Journal of Cleaner Production 43 (2013) 12e19

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Ecological and economic evaluation of a novel glycerol based biocide-free metalworking uid
Hubertus Wichmann a, *, Heiko Stache a, Christiane Schmidt a, Marius Winter b, Ralf Bock b, Christoph Herrmann b, Muet Bahadir a
a b

Institute of Environmental and Sustainable Chemistry, Technische Universitt Braunschweig, Hagenring 30, 38106 Braunschweig, Germany Institute of Machine Tools and Production Technology, Technische Universitt Braunschweig, Langer Kamp 19b, 38106 Braunschweig, Germany

a r t i c l e i n f o
Article history: Received 18 September 2012 Received in revised form 13 December 2012 Accepted 30 December 2012 Available online 5 January 2013 Keywords: Cooling lubricant Glycerol Metal machining Alternative metalworking uid

a b s t r a c t
Worldwide, huge amounts of mineral oil containing metalworking uids (MWF) are applied for industrial metal machining. Future challenges in the eld of lubricant usage are to overcome the consumption of nite resources and to solve problems like compatibility of MWFs to human health and environment as well as laborious deoiling and costly disposal. In this context, ecological and economic properties of a novel glycerol/water-based MWF are introduced. Investigations revealed that if a proportion of !35% of the biostatic trihydric alcohol glycerol was present in the MWF, the addition of biocides for uid protection was unnecessary. Technical grade glycerol, a renewable by-product from the biodiesel market, proved a sufcient purity for application. Compared to common MWFs, the cleaning of metal surfaces just by rinsing with water was distinctly facilitated because of the water solubility of all uid components. A disposal of the MWF at the end of service life or the wash waters had not to be considered because of the microbiological degradability of the organic components of the diluted MWF. The novel glycerol-uid is available for energetic or even material recovery which contributes to cost reduction and covers the aspect of sustainability. Concerning the costs of application of the novel MWF in industrial production processes, the uid even nowadays appears to be competitive to many common mineral oil based lubricants. 2013 Elsevier Ltd. All rights reserved.

1. Introduction The consumption of metalworking uids (MWF) in Germany amounts to 740 kt a1, comprising about 70 kt of mineral oil components (BAWA, 2011). Today, the most frequently applied MWF are emulsions consisting of water, mineral oil components and additives. These emulsions are prone to biological infestation and thus have to be preserved by the addition of biocides that are harmful to health by e.g. causing skin irritations (Mang and Dresel, 2007; Rocker, 2010). In general, the use of mineral oil based MWFs has to be viewed critically because of the hazard potential towards human health and the natural environment at each life cycle stage from resource extraction to disposal (Dettmer, 2004). More than 1000 kt a1 of oil-containing washing liquids result from an extensive cleaning of metal surfaces. The problem areas of

* Corresponding author. Tel.: 49 531 391 5962; fax: 49 531 391 5799. E-mail address: hu.wichmann@tu-bs.de (H. Wichmann). 0959-6526/$ e see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jclepro.2012.12.042

conventional MWF application are in particular the consumption of nite resources, the low compatibility to human health and environment, the laborious deoiling of workpieces and swarf and the residue disposal. Recently, a MWF based on glycerol and water could be developed that achieves good technical performance without having the disadvantages specied above. The technical properties of the uid were already described in Winter et al. (2012). The development of the new MWF opens the opportunity for the replacement of mineral oil by the regrowing raw material glycerol that results as a byproduct from the biodiesel production and nowadays is just burnt in amounts of 300e500 kt a1 worldwide because of lacking industrial demand (Katryniok et al., 2009). In this paper the ecological and economic aspects in context with the use of the new MWF are presented. These comprise the biostatic effect of the glycerol, minimum proportion and minimum quality of the glycerol in the uid needed, workpiece and swarf cleaning, options for the subsequent use of the MWF after application as well as the cost trends.

