Porast ekološke svijesti potakao je istraživanja sirovina obnovljivih izvora i u industriji maziva. Zbog sve veće potrošnje raznih vrsta maziva, koja su uglavnom mineralne i sintetske sirovinske osnove, dolazi do akcidentnog, ali i neizbježnog dospijeća znatnih količina maziva u okoliš. Stoga biološki lako razgradiva maziva proizvedena iz prirodnih ulja i masti dobivaju na važnosti ukoliko je njihova primjena moguća. Biološki lako razgradiva maziva proizvedena klasičnim postupkom iz visokokvalitetnih prirodnih ulja i masti mogu biti višestruko skuplja. Niže cijene otpadnih prirodnih ulja i masti čine biološki lako razgradiva maziva konkurentnijima na tržištu.
U ovome radu biti će prikazan i postupak kemijske sinteze u kojem je biodizelsko gorivo (smjesa metilnih estera masnih kiselina) sirovina za pripremu TMP (trimetilolpropan) maziva.The increase of ecological concern inspires research of raw materials from renewable sources in lubricant industry. Growing consumption of different lubricant types which are mostly mineral based or synthetic, leads to accidental but unavoidable inflow of considerable lubricants quantity into the environment. Therefore biodegradable lubricants produced from natural oils and fats become important if application is possible. Biodegradable lubricants produced by classical procedure from high quality natural oils and fats can be several times more expensive compared to conventional lubricants. Lower prices of waste natural oils and fats makes biodegradable lubricants much more competitive on the market. In this work the procedure of chemical synthesis, in which biodiesel (mixture of fatty acid methyl esters) is the raw material for TMP lubricants preparation will be presented as well

Jasenka Petran

Ljiljana Pedišić

Mirko Orlović

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J. Petran et al. Biomaziva... goriva i maziva, 47, 6 : 463-478, 2008. 471 Jasenka  Petran,  Ljiljana  Pediši ć, Mirko Orlovi ć, Štefica Podolski,  Vesna Brada č ISSN 0350-350X GOMABN 47, 6, 463 - 478 Pregledni rad/Review UDK 621.892.31/.32 : 621.899 : 665.7.032.52.001.18 : 66.094.942 : 547.295.8 ' 26 : 547.426.001.37  BIOLUBRICANTS FROM NATURAL WASTE OILS AND FATS Abstract The increase of ecological concern inspires research of raw materials from renewable sources in lubricant industry. Growing consumption of different lubricant types which are mostly mineral based or synthetic, leads to accidental but unavoidable inflow of considerable lubricants quantity into the environment. Therefore biodegradable lubricants produced from natural oils and fats become important if application is possible. Biodegradable lubricants produced by classical procedure from high quality natural oils and fats can be several times more expensive compared to conventional lubricants. Lower prices of waste natural oils and fats makes biodegradable lubricants much more competitive on the market. In this work the procedure of chemical synthesis, in which biodiesel (mixture of fatty acid methyl esters) is the raw material for TMP lubricants preparation will be presented as well. 1. Introduction Modern society is supplied with energy and general use of products based on the fossil raw materials. Resources of fossil origin are limited, but we are still not familiar with alternative energy and raw material. Research teams from the area of natural, technological, economic and social sciences are facing the challenges of the future sustainable development [1].  Biolubricants (bio base oil + additives) are a partial alternative to petrochemical products. The higher price of biolubricants restricts their use even in the ecologically endangered areas with soil and water inevitably polluted by petrochemical lubricants. On the European lubricant market the annual consumption of biolubricants is reaching 172000 tons, Germany and the Scandinavian countries being the biggest consumers of biolubricants [2]. For the time being, the insecurity of raw material availability (vegetable oil and animal fat) is the main obstacle for the development of new technologies in the production of bio base oils. It is probably just a matter of time, depending on the number of population on our planet, when neat oil and fat (coming from those Biomaziva... J. Petran et al. 472 goriva i maziva, 47, 6 : 463-478, 2008. species that do not participate in the human nutrition chain) will be allowed in the production of non-food products. The Figure 1 shows the evaluation of oils and fats distribution in the world today [3]. Already used oils and fats (˝waste˝) from the human nutrition chain present an interesting raw material basis [4].                      