Major pathways for used oil disposal and recycling. Part 1

One of the main concerns with lubricating oil relates to used oil management for both industrial and engine oils, although the environmental impact of gasoline and diesel engine oils is the most critical. Provided that efficient management systems are in place, most used oil should not reach the environment, so, the major question is how to dispose of collected used oil. The first option lies in burning it as a fuel, the second in recycling (reclaiming, reprocessing, re‐refining). The latter allows recovery of mineral base oils, which are valuable constituents of crude oil. Mobile (on site) and fixed plants for industrial oil recycling will first be discussed, and the paper will look at the most modern re‐refining processes that produce base oils of as high quality as virgin base oils. Based on current re‐refining experience, the quality of finished lubricants blended from re‐refined base stocks is also noted. Re‐refining today may be of significant benefit to the economy and can, of course, protect the environment. All modern re‐refining technologies produce small amounts of by‐products in which toxic materials may have been concentrated. A final aspect of reprocessing used oil is to integrate it, after hydrogen treatment, into existing refineries. This valuable raw material can then be directly routed to a lube oil unit or even to a cracking unit for conversion to gasoline. The integration of used oil treatment processes into selected refineries may be the most effective pathway to used oil disposal. In this first part, the author looks at the nature of the problems associated with used oil, its use as a fuel, and simple recycling. He then goes on to look at major re‐refining processes, starting with hydrogenation (KTI, Mohawk, BERC/NIPER, and PROP technologies). Part 2 will describe other processes, including a range of vacuum distillation/clay treatment technologies.     

Rerefining of used oils — a review of commercial processes

The total demand for lubricants in India is in the region of 855,000 tonnes a year. This constitutes 1.5% of total petroleum products consumption. Presently, there are three lubricant refineries in the country with a total installed capacity of 535,000 tonnes. The shortfall, of about 370,000 tonnes (approximately 45% of demand), is met through imports. In addition, there are generated 60,000–65,000 tonnes a year of base oil through rerefining of used oils. The three refineries are being expanded in order to raise base oil production to 810,000 tonnes per annum. Some other refinery projects are also under consideration and approval by the government. The current expansion programmes, together with the projected new refineries, are expected to make India self-sufficient in terms of base stock production lubricant. Overall, lubricant production in India is entirely dependent on imported lubricant-bearing crudes, and not on the indigenous crudes, which are non-lube bearing. With recent advances in engine design, together with improved lubricant quality through high-performance lubricants, the consumption, or demand rate, has been in decline or unchanging in most countries. In India, a gap still exists between production and demand of lubricants, necessitating import. Since they are a high-value, non-energy product, lubricant conservation measures are therefore essential. Interest in rerefining of used oil is increasing, with more and more emphasis on making the processes environmentally friendly. The conventional acid-clay rerefining process is environmentally unfriendly, and hence needs modification. An attempt is made in this paper to highlight various rerefining processes available. The relative merits and demerits of each process are discussed, and among the various processes, that based on molecular/high vacuum distillation is covered in detail.     

Viscosity and working efficiency analysis of soybean oil based bio-lubricants

This article presents significant data about viscosity and working efficiency analysis for developing the soybean oil based bio-lubricants. A suitable viscosity or viscosity index (VI) plays a very important role in a lubricant, which can avoid collision and rubbing between components of mechanical devices in work as well as optimize working efficiency of a machine. In general, low friction between devices can increase working efficiency of a machine, but low viscosity of a lubricant will easily cause collision and rubbing between components of mechanical devices in work. A too viscous lubricant also requires a large amount of energy to move, but a too thin lubricant will easily cause rubbed devices and increased friction. To replace the mineral oils and syntholubes, the soybean oil is recently become one of the most actively studied oils due to its eco-friendly organic property and lower cost. This work used mixtures of the original soybean oil, the epoxidized soybean oil, and the hydrogenated soybean oil as the base oils. Applications are focused on developing engine bio-lubricants. The results show that the epoxidized soybean oil has extremely large viscosity in comparison with the engine lubricants as well as the original soybean oil, whereas the hydrogenated soybean oil is clearly opposite. This viscosity analysis offers good informations to fit viscosity of the engine lubricants by mixing the three soybean oils as base oils.     

