, wherein said high viscosity hydrotreated naphthenic oil has an aromatic carbon content in a range of 10% to 20%.
8. A feed composition according to claim 1, wherein said composition comprises 50-80% hydrotreated naphthenic oil and 20-50% refined vegetable oil.
9. A feed composition according to claim 1, wherein said composition comprises 50% or less hydrotreated naphthenic oil and 50% or more refined vegetable oil.
10. A feed composition according to claim 1, wherein said feed composition is formed from sonochemical copolymerization of the constituent components.
11. A feed composition according to claim 1, wherein for vegetable oil compounds a)-c), the polyunsaturated fatty acid (PUFA) content is less than 5%.
12. A feed composition according to claim 1, wherein for vegetable oil compounds a)-c), the feed composition further includes an amount of linseed oil.
13. A feed composition according to claim 12, wherein said amount is provided as less than 10% of the total weight of the composition.
14. A feed composition according to claim 1 , wherein the provision of aann aammoouunntt of linseed oil increases the formation of branched copolymers in the composition.
15. A biodegradable bright stock formed from a feed composition as defined in any of claims 1 -14.
16. A bright stock composition, which is inherently biodegradeable in accordance with OECD Test No. 301B, obtained by sonochemical co-polymerization of a feed containing 50-80% hydrotreated naphthenic oil and 20- 50% refined vegetable oil.
17. A readily biodegradable bright stock composition obtained by sonochemical co-polymerization of a feed containing less than 50% hydrotreated naphthenic oil and more than 50% refined vegetable oil.
18. A method of making a bright stock / feed composition for a bright stock, said method including the steps of: a) premixing raw materials and loading a feed into the reactor, said raw materials including a feed composition as defined in any of claims 1 -14; b) triggering polymerization using sonic activation or cavity blending; and c) controlling the blend temperature and viscosity using suitable control devices such as a thermocouple and a vibrating viscometer, or the like.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB2017170.8A GB202017170D0 (en) | 2020-10-29 | 2020-10-29 | Biodegradable bright stock preparation and a method of manufacturing thereof |
| PCT/GB2021/052789 WO2022090712A1 (en) | 2020-10-29 | 2021-10-27 | Biodegradable bright stock preparation and a method of manufacturing thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4237518A1 true EP4237518A1 (en) | 2023-09-06 |
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ID=73776550
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP21819170.8A Pending EP4237518A1 (en) | 2020-10-29 | 2021-10-27 | Biodegradable bright stock preparation and a method of manufacturing thereof |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP4237518A1 (en) |
| GB (1) | GB202017170D0 (en) |
| WO (1) | WO2022090712A1 (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2071551A (en) | 1935-08-23 | 1937-02-23 | Standard Oil Dev Co | Apparatus for voltolization |
| GB488026A (en) | 1936-01-31 | 1938-06-28 | Standard Oil Dev Co | Improvements relating to voltolized oils |
| US2274636A (en) | 1938-09-21 | 1942-03-03 | Standard Oil Dev Co | Electrodes for voltolization |
| DE69130641T2 (en) | 1990-10-12 | 1999-05-06 | Int Lubricants Inc | TELOMERIZED EDIBLE OILS AS LUBRICANT ADDITIVES |
| US5229023A (en) | 1990-10-12 | 1993-07-20 | International Lubricants, Inc. | Telomerized triglyceride vegetable oil for lubricant additives |
| US9315756B2 (en) * | 2012-04-06 | 2016-04-19 | Exxonmobil Research And Engineering Company | Bio-feeds based hybrid group V base stocks and method of production thereof |
| BE1023805B1 (en) | 2016-06-30 | 2017-07-26 | Green Frix | DEVICE FOR THE ELECTRICAL TREATMENT OF A FATTY BODY OF VEGETABLE ORIGIN |
-
2020
- 2020-10-29 GB GBGB2017170.8A patent/GB202017170D0/en not_active Ceased
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2021
- 2021-10-27 WO PCT/GB2021/052789 patent/WO2022090712A1/en unknown
- 2021-10-27 EP EP21819170.8A patent/EP4237518A1/en active Pending
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| WO2022090712A1 (en) | 2022-05-05 |
| GB202017170D0 (en) | 2020-12-16 |
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