ARTICLE pubs.acs.org/EF
Comparison of Biomass-Derived Turbine Fuels with the Composition-Explicit Distillation Curve Method Thomas J. Bruno* and Evgenii Baibourine Thermophysical Properties Division, National Institute of Standards and Technology Boulder, Colorado 80305, United States ABSTRACT: In recent years, civilian and military users of aviation kerosene have been interested in expanding the scope of fuel feed stocks to include nonpetroleum sources. The most well-known examples of such alternative sources of fuel are the FischerTropsch fluids made from coal and natural gas. In addition to these feed stocks, there is great interest in biomass derived sources for aviation fuels. It is unlikely that a completely new, drop-in replacement fuel will be successful in the foreseeable future, but an intermediate goal is to extend or enhance present petroleum derived stocks. For this to be done on a rational basis, careful attention must be paid to fuel properties, one of the most important of which is the fluid volatility as expressed by the distillation curve. In this paper, we apply the composition explicit distillation curve method to examine three aviation fuels made from camelina (a genus within the flowering plant family Brassicaceae), from castor seed (Ricinus communis), and from plant isoprenoid feed stocks. We also use this method to compare the properties of these fluids with JP-8 and an earlier bio derived synthetic aviation kerosene made with reclaimed waste grease. We found that both the fuels derived from plant isoprenoids and from camelina vaporized at lower temperatures than did a typical JP-8 through the entire distillation curve. In contrast, the fuel derived from castor seed vaporized at higher temperatures than did the plant and camelina fuels, and also JP-8, through the entire curve. The distillation behavior of the plant isoprenoid fuel is most striking in that the distillation curve is rather more flat than the curve for a typical petroleum derived turbine fuel or for the alternatives we have examined. It is likely to be more suitable as a blending stock than a drop in replacement. More research will be needed to ensure that there would be no combustor operability issues as a result of the flat curve.
’ INTRODUCTION In recent years, civilian and military users of aviation kerosene (for gas turbine engines) have been interested in expanding the scope of fuel feed stocks to include nonpetroleum sources.1 There are many reasons for this, the most important of which are guarding against potential supply disruptions, overcoming the dependence on foreign sources of petroleum, overcoming the vulnerability of large centralized refineries (to both weather events and terrorist acts), and mitigation of the rising costs of current fuel streams.1 The most well-known such fuels are the synthetic isoparaffinic kerosenes, especially the fluids made with the FischerTropsch process. These include fluids made from natural gas and coal and mixed fluids that contain large quantities of coal oil products.2 The consideration of biomass derived feed stocks for turbine engine fuel has been slower because of the reluctance to introduce oxygenated fluids as potential finished fuels. For this reason, the focus of research and development on biomass derived turbine fuels has been on more extensively treated fluids than, for example, biodiesel fuel. An example is the synthetic isoparaffinic kerosene, BIO-SPK.3 This fluid was converted to an isoparaffinic kerosene from a feed stock of animal fats, used cooking greases, and recovered brown greases. These feed stocks are lower in quality and cost than pure fats, at typically half the cost of fat from full-fat soybeans. The reaction is carried out by combined hydrodeoxygenation and hydrogenation (HDO) of fatty acids on a sulfided nickel molybdenum (NiMo) catalyst in a tubular reactor at a temperature of 400 °C (750 °F). This results in a stream of C14 to C18 normal paraffins that are then hydroisomerized and hydrocracked over a metallic catalyst (typically platinum) on a Lewisacidic support (typically silicaalumina). This article not subject to U.S. Copyright. Published 2011 by the American Chemical Society
There are many factors that must be considered when evaluating the applicability of a fuel for use as a drop-in replacement or as an additive or enhancer.2,4 Among the most important factors are the thermophysical properties of the fluid, including the volatility, density, heat capacity, transport properties, etc. Of these properties, the volatility is critical because it is very sensitive to compositional variability and is crucial for engine operation. We used for this purpose the composition-explicit or advanced distillation curve method. This technique allows for the measurement of volatility of the complex fluid and, in addition, allows the temperature data grid to be related to the fluid composition. Moreover, all characteristics that can be determined from the fractional composition are accessible as well, including thermochemical properties. Advanced Distillation Curve Measurement. In earlier work, we described a method and apparatus for an advanced (or composition explicit) distillation curve (ADC) measurement that is especially applicable to the characterization of fuels.514 This method is a significant improvement over current approaches, featuring (1) a composition explicit data channel for each distillate fraction (for both qualitative and quantitative analysis), (2) temperature measurements that are true thermodynamic state points that can be modeled with an equation of state, (3) temperature, volume, and pressure measurements of low uncertainty suitable for equation of state development, (4) consistency with a century of historical data, (5) an assessment of Received: January 20, 2011 Revised: March 4, 2011 Published: March 06, 2011 1847
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Table 1. Listing of the Major Components of the (a) Camelina Derived Aviation Fuel, C-HRJ,a (b) Castor Derived Aviation Fuel, Cs-HRJ,b and (c) Cell Culture Derived Aviation Fuel, CSKc RT (min)
compound
CAS no.