Synthesis of some additives from upgraded petroleum residues of lubricant oil refineries

Aromatic extract residues occur as by‐products in petroleum refineries, through the process of refining lubricant oil. These residues are considered as having low economic value, and their disposal may even cause problems for the refineries. The present work looks at upgrading these residues by using them to synthesise different petroleum additives, e.g., antioxidants, ashless dispersants, pour‐point depressants, and flow improvers for lubricating crankcase oils and for fuels. The antioxidants were synthesised by reacting mono‐aromatics with phosphorus pentasulphide (P₂S₅) in the presence of zinc oxide (ZnO). Ashless dispersant additives were synthesised by reacting alkylated mono‐aromatics (using chlorinated paraffin wax as an alkylating agent) with formaldehyde solution (37%) in the presence of polyisobutylene succinimide. Fuel pour‐point depressants and flow improvers can be synthesised by acylating di‐aromatics via a Friedel‐Crafts reaction. Comparative evaluation of the synthesised products with commercial additives showed them to have good comparative performance properties.     

Mixtures of vegetable oils and di‐2‐ethylhexyl‐sebacate as lubricants

Lubricants based on vegetable oils are growing in popularity in various applications. Environmentally friendly, vegetable oils and their derivatives constitute alternatives to mineral‐based lubricants. Soybean oil, sunflower oil and rapeseed oil have better viscosity indices than mineral oils and even some synthetic oils, are biodegradable and have low production costs. However, vegetable oils have disadvantages, such as poor thermo‐oxidative stability due to the carbon–carbon double bonds and poor low‐temperature properties, which limit their use as lubricant base stocks. This study describes new base‐stock oils obtained from mixture of vegetable oils and di‐2‐ethylhexyl‐sebacate synthetic oil, which become lubricants when additives are introduced. These mixtures offer a large range of kinematic viscosities, while their pour points are under −33°C and their flash points over 240°C. The copper strip corrosion test result is 1a. The diameters of wear scars measured under four‐ball testing (40dyn) are less than 1mm. A differential scanning calorimetry study and a thermo‐gravimetric study under a nitrogen atmosphere for the mixed oils are reported. In the former study two‐endothermic processes were observed between −15°C and −50°C. In the thermo‐gravimetric analysis curve the weight loss is specific for each vegetable and synthetic oil component. From these studies a higher thermal stability was observed for vegetable oils than for ester oils, and it was concluded that the mixtures of vegetable and synthetic oils of diester type are physically homogeneous mixtures. The low production cost of lubricants based on vegetable oils makes them attractive alternatives for mineral oil based lubricants. Overall the mixtures of vegetable and ester oils can be competitive base oils for environmentally friendly lubricants. Copyright © 2006 John Wiley & Sons, Ltd.     

Suitable additives for vegetable oil‐based automotive shock absorber fluids: an overview

Formulation of a cost‐effective, high‐performance and eco‐friendly lubricant, largely depends on the base oil quality, then the selection of suitable additives and their proportions. Vegetable oils, identified to be eco‐friendly, renewable, future‐available and cost‐effective treasures for lubricant formulation, apart from processing, will rely much on suitable additives to meet the performance requirements for automotive shock absorber (ASA) fluids. Additives that will guarantee performance, longevity and eco‐friendliness of formulated vegetable‐based functional fluids have to be uncommonly effective, resistant to depletion, non‐toxic and highly biodegradable. Their selection in these regards will require skills and experience, which will harness the various arms of synergism as effective tools to succour the known weaknesses of the base oil. This is a review on additives that could be used in formulation of vegetable oil‐based (ASA) fluids. The outcome shows that there are customary and novel additives that are suitable for formulating vegetable oil‐based ASA fluids. Copyright © 2016 John Wiley & Sons, Ltd.     