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2. Material and methods 2.1. The biostatic effect of glycerol in MWF test mixtures 2.1.1. Determination of the biostatic effect via testing the biological oxygen demand (BOD) Information was gained about microbiological long-term stability of glycerol/water mixtures and the readily formulated MWF by BOD analyses according to DIN EN 1899 part 1 and 2 (1998). For this purpose, a test duration of 20 days was chosen in order to get indications for a possible delay or inhibition in bacterial growth inside the glycerol MWF. At best, no oxygen consumption by microorganisms should be detectable due to a minimum glycerol proportion which has to be determined, inhibiting the breakdown of the nutritive medium. For measuring the BOD, the samples under consideration were spiked with microbial polluted water (inoculum). Furthermore, apart from a nutrient salts mixture according to DIN EN 1899 (1998), glucose and glutamic acid were added that can easily be degraded by microorganisms. During nutrient degradation, aerobic bacteria and fungi consume oxygen coming from the headspace above the test solutions. A simultaneous trapping of the released CO2 results in a pressure drop in the bottles, measured by sensors (OxiTop-Messsystem, WTW, Germany) and used to determine the BOD. The tests were performed at a temperature of 20  C. Besides a control for the inoculum and a blank determination, four BOD determinations were performed in parallel. The following glycerol/ water-mixtures were tested at pH 7.2 (all vol.% of glycerol): 23, 25, 27, 29, 31, 33, 35 and 37. Adjusted to pH 9.0, the tests comprised mixtures with 15, 19, 23, 27, 31, 35 and 39 vol.% of glycerol. As a contribution to dened experimental conditions, distilled water and glycerol of high pharmaceutical grade were used for the preparation of all uid variants. 2.1.2. Test cycle of inoculation During routine use of the MWF, it is continuously contaminated with microorganisms. In order to simulate a repeated input of microorganisms into the MWF, a test cycle of inoculation was performed with different glycerol/water-mixtures according to the test method 019 after Schlke and Mayr GmbH (2004). For this purpose, different sample variants were prepared in 250 mL Erlenmeyer asks and incubated lightproof under stirring in series at 25  C and 35  C. Every third or fourth day, microbial polluted water (!105 colony forming units (CFU) mL1) was added to the samples and the glycerol content as well as the pH value were readjusted. Before each inoculation, the concentrations of the microorganisms in the test mixtures were determined with the aid of a nutrient agar (Merck Envirocheck Contact TVC). After incubation of the agar for 3 d at 30  C, the microbiological pollution of the samples was evaluated according to the CFU values. The sample variants used for the test cycles of inoculation contained glycerol between 0 and 40 vol.%. Partly, the pH value was raised from 7.2 to 9.0 with 0.1 M NaOH and peptone was added as an additional nutrient in an amount of 10 mg 100 mL1. The nutrient salt solution, prepared according to DIN EN 1899 (1998), was applied in the test cycles of inoculation as well. The investigation of the biological stability of the readily additivated glycerol-MWF was performed similar to that of the glycerol/ water-mixtures as described above. These solutions additionally contained the set of additives in a constant amount. The composition of the MWF-variant applied for these tests was as follows: 25 g/L polyethylene glycol-monooleate, 20 g/L polyethylene polypropylene glycol, 3.5 g/L 2,5-dimercapto-1,3,4-thiadiazole, 4.0 g/L 6-[[(4-methylphenyl)sulfonyl]amino] hexanoic acid, 10 g/L triethanolamine and 1.0 g/L 2-amino-2-methyl-1-propanol. The