RMM
area %
(a) 2.498
2,5-dimethylheptane
2216-30-0
128.26
4.15
2.723
4-methyloctane
2216-34-4
128.26
10.69
3.053
n-nonane
111-84-2
128.26
4.08
3.314
2,5-dimethyloctane
15869-89-3
142.28
5.13
3.409
3,6-dimethyloctane
15869-94-0
142.28
4.17
3.742
2-methylnonane
871-83-0
142.28
8.49
3.838
3-methylnonane
5911-04-6
142.28
4.15
4.198 4.46
n-decane 2,5-dimethylnonane
124-18-5 17302-27-1
142.28 156.31
3.54 6.15
4.661
3-methyldecane
13151-34-3
156.31
2.84
5.053
2-methyldecane
6975-98-0
156.31
5.79
5.154
4-methyldecane
2847-72-5
156.31
2.45
5.577
n-undecane
1120-21-4
156.31
2.18
5.812
3-methylundecane
1002-43-3
170.33
3.76
6.38
5-methylundecane
1632-70-8
170.33
5.33
n-dodecane coeluting C-15 components
112-40-3 N/A
170.33 212.39
4.39 2.39
7.246 10.637
(b) 1.758
3,5-dimethylheptane
926-82-9
128.26
1.67
1.837
4-methyloctane
2216-34-4
128.26
3.44
1.863
3-methyloctane
2216-33-3
128.26
2.07
1.959 2.063
n-nonane 2,5-dimethyloctane
111-84-2 15869-89-3
128.26 142.28
2.97 2.92
2.103
3,6-dimethyloctane
15869-94-0
142.28
1.13
2.134
2,6-diomethyloctane
2051-30-1
142.28
1.55
2.237
2-methylnonane
871-83-0
142.28
6.69
2.283
3-methylnonane
5911-04-6
142.28
3.73
2.439
n-decane
124-18-5
142.28
7.94
2.529
2,3,3-trimethyloctane
62016-30-2
156.31
1.04
2.56 2.62
2,5-dimethylnonane 6-ethyl-2-methyloctane
17302-27-1 62016-19-7
156.31 156.31
1.86 1.06
2.664
3,7-dimethylnonane
17302-32-8
156.31
2.03
2.779
3-methyldecane
13151-34-3
156.31
1.17
2.815
5-methyldecane
13151-35-4
156.31
6.04
2.919
4-methyldecane
2847-72-5
156.31
2.28
3.146
n-undecane
1120-21-4
156.31
6.72
3.288
3-methylundecane
1002-43-3
170.33
1.05
4.075 8.171
n-dodecane n-pentadecane
112-40-3 629-62-9
170.33 212.41
1.38 1.19
8.812
n-hexadecane
544-76-3
226.44
1.04
RT (min)
compound [generic name]
CAS no.
RMM
area %
(c) 4.207
3,6-dimethyloctane
15869-94-0
142.28
4.34
5.147
cis-1-methyl-4-(1 methylethyl) cyclohexane [cis-p-menthane]
6069-98-3
140.26
47.14
5.356
trans-1-methyl-4-(1-methylethyl) cyclohexane [trans-p-menthane]
1678-82-6
140.26
22.43
5.888
ortho-, meta-, and para-1-methyl-4-(1-methylethyl) benzene [cymene]
(o) 527-84-4 (m) 535-77-3 (p) 99-87-6
134.21
25.77
a,b,c
Listed with each compound are the gas chromatographic retention times (RT, in minutes), the CAS registry number, the relative molecular mass, and the uncorrected peak area. The chromatographic details are provided in the text. We have provided the generic names for selected components in brackets. Note that the three isomers of 1-methyl-1-methylethyl benzene coelute in the peak centered at a retention time of 5.888 min. The chromatographic details are provided in the text.
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Energy & Fuels the energy content of each distillate fraction, (6) trace chemical analysis of each distillate fraction, and (7) a corrosivity assessment of each distillate fraction. The very significant advantage offered by the approach discussed in this paper is the ability to model the distillation curve resulting from our metrology with equation of state based models.1520 Such thermodynamic model development is simply impossible with the classical approach to distillation curve measurement or with any of the other techniques that are used to assess fuel volatility or vapor liquid equilibrium. We have applied this metrology to azeotropes,21 gasolines,12,2225 diesel fuels,24,2631 aviation fuels,3,9,3240 rocket propellants,38,39,41,42 crude oils,4345 and herein we apply it to several renewable gas turbine fuels. Moreover, the method has also been applied to the volatility simulation of heavy oils.46 Aviation Fuels from Camelina, Castor, and Host Cell Fermentation. In this paper, we present for comparison volatility measurements on three prototype aviation turbine fuels that are derived from biomass feed stocks. The first fluid we report in this paper was a fuel made from camelina (a genus within the flowering plant family Brassicaceae).47,48 This plant produces material with a high lipid content, making it worth considering as an energy feed stock source. Perhaps the most significant advantage is the low water requirement of this plant, allowing it to be grown in semiarid regions and as a rotation crop cycled with wheat.49 In this respect, the energy production application does not compete with food crops, nor does a large water demand require diverting irrigation capacity from food crops. Other oil crops that showed early promise, such as jatropha, suffered from a larger than expected water demand. The production of the finished fuel from the camelina extract requires hydrodeoxygenation and hydroprocessing (as did BIOSPK that we measured previously); the product is often called hydrotreated renewable jet (HRJ) fuel. We note inter alia that the reader might encounter a more general (and recent) usage: “hydroprocessed” renewable jet fuel. In this paper, we refer to the camelina derived fluid as C-HRJ. This fuel has been used in blends for test flights by KLM Royal Dutch Airlines,50 Japan Airlines,51,52 the United States Navy (FA-18 Hornet fighter jet), and the United States Air Force (A-10).53 The application of a castor oil feedstock is being examined by collaboration between NASA and commercial processors in the United States and Israel. Castor oil is made from the seed (often improperly considered a bean) of the flowering plant Ricinus communis, which like camelina, does not have a large water demand. A high oil content can be extracted from the seed (at 4060%, mass/mass) that is rich in triglycerides, mainly ricinolein. The seed also contains ricin, a toxin, which can be problematic for harvesting and processing. Processing extracted castor oil into a finished fuel requires hydrotreating similar to that used for the camelina oil. In this paper, we refer to this fluid as castor hydrotreated renewable jet fuel, Cs-HRJ. We have also examined a fuel that was prepared by performing a fermentation reaction of a sugar with a recombinant host cell.54 This results in the formation of isoprenoids, a large and highly diverse group of natural products with many functions in plant primary and secondary metabolism.55 These compounds are synthesized from common prenyl diphosphate precursors through the action of terpene synthases and terpenemodifying enzymes such as cytochrome P450 monooxygenases. In this paper, we refer to this fluid as cellular synthetic kerosene, CSK.