Consumption area Picture 1: Global distribution evaluation of oils and fats consumption today 2. Oils and fats – the raw material basis of oleoch emistry Oil and fat are natural compounds with the dominant triglyceride chemical structure (compounds with three ester functional groups –CO-O-). The processing of oil and fat started with the invention of soap (by treating the raw fatty material with leach) which is ascribed to the Arabs. Today oils and fats are raw materials used in oleochemistry which is an important segment of chemical industry. The Figure 2 shows the distribution of the most abundant natural oils and fats in the global production. Physical and chemical properties of fats and oils sum up the properties of particular triglyceride structures. High proportion of some triglyceride has a great influence on the final properties of fats and oils. Complex oleochemical processes are adjusted to heterogeneous content of a raw material. The most significant process is chemical fat and oil splitting, the result of which is fatty acid blend, whose content can be optimized for the further treatment by separation processes.  The preparation processes for fatty esters and amides which serve as base oils include these reactions: esterification, preesterification and amidation.   130105187020406080100120140Ukupno Hrana Petrokemija Stočna hrana81%13%6%Total                Food Petrochemistry Stock foodConsumptionx 106tConsumptionx 106tJ. Petran et al. Biomaziva... goriva i maziva, 47, 6 : 463-478, 2008. 473                 Oil/fat: 1 - soybean oil, 2 - palm oil, 3 - rapeseed oil, 4 - sunflower oil, 5 - tallow,  6 - butter, 7- laurin (C12-C14) Figure 2: Mass portion of natural oil/fat in total mass of their global production 2.1. Esterification reactions  fatty acids              +                 primary alcohol                       ------>  fatty acid esters                                        (petrochemicals or bioalcohol)  fatty acids              +              secondary alcohol                     ------>  fatty acid esters                                                (petrochemicals) 2.2. Preesterification reactions  2.2.1. ester  A + alcohol  B    --------> ester  B + alcohol  A 2.2.2. fatty acid  A + ester  B -------> ester  A + fatty acid  B 2.2.3. ester  A + ester  B  --------> ester  C + ester  D 2.3. Amidation reaction  fatty acids           +          ammonia (petrochemical)                ------> fatty acid amides fatty acids           +          amines (petrochemicals)                 ------> fatty acid amides 3025148107 6%1234 5 6 7Biomaziva... J. Petran et al. 474 goriva i maziva, 47, 6 : 463-478, 2008. 3. Base oils based on natural triglycerides and syn thetic fatty esters For the production of lubricants of shorter biodegradation, mineral base oils can be substituted by bio base oils which are, by their chemical content, natural esters (triglycerides in oils and fats) and synthetic fatty esters. Diversity of biolubricants is based on the mutual solubility of oils and fats (which are dominated by the triglyceride structure) and synthetic fatty esters as base oils. Synthetic fatty esters are an important raw material basis in chemical and processing industry. During the last decade the production capacities of fatty acid methyl esters (known as biodiesel fuel) have been growing in many EU countries [5]. The Figure 3 shows the processing of oil and fat scheme in Germany in the period between 2000-2005. The 2003/30/EU directive of the European parliament and council promotes the use of biofuels and other renewable energy-generating products in transportation. Biodiesel fuel is included in these biofuels [6]. Fatty acid methyl esters (biodiesel) globaly tend to be implemented in production of biodegradable lubricating oils [7].     Figure 3: Oil/fat processing in Germany (2000-2005)  Important synthetic fatty esters as base oils are: monoglycerides and diglycerides. They are prepared by strictly controlled reactions of esterification and preesterification. J. Petran et al. Biomaziva... goriva i maziva, 47, 6 : 463-478, 2008. 