Fuel 115 (2014) 8896

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Fuel
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Application of hydrotreated vegetable oil from triglyceride based biomass to CI engines A review
Soo-Young No
Department of Biosystems Engineering, Chungbuk National University, Cheongju 361-763, Republic of Korea

a r t i c l e

i n f o

a b s t r a c t
This review will be concentrated on the application of hydrotreated vegetable oils (HVO) produced from the triglycerides based biomass such as vegetable oil, animal fat, waste cooking oil and algae to compression ignition (CI) engines. Main problem in the application of HVO to CI engines is the poor low-temperature properties. The upgrading technology of cold ow properties of HVO reported in the literature can be categorized with four ways as isomerization, addition of ow improver, reaction temperature control and co-processing with petroleum derived raw materials. The advantages of hydrotreating over transesterication are lower processing cost, compatibility with infrastructure, NOx emission reduction, and feedstock exibility. Combustion and emission characteristics of neat HVO, blends of HVO with petrodiesel and HVO with additives were widely investigated by many researchers. The use of HVO enables appreciable reductions in NOx, PM, HC and CO emissions without any changes to the engine or its control in heavy-duty engines. HVO could play an important role in providing an sustainable source of transportation fuels during the coming decades. In addition, HVO obtained from inedible vegetable oil and application of it to CI engine will be the subjects of future research in the production and application of HVO. The technologies for the reduction of NOx and PM in CI engines fuelled with HVO can be categorized with engine optimization and fuel optimization. The engine optimization technology is more effective than the fuel optimization technology. 2013 Elsevier Ltd. All rights reserved.

Article history: Received 20 December 2012 Received in revised form 20 June 2013 Accepted 1 July 2013 Available online 13 July 2013 Keywords: Hydrotreated vegetable oil (HVO) Compression ignition (CI) engine NOx Particulate matter Upgrading

Contents 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Hydrotreated vegetable oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. Fuel properties of HVO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Upgrading methods of low-temperature properties of HVO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Application of HVO to CI engine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Spray characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Combustion and emission characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 89 90 91 92 92 92 94 95 95

3.

4. 5.

1. Introduction As crude oil prices currently continue to increase, it is likely that biofuels will play an important role in the future energy market of world. Generally, biomass-derived feedstocks for the production of
Tel.: +82 4312612583; fax: +82 4312714413.
E-mail addresses: sooyoung@chungbuk.ac.kr, sooyoung@cbnu.ac.kr 0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.fuel.2013.07.001

liquid biofuels can be classied into the following three categories according to the source, i.e. triglyceride-based biomass, starch- and sugar-derived biomass, and cellulosic biomass [1]. A variety of liquid biofuels can be produced from triglycerides based biomass such as vegetable oils, animal fats, waste cooking oils and microalgal oils as shown in Fig. 1. Currently, vegetable oils may be main resources for liquid fuels as petroleum alternatives. Straight vegetable oils (SVO) without any production process can be applied

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Feedstocks

Biomass based on tryglyceride (Vegetable oils, animal fats, waste materials, algae)

Production Process

Direct use

Dilution with hydrocarbon fuel or water

Pyrolysis (thermal cracking)

Transesterification

Hydrotreating

Catalytic cracking

Biofuels

Straight Vegetable oil

Blended diesel or emulsion

Pyrodiesel

Biodiesel Butobiodiesel

Hydro treated Vegetable oil

Bio-gasoline

Fig. 1. Overview of feedstocks and production process for liquid biofuels from triglycerides-based biomass.

directly to CI engines [2]. Considerable efforts have already been made to develop the vegetable oil derivatives through dilution or emulsion with petrodiesel [3]. Thermal cracking (pyrolysis) can be used to convert edible or inedible oils into valuable liquid derivatives called pyrodiesel [4]. Biodiesel, dened as the mono-alkyl esters of vegetable oils or animal fats, is usually obtained by transesterication from fatty acids based on triglyceride [58]. The application of biodiesel produced from inedible vegetable oils is of signicance because of the great need for edible vegetable oils as food [9]. However, hydrotreating or hydrogenation process instead of transesterication is introduced, and therefore, hydrotreated vegetable oils (HVO) or renewable diesel which is mainly consisted of parafnic hydrocarbons are obtained [10,11]. Catalytic cracking has been used in an effort to control the types of products generated by triglyceride cracking, using a vast variety of catalysts and a gasoline-like fuel called bio-gasoline is more likely to be formed than a diesel like fuel [12]. Liquid biofuels can be applied to typically diesel engine for transportation [13] and agricultural machinery [14], stationary diesel engine for power generation [15], gas turbine for power generation [16] and boiler for heating or power generation [17]. However, the discussion for the application of liquid biofuels in this study will be mainly limited to HVO as petroleum alternatives, vegetable oil as a feedstock, and the diesel engine for transportation and agricultural machinery. It is expected that in the USA only, the biofuels such as HVO, biodiesel and BTL (biomass-to-liquid) together will probably alternate around 410% diesel fuel used in 2020 [18]. According to Kuronen et al. classication [19], biodiesel, HVO and BTL diesel belong to 1st, 2nd and 3rd generation biobased diesel fuels, respectively. The 1st generation means the commercial production from 1990s. HVO has been classied as the 2nd generation biofuel because commercial production began during this decade. In addition, BTL diesel which is coming into the commercial market during the next decade (2010s) belongs to 3rd generation biofuel. Although biodiesel is an environmentally attractive alternative to petrodiesel, Moser [7] argued that high feedstock cost, inferior storage and oxidative stability, lower caloric value, inferior lowtemperature operability and in some cases, higher NOx emissions are the disadvantages of biodiesel. In addition, he had already

