The IFP and Yellowdiesel Processes for Biodiesel Production Biodiesel is a renewable fuel comprising monoalkyl fatty esters.

It can be madefromvegetable oils, animal fat, and even recycled grease from the food industry [194,195]. 4.3 Advanced Process Solutions Using Heterogeneous Catalysis j 169

Figure4.31 AsimplifieddesignschemeoftheAlkyCleanprocess,using three reactors in a cyclic configuration. At any given time,two reactors are used for alkylation, while the catalyst in the thirdreactor is regenerated Remarkably, it is the only alternative fuel with an overall positive life-cycle energy balance, yielding as much as 3.2 units of fuel product energy for every unit of fossilenergyconsumed,comparedto0.83unitsforpetroleumdiesel.Biodieselhasseveraladvantages over petroleum diesel: it is safe, renewable, nontoxic, and biodegradablein water (ca. 98% biodegrades in just a few weeks). It has a lower content of sulfurcompounds[196],andahigh ashpoint(

> 130 C).Furthermore,itisalmostneutralwith regard to CO 2 emissions, and emits less hydrocarbons (80%) and particulates( $ 50%) (see Table 4.3). Finally, biodiesel production enjoys a positive social impact,by enhancing rural revitalization.

Table 4.3 Average emissions from biodiesel compared to conventional diesel. Emission type [a] B20/% B100/% Total unburned hydrocarbons 20 67CO 12 48CO 2 16 79Particulate matter 12 47NO x 2 10SO x 20 100Polycyclic aromatic hydrocarbons (PAHs)

13 80Nitrated PAHs 50 90

The world interest in biodiesel has accelerated tremendously, owing to recent legislation curbing vehicle emissions, and the increasing price of petroleum [196].Although biodiesel contains no petroleum products, you can blend it with conven-tionaldiesel.B20,ablendof 80%petroleumdieseland20%biodiesel,canbeusedinregulardieselengines(infact,usingB20inbusesa ndtrucksreducestheblacksmokeemittedduringacceleration[195]).Biodieselcanalsobeusedinitspure form(B100),but this requires minor engine modi cations [197]. Incidentally, the idea of usingvegetable oil as fuel for diesel engines is over 100 years old Rudolf Diesel himself demonstrated the performance of his engine using peanut oil as fuel [198].The current biodiesel manufacturing processes primarily employ transesteri ca-tion of triglycerides with methanol using NaOH as a base catalyst, or batch esteri -cation of fatty acids catalyzed by H 2 SO 4 [199,200]. However, these processes haveseveral disadvantages: soap formation (with the NaOH catalyst), shifting the equi-librium to fatty esters by using an excess of alcohol that must be separated andrecycled, homogeneous catalysts that require neutralization (causing salt wastestreams), expensive separation of products from the reaction mixture, and relatively high investment and operating costs.In 2005, the French petroleum institute (IFP) disclosed a novel biodiesel process,calledEster f.Startingfromtriglycerides,thetransesteri cationstepwasperformedusing a solid catalyst, a mixed Zn/Al oxide [201]. The process runs at highertemperature and pressure than the homogeneous one, and uses an excess of methanol, which is vaporized and recycled. It has two reactors and two separators,which are needed for shifting the methanolysis equilibrium (Figure 4.32). At each

Figure 4.32 Simplified schematic of the IFP Esterfif biodieselprocess, based on two consecutive reactor/separator stages.

4.3 Advanced Process Solutions Using Heterogeneous Catalysis

Figure 4.33 Simplified schematic of the Yellowdiesel catalyticdistillation process for making biodiesel from high-FFA oils, byintegrating the reaction and separation in one reactive distillationcolumn using a solid acid catalyst

stage the excess of methanol is removed by partial evaporation, and the esters andglycerol are separated in a settler.Asecondalternative,developedbyYellowdieselin2006[75,76],isespeciallysuitedtomixedfee dstockswithhighfree fatty acid(FFA) content, suchasused cooking oilandlow-grade grease. The process combines the reaction and the separation in one step,using reactivedistillation (alsoknownas catalyticdistillation ;seeFigure4.33)[202,203].This intensi

es mass transfer, allows energy integration in situ , reduces equipment costs, and simpli es the process owsheet and operation [204 206]. Furthermore,the thermodynamic equilibrium of the reaction can be shifted, by controllingthe vapor/liquid equilibrium in the column. The rst pilot biodiesel plant basedon this process (2500 tpa), built by Fertibom, will come on stream inRio de Janeiro in2008.LiketheAVADAandtheAlkyCleanprocesses,thesetwoprocessesalsoreplacetheliquid acid/base catalysts with solid acids and bases [192]. Although the reactionmechanism for the heterogeneous acid-catalyzed esteri cation is similar to thehomogeneouslycatalyzedone[207,208],thereisanimportantdifferenceconcerningtherelationship betweenthesurfacehydrophobicityandthecatalyst sactivity.Thisisespeciallytrueforfattyacids,whic hareverylipophiliccompounds.Onecanenvisagethree cases: First, if there are isolated Brnsted acid sites surrounded by a

Figure 4.34 In fatty acid esterification, the catalyst surfacehydrophobicity is a key factor. Too few acid sites result in lowactivity, but too many lead to water adsorption and deactivation hydrophobic environment, the hydrophobic tail of the acid would be adsorbedparallel to the hydrophobic surface (Figure 4.34 top). Second, if there are a few acidsites in the vicinity, the fatty acid molecules could be adsorbed perpendicular to thesurface,withthetailsformingalocalhydrophobicenvironment(Figure4.34middle).Finally, in the case of a very acidic and/or hydrophilic catalyst (many adjacent acidsites and/or hydroxyl groups), the by-product water from the esteri cation would beadsorbedonthesurface,andthecatalystwouldloseitsactivity(thewaterlayerwouldprevent the access of fatty acids to the catalyst, Figure 4.34 bottom). Thus, there is atrade-off between reactivity and surface hydrophobicity