solutions only differed in the glycerol content that was between 30 and 40 vol.%. In contrast to the tests described above, no nutrients and peptone were added to the MWF, which resulted in a constant pH value of 9.0. Only the nutrients glucose and glutamic acid were added to a few of the test mixtures. 2.1.3. Microbial growth in the grinding machine In completion to these microbiological tests a grinding machine was investigated that was operated with the MWF containing 40% of glycerol. Inside the machine four glass slides were xed at different positions on which spray mist was collected during a 4 d grinding of 100Cr6 steel. After a standby time of another 8 d at ca. 20  C without operating the machine, colony counts (CFU) were done for the wetted slides and further six surface positions inside the machine. For this, nutrient agar plates (Envirocheck Contact TVC, Merck) were slightly pressed on the surfaces for 10 s. Additionally, the used MWF in the tank of the grinding machine was tested as well. After sampling, the nutrient media were incubated lightproof for 3 d at 30  C. The colony growth on the agar plates gave hints towards the microbial pollution of the grinding machine. 2.2. Minimum glycerol quality required The following ve glycerol qualities, all produced in Germany, were chosen for the investigations: 1. Glycamed 99.7%, rened glycerol, pharmaceutical grade, Glaconchemie, Merseburg 2. Glycamed 86.5%, rened glycerol, pharmaceutical grade, Glaconchemie, Merseburg 3. Glycatec 99.5%, rened glycerol, technical grade, Glaconchemie, Merseburg 4. Glycerol 99%, rened glycerol, technical grade, Applichem, Darmstadt 5. Rohglycerin, crude glycerol from biodiesel production, Thringer Methylesterwerke GmbH, Harth-Pllnitz According to their specications, the rst two glycerol products represent the highest grade of purity. They only differ in their water content. Both products can be applied as food additives and they meet the requirements of the European Pharmacopoeia. Glycatec 99.5% and Glycerol 99% are described as technical grade. Compared to the Glycamed products, the technical grades have a higher specied limit of organic impurities. The water contents are given as 0.2% for Glycatec 99.5% and <0.5% for Glycerol 99%. The lowest purity grade is represented by the crude glycerol originated from a rape seed mill plant. According to its specication it consists of about 74.1% glycerol, 9.2% water, 8.6% organic impurities and 8.1% ash forming compounds. The ve glycerol qualities were subjected to a sensory testing, considering the appearance, the colour and the smell of the products. Subsequently, microwave-induced digestions were done with nitric acid and hydrogen peroxide. Element contents were determined by optical emission spectrometry equipped with an inductively coupled plasma (ICP-OES). The practical limits of detection of the elements Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Hg, K, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Sn, Sr, Ti, V, W and Zn were between 1 mg L1 and 5 mg L1; Fe had a limit of 15 mg L1. The ICP-OES settings are listed in Table 1. Volatile organic compounds were enriched and measured by Headspace-SPMEeGC/MS. Headspace vials (20 mL) were lled with 10 mL of the glycerol specimen. Volatile compounds were enriched from the gas phase by solid phase micro extraction (SPME) with the settings given in Table 2. Desorption, separation and measurement

14 Table 1 Operation parameters for ICP-OES. Instrument Nebulizer HF-power Plasma gas Auxiliary gas Measurement time Stabilization time Rinsing time Repetitions

H. Wichmann et al. / Journal of Cleaner Production 43 (2013) 12e19

Vista-MPX, Varian/Agilent, Darmstadt Sea-Spray-Nebulizer, 40 psi 1.20 kW 15.0 L Ar min1 1.5 L Ar min1 20 s 35 s 30 s 3

of the analytes were performed with gas chromatography coupled to mass spectrometry (GC/MS; Table 2). 2.3. Cleaning of metal surfaces For rinsing tests with water, ne metal splinters were taken that were produced by grinding a 100Cr6 steel and that were isolated from the glycerol-MWF with the aid of a cellulose band lter. In one exemplarily described experiment, 4.558 g of this swarf was weighed into a paper lter, covered and rinsed ve times with portions of 40 mL deionized water and subsequently dried. From these ve water fractions, the glycerol contents (glycerol UV-test, R-Biopharm, Germany) and the total organic carbon (TOC) (cuvette test LCK 381, Hach Lange GmbH, Germany) were determined. Furthermore, the TOC contents of the swarf before and after rinsing were measured. Since no standard procedure was available to determine the TOC of metal surfaces, the cuvette test was modied in a way that metal splinters were weighed into the reaction vials instead of water samples. 3. Results and discussion 3.1. The biostatic effect of glycerol One goal of the research work was to avoid the addition of biocides to the new MWF. This appeared to be possible because glycerol, like all short-chained alcohols, shows a biostatic effect against bacteria and fungi if its concentration in the water-based uid was chosen sufciently high. In the following, the results of the investigations concerning this aspect are introduced. 3.1.1. Biostatic effects of glycerol/water-mixtures BOD determinations were performed as described in Section 2.1. The tests with glycerol/water-mixtures at uninuenced pH 7.2
Table 2 Operation parameters for headspace-SPMEeGC/MS. Headspace-SPME Fibre coating Sample volume Equilibration Extraction Desorption GC/MS Instrument Detector Inlet temperature Injection mode Capillary column Carrier gas Temperature program Measuring mode 50/30 mm DVB/Carboxen/PDMS 10 mL 40 min, 50  C 20 min, 50  C at 260  C 6890 Series GC System, Agilent, Bblingen 5973 Network Mass Selective Detector, Agilent, Bblingen 260  C Splitless DB 1301 (60 m, 0.32 mm I.D., 1 mm lm), J & W Scientic, Agilent, Bblingen He, 1 mL min1 40  C (5 min) / 5  C min1 160  C (2 min) / 10  C min1 260  C (10 min) EI: 70 eV Full-Scan-Mode: mass range 45e300 amu