predicted that biodiesel in the coming years may face competition from non-ester renewable diesel fuel such as HVO. Biodiesel have the detrimental effect such as increase of NOx emissions, deposit formation, problem of storage stability, more rapid aging of engine oil or poor cold properties [20]. The advantages of hydrotreating over transesterication include lower processing cost, compatibility with infrastructure, existing engines and fuel standards, and exibility in terms of feedstock [21]. The review by Huber and Corma [1] provides a useful overview for the production of biofuels by catalytic cracking and hydrotreating of biomass-derived feedstocks. They introduced the hydrotreating of biomass-derived feedstocks such as lignin and triglycerides. A comparison of biodiesel and HVO in a general aspect such as fuel production and energy balance, fuel properties, environmental effects including exhaust emissions and co-products was conducted by Knothe [10]. It has been stated in this study that biodiesel performs appreciably better than HVO in terms of PM and CO emissions, with HVO having an advantages in terms of NOx and HC emissions. Hydrotreating of vegetable oils was classied by Naik et al. [22] as one of conversion processes for the production of second generation biofuels. However, the discussion in their review was only limited to one specic work related to HVO produced under a commercial trade name. Hartikka et al. [23] recently reviewed fuel properties of HVO, engine performance and emission characteristics of diesel engines fuelled with HVO. Most data are for papers presented by researchers working for Nestle Oil Corp., Finland. They concluded that HVO can be used as a drop-in-fuel for both modern and aged diesel engines. It is clear from the existing reviews discussed in the above that review related to the application of HVO for alternative fuel to CI engines could not be found except the review by Hartikka et al. [23]. In this work, an attempt has, therefore, been made to review the researches done on the application of HVO as substitute fuel to CI engines.

2. Hydrotreated vegetable oil HVO as an alternative fuel has received remarkable attention for ground, marine and aviation applications. As renewable or bio-jet

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fuels, aviation biofuels produced from triglycerides through hydroprocessing are termed as hydrotreated renewable jet (HRJ) [24], hydroprocessed renewable jet (HRJ) [2527], hydroprocessed esters and fatty acids (HEFA), bio-SPK and green jet [25,26]. Besides the aforementioned term, Li et al. [28] recently used the term non-ester biofuels for hydrotreated renewable jet (HRJ). They pointed out that the benets of non-ester fuels may include (1) higher energy content than ester-based fuels such as fatty acid methyl esters (FAMEs) and alcohols, (2) excellent combustion quality, similar to FischerTropsch fuels, (3) good low-temperature properties and superior thermal and storage stabilities. In this case, the use of HVO for aviation application is mainly in gas turbine engines. In this review, the discussion will be focused on the application of HVO to CI engines for ground and marine application only. The terms hydrotreated vegetable oil (HVO) [19,20,2935], hydrogenated (hydrogenating) vegetable oil [1] renewable diesel (fuel) [7,10,18,20,3638], second generation biodiesel [22,39,40], parafnic diesel fuel [41], parafnic renewable diesel [42,43], non-esteried renewable diesel (NERD) [28], hydroprocessed vegetable oil [21], green diesel [18,44], Bio-Hydrogenated Diesel (BHD) [45], hydro-treated biodiesel [46] super cetane [21], biocetano [47] and hydrogenationderived renewable diesel (HDRD) [39] have been used interchangeably for bio-based alkanes (formerly called the parafn)/olen (recently called the alkene) mixtures, with the chemical structure Cn H2n+2, originating from vegetable oil or animal fat [30]. It may be noted that hydrotreated renewable diesel (HRD) or (hydrotreated) algae biofuel are also used for biofuel from microalgae oil [4850]. It should be pointed out that parafnic diesel fuel includes the diesel fuel produced on the basis of synthesis gas from natural gas, coal or biomass (GTL, CTL or BTL, respectively), as well as HVO [41,42]. In addition, Knothe [10] emphasized that renewable diesel will be the most appropriate term for petrodiesel-like fuels derived from biological sources. In addition, it should be noted that farnesane (an isoprenoid) and all biomass-derived alkanes/olen mixtures through multiple fermentation technologies are also classied as renewable diesel [51]. It is clear from the literature that the different terms are used to dene the same kind of fuel produced from triglycerides, and conversely, that one term such as renewable diesel is applied to different types of fuels. Therefore, to avoid the misleading, hydrotreated vegetable oil (HVO) will be mainly used in this review. In addition, the term petrodiesel will be used for the conventional diesel fuel which is derived from petroleum, according to the suggestion by Knothe [10]. To obtain the HVO, the triglyceride is hydrogenated in the rst step and broken down into various intermediates, mainly monoglycerides, diglycerides, and carboxylic acids. These intermediate are then converted into alkanes by three different pathways: decarboxylation, decarbonylation (both removing a carbon atom from the initial intermediate), and hydrodeoxygenation (with no carbon removal) at the temperatures above 300360 C and pressure at least 3 MPa. Propane, water, carbon monoxide and carbon dioxide are produced as side-products [40,52]. Table 1 shows the difference of production process between biodiesel and HVO. It is clear from Table 1 that HVO can be obtained from the widely different process, co-reagent, catalyst and by-product with biodiesel. Recently Krar et al. [53] suggested that HVO with more advantaTable 1 Comparison of fuel production process between biodiesel and HVO. Feedstock Biodiesel Hydrotreated vegetable oil
a