Application of quantitative 13C nuclear magnetic resonance spectroscopy to the characterisation of solvent‐refined aromatic‐rich lubricant base oils

Nuclear magnetic resonance (NMR) spectroscopy has emerged as a powerful technique for studying the molecular composition of base oil matrices. The usefulness of this technique lies in its ability to explain the chemistry involved in the molecular changes observed in various lubricant refining and extraction stages. This paper discusses the use of this technique in understanding the variation of gross properties observed in base oils during lubricant processing steps. The variations in weight percent of sulphur, viscosity index (VI), Conradson carbon residue (CCR), characterisation factor (K_UOP), etc., are explained at the molecular level using high‐resolution quantitative ¹H and ¹³C NMR. A single well‐recorded quantitative spectrum of a sample can be used to generate sufficient information on the different properties used for the specification of base oils.     

Tribological degradation of two vegetable‐based lubricants at elevated temperatures

Renewable‐based lubricants are being considered as potential alternatives to petroleum‐based lubricants for various reasons, mainly increased environmental sensitivity. However, understanding the tribological performance of such vegetable‐based lubricants under elevated temperatures is critical for their industrial implementation. This study focuses on the friction and abrasion rate characteristics of soybean and sunflower base oils in comparison to a base mineral oil under sliding wear at elevated temperatures. It was found that the abrasion rate and friction were less severe for the vegetable‐based lubricants up to temperatures around 100°C. The observed performance of the vegetable‐based lubricants was verified using a kinetic reaction mechanism model of lubricant degradation. Copyright © 2007 John Wiley & Sons, Ltd.     

Improvement of thermooxidative stability of non‐edible vegetable oils of Indian origin for biodegradable lubricant application

For environmental reasons, as well as the dwindling source of petroleum, a new class of environmentally acceptable and renewable lubricants based on vegetable oils is available. Even though vegetable oils possess excellent lubricant‐related properties, there are some concerns about using it as lubricant base oil. Still, unmodified and modified varieties of soybean, rapeseed, sunflower and canola oils have been in use in the USA and Europe. In India, with the shortage of edible oil, alternate sources of vegetable oils stocks are being explored. With this aim, a comprehensive study has been conducted earlier in the authors' laboratory. In this study, numerous options of non‐edible vegetable oil sources were explored, and a few potential vegetable oils were studied in the laboratory. It was found that even though the oils performed much better in comparison with other vegetable oils, it still required improvement in thermooxidative stability. Therefore, in the later part of the study, different options were explored to improve thermooxidative stability. With a background on the initial studies of the authors as described above, the present paper deals with the studies on improvement of these non‐edible candidate vegetable oils of Indian origin for lubricant by treating with selected antioxidants for applying them in lubricants. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of mechanical shear on the thin‐film properties of base oil‐polymer mixtures

The thickness and frictional characteristics of thin lubricant films are known to affect the fuel economy properties of oils. The base oil and polymer compositions of the lubricant are generally considered to be critical chemical factors that can influence these thin‐film lubricant properties in new oils. However, it is important to produce lubricants with good fuel economy properties that are maintained after the lubricant is degraded. Lubricants in use can undergo oxidation and mechanical shear degradation. The effect of oxidation degradation on thin‐film physical properties has previously been studied. This paper investigates the effect of mechanical shearing on thin‐film properties. Dispersant olefin copolymers are found to reduce thin‐film friction in simple mixtures and in fully formulated oils. In simple mixtures, shearing the dispersant olefin copolymers does not affect the friction‐reducing ability of these polymers. In fully formulated oils, even though shearing diminishes to a degree the friction‐reducing ability of dispersant olefin copolymers, these copolymers can still provide significant friction reduction.     