revealed the results that are depicted in Fig. 1. Those resulting from glycerol/water-mixtures adjusted to more practice-relevant pH 9.0, as being a contribution to corrosion protection in MWF, are shown in Fig. 2. According to Fig. 1, the experiments showed that glycerol contents less than 33% were not suitable for a long-term conservation of the glycerol/water-mixtures at pH 7.2 against microbial infestation. At glycerol contents of 23%e29%, it could be observed that initially added microorganisms were able to adapt to the milieu conditions and cause oxygen depletion at least after a lag-phase of several days. The lag-phase was extended with the rising proportion of glycerol in the test mixtures. After a couple of days the BOD of the samples reached the value of the controls and exceeded it during the following days. This latter nding can be seen as a conrmation for glycerol being a suitable nutrient at sufciently low concentrations. At a glycerol content of !35% no oxygen consumption was observed within 20 days; a growth of the microorganisms was thereafter suppressed. An increase of the pH from 7.2 to 9.0 led to prolonged lag-phases (Fig. 2). Once more, the threshold value for microbial preservation was about 35% glycerol. By the use of lower glycerol amounts the growth of microorganisms could not be suppressed within a period of 20 days. 3.1.2. Test cycles of inoculation In the course of the test cycles of inoculation it was shown that glycerol/water-mixtures with less than 30% glycerol were highly contaminated with germs. At glycerol contents of 35% and 40% the preservative effect of the glycerol was demonstrated, resulting in no or tolerably low CFU-pollution of 103 CFU mL1 within 36 days. Furthermore, it was found that mixtures with a glycerol content of 25% and 30% and an alkaline pH value of 9.0 inhibited the

290 240 190 140 90 40 -10 0 5 10 day 290 240 190 140 90 40 -10 15 20

BOD [mg O2/L]

BOD [mg O2/L]

10 day

15

20

DVB: Divinylbenzene; PDMS: Polydimethylsiloxane.

Fig. 1. BOD20-data of different glycerol/water-mixtures at pH 7.2.

H. Wichmann et al. / Journal of Cleaner Production 43 (2013) 12e19

290 240 190 140 90 40 -10 0 5 10 day 15 20

15

content for 20 days. MWF-variants with less than 30% glycerol were not considered because they are not relevant from the technical point of view (Winter et al., 2012). The test cycle of inoculation experiments performed with variants of the new MWF likewise revealed a sufcient protection starting from 30% glycerol content. Detailed toxicological investigations, not topic of this paper, pointed at the additive 2,5-dimercapto-1,3,4-thiadiazole to cause the slightly strengthened biostatic effect of the MWF. It is therefore aspired to replace this additive by a more environmentally compatible sulphur carrier. 3.1.4. Growth of microorganisms inside the grinding machine The sampling was performed as described in Section 2.1. After incubating the nutrient agar plates, colony forming units (CFU) were determined as follows: 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11.
0 5 10 15 20

BOD [mg O2/L]

290 240 190 140 90 40 -10 day

Glass slide in a distance of 1 m from the grinding wheel 1 CFU Glass slide in a distance of 0.5 m from the grinding wheel 3 CFU Glass slide in the aeration system 0 CFU Glass slide inside the MWF tank above the uid 1 CFU Surface close to the grinding wheel 0 CFU Surface of the MWF outlet 1 CFU Surface of the return ow of the MWF to the tank 0 CFU Surface of the lamp above the grinding wheel 0 CFU Surface of the lter belt 1 CFU Surface of the grinding wheel 0 CFU MWF inside the tank 0 CFU

BOD [mg O2/L]

Fig. 2. BOD20-data of different glycerol/water-mixtures at pH 9.0.

microbial growth in the uid but did not result in a complete preservation. 3.1.3. Biostatic effects of MWF-variants The BOD20 determinations with completely additivated MWF-variants revealed the results depicted in Fig. 3. From Fig. 3 it can be seen that there was no increase of BOD in any of the test solutions compared with the control. The growth of the microorganisms added to the solutions was suppressed. Even with the nutrients glucose and glutamic acid present in the test solutions, no increase of BOD was observed. Different from the experiments with pure glycerol/water-mixtures (s. Fig. 2, esp. 31% glycerol), a complete protection against microbial infestation was observed even when testing a MWF-variant with 30% glycerol