ARTICLE
’ EXPERIMENTAL SECTION The renewable aviation fuels used in this work (C-HRJ, Cs-HRJ, CSK) were obtained from the Propulsion Directorate of the Air Force Research Laboratory at Wright Patterson Air Force Base in Ohio. These fluids were stored at 7 °C to preserve any volatile components. No phase separation was observed as a result of this storage procedure, even after several months. Each fuel was examined by gas chromatography (30 m long capillary column of 5% phenyl95% dimethyl polysiloxane having a thickness of 1 μm, flame ionization detection, and mass spectrometric detection). The temperature programs differed slightly in order to optimize the chromatography for each of the fuels (C-HRJ, 65 °C for 2 min, 10 °C per min to 225 °C; Cs-HRJ, 100 °C for 2 min, 10 °C per min to 250 °C; CSK, 70 °C for 2 min, 9 °C per min to 100 °C, then 4 °C per min to 115 °C).56,57 We have compared these new fluids to a fluid we measured previously, made from waste brown grease (called BIO-SPK) and also to a flightline JP-8 (a sample of JP-8 with a full additive package). Both of these were also obtained from the Propulsion Directorate of the Air Force Research Laboratory at Wright Patterson Air Force Base. The C-HRJ, Cs-HRJ, CSK, and BIO-SPK are all prototype fluids for which there are limited quantities for research and evaluation only. The JP-8 is from a batch of a commodity fluid produced in large quantities. The analysis details for this fluid were presented earlier.40 In Table 1, parts a, b, and c, we present a listing of the compounds found to be in excess of 2% of the total uncorrected area counts listed in order of retention time for the three renewable fluids. Identifications were made on the basis of the mass spectra, with the aid of the NIST/ EPA/NIH Mass Spectral Database and also on the basis of retention indices. These analytical results (compositions and relative quantities of components) are consistent with our knowledge of the nature of the feed stock and the processing methods used to obtain each fluid. We will note later in this paper that these analyses are also consistent with the results from the composition explicit data channel of the ADC. No dye or taggant was found in any of the fluids. The constituents of C-HRJ and Cs-HRJ are typical for a complex fuel mixture, consisting primarily of linear and branched paraffins. We note that many other components were also identified in this fluid, but they are not listed because they fall below the 2% threshold we have set for the most prevalent compounds to examine. Thus, it may appear at first to be surprising to see ndodecane, followed by a cluster of pentadecane isomers; tridecane and tetradecane isomers are present but below 2%. The constituents of CSK are all closely boiling cyclic compounds, except for the small quantity of 3,6-dimethyoctane. The o-, m-, and p-cymenes were found in a chromatographic cluster that was not resolved to baseline, thus the area % is provided as a composite. The n-hexane used as a solvent in this work was obtained from a commercial supplier and was analyzed by gas chromatography (30 m capillary column of 5% phenyl95%-dimethyl polysiloxane having a thickness of 1 μm, temperature program from 50 to 170 °C, 5 °C per minute) with flame ionization detection and mass spectrometric detection. These analyses revealed the purity to be approximately 99.9% (mass/mass), and the fluid was used without further purification. The method and apparatus for the distillation curve measurement has been reviewed in a number of sources (see refs 413), so additional general description will not be provided here. The required volume of fluid for the distillation curve measurement (in each case, 200 mL) was placed into the boiling flask with a 200 mL volumetric pipet and an automatic pipetter. The thermocouples were then inserted into the proper locations to monitor Tk, the temperature in the fluid, and Th, the temperature at the bottom of the takeoff position in the distillation head. Enclosure heating was then commenced with a four-step program based upon a previously measured distillation curve. This program was designed to impose a heating profile on the enclosure that led the fluid temperature by approximately 20 °C. Volume measurements were made 1849
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Table 2. Comparison of the Initial Boiling Temperatures of CSK, C-HRJ, and Cs-HRJ, Presented As the Average of Six Separate Measurementsa observed temperature onset sustained vapor rise
C-HRJ °C (82.30 kPa)
Cs-HRJ °C (83.90 kPa)
CSK °C (83.75 kPa)
BIO-SPK °C (83.13 kPa)
JP-8 °C (83.90 kPa)
90.5
104.6
107.7
141.2
127.4
167.7 172.1
183.7 188.0
169.4 171.2
185.2 188.4
173.9 182.5
a
These temperatures have been adjusted to 1 atm with the Sydney Young equation. The pressures at which the measurements were made are provided for each fuel to permit recovery of the actual measured temperature. The uncertainty (with a coverage factor k = 2) in the onset and sustained bubbling temperatures is ∼2 °C. The uncertainty in the vapor rise temperature is actually much lower, at ∼0.3 °C. For comparison, we have included initial boiling temperatures for BIO-SPK and JP-8. in the level-stabilized receiver, and sample aliquots were collected at the receiver adapter hammock. In the course of this work, we performed six complete distillation curve measurements for each of the fluid samples. Since the measurements of the distillation curves were performed at ambient atmospheric pressure (measured with an electronic barometer), temperature readings were corrected for what should be obtained at standard atmospheric pressure (1 atm = 101.325 kPa). This adjustment was done with the modified Sydney Young equation, in which the constant term was assigned a value of 0.000109.5861 This value corresponds to a carbon chain of 12. In the chemical analysis of the aviation fuel samples (see above), as well as in previous work on aviation turbine fuel, it was found that n-dodecane can indeed represent the fluid as a very rough surrogate.6264 The magnitude of the correction is of course dependent upon the extent of departure from standard atmospheric pressure. The location of the laboratory in which the measurements reported herein were performed is approximately 1650 m above sea level, resulting in a typical temperature adjustment of 7 °C. The actual measured temperatures are easily recovered from the Sydney Young equation at each measured atmospheric pressure. We note that constant term used may not be the optimal for CSK; however, no data are available to produce an improved correlation. We therefore consider it better to hold this term constant for all the samples than to use a questionable estimate. The uncertainty introduced by this selection is expected to be far less than the experimental uncertainty of the temperatures.