geous low-temperature properties from sunower oil can be obtained by CoMo/Al2O3 catalyst. In addition, the effect of six different types of catalysts on the hydroprocessing of soybean oil to produce HVO were examined by Veriansyah et al. [54]. Out of Ni/ SiO2Al2O3, Pd/cAl2O3, Pt/cAl2O3, Ru/Al2O3, CoMo/cAl2O3, NiMo/cAl2O3, they found that Ni, NiMo and CoMo are suitable for use in hydroprocessing of soybean oil in terms of higher conversion, higher oxygen removal capabilities and low cost, etc. A number of manufacturers around the world, i.e. Neste Oil (Finland), Conocophillips (United States, Ireland), Syntroleum (United States), Universal Oil Products (UOP)-Eni (UK, Italy), Nippon Oil (Japan) and SK energy (Korea) have been developed HVO rening processes and tested them in commercial trials. The NExBTL (an acronym for next generation bio-to-liquid) is the trade name of the HVO produced by Neste Oil Corporation. The HVO produced by UOP/Eni Econing process has the trade name Green Diesel. The HVO produced by SK energy was referred to as HBD (hydrogen-treating biodiesel) [55]. According to the papers presented in SAE conferences, Neste Oil Co. had initially used the term NExBTLbiodiesel fuel for the second generation on 2005. In 2007, they introduced the term hydrotreated vegetable oil (HVO) for NExBTL [19] and the term renewable diesel (fuel) after 2008 [20,56]. According to Stumborg et al. [21], the advantages of hydrotreating over transesterication in the Canadian context include lower processing cost (50% that of transesterication), compatibility with infrastructure, engine and fuel standards, and feedstock exibility. However, Kann et al. [57] argued that by their calculations the hydroprocessing costs are higher than those of the transesterication process. 2.1. Fuel properties of HVO The fuel properties of different HVOs are listed in Table 2 and compared to FAME (fatty acid methyl ester) and petrodiesel (EN 590) as given in Kalnes et al. [58], Kalnes et al. [44] and Arvidsson et al. [30]. The different names from the commercial trade name or name given in the literature are addressed in Table 2 for the differentiation of one from another. In particular, the fuel properties of NExBTL is the summarized one from Rantanen et al. [59], Aatola et al. [20], Murtonen et al. [29], Arvidsson et al. [30], Hulkkonen et al. [60], Kopperoinen et al. [61], Sugiyama et al. [62], Lehto et al. [63] and Imperato et al. [64]. It should be pointed out that the fuel properties of isomerized NExBTL are also included in the data of NExBTL. It is clear from Table 2 that HVO is not oxygenated fuel and density and kinematic viscosity for it are lower than that of petrodiesel and biodiesel. In addition, HVO has ultra-low sulfur content and high cetane number and heating value which is much benecial in fuel for CI engines. The HVO is also a straight-chain parafnic hydrocarbon in the diesel boiling range. According to Koyama et al. [65], palm HVO had higher oxidation stability and cetane number than palm biodiesel, but showed poor low-temperature performance than that of petrodiesel. HVO does not contain unsaturated compounds because it basically a mixture of normal- and iso-parafns. Accordingly, the oxidation stability of HVO is superior to that of biodiesel [62]. It is known that the properties of HVO are very similar to GTL and BTL diesel fuel which is another parafnic fuel and produced by FischerTropsch synthesis [20].

Process Transesterication (mainly methanol) Hydrotreating

Co-reagent Alcohol Hydrogen

Catalyst Sodium alkyate sodium or potassium hydroxide NiMo, CoMo, NiW/cAl2O3, etc.

Co-product Gylcerol Propane

VOa VO

VO: vegetable oil.

S.-Y. No / Fuel 115 (2014) 8896 Table 2 Fuel properties of petrodiesel, biodiesel and renewable diesels. Petrodiesel Density (kg/m3)a Viscosity (mm2/s)b Cloud point (C) Distillation (C)c Heating value (MJ/kg) Cetane number Sulfur content (mg/kg) Oxygen content (wt%) 835 3.5 5 350 43 53 <10 0 Biodiesel 885 4.5 5 to 15 355 38 5065 <1 11 HVO 775 785 2.9 3.5 5 to 30 295 300 44 8499 0 0 Green diesel 780 10 to 20 265 320 44 7090 <1 0 NExBTL 780 785 3.03.5 15 295 300 44 9899 <10 0 IsoBHD 777 2.64 5 293 47 86 <1 0