475 3.1. Esterification reactions  RCO2H           +          C3H8O3                                 RCO2C3H7O2   +    H2O fatty acid                     glycerol                            monoglyceride            water  RCO2C3H7O2       +       RCO2H                            (RCO2)2C3H6O   +    H2O     monoglyceride            fatty acid                          diglyceride                   water 3.2. Preesterification reactions (triglycerides = oil or fa t )   (RCO2)3C3H5    +      C3H8O3                       RCO2C3H7O2  +  (RCO2)2C3H6O      triglyceride           glycerol                     monoglyceride            diglyceride  (RCO2)2C3H6O      +           C3H8O3                              2 RCO2C3H7O2      diglyceride                     glycerol                             monoglyceride Glycerol can be of natural or synthetic origin. Natural glycerol is a by-product of the fatty acid production from natural oil and fat, as well as a by-product of synthesis of biodiesel fuel from plant oil and methyl alcohol. Synthetic glycerol is prepared in the hydrolysis reaction of epichlorhydrine (also a synthetic petrochemical).  4. Biodiesel fuel – raw material for preparation of  TMP base oils  Synthesis of biodiesel fuel (a blend of fatty acid methyl esters) is the first stage of synthesis of trimethylolpropane (TMP) base oils. Prepared fatty acid methyl esters are transformed in the second level by preesterification with trimethylolpropane (1,1,1 tri – hydroximethyl propane) in the new ester structures which proved to be excellent base oils (TMP – base oils).  Vegetable oils with high content of oleic acid in triglyceride structure show suitable properties as the raw material for TMP-base oils. High content of oleic triglycerides in some oleaginous plants is achieved by genetic engineering.  I stage glycerol – trioleate   +  3 CH3OH  -------->   3 CH3C16H30CO2CH3      +      C3H8O3                                    methyl alcohol            oleic acid methyl ester          glycerol                                                                         or  methyl oleate II stage  3 CH3C16H30 CO2CH3 + (HOCH2)3CC2H5 ---> (CH3C16H30CO2CH2)3CC2H5 + 3 CH3OH oleic acid                trimethylolpropane               trimethylolpropane                methyl methyl ester                                                          trioleate                              alcohol  Regardless of chemical composition of triglycerides (oils and fats) the first stage of synthesis can be conducted under very convenient conditions: with the temperature up to 100 0C, atmospheric pressure; the separation techniques (by which the optimal Biomaziva... J. Petran et al. 476 goriva i maziva, 47, 6 : 463-478, 2008. cut into fraction can be achieved: fractional distillation, fractional crystallization); the second stage synthesis does not require a significant energy input. Splitting of oils and fats, in order to produce fatty acids (the raw material for the preparation of fatty esters) require much greater energy input (Fig.4). Synthesis of fatty acid methyl esters can also be conducted from ”waste” oils and fats from the nutrition chain [8].  Plant oil derivatives with high content of oleic acid in a ester form (isopropyl oleate, TMP trioleate, pentaerythritol tetraoleate) as one of the components which gives some of the lubricant properties, are the best stimulation for the chemical synthesis researchers who are looking for new structures, and some of them will certainly be applied in lubricants.                  Figure 4: Scheme of preparation processes for fatty acid esters 5. Properties of base oils based on natural triglyc erides and synthetic fatty esters Fatty acid methyl ester (biodiesel fuel) has been synthesized in the process developed at the Company INA d.d. Zagreb [8] in semi-industrial scale, whose properties comply with the stringent requirements of the international standards. Nevertheless, these products have a poor oxidation stability influenced by not only the production processes, but also storage and handling conditions and the autooxidation process. Free radicals produced by autooxidation make long-chained and network structures, and all these structures produce undesirable sludge. Oxidation stability is improved by adding additives, so called antioxidants [9]. By Oil Fat High temp. High pressure Fatty acids Fatty acids  separated by fractional distillation Fatty acids separated by fractional crystalisation Esterification by alcohol Esterification by alcohol Oil Fat Fatty acid methyl esters  BIODIESEL 60 – 100°C Methanol Fatty acids separated by fractional distillation Fatty acids separated by fractional crystalisation Preesterification  by alcohol Preesterification  by alcohol J. Petran et al. Biomaziva... goriva i maziva, 47, 6 : 463-478, 2008. 477 adding different types of additives to a lubricant based on esters desirable properties can be provided [10]. The comparison of base oil properties of mineral and natural origin is shown in the Table 1. Apart from faster biodegradation, some of the applicational properties of natural and synthetic fatty esters are better than mineral base oil properties. These products are advertised as "renewable, bio, green, ecological, naturally biodegradable" since they are more human- and environmentally friendly than those products of specifically petrochemical origin.  