Biobased dry‐film metalworking lubricants

Metalworking lubricants must allow the manufacture of acceptable products at competitive cost without causing harm to operators or the environment. One way of attaining such a goal is through the use of biobased raw materials in lubricant formaulations. Biobased materials are generally non‐toxic, easily biodegradable, and abundantly available from renewable agricultural sources. However, successful application of biobased marterials in lubrication requires a thorough understanding of the tribochemical properties of these agricultural products. Recent studies have shown that biobased lubricants comprising starch and vegetable oils have promising lubrication properties. This paper discusses investigations into the effect of film thickness on the friction properties of dry‐film lubricants formulated from starch‐soybean oil composites.     

Mixture of safflower oil and synthetic ester as a base stock for biodegradable lubricants

Biodegradable industrial lubricant applications are gaining popularity with growing environmental concern and stringent government regulations. Plant oils are major base stocks for eco‐friendly green lubricants. However, because of their poor oxidation stability, their applications are restricted to limited usages. Improvements of these plant oils can be made either by addition of functional additives or by chemical/genetic modifications. This paper evaluates the synergistic approach of phenolic and aminic antioxidants in safflower oil. Further, to enhance the oxidation properties of the plant oil, we incorporated and studied synthetic esters (SEs) for thermo‐oxidative stability by using rotating pressure vessel oxidation test and differential scanning calorimeter. The combination of phenolic and aminic antioxidants at a 2 : 1 ratio exhibited the best synergistic effect, when incorporated into a combination of plant oil and SE. In addition to thermo‐oxidative properties, the tribological properties of neat base stocks were also studied. A substitute of mineral oil‐based lubricants can be formulated cost effectively by using an appropriate mixture of plant oil and SE. Copyright © 2013 John Wiley & Sons, Ltd.     

Lubricating oil additives and the environment — an overview

In this paper are reported some practical considerations relating to lubricant additive manufacture, and to additivated lubricants' impact on the environment. Widely used engine oil additives are mainly dithiophosphates, overbased calcium sulphonates, succinimidic dispersants, and polymer VI improvers. Production of these additives creates a potential environmental problems due to the hazardous emissions such as H₂S and HCl and sludge obtained during purification. New processes are described which lead to the reduction of toxic and other harmful pollutants. Gear oil additives, although these may be used in lower amounts, also make for ecological problems. A high quantity of sulphur-containing waste water is produced during manufacture of sulphurised EP additives. Some possibilities for recovering sulphur from this waste water are presented. The reduction of the chlorine content in EP additives is another important task, and new processes to produce EP additives with low residual chlorine content are discussed. Metal working fluid additives comprise emulsifiers, corrosion inhibitors, antiwear and EP additives. Their fabrication usually produces toxic and harmful residual products. Additivated lubricants may promote ecological injury. Oil leakage from engines working in harbours, parks, and entertainment areas are dangerous and difficult to avoid. To counter this, biodegradable base stocks were developed, but there are few data concerning the biode-gradability of the additives used. Used oils are generally collected and recovered, but a significant quantity of used oil is directly burned. Burning of additivated used oils in incorrect equipment leads to dangerous emissions, such as sulphur oxides. Because sulphur-containing additives cannot be replaced in engine oils or gear oils, the main ecological measure is the reduction of the quantity of used oils burned.     

Vegetable oil derivatives: environment‐friendly lubricants and fuels

A critical appraisal is made of the applications of vegetable oils, the fatty esters complex and synthetic esters as rapidly biodegradable and non‐toxic lubricants and fuels in the developed countries of America, Europe and Asia. The criteria employed for assessing the toxicity and biodegradability of the various fluids and limits set by various state and regional organizations are reviewed. The properties of vegetable oils, fatty esters, chemically modified esters and synthetic esters relevant for performance as lubricants in various applications such as hydraulic oils, refrigeration oils, chainsaw lubricants, metalworking fluids, engine oils, two‐stroke oils, mould release lubricants, greases, gear and transmission oils vis‐à‐vis conventional mineral oils and greases for corresponding applications are compared. The advantages, such as high lubricity, viscosity–temperature relationship, low lubricant consumption, energy efficiency combined with public health, safety and environmental contamination, more than offset the disadvantages of initial costs in most of these applications. It has been suggested that modified and stabilized oils of wasteland and forest origin and other non‐edible oils and their chemically modified derivatives can be produced at relatively cheaper cost than similar oils marketed in the developed world and can be introduced in India with immense environmental and performance benefits, particularly in applications involving high environmental contamination safety and public health. When blended with highly refined diesel fuels, methyl esters can work as highly efficient environment‐friendly fuels particularly for applications in passenger transport, light commercial vehicles and generators. Copyright © 2006 John Wiley & Sons, Ltd.     