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2.2. Upgrading methods of low-temperature properties of HVO It is well known that the major problem of HVO is generally poor low-temperature properties, as displayed by cloud point, pour point and cold lter plugging point (CFPP) in excess of 20 C (see Table 2). The main ways of upgrading technology of cold ow properties of HVO reported in the literature can be classied in four categories: isomerization, addition of ow improver, reaction temperature control and co-processing with petroleum-derived raw materials as follows. (1) Isomerization: this method is designated as two-stage upgrading by Simacek and Kubicka [67] because this process is composed of isomerization following the hydroprocessing. Catalytic hydroisomerization may be applied to solve the problem of low-temperature properties, i.e. cloud point and CFPP values [40,45]. The low-temperature properties of HVO can be upgraded by subsequent catalytic isomerization of n-alkanes [37]. The terms bio gas oil [53,68], iso-HVO [45,60] or iso-BHD [45] are used to refer to isomerized HVO. Even though Pt/ZSM-22, Pt/ZSM-23, Pt/SAPO-11, Pt/ SAPO-41 catalysts were found to be very effective for the isomerization of HVO, Hanscok et al. [68] concluded that Pt anchored to zeolite HZSM 22 at temperatures of 280370 C and under the pressure of 3.58 MPa is suitable for the isomerization of sunower HVO. While the original CFPP of sunower HVO was +23 C, they obtained products having the high cetane number of from 81 to 84 and good cold ow properties, i.e. CFPP of the products ranges from 18 to 14 C). (2) Addition of ow improver: to improve low-temperature properties, the performance of two different ow improvers (Keroux 3566 and Inneum R288) was investigated by Simacek et al. [66]. They found that the addition of ow improvers to these blends was ineffective in lowering CFPP. According to Smiacek et al. [37], most HVO often yields n-alkanes with high concentration of n-heptadecane and n-octadecane. The sum of these two hydrocarbons typically reaches around 7090%. While these hydrocarbons have an excellent cetane rating, their low-temperature properties are poor and thus prevent their use as a diesel fuel blending component in concentrations higher than 510%. In their subsequent work [37], the effect of content of ow improvers, i.e. Inneum R288 and Innneum R591 on CFPP for neat sunower HVO and blends with petrodiesel was studied. They found that the neat HVO was less sensitive to the addition of ow improvers. Moreover, the effect of both ow improvers in the blends containing more than 10 wt% of HVO was negligible. (1) Control of reaction temperature: hydroprocessing of neat sunower oil was carried out by Simacek et al. [37] at 360420 C and 18 MPa to investigate the effect of reaction temperature on the cold ow properties of neat HVO and blends with petrodiesel. In this study, the physico-chemical properties of sunower HVO obtained at 420 C were very close to those of a standard neat petrodiesel. The product showed also excellent low-temperature properties (cloud point 11 C, CFPP 14 C). In this case, they emphasized that this excellent low-temperature properties were reached without any separate isomerization process without sacricing the high octane index of 65. They found that the diesel fuel blends containing from 10 to 50 wt% of the sunower HVO obtained at 420 C met the diesel fuel specications. (2) Co-processing with petroleum-derived raw materials: Simacek and Kubicka [67] had classied vegetable oil co-processing with petrodiesel as one of several ways to

Petrodiesel: ULSD (ultra low sulfur diesel). HVO: hydrotreated vegetable oil [20,30,59]. NExBTL: next generation biomass-to-liquid [34]. Green diesel: [44,58]. iso-BHD [45]. a at 15 C. b at 40 C. c 90 vol%.

The blends of HVO with petrodiesel can also applied to CI engines. The most fuel properties of mixed fuels containing the rapeseed HVO in the range of 530 wt% and petrodiesel were similar to or better than those of neat petrodiesel. However, low-temperature properties were worse. To improve it, the performance of two different ow improvers (Keroux 3566 and Inneum R288) was investigated by Simacek et al. (2010, 3351). They found that the addition of ow improvers to these blends was ineffective in lowering CFPP. According to Smiacek et al. [66], most HVO often yields n-alkanes with high concentration of n-heptadecane and n-octadecane. The sum of these two hydrocarbons typically reaches around 7090%. While these hydrocarbons have an excellent cetane rating, their low-temperature properties are poor and thus prevent their use as a diesel fuel blending component in concentrations higher than 510%. The upgrading methods of cold ow properties of HVO will be discussed in the next section. The use of two different blends of algae-derived HRD had received considerable attention recently for marine application. One blend of HRD and NATO F-76 Millitray Distillate (F-76) was recently introduced in the study of spray characteristics in twinuid airblast atomizer [49] and another blend of HRD and ultra low sulfur diesel (ULSD) was also tested in the marine diesel engine [48]. The fuel properties of both blends are summarized in Table 3.

Table 3 Fuel properties of different blends of HRD. ULSD Density (kg/m3)a Viscosity (mm2/s)b Surface tension (kg/s2) Heating value (MJ/kg) Cetane index 828.6 3.48 0.02876 42.938 51 A50 804 2.5 43.400 65 F-76 830.3 3.12 0.02862 Algae HRD/ F-76 blend 811.1 4.56 0.02771

ULSD, A50: [48]. F-76, Algae HRD/F-76 blend: [49]. a at 15 C. b at 40 C.