Table 1: Comparison of lubricant properties related to the base oil origin  Base oil of  mineral origin Base oil of  natural origin  Lubricant Mineral oil Synthetic oil Synthetic oil based on natural oil and fat  Natural oil and fat Wear protection + ++ ++ ++ Lubrication + ++ ++ ++ Stability + ++ ++ - Toxicity - + + ++ Biodegradation - - + + ++ Saving fossil resources - - - - + ++ Price, Euro / L 1 5 5 3 Marks: + = good, ++ = excellent, - = lack of, - - = lack of-bad  Synthetic base oils based on natural oil and fat have some advantages when compared to natural triglycerides (oils and fats), they are of the equal quality and they do not tend to produce sludge, deposits and resin. Synthetic oil based on natural oil and fat have good lubrication properties, good viscosity index, less need for lubrication additives and they are less toxic. Their disadvantages are doubtful compatibility with mineral oils and seal materials. Stabilizers need to be added due to their tendency to oxidation and hydrolysis; they are 3-5 times more expensive than mineral oils.  6. Conclusion Natural oil, natural fat and synthetic oil based on the natural oil and fat are applied in lubricants. It has been estimated that today's portion of these oils which serve as lubricants is: 1 % in motor oils, 10 % in hydraulic oils and 10 – 20 % in oils in material treatment. These numbers also tend to grow.  Market surplus management of hygienically and sanitary clean oil and fat (butchery waste, oil and fats from restaurants and households) provides a lower price of raw materials. Biomaziva... J. Petran et al. 478 goriva i maziva, 47, 6 : 463-478, 2008. Some of the possible chemical synthesis processes of synthetic oils (biodiesel interphase), from natural oil and fat, especially waste oil and fat, are promising from the techno-economical and ecological standpoint. References [1] BIOSTAB Project results, EC 5th Framework programme Quality of Life and Management of Living Resources Key action Sustainable Agriculture, Fisheries and Forestry, Graz, July, 2003. [2. Whitby, R.D., Bio-Lubricants: Applications and prospects, 15th International Colloquium Tribology, TAE, Stuttgart, 2006. [3] UFOP– Information Union zur Foerderung von Oel und Proteipflanzen (2005.) [4] Falk, O.; Entwicklung von oxidationsstabilen Schmierstoff-Grundölen auf Basis von Monoalkylestern aus Altspeise- und Tierfetten, Dissertation, 2004  [5] Fachagentur Nachwachsende- Rohstoffe e.V. (2005.) [6] Norma DIN EN 14214, 2001: Fettsäure-Methylester (FAME) für Dieselmotoren. Anforderungen und Prüfverfahren. [7] Da Silva, J.A.C., Habert, A.C., Freire, D.C.; Development of a biodegradable lubricant from castor biodiesel esters, 17th International Colloquium Tribology, TAE, Stuttgart, 2008. [8] Patent-HR P20030177 (Postupak pripreme metilnih estera masnih kiselina dobivenih iz repičinog ulja; INA-industrija nafte d.d.) (Preparation process for fatty acid methyl esters produced from rapeseed oil ) [9] Westbrook, S. R.; An Evaluation and Comparison of Test Methods to Measure the Oxidation Stability of Neat Biodiesel, Report to National Renewable Energy Laboratory, U.S. Department of Energy, SAD, 2005. [10] Clarens, A.F., Zimmerman, J.B., Landis, H.R, Hayes, K.H., Skerlos, S.J.; Experimental comparison of vegetable and petroleum base oils in metalworking fluids using the tapping torque test, Proceedings of Japan-USA Symposium on Flexible Automation, Denver, SAD, 2004.  UDK ključne riječi key words 621.892.31/.32 bazno mazivo ulje, organskog polusintetskog porijekla semisynthetic organic base lubricating oil 621.899 bazno mazivo ulje, iz otpadnih organskih sirovina lubricating oil of organic waste origin 665.7.032.52 naftni i slični produkti dobiveni preradom biljnih ulja petroleum and related products worked-up from vegetable oil .001.18 gledište predvidivog razvoja viewpoint of predictable develoment 66.094.942 transesterifikacija transesterification 547.295.8 ' 26 esteri masnih kiseline fatty acid, esters 547.426 trimetilolpropan (TMP) trimethylolpropane (TMP) .001.37 gledište evaluacije evaluation viewpoint Authors Jasenka Petran1, Ljiljana Pedišić2, Mirko Orlović1, Štefica Podolski1, Vesna Bradač3 1) INA-Industrija nafte, d.d., Sector of research&development, jasenka.petran@ina.hr 2) MAZIVA-ZAGREB Ltd., Member of INA Group, Zagreb 3) CROSCO Ltd., Member of INA Group, Zagreb Received 18.9.2008. 