’ RESULTS AND DISCUSSION Initial Boiling Temperatures. During the initial heating of each sample during the distillation, the behavior of the fluid was carefully observed. Direct observation through the bore scope ports allowed the measurement of the onset of boiling behavior for each fluid. Typically, during the earlier stages of a measurement, the first bubbles will appear intermittently and are rather small. These bubbles cease if the stirrer is stopped momentarily. The temperature at which this bubbling is observed is called the onset temperature, and it is typically associated with the release of dissolved atmospheric gases and very light hydrocarbon gases. Sustained bubbling which occurs subsequent to onset is characterized by larger, more vigorous bubbles and is still observed when the stirring is briefly stopped. The onset and sustained temperatures are typically used as diagnostics. Finally, vapor is observed to rise into the distillation head, causing an immediate response on the Th thermocouple. This temperature has been shown to be the initial boiling temperature (IBT) of the fluid. Furthermore, this temperature is of low uncertainty and thermodynamically consistent, and it can therefore be modeled theoretically with an equation of state. Experience with previous mixtures, including n-alkane standard mixtures that were prepared gravimetrically, indicates that the uncertainty in the onset of bubbling temperature is
approximately 2 °C. The uncertainty in the vapor rise temperature is 0.3 °C. The repeatability of the pressure measurement (assessed by logging a pressure measurement every 15 s for the duration of a typical distillation) is 0.001 kPa. In Table 2, we present the onset temperatures for the fluids measured in this work. For comparison, we also present data for BIO-SPK (made by the FT process from brown grease), and a typical JP-8 (with the full additive package). We note that the initial boiling temperatures of the C-HRJ and the CSK are remarkably similar at approximately 171172 °C. This is approximately 10 °C lower than a that of a typical petroleum derived JP-8 and nearly 20 °C lower than that of Cs-HRJ and BIO-SPK. The IBT behavior of C-HRJ and CSK is the result of a suite of light components that are present in each of the fluids but at a low concentration (that is, they are below 2% in raw area counts and are not included in Table 1a,b). The Cs-HRJ is demonstrably more concentrated in heavier, larger components, consistent with the analytical data in Table 1. Distillation Curves. During the measurement of the distillation curves, both the kettle and head temperatures were recorded (Tk and Th, respectively). The ambient pressure was also recorded and used to correct the temperatures to atmospheric pressure by use of the modified Sydney Young equation. Each curve was measured six times, and the repeatability in temperature was 0.3 °C. The uncertainty in the volume measurement that is used to obtain the distillate volume fraction was 0.05 mL in each case. The repeatability of the pressure measurement (assessed by logging a pressure measurement every 15 s for the duration of a typical distillation) was 0.001 kPa. Head and kettle temperatures, as well as the measured atmospheric pressure, are presented as a function of distillate cut for a representative measurement for each fluid in Table 3. As with the initial boiling temperatures, the distillation data for BIO-SPK and a typical JP-8 are also provided. The distillation curves are plotted in Figure 1, where the initial boiling temperatures are indicated on the y-axis as a hatch mark. The distillation curves for the C-HRJ fluid and the CSK are consistent with the measured initial boiling temperatures. The curves appear to originate from nearly the same onset. The remainder of the distillation curve for C-HRJ has the familiar sigmoidal shape that is characteristic of a complex fluid containing a variety of compounds that boil over a wide range. This observation is consistent with the composition listed in Table 1a. On the other hand, the curve for CSK is essentially flat, consistent with a simple mixture containing very few components that have very similar boiling temperatures. This is also consistent with the measured composition, shown in Table 1c. We note that the curves for both C-HRJ and CSK are below that of the typical petroleum derived JP-8 and significantly below the curves of Cs-HRJ and BIO-SPK. The distillation curves of C-HRJ and the representative JP-8 approach one another later in the 1850
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Table 3. Representative Distillation Curve Data for C-HRJ, Cs-HRJ, and CSK, with data for BIO-SPK and JP-8 Provided As a Comparisona C-HRJ (82.30 kPa)
Cs-HRJ (83.9 kPa)
CSK (83.75 kPa)
BIO-SPK (83.13 kPa)
JP-8 (83.90 kPa)
distillate volume fraction, %
Tk, °C
Th, °C
Tk,°C
Th, °C
Tk, °C
Th, °C
Tk,°C
Th, °C
Tk,°C
Th, °C
5
173.3
164.6
190.2
173.2
171.4
169.8
192.6
172.5
185.4
174.7
10
174.7
166.0
192.4
176.8
171.4
169.8
196.8
180.5
187.7
178.9
15 20
176.4 178.3
168.3 170.9
194.5 197.2
177.4 183.7
171.5 171.4
169.8 169.9
200.6 204.4
186.5 189.9
189.9 192.3
182.3 184.8
25
180.4
173.2
199.6
187.0
171.5
169.9
208.7
194.9
194.9
188.4
30
182.8
175.8
202.9
188.9
171.5
170.0
213.1
201.2
197.4
186.0
35
185.4
178.4
206.5
193.4
171.5
170.1
217.5
206.1
199.8
191.9
40
188.3
180.9
210.0
196.4
171.5
169.9
221.8
210.3
202.6
194.6
45
191.3
184.2
214.5
204.0
171.5
169.8
226.3
215.4
204.7
194.1
50
195.2
188.1
220.0
205.1
171.5
170.0
231.1
219.2
208.7
196.0
55 60
199.1 203.7
191.6 196.3
225.5 232.0
212.4 223.1
171.5 171.5
170.0 170.1
235.5 240.3
224.7 231.4
212.0 215.8
196.1 197.8
65
208.9
201.3
239.9
230.0
171.5
170.1
244.8
235.7
220.2
204.5
70
215.2
207.9
248.2
238.6
171.5
170.1
249.7
242.5
224.8
206.8
75
222.7
215.1
256.4
246.9
171.8
170.1
254.6
246.8
229.6
216.4
80
228.6
221.2
264.6
255.9
171.9
170.4
259.4
251.6
234.9
220.8
85
237.7
231.4
271.7
265.1
171.7
170.6
264.7
257.8
241.3
227.2
90
246.2
239.1
276.6
270.8
171.6
170.8
270.1
264.1
248.4
229.2
a
The uncertainties are discussed in the text. These temperatures have been adjusted to 1 atm with the Sydney Young equation; the experimental atmospheric pressures are provided to allow recovery of the actual measured temperatures.