Study of some non-edible vegetable oils of Indian origin for lubricant application

Due to growing environmental concerns, eco-friendly processes and materials have become one of the key interests of research and in the area of tribology, natural esters are gaining popularity as lubricants. Natural esters are being used in many applications as eco-friendly lubricant base. In Europe, canola/rapeseed oil and sunflower oil are mainly used, whereas in the USA, soybean oil is in use for formulating environmentally friendly lubricants. Native and genetically modified high oleic varieties of these oils are being widely used. In the Indian scenario, since the above-mentioned oils are scarcely available for industrial applications, there is a need to look for other viable alternatives. Some candidate non-edible vegetable oils of Indian origin were selected which were unexplored or less explored in the field of lubricant application, and their suitability in lubricant application focusing mainly on physico-chemical characteristics, thermo-oxidative stability and lubrication characteristics was studied. These oils were found to be promising candidates for application in lubricants in view of their physico-chemical characteristics and better thermo-oxidative and hydrolytic stability. Copyright © 2007 John Wiley & Sons, Ltd.     

Temperature—friction characteristics of cylinder lubrication in large,slow, cross‐head marine diesel engines under boundary lubrication conditions

In large, slow, cross‐head marine diesel engines research has increasingly shown that the lubrication regime between piston rings and cylinder liner at top dead centre is of the boundary lubrication type due to the high gas pressure, low sliding speed, and high temperature. This means that the tribological properties of piston ring, cylinder liner, and cylinder lubricant in these types of engine under boundary lubrication conditions should be considered simultaneously when friction and wear between the piston ring and cylinder liner are studied. Until now there has been no standard method to evaluate boundary lubrication performance. There are a few traditional methods used in lubricant research, but their results are not correlated with service conditions. It is important to find a suitable method to evaluate the boundary lubrication performance of lubricants at the laboratory testing stage or before the engine testing stage. The important parameters, such as sliding speed, normal load, materials of the contacting pairs, and lubricant, need all to be controlled. In this paper a systematic experimental procedure, the ‘five times heating and cooling test’, is introduced to assess lubricant properties under boundary lubrication conditions. Most of the parameters mentioned above are controlled. The model contact, of pin‐on‐plate form, is made from the actual piston and liner materials used in a large‐bore, slow, cross‐head marine diesel engine. The temperature characteristics of different blends of lubricants are investigated under boundary lubrication conditions using a pin‐on‐plate reciprocating test rig. These blends of lubricants have the same additives but different base fluids; they nevertheless fulfil the physical and chemical requirements of a real marine diesel engine. The test temperature range is from room temperature to the working temperature of the top piston ring. The experiments show that there are different temperature—friction characteristics for lubricants with different bases and the same additive package and there are also different temperature—friction characteristics during heating up and cooling down for each blend. Single‐base lubricants have more promising temperature—friction characteristics than those of a blend of a high‐viscosity base and a low‐viscosity base at high temperature.     