Croatian

BIOLUBRICANTS FROM NATURAL WASTE OILS AND FATS

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J. Petran et al. Biomaziva... goriva i maziva, 47, 6 : 463-478, 2008. 463 Jasenka Petran, Ljiljana Pedišić, Mirko Orlović, Štefica Podolski, Vesna Bradač ISSN 0350-350X GOMABN 47, 6, 463 - 478 Pregledni rad/Review UDK 621.892.31/.32 : 621.899 : 665.7.032.52.001.18 : 66.094.942 : 547.295.8 ' 26 : 547.426.001.37 BIOMAZIVA IZ PRIRODNIH OTPADNIH ULJA I MASTI Sažetak Porast ekološke svijesti potakao je istraživanja sirovina obnovljivih izvora i u industriji maziva. Zbog sve veće potrošnje raznih vrsta maziva, koja su uglavnom mineralne i sintetske sirovinske osnove, dolazi do akcidentnog, ali i neizbježnog dospijeća znatnih količina maziva u okoliš. Stoga biološki lako razgradiva maziva proizvedena iz prirodnih ulja i masti dobivaju na važnosti ukoliko je njihova primjena moguća. Biološki lako razgradiva maziva proizvedena klasičnim postupkom iz visokokvalitetnih prirodnih ulja i masti mogu biti višestruko skuplja. Niže cijene otpadnih prirodnih ulja i masti čine biološki lako razgradiva maziva konkurentnijima na tržištu. U ovome radu biti će prikazan i postupak kemijske sinteze u kojem je biodizelsko gorivo (smjesa metilnih estera masnih kiselina) sirovina za pripremu TMP (trimetilolpropan) maziva. 1. Uvod Opskrba modernog društva energijom i proizvodima opće uporabe temelji se na fosilnim sirovinama. Resursi fosilnog porijekla su ograničeni a alternativni energetski i sirovinski izvori od većeg značaja još nisu poznati. Timovi istraživača prirodnih, tehnoloških, gospodarskih i socijalnih znanosti suočili su se s izazovima budućnosti održivog razvoja [1].  Biomaziva (bio bazno ulje + aditivi) djelomična su alternativa petrokemijskim proizvodima. Njihova viša cijena ograničava uporabu i na ekološki osjetljivim područjima, u čije tlo i vodu neizbježno dospijeva mazivo petrokemijske osnove. Na europskom tržištu maziva godišnja potrošnja biomaziva dostiže 172000 tona, a najveća je u Njemačkoj i skandinavskim zemljama [2]. Nesigurnost raspoloživosti sirovine (biljna ulja i masti životinjskog porijekla) za sada su prepreka razvoju novih tehnologija proizvodnje bio baznih ulja. Vjerojatno je pitanje vremena, koje ovisi o broju stanovnika našeg planeta, kada će za proizvodnju proizvoda, koji nisu hrana, biti dopuštena uporaba svježih ulja i masti isključivo onih vrsta koje ne sudjeluju u lancu ljudske prehrane. Na slici 1 prikazana Biomaziva... J. Petran et al. 464 goriva i maziva, 47, 6 : 463-478, 2008. je procjena raspodjele potrošnje ulja i masti danas u svijetu [3]. Interesantna sirovinska osnova su jednom korištena ulja i masti ("otpad") iz lanca ljudske prehrane [4].                      Područje potrošnje  Slika 1: Procjena raspodjele potrošnje ulja i masti danas u svijetu 2. Ulja i masti – sirovinska osnova oleokemije Ulja i masti prirodni su spojevi u kojima dominira kemijska struktura triglicerida (spojevi s tri esterske funkcionalne grupe -CO-O-). Prerada ulja i masti započinje otkrićem sapuna (obrada sirovina lužinama) koje se pripisuje drevnim Arapima. Danas su ulja i masti sirovine za oleokemiju, koja je važni segment kemijske industrije. Slika 2 prikazuje raspodjelu najzastupljenijih prirodnih ulja i masti u svjetskoj proizvodnji. Fizikalno-kemijska svojstva masti i ulja suma su svojstava pojedinih trigliceridnih struktura. Visoki udio nekog triglicerida ima veći utjecaj na konačna svojstva masti i ulja. Složeni procesi oleokemije podešeni su heterogenom sastavu sirovine. Najznačajniji proces je kemijsko cijepanje masti i ulja, kada nastaje smjesa masnih kiselina, čiji je sastav moguće optimirati za daljnju preradu postupcima separacije. Procesi pripreme masnih estera i amida kao baznih ulja obuhvaćaju reakcije esterifikacije, preesterifikacije i amidacije.   1 3 01 0 51 8702 04 06 08 01 0 01 2 01 4 0Ukup no Hrana P e tro ke m ija S to čna hrana81%13% 6%Potrošnja, x 106tonaPotrošnja, x 106tonaJ. Petran et al. Biomaziva... goriva i maziva, 47, 6 : 463-478, 2008. 