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improve low-temperature properties of HVO discussed in the above. The terms renewable liquid alkanes [69], renewable diesel [36], hybrid biofuel [33], green diesel [67], second generation diesel fuel and diesel fuel with biocomponent [40] have been used interchangeably for the products from co-processing of vegetable oil and petrodiesel mixtures. In addition, co-processing triglycerides with conventional petroleum fractions on an industrial scale has been developed by Petrobas under the name of H-Bio [67]. H-Bio is produced from hydroprocessing of the blends of vegetable oils (10 vol%) such as soybean, sunower, palm or cottonseed oils with petrodiesel. A comprehensive review of co-processing vegetable oils with petroleum feedstocks was recently reported by Al-Sabawi and Chen [70]. Performance and emission characteristics of three different fuels, i.e., petrodiesel, petrodiesel mixed with biocomponent, and DF blended with rapeseed methyl ester (RME 5 vol%) and biocomponent (1 vol%) were tested in a vehicle with 5 cylinders DI diesel engine equipped with unit injector system [40]. Here, biocomponents refer to the products from co-processing of petrodiesel and rapeseed oil (6.5 vol%). The brake specic fuel consumption for petrodiesel with biocomponent is slightly higher because of having lower heating value compared to petrodiesel. As an indicator of soot emission, opacities of tested fuels with biocomponents compared with petrodiesel decreased. It was found that CO, HC and NOx emissions of DF with biocomponent were observed to be similar in comparison with petrodiesel. In addition, unregulated emissions such as VOC and aldehydes were remarkably reduced in the case of DF with biocomponents. 3. Application of HVO to CI engine HVO can be used neat as a diesel fuel, as a blending agent for petrodiesel or as a blended fuel with additives in CI engines. The research on the application of HVO to diesel engines is normally related to spray, combustion and emission characteristics. Therefore, in this review, spray characteristics will be discussed at rst and then combustion and emission characteristics will be followed for blended HVO, neat HVO and HVO with additives in order. In addition, the renewable diesel produced from algae for the application of marine engine will be differentiate with HVO by using the term HRD. 3.1. Spray characteristics Very limited number of papers related to the spray characteristics of HVO in CI engine conditions has been found in the literature. The comparison of macroscopic spay characteristics such as spray penetration and spray angle between isomerized HVO and petrodiesel was conducted by Hulkkonen et al. [60] for two nozzle orice diameters of 0.08 and 0.12 mm in common rail injector and three injection pressures of 45, 100 and 198 MPa. No remarkable and consistent difference in spray penetration was found between petrodiesel and isomerized NExBTL. However, it is interesting to note that no considerable difference in spray penetration for different orice diameters is found. This results are not coincident with the literature [71,72]. They also found that spray angle of HVO is slightly higher than that of petrodiesel. This will be due to the lower viscosity of HVO. As same as the general results for petrodiesel, spray angle of HVO increases appreciably with increase in orice diameter and diminishes with increase in liquid viscosity and injection pressure. They emphasized that the macroscopic spray characteristics of HVO is very similar with those of GTL because of same parafnic hydrocarbons. The comparison of their experimental results and empirical or theoretical correlations are not

included. In addition, the researches on microscopic spray characteristics of HVO in CI engine conditions are required. The inuence of neat HVO (NExBTL) on spray characteristics in a direct injection diesel engine with CRDi were investigated by Sugiyama et al. [62]. Their results reveal that spray penetration, spray angle and SMD were virtually the same for HVO and petrodiesel sprays. The tendency for spray penetration and spray angle is in agreement with the results of Hulkkonen et al. [60]. In addition, no major differences in spray structures from ten nozzle holes at 1 ms after spray start were found. Chen et al. [38] recently investigated the macroscopic and microscopic spray characteristics of diesel fuel and several alternative fuels including HVO from a single hole nozzle using a common rail injection system. The alternative fuels studied include biodiesel derived from waste cooking oil (B100), 20% biodiesel blended diesel fuel (B20), HVO produced from canola oil and jet fuel (Jet-A). Droplet size decreased around 50% from 30 MPa to 100 MPa injection pressure increase for all the fuels considered. Spray tip penetration at injection pressure of 100 MPa were about 40% longer than those at 30 MPa, and this trend was more pronounced for HVO and jet fuel. The HVO stands out among the biofuels by showing smaller SMD than petrodiesel. They found that effect of injection pressure on spray angle was not evident for all the fuels considered. This is maybe due to the selection of measurement location of spray angle. Spray angle generally increases considerably with increase in orice diameter and decreases with increase in density of ambient air, fuel viscosity and injection pressure of fuel [72,73]. Recently, a study on the spray characteristics of HRD blend fuel was conducted by Legg et al. [49]. In this investigation of atomization performance of several alternative fuels in a twin-uid airblast atomizer, algae-derived HRD was included for a blend with NATO F-76 Military Distillate (F-76). Even though the blending ratio was not clearly explained in their study, it can be assumed with 50:50 blend by volume of HRD with F-76 from the other study [48]. This specically designed fuel is the military diesel fuel typically used by the Navy for ship propulsion [48]. They found that algae HRD/F-76 blend is similar in properties such as density, viscosity and surface tension to the conventional petrodiesel, with minor difference in viscosity and density as shown in Table 3. According to the investigation of breakup process and measurement of droplet size, they concluded that algae HRD/F-76 blend exhibited very similar atomization characteristics with petrodiesels (ULSD and F-76). It is clear from the literature review that more researches are required for the effect of HVO on spray characteristics in diesel engines, in particular for the blended HVO with petrodiesel. 3.2. Combustion and emission characteristics Exhaust emissions of three cars using HVO called NExBTL blends (5, 15, 20 and 85 vol%) were tested and compared two different petrodiesels by Rantanen et al. [59]. They found that HVO in petrodiesel blends decreased both regulated and unregulated exhaust emission components. Decrease in CO, HC, and PM emissions was dependent on the proportion of HVO. However, it should be pointed out that clear NOx emission reduction was not seen with cars in this study. Murtonen et al. [29] reported the emission results with biodiesel, HVO, F-T diesel (GTL) and petrodiesel in three engines and ve city buses. Biofuels such as biodiesel and HVO were studied as neat and restrictedly as a 30% blend with petrodiesel. They found that in most cases all regulated emissions such as NOx, PM, CO and HC decreased with HVO and GTL fuel compared to petrodiesel. With biodiesel from rapeseed oil, i.e. rapeseed methyl ester, NOx emissions were higher compared to petrodiesel, but other emissions were reduced.