The low numbers of CFU determined on the nutrient agar plates illustrated that only very few microorganisms could survive inside the grinding machine which is commonly accepted. Therefore, it can be assumed that there will be no microbial contamination in the cooling lubricant cycle when the new glycerol-based MWF is used with a glycerol content of 40%. Thus, the preserving effect of the glycerol-based MWF could nally be conrmed in a practical test. Considering all results, it can be concluded that during usage of the new MWF a minimum glycerol content of 30e35% should be assured in order to prevent microbial infestation. For safeguarding reasons a glycerol content of 40% would be best, because this proportion of glycerol in the lubricant turned out to have the best technical performance, as well (Winter et al., 2012). 3.2. Required minimum quality of the glycerol applied as MWF component Besides water, glycerol represents the other main component of the MWF and hence also the main cost factor. Glycerol is commercially available in different qualities. One with a higher purity is expectedly connected to a higher price. Thus, from the economic point of view, a low cost glycerol quality should be applied which in turn does not negatively affect the technical performance of the MWF. Glycerol qualities of different clean-up stages were chosen and investigated by sensory and chemical analyses. Based on these results, the glycerol qualities were evaluated for the application in the MWF. 3.2.1. Sensory evaluation Glycamed 99.7%, Glycamed 86.5%, Glycatec 99.5% and Glycerol 99% were clear colourless liquids without sensory differences. In contrast to those, the crude glycerol originated from a rape seed mill plant had a clearly perceptible unpleasant odour. Furthermore, it was cloudy and brown-coloured and contained

290 240 190

BOD [mg O2/L]

140 90 40 -10

10 day

15

20

Fig. 3. BOD20-data of completely formulated MWF-variants with different glycerol contents (pH 9).

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H. Wichmann et al. / Journal of Cleaner Production 43 (2013) 12e19 Table 4 Results of the headspace-SPMEeGC/MS investigations of the crude glycerol. RT [min] Substance Acetic acid methylester Propionic acid methylester Acetic acid 2-Methylpropionic acid methylester 2,4,4-Trimethyl-1-pentene Butyric acid methylester Propanoic acid 2-Hydroxypropanoic acid 2-Methylbutyric acid methylester Pentanoic acid methylester Butanoic acid 4-Methylpentanoic acid methylester RT [min] 23.0 23.5 24.0 24.4 26.4 26.9 27.5 28.9 29.9 33.2 40.5 Substance Hexanoic acid methylester Pentanoic acid Tert.-octylthiol 3-Methoxy-1, 2-popanediol 6-Heptenoic acid methylester Hexanoic acid 2-Propyl-1-pentanol Glycerol Octanoic acid methylester Octanoic acid Dinonanoic acid dimethylester

black particles that were accumulated in the surface region of the liquid. 3.2.2. Element concentrations As a result of the elemental analysis none of the elements listed in Section 2.2 could be measured above the limits of detection in the pharmaceutical and technical glycerol qualities (Glycamed 99.7%, Glycamed 86.5%, Glycatec 99.5% and Glycerol 99%). The analysis of the crude glycerol, however, revealed the element concentrations listed in Table 3. As can be seen from Table 3, especially K, Na, P and S were present in the crude glycerol in partly high concentrations. Probably these elements originate from the rape seeds or from the production and rening processes. 3.2.3. Volatile organic compounds For Glycerol 99%, headspace-SPMEeGC/MS measurements (Section 2.2) revealed no other signals than that of glycerol itself. For Glycamed 99.7%, Glycamed 86.5% and Glycatec 99.5%, there were two signals visible in the gas chromatograms, one of glycerol at Rt 29.5 min and another one of the glycerol derivative 3-methoxy-1,2-propanediol at Rt 24.4 min. In contrast to the previous measurements, those of the crude glycerol revealed a gas chromatogram rich of signals. The substances listed in Table 4 were identied as most likely components of this glycerol sample with the aid of the computer-based spectra library Class 5000 NIST (Shimadzu). The volatile organic compounds of the crude glycerol were mainly acids and the corresponding methyl esters. It has to be expected that they are by-products of the saponication and methylation of plant oils in the course of biodiesel production. It is separated from the biodiesel and it can be rened to different qualities. In summary, sensory and chemical analyses revealed that the investigated pharmaceutical as well as technical glycerol qualities are suitable for an application in the new MWF. In samples of both quality levels no volatile organic impurities or at least one toxicologically irrelevant glycerol monomethylether could be identied. Therefore, health risks for the technicians working with the new MWF caused by volatile toxic impurities of the glycerol component can be excluded. By elemental analyses it was proven that the glycerol samples were not polluted with ash forming compounds in detectable concentrations. This reduces the danger of precipitate formation followed by blocking of lter and pump systems of the grinding machine. Crude glycerol from biodiesel production is however not suited for MWF preparation. Even after ltering off solid particles, for example free fatty acids or ash forming substances would result in insoluble sediments inside the MWF cycle of the machine by polymerization or precipitation of e.g. sulphates, sulphides or phosphates. Moreover, volatile organic compounds (Table 4) as part of this glycerol quality would cause unpleasant odours reducing the market acceptance. In consequence, from the technical and
Table 3 Element concentrations of crude glycerol. Element Ca Fe K Mg Na Ni P S Concentration [mg L1] 16.0 22.8 48,800 2.32 437 4.80 1260 40,100