465               Vrsta ulja/masti: 1 - sojino ulje, 2 - palmino ulje, 3 - repičino ulje, 4 - suncokretovo ulje, 5 – loj, 6 - maslac, 7- laurin (C12-C14) Slika 2: Maseni udio prirodnih ulja/masti u ukupnoj masi njihova svjetskog proizvoda  2.1. Reakcije esterifikacije masne kiseline    +            primarni  alkohol                  ------>  esteri masnih kiselina                                     (petrokemikalije ili bioalkohol)  masne kiseline    +          sekundarni alkohol                ------>  esteri masnih kiselina                                              (petrokemikalije) 2.2. Reakcije preesterifikacije 2.2.1. ester  A + alkohol  B    --------> ester  B + alkohol  A 2.2.2. masna kiselina  A + ester  B -------> ester  A + masna kiselina  B 2.2.3. ester  A + ester  B  --------> ester  C + ester  D  2.3. Reakcija amidacije masne kiseline     +      amonijak (petrokemikalija )      ------>  amidi masnih kiselina masne kiseline     +      amini  (petrokemikalije)            ------>  amidi masnih kiselina 3025148107 6%1234 5 6 7Biomaziva... J. Petran et al. 466 goriva i maziva, 47, 6 : 463-478, 2008. 3. Bazna ulja na osnovi prirodnih triglicerida i sintetskih masnih estera Za proizvodnju maziva kraće biološke razgradnje, mineralna bazna ulja moguće je zamijeniti bio baznim uljima koja su po kemijskom sastavu prirodni esteri (trigliceridi u ulju i mast) te sintetski masni esteri. Raznolikost biomaziva temelji se na potpunoj međusobnoj topljivosti ulja i masti (u kojima dominira trigliceridna struktura) i sintetskih masnih estera kao baznih ulja. Sintetski masni esteri važna su sirovinska osnova u kemijskoj i prerađivačkoj industriji. U proteklom desetljeću u velikom broju zemalja EU rastu kapaciteti proizvodnje metilnih estera masnih kiselina poznatih pod nazivom biodizelsko gorivo [5]. Slika 3 prikazuje stanje prerade ulja i masti u Njemačkoj u razdoblju od 2000.- do 2005. godine. Smjernica 2003/30/EU Europskog parlamenta i savjeta promiče uporabu biogoriva i drugih obnovljivih energenata u prometu, a među biogorivima je to biodizelsko gorivo (biodizel) [6]. Metilni esteri masnih kiselina (biodizelsko gorivo) u cijelom svijetu se nastoje ugraditi u biorazgradljiva maziva ulja [7].               Slika 3: Prerada ulja/masti na primjeru Njemačke u razdoblju 2000.-2005. g.  Važni sintetski masni esteri kao bazna ulja su: monogliceridi i digliceridi. Pripremaju se strogo kontroliranim reakcijama esterifikacije i preesterifikacije. 3.1. Reakcije esterifikacije  RCO2H           +          C3H8O3                                 RCO2C3H7O2   +    H2O masna kiselina               glicerin                                   monoglicerid            voda  RCO2C3H7O2       +       RCO2H                            (RCO2)2C3H6O   +    H2O    020040060080010001200140016001800Prerada, x 103 tona2000 2001 2002 2003 2004 2005GodinaBiodieselMazivaOleokem ijaJ. Petran et al. Biomaziva... goriva i maziva, 47, 6 : 463-478, 2008. 467   monoglicerid              masna kiselina                          diglicerid               voda 3.2. Reakcije preesterifikacije ( trigliceridi = ulje ili mast )   (RCO2)3C3H5    +      C3H8O3                       RCO2C3H7O2  +  (RCO2)2C3H6O      triglicerid                   glicerin                         monoglicerid            diglicerid  (RCO2)2C3H6O      +           C3H8O3                              2 RCO2C3H7O2        diglicerid                          glicerin                                 monoglicerid Glicerin može biti prirodnog ili sintetskog porijekla. Glicerin prirodnog porijekla je nusproizvod proizvodnje masnih kiselina iz prirodnih ulja i masti, kao i nusproizvod sinteze biodizelskog goriva iz biljnih ulja i metilnog alkohola. Sintetski glicerin se priprema reakcijom hidrolize epiklorhidrina (također sintetske petrokemikalije). 4. Biodizelsko gorivo - sirovina za pripremu TMP – baznih ulja  Sinteza biodizelskog goriva (smjesa metilnih estera masnih kiselina) prvi je stupanj sinteze trimetilolpropan (TMP) – baznih ulja. Pripremljeni metilni esteri masnih kiselina prevode se u drugom stupnju preesterifikacijom s trimetilolpropanom (1,1,1 tri – hidroksimetil propan) u nove esterske strukture koje su se pokazale izvrsnim baznim uljima (TMP - bazna ulja).  