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Paum et al. [74] reported the experimental results obtained with neat HVO, different blends of HVO and petrodiesel in CI engine with CRDi. The measurement of regulated emissions in two-liter, four-cylinder diesel engine using an engine test rig as well as chassis dynamometer test bench were also performed in their study. Their results showed that neat HVO can reduce PM emissions up to 50% compared to petrodiesel due to its free of aromatic compounds. They emphasized that in case of the application of neat HVO, the reduction in soot emissions is a outcome of particles with smaller diameter, not because of a reduction in particulate number. In addition, a reduction of up to 50% in both HC and CO emissions can be achieved compared to petrodiesel. However, NOx emission did not show any signicant variations on the chassis dynamometer test, although there was a slight reduction of NOx emissions on the engine test rig. They pointed out that the engine efciency can be held constant for diesel 80%: HVO 20% and diesel 50%: HVO 50% blends. This leads to the reduction of CO2 emissions by around 5%. The effect of isomerized HVO on exhaust emissions and fuel consumption in 17 city buses were investigated by Erkkila et al. [75] with different fuel injection and after-treatment system of exhaust emissions. The test in the city buses is meaningful because the effects of the changes in fuel chemistry and physical properties depend on the technology, after-treatment system and sophistication of the engine. They concluded that average emission reduction for neat HVO compared to petrodiesel were NOx of 10%, PM of 30%, CO of 29% and HC of 39%. It should be noted that in CRDi engines, PM emissions of 36% in average can be achieved, while no signicant difference in NOx between neat HVO and petrodiesel. In addition, for neat HVO, weight based fuel consumption was decreased by 2.3%, while the volume based consumption increased 4.6% compared to petrodiesel on an average. For in-line fuel injection systems of eight buses, NOx and PM emissions were decreased with increase in HVO content in regular EN 590 diesel fuel. For buses equipped with common-rail injection systems, the effect of HVO content in the blended diesel fuel on NOx emission varied remarkably by bus type and even by bus individual. Of four buses, NOx emissions increased with increase in HVO content for one bus with EGR technology and decreased for one bus with SCR technology. Two other common-rail buses revealed no effect of HVO content. However, PM emission decreased signicantly with increase in the HVO content in the blended diesel fuel. In the test of three fuels, i.e. sulfur free EN 590 diesel fuel, neat HVO and a 30% HVO + 70% diesel fuel blend (EN590-30 fuel) in a heavy duty DI diesel engine, Aatola et al. [20] concluded that the use of HVO enables reductions in CO, HC, NOx and smoke emissions without any changes to the engine or its control. With the default injection timing settings of the test engine, the use of neat HVO led to 6% lower NOx and to 35% lower smoke compared with diesel fuel. When NOx emission of the engine was kept equal with all test fuels, the use of neat HVO led to 37% lower smoke and to 6% lower SFC that the use of diesel fuel. In addition, with the constant SFC of the engine for all fuels, the application of neat HVO led to 16% lower NOx and to 23% lower smoke than the use of diesel fuel. These result is very similar with the effect of neat HVO on exhaust emissions obtained by Kuronen et al. [19]. In addition, Aatola et al. [20] argued that HVO do not have the detrimental effects of biodiesel such as the increase of NOx emission, deposit formation, the problem of storage stability, more rapid aging of engine oil and poor low-temperature properties. HVO has potential advantages with respect to both petrodiesel and biodiesel in terms of production costs, exhaust emissions and adaptability to current engine designs. In the case of renewable diesel, all regulated emissions as well as fuel consumption can be reduced [19,20,59]. However, there are some properties of HVO that may limit its capability to replace petrodiesel, i.e. too high