Figure 1. Representative distillation curves of HRJ and CSK, adjusted to 1 atm with the Sydney Young equation. Each curve was measured six times. The initial boiling temperature is indicated on the y-axis as a hatch mark. For comparison, the previously measured curves for BIO-SPK and JP-8 are also shown.
vaporization, however. The castor based Cs-HRJ vaporizes at higher temperatures than the C-HRJ and the CSK and is in fact somewhat similar to the BIO-SPK, especially early and late in the distillation curves. In the middle of the curves, the Cs-HRJ vaporizes at between 5 and 10 °C lower than the BIO-SPK. While we have not examined a full range of JP-8 (with the complete additive package) samples with the ADC, we have done so for a number of representative samples of Jet-A. Jet-A and JP-8
are very similar, except for the additives, and Jet-A is often used as a base fluid for research on turbine kerosenes.36 Realizing that our comparison in the above paragraph with a single sample of JP-8 allows only limited conclusions to be drawn, we also compared the volatility behavior of C-HRJ with the range of volatility that we have seen for Jet-A.13,65 We found that C-HRJ lies below the range of distillation curves of Jet-A until the 80% distillate volume fraction is reached. 1851
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Table 4. Summary of the Results of the Moiety Family Analyses for (a) C-HRJ, (b) Cs-HRJ, and (c) CSK Performed with Modifications of ASTM Method D2789 volume fraction (%)
paraffins
monocyclo-paraffins
composite
74.3
20.6
0.025 10
73.7 74.0
23.7 21.9
20
74.4
30
74.5
35
dicyclo-paraffins
alkylbenzenes
indanes and tetralins
naphthalenes
2.2
0.5
0.0
2.3
1.2 2.0
0.4 0.4
0.0 0.0
1.0 1.6
21.7
2.0
0.3
0.0
1.6
21.6
1.9
0.3
0.0
1.7
74.6
21.4
2.0
0.3
0.0
1.7
40
74.7
21.0
2.1
0.3
0.0
1.9
45
74.7
21.1
2.0
0.2
0.0
1.9
50
74.8
20.7
2.1
0.3
0.0
2.1
60 70
74.9 75.0
20.4 19.9
2.2 2.0
0.3 0.4
0.0 0.0
2.2 2.6
80
74.9
19.6
2.1
0.3
0.0
3.1
90
74.8
19.1
2.3
0.4
0.0
3.4
composite
71.4
22.8
3.2
0.4
0.0
2.2
0.025
69.6
25.1
3.2
0.5
0.0
1.6
10
70.5
24.2
3.2
0.4
0.0
1.7
20
70.7
23.7
3.3
0.5
0.0
1.8
30 35
71.2 71.4
23.4 23.2
3.2 3.1
0.5 0.4
0.0 0.0
1.8 1.9
40
71.4
23.1
3.2
0.5
0.0
1.9
45
71.5
22.9
3.1
0.5
0.0
2.0
50
71.5
22.8
3.2
0.4
0.0
2.0
60
71.6
22.5
3.3
0.5
0.0
2.2
70
71.6
22.3
3.3
0.4
0.0
2.4
80
72.0
22.0
3.1
0.4
0.0
2.6
90
72.9
21.5
2.7
0.3
0.0
2.6
composite
5.3
44.9
23.2
22.5
3.5
0.6
0.025
4.8
53.2
24.3
15.2
1.9
0.6
10
4.7
53.1
24.1
15.7
1.8
0.5
20
0.8
53.9
25.2
17.4
2.1
0.5
30
1.9
52.2
24.6
18.6
2.2
0.6
35
1.4
52.9
24.6
18.4
2.2
0.6
40 45
2.0 4.9
52.0 51.1
24.2 23.5
18.9 17.8
2.3 2.0
0.6 0.6
50
2.9
51.7
24.0
18.5
2.2
0.6
60
3.2
51.6
23.8
18.7
2.2
0.6
70
3.2
51.4
23.6
19.1
2.3
0.6
80
1.5
51.4
23.9
20.1
2.4
0.6
90
1.6
50.1
23.4
21.8
2.6
0.6
(a)
(b)
(c)
Examination of the Tk and Th temperatures for CSK shows an average difference of 1.5 °C. As we have noted in prior work, convergence of Tk and Th is an indication of azeotropy among one or more pairs of components in the mixture being distilled. Indeed, a search of the literature reveals that azeotropy of pcymene has been noted; a positive (low boiling) azeotrope forms between p-cymene and 2-butoxyethanol.66 Although this compound is not present in the analysis of CSK, a careful examination for such phenomena is warranted. In the case of CSK, however, no
convergence is observed; the close proximity of Tk and Th is observed throughout the distillation curve. This observation is therefore merely an indication of a simple mixture of closely boiling constituents; no indication of azeotropy among the major constituents (p-cymene and the menthanes) had been reported in the literature.66 Indeed, the separation of cymenes and menthanes has been studied because of its industrial importance. This separation can be affected by distillation with a column comprised of 58 theoretical plates and 71 actual plates, thus extractive 1852
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Figure 2. Results of the moiety family analysis done with a modification of ASTM method D2789. For comparison, the previously measured analyses for BIO-SPK and JP-8 are also shown.