Influence of lubricant on gear failures — test methods and application to gearboxes in practice

Base oil type, oil viscosity, and additive type and content have a strong influence on typical gear failures. As it is not possible to quantify the influence of a lubricant on load‐carrying capacity simply from a knowledge of the physical or chemical oil data, many test methods have been developed for the evaluation of mechanical—technological lubricant properties. Simple low‐cost bench test methods often show poor correlation with practice. From both experience and systematic investigation, it can be seen that testing of gear lubricants can be performed adequately only in gear test rigs using specified test gear geometry. The standard FZG back‐to‐back gear test rig has been developed over many years and improved for different types of gear failure simulation. The standard FZG oil test A/8.3/90 is widely used for the evaluation of the scuffing properties of industrial gear oils. Automotive gear oils of GL4 level can be tested in the step test A10/16.6R/90, and axle oils of GL5 level in the shock test S‐A10/16.6R/90. For slow‐speed regimes, the C/0.05/90:120/12 wear test can be used. The influence of lubricants on the micropitting performance of gears can be evaluated in the GF‐C/8.3/90 micropitting test. Different pitting tests are available, as single‐stage (PT‐C/9:10/90) or load spectrum (PT‐C/LLS:HLS/90) tests. The aim of this paper is to describe the influence of the lubricant on the different failure modes in gears, how to quantify this effect in adequate test methods, and how to introduce the results of such tests as determining values of the lubricant into load‐carrying capacity rating methods.     

Influence of Lubricant Properties on ARKL Temperature Rise and Transmission Efficiency

It has been suggested in the literature that the ability of a lubricant to produce low “end of test temperature” (EOTT) in the achsialrillenkugellager (ARKL)—that is, axial groove ball bearing—thrust bearing test is an indicator of its likely efficiency in vehicle transmissions. Based on this, the current study has used regression analysis to correlate the ARKL EOTT with a range of physical and friction properties of a set of 26 lubricants. The latter have been selected to span a wide variety of base oil and additives types. It has been found that the most important lubricant property in determining ARKL EOTT is the elastohydrodynamic (EHD) friction or traction coefficient at low slide–roll ratio. Lubricants with low EHD friction were found to give low EOTT. Two lubricant properties of secondary importance have been identified. One is the lubricant viscosity index (VI), where a high VI contributes to high EOTT. The second is the heat transfer capability of the fluid, where a high capability was found to correlate with lower EOTT.

The findings help clarify how low EOTT in the ARKL test can be achieved via lubricant composition. If the correlation between ARKL and transmissions that has been suggested in the literature is valid, then these findings are transferable to the design of high efficiency transmission lubricants.     

Total vegetable oil greases

A grease has two major constituents, namely, a lubricant, that performs the function of lubrication; and a gellant, that provides a solid continuous phase, occludes the lubricant, and gives apparent physical structure to the grease. Generally, the gellant is 5–30% and the lubricant 65–90%, additives and fillers making up the rest. In conventional greases, the gellant is a vegetable oil soap, and the lubricant is a liquid oil of petroleum origin or is a synthetic. Such greases have limited biodegradability, because the major constituent, i.e., the lubricant, is normally not biodegradable. In total vegetable oil grease, both the gellant and the lubricant are derived from vegetable oils, giving a grease of potentially high eco‐compatibility. Esters, dibasic acid esters, and alkylated esters of vegetable oil are known to be high‐quality lubricants. These can be used with soap stocks prepared from vegetable oils to give a grease of total vegetable oil origin. The vegetable‐oil based lubricants and soaps are prepared separately and combined in appropriate proportions to give a grease of the required specifications. Alternatively, esterification and saponification can be carried out simultaneously to give a grease of the desired specifications, where an alkali will be the catalyst for esterification, and reactant for saponification. In this paper, the process parameters, and kinetics of these simultaneous reactions are discussed. The results of experimental evaluation of some of these greases are also presented.     

Experimental measuring procedure for the friction torque in rolling bearings

The reduction of the power loss generated in mechanical transmissions and the use of low friction biodegradable lubricants has been attracting considerable attention in recent times. Therefore, it is necessary to develop methods to test and evaluate the performance of such lubricants and compare them with conventional ones. In this sense, a Four‐Ball Machine was modified allowing the test of rolling bearings. A 51107 thrust ball bearing was used to test two different greases and the corresponding base oils. Friction torque and operating temperatures were continuously monitored to quantify the power loss and the heat evacuation for each lubricant tested. Copyright © 2010 John Wiley & Sons, Ltd.