cetane number for requiring adjustments in the electronic control of the engine, low lubricity and cold ow property, etc. Blending HVO with petrodiesel will be expected to depress the cetane number and cold ow temperatures, as well as to raise the lubricity of the HVO enough so that it can be used with no engine modications. To compromise between lubricity and cetane number, Lapuerta et al. [52] suggested the blending strategies that low or medium HVO concentrations in blends is preferable and blends more than HVO 50 would not be recommended. As mentioned above, one of method to avoid the low-temperature properties of HVO is the introduction of catalytic isomerization process. Emission characteristics of palm B5, four B5 blends with isomerized palm HVO (5%, 10%, 20% and 30%, hereafter isoHVO5, iso-HVO20, etc.) were measured in the vehicle with four cylinder diesel engines equipped with in line injection system [45]. In this study, HVO was referred to Bio-Hydrogenated Diesel (BHD) and isomerized HVO to iso-BHD. They found that PM is remarkably decreased by more than 24% for all iso-HVO blends, and NOx is also reduced for all iso-HVO blends and by approximately 14% for the iso-HVO 20. It is likely that reduction in NOx emission is related to the increase of cetane number with increase in iso-HVO concentration. They also found that volumetric fuel consumption and CO2 emission are decreased with increase in the concentration of iso-HVO in the blends. They also conducted the experiments on driveability, startability and cold ow eld trial, etc. For the introduction of new fuels in CI engines, the proper operation of aftertreatment system for exhaust gas with these fuels should be guaranteed. It is known that biodiesel have a strong effect on the lubricant oil dilution during DPF (diesel particulate lter) regeneration due to deeper spray penetration resulting from larger droplet diameters and can lead to a signicant disadvantages compared to petrodiesel. Due to the different fuel properties of HVO compared to petrodiesel, Paum et al. [74] investigated the effect of such factors on the lubricant oil dilution in the regeneration of DPF. They found that with increasing of HVO contents in the mixed fuel with petrodiesel, the amount of large droplets is increased as similar with the case of biodiesel. The comparison of DPF regeneration frequency with neat HVO, HVO 30 (30/70 vol% blend of HVO and petrodiesel) and B10 was conducted in a passenger car by Kopperoinen et al. [61]. In this study, post-injection system of fuel into cylinders was introduced for the regeneration of DPF. In this experiment, the lowest soot accumulation rate was found with neat HVO. Therefore, the regeneration frequency would have been about 600 km with neat HVO instead of about 400 km with other fuels. They concluded that this has led to the reduction of fuel consumption and CO2 emissions by about 1.5%. In a study of bus eet operation on HVO (NExBTL) conducted by Makinen et al. [42], emission data on consuming 30% blend of HVO and 100% HVO were compared to conventional petrodiesel (EN590) on 300 city buses. In comparison with petrodiesel, usage of HVO100 in the eld test resulted in average 10% reduction in NOx and 30% reduction in PM. This study has demonstrated that increase of HVO contents in blends results in decrease in both NOx and PM. The inuence of HVO (NExBTL) on combustion and emission characteristics in a direct injection diesel engine with CRDi were investigated by Sugiyama et al. [62]. Their results reveal that HVO can reduce HC and PM emissions due to high cetane number and zero aromatics. However, there was no signicant difference in NOx emissions between HVO and petrodiesel when the measurement carried out in a passenger car without aftertreatment system. In order to reduce NOx emissions, the test of Miller cycle and EGR using HVO in high speed diesel engine was performed by Lehto et al. [63]. In this study, Miller timing is achieved by early intake

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valve closing angle. They found that use of Miller timing and EGR with HVO reduces NOx emissions. Furthermore, advanced injection timing used together with sufcient Miller timing leads to considerable reduction in both NOx and PM emissions simultaneously. In their subsequent work [64], the combined use of Miller cycle and internal exhaust gas recirculation (IEGR) using HVO in medium-speed CI engine at low engine load was conducted. They summarized that the use of mere Miller cycle at low engine load is not so benecial with HVO, because of too long ignition delay and the occurrence of irregular combustion. Even though the previous studies on the application of Miller cycle and IEGR was performed at low load, the analysis of the performance and the combustion of a large-bore single-cylinder medium speed engine running with HVO at high load was recently reported by the same research group [76]. They summarized that NOx emission had been reduced nearly by 50% operating with HVO and proper valve timing without increasing the fuel consumption and soot emission. Two truck engines, one was Euro 4 research truck engine with common rail injection system and EGR and another was Euro prototype with EGR, showed clear reduction of NOx and PM emissions with HVO compared to petrodiesel [19]. In addition, NOx was linearly reduced with the increase of HVO blending ratio and PM reduction was remarkable at more than 50% blending ratio. The benecial effect of HVO on CO and HC emissions was seen from 10% of blending ratio. In their continued test, two city buses, one with common rail and SCR (bus A) and another with unit injector and EGR + DOC (bus B), were introduced to test the neat HVO. NOx emission was reduced with HVO about 7% for bus A and 9% for bus B compared to EN 590 fuel. PM emission was remarkably decreased 30% for bus A and 46% for bus B compared to EN 590 fuel. Reduction of CO was seen on both buses fuelled with HVO, meanwhile differences in HC emission were not signicant. It is noted that they had measured the unregulated emissions and other fuel properties such as injector fouling, lubricity and oxidation stability, etc. The impacts of two biodiesels i.e. a soy-biodiesel and a animal fat biodiesel, HVO and GTL on NOx emissions from heavy duty engines was studied using a California Air Resources Board (CARB) certied diesel fuel by Hajbabaei et al. [56]. In this study, the HVO was a NExBTL produced from palm oil. Two heavy duty diesel engines, one with no exhaust aftertreatment and another with a diesel particulate lter (DPF) were tested on an engine dynamometer over four different test cycles. Signicant reduction in NOx emissions with the HVO (R20: 2.94.9%, R50: 5.410.2% and R100: 9.918.1%) were observed over all the cycles. It is known that the utilized fuel, engine condition and technology affect the surface ne structure and oxidation characteristics of soot particles. Accordingly, the comparison of oxidation characteristics and surface structure of soot particles between petrodiesel and HVO was conducted by Happonen et al. [35]. They found that even though there are differences in chemical composition for two fuels, the surface structure of soot particles and their oxidation characteristics remain unaffected. Therefore, they concluded that the oxidative aftertreatment devices designed for petrodiesel should operate well also with the studied HVO. Murtonen et al. [43] presented the results of a study on emission reduction with HVO by optimizing engine settings or adding oxygenate in single cylinder research diesel engine. The introduction of optimized engine settings with HVO produced 4161% and 3154% reduction of PM and NOx emissions, respectively. In addition to the adjusted engine parameters, the use of a blend of 80 wt% HVO and 20 wt% DNPE (Di-n-pentyl ether) resulted in the decrease of PM emission without increasing NOx emissions. They pointed out that the slightly increased aldehyde emission was a minor demerit for optimized engine setting and oxygenated HVO.