distillation (such as that typically applied to azeotropes) is commonly used.67,68 The comparison of Tk and Th for C-HRJ shows an approximately constant difference of 7.4 °C. Thus, for this fluid, no azeotropy is observed. For Cs-HRJ, we note that for the first half of the curve, a difference of approximately 14 °C is observed, while for the latter half of the curve, this difference decreases to approximately 8 °C. This convergence is not enough to signal azeotropy, and indeed no azeotropic pairs are found among the heavier components in Table 1.
While data measured with the ADC approach are different from that of the traditional ASTM D-86 method, we can use the large quantity of D-86 data to estimate the variability of JP-8. Historically, this temperature range is significant, with a maximum range of 30 °C ((15 °C). Thus, the boiling range of the renewable fuels largely lies outside the range of experience with current jet fuels. It is possible, however, that 50/50 blends of these fuels with current jet fuels will be within historical experience. 1853
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Energy & Fuels Composition Explicit Data Channel. As described in the Experimental Section, sample aliquots of 7 μL were taken during the course of the distillation at selected volume fractions. These were then dissolved in a known mass of solvent (n-hexane). This solvent was chosen because it does not interfere with the subsequent analysis. The chromatographic peak of n-hexane elutes before the components of the fuels, so the solvent does not hamper the examination of any of the fuel components. The samples were analyzed by GCMS. While a detailed peak by peak comparison can be made for each fuel as a function of distillate fraction, a survey comparison can be done with an analysis method that is based on ASTM Method D-2789.69 In this method, one uses the GCMS to classify hydrocarbon samples into six different types, based entirely on the fragmentation behavior observed in mass spectra. The six different moieties are paraffins, monocycloparaffins, dicycloparaffins, alkylbenzenes (or aromatics), indanes and tetralins, and naphthalenes. While this method has many limitations and sources of uncertainty (we have reviewed the pitfalls elsewhere9) and is only specified for use on low olefinnic gasoline samples, it is routinely used for all types of fuel. Interpretation of these results should primarily emphasize fuel to fuel comparisons and secondarily emphasize detailed comparisons among the moieties in a given fuel. Thus, a comparison of the paraffinic content from two different fuels is very informative, while the comparison of the paraffinic content with the tetralin content in a given fuel should be approached with more caution. The results of these analyses for C-HRJ, Cs-HRJ, and CSK and (as percent volume fractions) are presented in Table 4a,b,c, and are also shown graphically in Figure 2. We begin the discussion of the moiety families with CSK, since it is very different from the other two fluids. In contrast to most aviation turbine fuels, the CSK shows a very low paraffin content throughout the distillation curve. This is consistent with the composition provided in Table 1a; only one branched paraffin was identified, and this was at a low level. We find an appreciable quantity of monocyclic paraffins, also consistent with the analysis of Table 1a. These major constituents appear at a constant concentration through the curve, as is expected from the lack of slope of the temperature data grid of the curve. The distillation curve shows very little temperature change as the four major constituents vaporize, and the families of the compounds that are present do not change. Appreciable aromatic content is observed for CSK, as expected from Table 1a. Indeed, the only observable moiety change with distillate volume fraction is seen with the aromatic constituents, where the concentration changes from 16 to approximately 22% in volume fraction through the distillation. This is consistent with the analysis presented in Table 1a; the slightly different boiling temperatures of the ortho-, meta-, and para-isomers of 1-methyl-1-methylethyl benzene and their different concentrations cause the trend. The higher boiling isomers are present at somewhat higher concentration in the unresolved chromatographic peak cluster. Both of the HRJ fluids show a constant high level of paraffins (at a volume fraction of approximately 70%) through the distillation curve. This behavior is similar to that of the natural gas and coal derived FT fluids that we have examined in the past. At first glance this might appear to be similar in origin to the constant, high concentration of monocyclic hydrocarbons seen as a function of distillate cut in the CSK. In the case of the C-HRJ and Cs-HRJ, the underlying cause is very different, however. As seen in the distillation curves for these fluids, vaporization occurs
ARTICLE
over a temperature range of approximately 80 °C. Thus, in contrast to the CSK, the vaporization of C-HRJ is producing a suite of compounds that increase in boiling temperature as the distillation proceeds, while the composition of the CSK changes little. The temperature data grid of the distillation curve and the composition channel are complementary in this important respect. We also note for C-HRJ and Cs-HRJ a constant concentration of monocyclics (at a much lower volume fraction than is observed for CSK) of approximately 22%. This might at first seem surprising because the list of components in Table 1b contains no such compounds. One must remember, however, that this method uses mass spectral fragments in electron impact conditions to normalize and then subdivide moieties into chemical classes. Some of the characteristic fragments that are used in the analysis are common to more than