Kao osobito tražena sirovina za proizvodnju TMP - baznih ulja pokazala su se biljna ulja s visokim sadržajem oleinske kiseline u trigliceridnoj strukturi. Visok sadržaj oleinskih triglicerida u nekim vrstama uljarica postignut je genetskim inženjeringom.  I. stupanj  glicerin – trioleat   +  3 CH3OH  -----> 3 CH3C16H30CO2CH3      +      C3H8O3                             metilni alkohol     metilni ester oleinske kiseline       glicerin                                                                    ili  metil oleat II. stupanj 3 CH3C16H30 CO2CH3 + (HOCH2)3CC2H5  -->(CH3C16H30CO2CH2)3CC2H5  + 3 CH3OH metilni ester                   trimetilolpropan                 trimetilolpropan               metilni  oleinske kiseline                                                           trioleat                        alkohol  Bez obzira na kemijski sastav triglicerida (tj. ulja i masti) I. stupanj sinteze moguće je provesti uz vrlo povoljne uvjete: temperatura do 100 0C, atmosferski tlak, a tehnike separacije, kojima se postiže optimalan "rez" frakcija: frakcijska destilacija, frakcijska kristalizacija, kao i sinteza II. stupnja ne zahtijevaju bitni utrošak energije. Cijepanje ulja i masti, kako bi se proizvele masne kiseline (sirovina za pripremu masnih estera), zahtijevaju daleko veći utrošak energije (slika 4.). Sintezu metilnih estera masnih kiselina moguće je provesti i iz otpadnih ulja i masti iz lanca ljudske prehrane [8].  Biomaziva... J. Petran et al. 468 goriva i maziva, 47, 6 : 463-478, 2008. Derivati biljnih ulja s visokim sadržajem oleinske kiseline u obliku estera (izopropiloleat, TMP trioleat, pentaeritroltetraoleat) kao jedna od komponenti koja daje mazivu neko od njegovih svojstava, najbolji su poticaj istraživačima kemijske sinteze u traženju novih struktura, a neke od njih svakako će primjenu imati i u području maziva.                   Slika 4: Sheme postupaka pripreme estera masnih kiselina 5. Svojstva baznih ulja na osnovi prirodnih triglicerida i sintetskih masnih estera Postupkom razvijenim u tvrtci INA [8] u poluindustrijskom razmjeru sintetiziran je metilni ester masnih kiselina (biodizelsko gorivo), čija svojstva zadovoljavaju stroge zahtjeve međunarodne norme. Međutim, takvi produkti imaju slabu oksidacijsku stabilnost na koju, osim samog postupka proizvodnje, utječu i uvjeti skladištenja, manipulacije te pojava autooksidacije. Autooksidacijom nastali slobodni radikali u lančanoj reakciji stvaraju dugolančane i umrežene strukture, a sve strukture uzrokuju stvaranje nepoželjnih naslaga. Oksidacijska stabilnost poboljšana je dodatkom aditiva, tzv. antioksidansa [9]. Dodatkom drugih tipova aditiva mazivu na osnovi estera mogu se dati željena svojstva [10]. U tablici 1 prikazana je usporedba nekih svojstva baznih ulja mineralnog i prirodnog porijekla. Osim kraće biološke razgradnje, neka primjenska svojstva prirodnih i sintetskih masnih estera bolja su od svojstava mineralnih baznih ulja. Proizvodi se reklamiraju kao: "obnovljivi, bio, zeleni, ekološki, prirodni, biorazgradljivi", s  Ulje Mast Visoka  temp. Visoki tlak Masne  kiseline Masne kiseline  separirane frakcionom  destilacijom Masne kiseline  separirane frakcioniranom  kristalizacijom Esterifikacija  alkoholom Esterifikacija  alkoholom Ulje Mast Metilni esteri  masnih kiselina BIODIZELSKO GORIVO 60 – 100°C METANOL Metilni esteri separirani frakcionom  destilacijom Metilni esteri separirani frakcioniranom  kristalizacijom Preesterifikacija   alkoholom Preesterifikacija  alkoholom J. Petran et al. Biomaziva... goriva i maziva, 47, 6 : 463-478, 2008. 469 namjerom da se upozori kako su pogodniji za čovjeka i okoliš u odnosu na proizvode isključivo petrokemijske osnove.   