As another study of engine optimization trial, Happonen et al. [77] reported the experimental results of PM and NOx emissions for 50%, 70% and 100% engine loads with adjustments of engine parameters in single-cylinder research engine fuelled with HVO. The engine parameters adjusted in this study include intake valve closing, injection timing, injection pressure and EGR percentage. The results show that will all the loads considered in this study both particulate mass and NOx can be reduced over 25% by adjusting engine parameters. To investigate the effect of oxygenate addition to HVO on NOx and PM emissions as one of fuel optimization study, Happonen et al. [78] conducted the experiment with single-cylinder research engine running with the same fuel blend of Murtonen et al. [43]. Around 2530% reduction in particulate mass were observed with HVO + DNPE blend compared to HVO, but NOx emission was increased by 5%. Even though they mentioned that no studies were found in which oxygenates were blended to HVO, this is the contradict result for NOx emission with Murtonen et al. [43]. In order to achieve PM and NOx reduction simultaneously, they suggested that the introduction of EGR is essential. It is worth noting that the effects of the fuel blend on the hygroscopic properties of produced exhaust particles were studied. A small increase in the hygroscopicity of exhaust particles was observed compared to particles from HVO. In two studies performed by Khan et al. [48], Ghosh and Risley [50], performance and emission data from burning 50:50 blend of ULSD/HRD, designated in this study as A50, were compared to ULSD on four-stroke marine diesel engine from a Stalwart class vessel. They found that around 4.5% reduction in overall weighted fuel consumption was obtained when switching from ULSD to A50. They explained this better fuel economy is due to the higher heating value and higher cetane index of A50 as shown in Table 3. The operation of engine on A50 resulted in signicant reduction in pollutant emissions (NOx10%, PM25%, CO25% and CO18%). Accordingly, they concluded that HRD has the potential to substantially reduce pollutant emission without modifying the engine or infrastructure in the vessel. 4. Results and discussion Density and kinematic viscosity of neat HVO are lower than that of petrodiesel and biodiesel. In addition, neat HVO has ultra-low sulfur content and high cetane number and heating value which is much benecial in fuel for CI engines [79]. The blends of HVO with petrodiesel can also applied to CI engines. The most fuel properties of mixed fuels containing the rapeseed HVO in the range of 530 wt% and petrodiesel were similar to or better than those of neat petrodiesel. Main problem in the fuel properties of neat HVO and blends of HVO with petrodiesel is the cold ow properties. The upgrading methods of low-temperature properties of HVO can be divided into isomerization, addition of ow improver, reaction temperature control and co-processing with petroleumderived raw materials. Combustion and emission characteristics of neat HVO and blends of HVO with petrodiesel were widely investigated by many researchers. However, few studies have been conducted about the spray characteristics of neat HVO and blends of HVO with petrodiesel in CI engine conditions. HVO is a parafnic bio-based liquid, with the chemical structure Cn H2n+2, originating from vegetable oil or animal fat. HVO can be used in conventional diesel engines, pure or blended with petrodiesel. Although largely unproven, it is expected that HVO will substitute directly for or blend in any proportion with petrodiesel, without modication of CI engines. HVO is not widely available at present, but it is likely to become fully commercialized in the near future.

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Most studies considered in this review have shown that HVO generally reduces NOx emissions compared to conventional diesel fuel and biodiesel [19,20,29,56,63,64,74,75]. However, Rantanen et al. [59] and Sugiyama et al. [62] reported that NOx reduction shown in heavy- duty engine tests was not clearly seen with light-duty engine test. In addition, Paum et al. [74] observed a slight reduction of NOx emissions with HVO on the engine test bench, but no signicant variation on the chassis dynamometer test. Therefore, it can be emerged from this study that reduction of NOx emissions with the same HVO (NExBTL) cannot be found only for light-duty engine on particularly chassis dynamometer test. HVO could play an important role in providing an sustainable source of transportation fuels during the coming decades. However, there exists the limitation of feedstock selection for HVO production. According to the assessment of three biofuels, i.e. biodiesel, HVO and BTL, by Sunde et al. [80], HVO produced from wastes or by-products such as tall oil, tallow or used cooking oil is superior to biodiesel and BTL in terms of environmental life cycle and costs. The technology to reduce PM and NOx emissions in diesel engine fuelled with HVO can be grouped as engine optimization [20,43,63,77] and fuel optimization [43,78]. 5. Conclusions This paper reviews the application of HVO produced from triglyceride based biomass to CI engines. Of four upgrading technologies for low-temperature properties of HVO, isomerization is more preferably selected in the commercial production of HVO. To summarize, the use of HVO enables appreciable reductions in NOx, PM, HC and CO emissions without any changes to the engine or its control in heavy-duty engines. However, the inuence of HVO on NOx emission is not so clear because of various EGR-strategies. In addition, fuel injection system may require recalibration due to the low density and high cetane number of HVO. Of the technology to reduce PM and NOx emissions in CI engines fuelled with HVO, the engine optimization technology is more effective than the fuel optimization. Due to the problem of feedstock selection for HVO production, HVO obtained from inedible vegetable oil and application of it to CI engine will be the subjects of future research in the production and application of HVO to CI engines. References
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