one moiety. For example, m/z = 41 is an important marker for the monocyclic family. Although this fragment (CH2dCHCH2•) is abundantly produced by the fragmentation of cyclic species, it is also produced at moderate abundance by paraffinic species, but it is not considered in the paraffin summation.56 Indeed, each compound listed in Table 1b produces this fragment and contributes to what is perceived to be appreciable monocyclic content. These limitations (discussed above) do not effect fuel to fuel interpretation, provided the source of these responses is understood. Continuing with our analysis of the C-HRJ and CsHRJ, we note a very low level of aromatics that show a slight increase from 1.5 to 3%. These observations are consistent with the analysis; any aromatics present are in the peaks that are just above the noise level. Distillate Fraction Energy Content and Enthalpy Calculations. As we have previously demonstrated, it is possible to supplement the distillation curve with thermochemical data by use of the information available from the composition explicit data channel.14 This is significant because in an engine, the fuel undergoes droplet combustion, and a process similar to distillation takes place as the oxidation reactions occur. We can calculate a fractional enthalpy of combustion based on the measured mole fractions of the individual components in the distillate cuts. One simply multiplies the measured mole fraction by the pure component enthalpy of combustion: ΔHc ¼
∑xi ð ΔHi Þ
ð1Þ
where ΔHc is the composite enthalpy of combustion of the distillate fraction, xi are the mole fractions of the selected components of each distillate fraction, and ΔHi are the pure component enthalpies of combustion. The enthalpy of combustion of the individual (pure) components is taken from a reliable database compilation.70,71 We have previously presented a very detailed discussion of the uncertainty of the composite enthalpy of combustion derived from this procedure. The major sources of uncertainty that were considered were (1) the neglect of the enthalpy of mixing, (2) the uncertainty in the individual (pure component) enthalpies of combustion as tabulated in the database, (3) the uncertainty in the measured mole fraction, (4) the uncertainty posed by very closely related isomers that cannot be resolved by the analytical protocol, (5) the uncertainty introduced by neglecting components present at very low concentrations (that is, uncertainty associated with the chosen area cutoff), (6) the uncertainty introduced by a complete misidentification of a component, (7) the uncertainty in quantitation introduced by eluting peaks that are poorly resolved, and (8) 1854
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Table 5. Composite Enthalpy of Combustion, Presented in Units of kJ/mol, of Selected Distillate Fractions of C-HRJ, Cs-HRJ, and CSKa volume fraction (%) 0.025
C-HRJ 5767 (90)
Cs-HRJ
CSK
Table 6. Composite Enthalpy of Combustion, Presented in Units of kJ/g, of Distillate Fractions of C-HRJ, Cs-HRJ, and CSKa
BIO-SPK
volume fraction (%)
6252 (150) 6087 (130) 6872 (230)
C-HRJ
Cs-HRJ
CSK
BIO-SPK
0.025
44.3 (0.7)
44.3 (1.0)
43.5 (1.0)
44.2 (1.5)
10
5810 (290) 6313 (100) 6086 (420) 6934 (160)
10
44.3 (2.2)
44.2 (0.7)
43.5 (3.0)
44.2 (1.0)
20
6015 (170) 6368 (120) 6089 (310) 7030 (250)
20
44.3 (1.2)
44.2 (0.8)
43.5 (2.2)
44.2 (1.6)
30
6072 (230) 6419 (50)
6087 (300) 7197 (290)
30
44.3 (1.6)
44.2 (0.3)
43.5 (2.1)
44.2 (1.9)
35 40
6184 (220) 6449 (70) 6207 (220) 6475 (50)
6086 (340) 7333 (190) 6086 (160) 7428 (290)
35 40
44.3 (1.6) 44.3 (1.6)
44.2 (0.5) 44.2 (0.3)
43.5 (2.4) 43.5 (1.1)
44.2 (1.2) 44.1 (1.8)
45
6261 (200) 6504 (50)
6083 (110) 7537 (200)
45
44.3 (1.4)
44.2 (0.3)
43.5 (0.8)
44.1 (1.2)
50
6571 (140) 6535 (50)
6081 (70)
7576 (310)
50
44.2 (0.9)
44.2 (0.3)
43.4 (0.5)
44.1 (1.9)
60
6692 (230) 6950 (70)
6084 (210) 8153 (200)
60
44.2 (1.5)
44.2 (0.4)
43.4 (1.5)
44.1 (1.0)
70
7190 (280) 7179 (90)
6083 (220) 8619 (200)
70
44.2 (1.6)
44.1 (0.5)
43.4 (1.6)
44.1 (1.0)
80
7757 (150) 8525 (80)
6081 (460) 9215 (350)
80
44.1 (0.9)
44.1 (0.4)
43.4 (3.2)
44.0 (1.6)
90
8321 (350) 9334 (50)
6078 (350) 9572 (340)
90
44.1 (1.9)
44.0 (0.2)
43.4 (2.5)
44.0 (1.5)
a
Data for Bio-SPK are provided for comparison. Uncertainties are provided in parentheses.
Figure 3. The enthalpy of combustion as a function of distillate volume fraction for CSK, C-HRJ, and BIO-SPK. The uncertainty is discussed in the text. Note that for the 70% distillate fraction, the enthalpy of combustion of the JP-8 sample is provided for comparison.
the uncertainty introduced when experimental data for the pure component enthalpy of combustion are unavailable (and the Cardozo equivalent chain model must be used). It is usually not necessary to include all the components in the calculation. The components that we selected in this work are those that were present in excess of 2% of raw, uncorrected chromatographic peak area counts of each fraction analyzed. We present the enthalpy of combustion for C-HRJ, Cs-HRJ, and CSK in units of kilojoules/mole as a function of distillate volume fraction in Table 5 and Figure 3. For comparison, in Figure 3 we also include data for BIO-SPK and one value for JP-8 at the 70% distillate fraction, measured earlier. Only one point is provided for JP-8 because different batches of this commodity fluid are known to be highly variable, yet still within acceptable specifications. The point we present in the figure is determined from the JP-8 sample measured taken from the WPAFB flightline, as mentioned earlier. We chose the 70% distillate fraction because in prior work we determined that at this fraction for JP-8 and Jet-A, the variability in the volatility and enthalpy of combustion is the widest.13
a
Data for Bio-SPK are provided for comparison. Uncertainties are provided in parentheses.