7.4 10.9 12.4 13.1 13.4 14.8 16.4 16.5 17.1 19.1 20.1 21.7

economic point of view the usage of glycerol of technical quality is preferred because it connects a comparably low price with a sufcient purity. 3.3. Cleaning metal surfaces and handling the grinding process material ows During machining of metal surfaces oily swarf is produced. Its annual amount in Germany is estimated to add up to 220,000 t (UMBW, 2012). After transporting the metal splinters out of the grinding machine, they are roughly separated from the MWF by ltration. The residual MWF content poses a problem for further material use of the splinters. Swarf with a content of at least more than 8% of organics is classied as hazardous waste giving rise to high disposal costs, whereas metal splinters with low organic contents can be sold to steelworks, foundries or cement plants (Liedtke et al., 2000; Schn, 2003). Similar problems are known for the workpieces mostly needing clean surfaces for subsequent processing. In case of glycerol-MWF application, the metal surfaces are mainly charged with glycerol, water and additives for corrosion protection and performance improvement. A simple rinsing with water was expected to result in a signicant reduction of the organic burden on any metal surface because of the water solubility of all uid components and in wash waters representing real solutions. 3.3.1. Cleaning operations For a verication of the hypothesis mentioned above, rinsing tests were performed as described in Section 2.3. Typical results are given in Table 5, listing glycerol and total organic carbon (TOC) contents of subsequent washing fractions resulting from rinsing swarf.

Table 5 Glycerol and TOC concentrations in wash water fractions of a swarf cleaning test. Glycerol [mg/L] Fraction Fraction Fraction Fraction Fraction 1 2 3 4 5 18,700 9230 812 91 13 TOC [mg/L] 11,900 5160 555 137 87

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As can be seen from Table 5, there was only little TOC to be found in the wash water fractions 4 and 5. After an application of 120 mL rinsing water (fractions 1e3) a good extraction yield was already gained. In total, 892 mg of organic carbon were removed from 4588 mg swarf by rinsing with 200 mL water. By this simple procedure, the TOC content of the swarf, resulting from a realistic grinding process with the new MWF, was reduced from 19.7 to 0.71 mass-%. Certainly, the extraction yield could even be increased by improving the wetting of the ne, adhering metal particles. This approach can be transferred to the workpiece cleaning, if necessary, just followed by the application of a corrosion protection. The aspect of easy metal surface cleaning points at an economic and ecological advantage of the new glycerol-based MWF, compared to conventional ooding as well as minimum quantity lubrication. 3.3.2. Utilization of wash waters and spent MWF Generally, conventional non-water-miscible or emulsied cooling lubricants have to be disposed of at high costs (VDI, 2008). The glycerol-MWF, however, shall be available for material or energetic recovery at the end of service life; under the aspect of sustainability disposal is not considered. The new MWF is completely water-soluble and contains 40% of glycerol that can be thermolysed or microbiologically degraded after dilution. The organic content of the wash waters shall be directly available for biological degradation. The utilization of crude glycerol resulting from the biodiesel production for biogas fabrication was already investigated. According to literature, the fermentation of glycerol guarantees a high yield of biogas of 850 L kg1 dry organic matter (oDM), resulting in an energy output of 1472 kWh t1 fresh matter. For comparison, the fermentation of grain or potato slop from the ethanol production yields 640e670 L biogas per kg oDM (KTBL, 2007). The addition of 5% crude glycerol to cattle manure resulted in an increase of the biogas output from 269 L kg1 oDM to 825 L kg1 oDM. This increase was higher than theoretically calculated which indicated a synergistic effect of the glycerol on the degradation of both substrates (Robra et al., 2010; Fountoulakis et al., 2010). Own investigations will follow on the inuence of additives and heavy metal contents of the spent glycerol-MWF and wash waters on the biogas production. Further modern utilization pathways for spent glycerol solutions might be the hydrothermal degradation of glycerol for the production of basic chemicals (Katryniok et al., 2009; Moeller et al., 2011) or electrical power generation by microbial fuel cells (Harnisch and Schroeder, 2010). Further investigations are currently conducted in this eld. 3.4. Economic perspectives 3.4.1. Mineral oil as base uids for MWFs In 2007, the global metalworking uid consumption was about 1.97 million tons (Gosaila, 2008). The basis of these MWF consists almost entirely of mineral oil (Mller and Nassar, 2002). According to the American Petroleum Institute (API), the base oils traded on the market are divided into ve groups. The groups are separated into different base uids with regard to their viscosity index and their share of saturates and sulphur. As part of this subdivision, MWF are often produced from the uids specied in Group I and Group II (Mang and Dresel, 2007). The Group I uids are at least rened and represent a mixture of hydrocarbons with different chain lengths with no or little uniformity. These hydrocarbons can be divided into parafnic, naphthenic and aromatic groups. The largest portion are parafnic base oils. They have a good viscosity/temperature characteristic, i.e. high viscosity index, adequate low-temperature