Tablica 1: Usporedba svojstava maziva u odnosu na porijeklo baznog ulja Bazno ulje  mineralnog porijekla Bazno ulje  prirodnog porijekla  Mazivo Mineralna ulja Sintetska ulja Sintetska ulja na osnovi prirodnih ulja i masti Prirodna ulja i masti Sprječava trošenje + ++ ++ ++ Podmazivanje + ++ ++ ++ Stabilnost + ++ ++ - Toksičnost - + + ++ Biološka razgradnja - - + + ++ Štednja fosilnih izvora - - - - + ++ Cijena, Euro / L 1 5 5 3 Oznake: + = dobro, ++ = odlično, - = nedostatak, - - = nedostatak-loše  Sintetska bazna ulja na osnovi prirodnih ulja i masti imaju prednost u odnosu na prirodne trigliceride (ulja i masti), ujednačene su kvalitete i ne podliježu stvaranju taloga i smola. Sintetska ulja na osnovi prirodnih ulja i masti dobrog su svojstva podmazivanja, dobrog su indeksa viskoznost, manje potrebe udjela aditiva za podmazivanje, manje toksičnosti. Nedostaci su upitna kompatibilnost s mineralnim uljima i materijalima iz kojih su proizvedene brtve, zbog sklonosti oksidaciji i hidrolizi zahtijevaju dodatak stabilizatora, a cijenom su 3 – 5 puta skuplja od mineralnih ulja. 6. Zaključak Prirodna ulja i masti te sintetska ulja na osnovi prirodnih ulja i masti primjenjuju se u mazivima. Procjene su da je sadašnji udio tih ulja u svojstvu maziva: 1 % u motornim uljima, 10 % u hidrauličnim uljima te 10 – 20 % u uljima za obradbu materijala a imaju i tendenciju rasta. Zbrinjavanje tržišnih viškova higijensko i zdravstveno ispravnih ulja i masti (klaonički otpad, ulja i masti iz gastronomije i domaćinstva) osigurava nižu cijenu sirovine. Jedan od mogućih postupaka kemijske sinteze sintetskih ulja (međufaza biodizel) iz prirodnih ulja i masti, a napose otpadnih ulja i masti tehnoekonomski i ekološki su obećavajući. Biomaziva... J. Petran et al. 470 goriva i maziva, 47, 6 : 463-478, 2008. Literatura [1] BIOSTAB Project results, EC 5th Framework programme Quality of Life and Management of Living Resources Key action Sustainable Agriculture, Fisheries and Forestry, Graz, July, 2003. [2]. Whitby, R.D., Bio-Lubricants: Applications and prospects, 15th International Colloquium Tribology, TAE, Stuttgart, 2006. [3] UFOP– Information Union zur Foerderung von Oel und Proteipflanzen (2005.) [4]. Falk, O.; Entwicklung von oxidationsstabilen Schmierstoff-Grundölen auf Basis von Monoalkylestern aus Altspeise- und Tierfetten, Dissertation, 2004  [5] Fachagentur Nachwachsende- Rohstoffe e.V. (2005.) [6] Norma DIN EN 14214, 2001: Fettsäure-Methylester (FAME) für Dieselmotoren. Anforderungen und Prüfverfahren. [7] Da Silva, J.A.C., Habert, A.C., Freire, D.C.; Development of a biodegradable lubricant from castor biodiesel esters, 17th International Colloquium Tribology, TAE, Stuttgart, 2008. [8] Patent-HR P20030177 (Postupak pripreme metilnih estera masnih kiselina dobivenih iz repičinog ulja; INA-industrija nafte d.d.) [9] Westbrook, S. R.; An Evaluation and Comparison of Test Methods to Measure the Oxidation Stability of Neat Biodiesel, Report to National Renewable Energy Laboratory, U.S. Department of Energy, SAD, 2005. [10] Clarens, A.F., Zimmerman, J.B., Landis, H.R, Hayes, K.H., Skerlos, S.J.; Experimental comparison of vegetable and petroleum base oils in metalworking fluids using the tapping torque test, Proceedings of Japan-USA Symposium on Flexible Automation, Denver, SAD, 2004.  UDK ključne riječi key words 621.892.31/.32 bazno mazivo ulje, organskog polusintetskog porijekla semisynthetic organic base lubricating oil 621.899 bazno mazivo ulje,  iz otpadnih organskih sirovina lubricating oil of organic waste origin 665.7.032.52 naftni i slični produkti dobiveni preradom biljnih ulja petroleum and related products worked-up from vegetable oil .001.18 gledište predvidivog razvoja viewpoint of predictable develoment    66.094.942 transesterifikacija transesterification 547.295.8 ' 26 esteri masnih kiseline fatty acid, esters 547.426 trimetilolpropan (TMP) trimethylolpropane (TMP) .001.37 gledište evaluacije evaluation viewpoint  Autori Jasenka Petran1, Ljiljana Pedišić2, Mirko Orlović1, Štefica Podolski1, Vesna Bradač3 1) INA-Industrija nafte, d.d., Sektor istraživanja i razvoja 2) MAZIVA-ZAGREB d.o.o., Član INA Grupe, Zagreb 3) CROSCO d.o.o., Član INA Grupe, Zagreb  Primljeno 18.9.2008. 

BIOLUBRICANTS FROM NATURAL WASTE OILS AND FATS

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