properties, and good stability (Mortier et al., 2010). The Group II base oils are produced by hydrocracking and isomerization reactions and have better properties than Group I oils, due to their lower grade of impurities as well as better thermal and oxidation stability. 3.4.2. Glycerol as base uid for MWF Glycerol can be classied as natural and as synthetic glycerol with respect to its manufacturing process. The natural glycerol can be produced by four methods: i.e. soap, fatty acid, and fatty ester production as well as microbial fermentation (Ayoub and Abdullah, 2012). The synthetic glycerol can be produced from propylene as feedstock with allyl chloride, acrolein and peracetic acid process. Furthermore, synthetic glycerol can be produced by fermentation of sugar (Chen and Chi, 1981). Between 1992 and 2010, the production of natural glycerol increased by 333% due to the fast growing production of biodiesel from vegetable oil thereby decreasing the synthetic production (Table 6). Besides the way how the glycerol can be produced, especially the purity has to be considered. Therefore, two main different qualities of glycerol can be distinguished as mentioned before: the crude and the puried/rened glycerol (Hazimah et al., 2003). Main distinguishing characteristic are the properties (glycerol content, water content, ash content, colour, etc.) of the two variants of glycerol (Ayoub and Abdullah, 2012). For example, crude glycerol has a purity of 60e80%, but puried and rened glycerol is generally close to 100% (Hazimah et al., 2003). Connected to the purity of the glycerol is the price. Especially the crude glycerol has a low economic value due to various impurities. These impurities can be removed by cost affecting rening processes. 3.4.3. Price development of glycerol and mineral oil base uids Fig. 4 shows the price development of the raw materials and the derived products mineral base oil and glycerol base uids. Two trends for the different uids can be recognized. Between 2001 and 2009, the price of mineral base oils (Group I) signicantly increased due to the price development of mineral oil, while on the other hand the price of rened glycerol decreased. Therefore, an almost proportional development between crude oil and mineral base oil becomes visible. In case of glycerol, the price of crude glycerol decreased above average as by-product of rising amounts of biodiesel. But the capacities for the purication of crude glycerol are still limited and only slowly expanded (Ayoub and Abdullah, 2012). The increase in prices of mineral crude oil and nally mineral base oil for MWF results partly from the depletion of nite resources and partly from the increasing demand of the developed and emerging countries (Gosaila, 2008). In the future, a continuation of these price trends is assumed. Thus, the production of crude glycerol will increase due to the strong interconnection with the biodiesel production. Basis for this is, among others, the political endeavours to cover the fuel

Table 6 Sources of the worldwide glycerol production during 1992e2010 (Ayoub and Abdullah, 2012; Bogaart, 2009). Glycerol source Natural glycerol Synthetic glycerol Other Total production World glycerol production (103 metric tons/year) 1992 562 83 0 645 1995 646 83 0 729 1999 678 63 42 783 2003 792 63 63 918 2005 1063 21 42 1126 2007 1495 5 20 1520 2008 1880 5 20 1905 2009 1760 5 16 1781 2010 1870 5 20 1895

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2000
Price (US-$ per ton)

1000
Price (US-$ per ton) Year

1500 1000 500 0

750 500 250

Year

Mineral base oil (Group I) Refined glycerol

Mineral crude oil (BRENT) Crude glycerol

Fig. 4. Price development of mineral crude oil and base oil and crude and rened glycerol (OMNI Tech International LTD., 2010; BP, 2011).

consumption with biofuels. For instance, in the European Union it is statutory that the biofuels should have at least a market proportion of 5.75% by the end of 2010. If the objective of the EU is achieved, the biodiesel production in Europe will increase by 10 million tons per year, which in turn will result in about 1 million tons of glycerol as by-product (Ayoub and Abdullah, 2012). At the same time, it is expected that the price of mineral base oil will increase due to the rising global demand for mineral oil based products such as fuels or lubricants. Transferred to the production of MWF, this means that the prices of mineral oil based lubricants will increase in the future. This results in an economic substitution potential of the mineral oil base uids by glycerol base once. Due to the use of mineral base oil for the production of water-miscible and non water-miscible MWF the substitution will be made gradually, depending on the content of mineral base oil in the MWF. In Fig. 5 the price curves for the mineral base oil and the glycerol base uid as function of their content in MWF are shown. Basis for the price curve are the market prices, according to ICIS pricing at the end of December 2011: 1095 USD per ton SN 150 (mineral base oil) versus 1367 USD per ton rened glycerol. The use of 40% rened glycerol could allow the substitution of lubricants having a mineral base oil content of more than 50% (variant 1). The use of 30% of rened glycerol enables even the substitution MWF with a mineral base oil content of more than 38% (variant 2). Other components that inuence the price of MWF are additives. Additives are used to improve the chemical and physical

properties of the lubricants. The use of additives depends on the machining task and the operating conditions. Therefore, the substances used and their amounts vary. A main advantage of glycerol-based MWF is its good lubricity and anti-wear properties. The need for further additives is reduced and only small amounts of corrosion protection are required. Furthermore, the use of biocides to eliminate microbacterial or fungal growth is not needed; only small amounts of corrosion protection are required (Winter et al., 2012). Mineral oil-based MWF often have to be enhanced with additives to achieve the desired lubrication properties, because a mineral base oil for a MWF has the similar tribological behaviour than water, when performing Reichert-measurements (Zein and Herrmann, 2010). However, there is no need for corrosion inhibitors and biocides unless an emulsion is used. 4. Conclusions From the technological point of view (Winter et al., 2012) as well as under environmental and economic aspects, the development of a novel, efcient and mineral oil free cooling lubricant based on water and glycerol as renewable raw materials was successfully achieved. By the application of glycerol which is non-hazardous to humans, the addition of biocides to the new MWF could be completely avoided. Compared to common MWF, a highly simplied cleaning of workpieces and swarf is enabled because of the complete water solubility of the glycerol-MWF. The organic components of the MWF as well as of the wash waters are easily biodegradable. Therefore, a costly disposal of spent lubricants can be replaced by diverse recycling pathways. The cascading usage especially of the glycerol in spent MWF meets the demands of future sustainable economics. Today, an important aspect is the comparably limited availability of polar or water soluble additives for such lubricating uids. In this sector, there is surely further demand for research and development (Wichmann et al., 2010). Furthermore, analytical procedures should be available that allow a determination of all additives of such polar MWF at any time. Against the background of rising mineral oil prices, caused by a constant or rising demand coupled with a decreasing amount of exploitable oil, rened glycerol is an economically interesting alternative as basis for MWF. An analysis of the costs of different metalworking base uids revealed that a glycerol/water uid with 40% glycerol in the base uid could replace a conventional uid with a portion of !50% of mineral base oil. If further production costs, like additive application, cleaning operations, and disposal/ cascading use, would be considered, the balance would turn out even much better for the novel glycerol based MWF. Nevertheless,

Substitutable mineral base oil content in the MWF (%) 0 10 20 30 40 50 60 70 80 90 100

1500

Price base fluid (USD / ton)

1200 900
2 1

600 300 0 0 10 20 30 40 50 60 70 80 Glycerol base fluid content in the MWF (%) Mineral base oil Glycerol base fluid 90 100

Fig. 5. Market price of mineral base oil and glycerol base uid and resulting substitution potential.

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this expectation can only be proven by practical application of the novel MWF in routine industrial production processes that is envisaged in the near future. Acknowledgement We express our sincere thanks to the Deutsche Bundesstiftung Umwelt (DBU) for funding the project "Development of a glycerol based biocide-free metalworking uid for industrial metal machining. References
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