We treat the behavior of CSK first, because for the entire distillation curve, the enthalpy of combustion of CSK shows little change. This behavior effectively mirrors the temperature grid of the distillation curve (Figure 1) and even the moiety family analysis (Figure 2). The composition of this relatively simple fluid changes little, thus the enthalpy of combustion on a molar basis is constant, represented well (within experimental uncertainty) by an average of 6084 kJ/mol, with an average uncertainty (over the distillation curve) of 257 kJ/mol. In contrast, the enthalpy of combustion of C-HRJ begins somewhat lower than that of CSK and shows a modest increase until the 35% distillation volume fraction is attained. Indeed, from the 5% fraction to the 40% fraction, the enthalpies of combustion for CSK and C-HRJ are relatively close within experimental uncertainty. A pronounced divergence is observed after the 45% distillate volume fraction. This is also mirrored on the distillation curve, where an increase in slope appears. This coincides with the vaporization of heavier compounds with higher enthalpies of combustion. The enthalpy of combustion of C-HRJ is similar in shape to that of BIO-SPK, although lower in magnitude by 12001500 kJ/mol. We note that the enthalpy of combustion of Cs-HRJ begins at a higher level than either C-HRJ or CSK and is relatively constant up to the 50% distillate fraction. Subsequent to this fraction, the enthalpies of combustion increases sharply and approaches that of BIO-SPK late in the curve. We observe that the difference in enthalpy of combustion is most striking at the end of the distillation curves. At the 90% fraction, the enthalpies of CSK, C-HRJ, Cs-HRJ, and BIO-SPK are 6078, 8321, 9334, and 9572 kJ/mol, respectively. We can also compare the enthalpy of combustion of the renewable fuels with that of the JP-8 sample (7372 kJ/mol, with an uncertainty of 200) at the 70% distillate volume fraction. Here we observe that the values are the same within experimental uncertainty. Although we express the enthalpy of combustion on a molar basis to facilitate calculations, other units are sometimes preferred. In practical terms, a mass or volume basis is often desired by aircraft operators. The conversion to a mass basis is simple, requiring only the relative molecular mass of each component used in the calculation. We present the enthalpy of combustion on a mass basis (in kilojoules/gram) of selected distillate cuts 1855
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Table 7. Composite Enthalpy of Combustion, Presented in Units of kJ/mL, of Distillate Fractions of C-HRJ, Cs-HRJ, and CSKa volume fraction (%)
C-HRJ
Cs-HRJ
CSK
BIO-SPK
0.025
32.0 (0.5)
31.7 (0.7)
35.1 (0.8)
32.6 (1.1)
10
32.0 (1.6)
31.7 (0.5)
35.1 (2.4)
32.6 (0.8)
20
32.0 (0.9)
31.8 (0.6)
35.1 (1.8)
32.7 (1.1)
30
32.1 (1.2)
31.8 (0.2)
35.1 (1.7)
32.8 (1.4)
35 40
32.2 (1.1) 32.2 (1.1)
31.9 (0.4) 31.9 (0.2)
35.1 (2.0) 35.1 (0.9)
32.8 (0.9) 32.9 (1.4)
45
32.2 (1.0)
32.0 (0.2)
35.1 (0.6)
32.9 (0.9)
50
32.3 (0.7)
32.0 (0.2)
35.1 (0.4)
32.9 (1.4)
60
32.4 (1.1)
32.5 (0.3)
35.1 (1.2)
33.2 (0.8)
70
32.7 (1.2)
32.5 (0.4)
35.1 (1.3)
33.4 (0.8)
80
33.0 (0.7)
33.6 (0.3)
35.1 (2.6)
33.7 (1.2)
90
33.6 (1.4)
34.2 (0.2)
35.1 (2.0)
33.8 (1.2)
a
Data for Bio-SPK are provided for comparison. Uncertainties are provided in parentheses.
for the three fuels in Table 6. Presenting the enthalpies of combustion on a volume basis is more uncertain because the density of each compound is necessary. While the density of the fuel itself varies little with composition, the density of the individual components can vary significantly with temperature. Moreover, there is often a lack of reliable density data at the temperatures of interest, especially reference quality data. These additional contributions to uncertainty must be considered upon conversion to the volume basis. For each of the fluids measured in this work, we present in Table 7 the enthalpy of combustion on a volume basis (in kilojoule/milliliter) of the same selected distillate fractions as in Tables 5 and 6. The temperature basis for this table was chosen as 25 °C. We note that on the basis of these units, the energy content is far more uniform over the distillation curve. This is primarily due to differences in density of the three fuels and changes in density with composition during the course of distillation.
’ CONCLUSIONS In this paper, we have presented our examination of the composition of three alternative synthetic kerosene turbine fuels (all of which are renewable) with the advanced or compositionexplicit distillation curve method. The advanced distillation curve method provided for accurate measurements that are suitable for equation of state development. Furthermore, we were able to obtain detailed compositional data as a function of distillate cut for each of the fuels. We analyzed the distillate fractions of each fuel for specific component information with a GCMS method. Finally, we combined the compositional information with thermochemical data for an explicit measure of the energy content of each fraction. These analyses were compared with a renewable synthetic turbine kerosene made from waste brown grease and a typical JP-8. We found that both the CSK and C-HRJ vaporized at lower temperatures than that of a typical JP-8, while the CsHRJ vaporized at higher temperatures, over the entire distillation curve. All vaporized at lower temperatures than the waste grease derived BIO-SPK, however. The distillation behavior of CSK is very different from that of C-HRJ or any typical turbine fuel we have examined. It is likely to be more suitable as a blending stock than as a drop-in replacement. Indeed, this was anticipated in the
patent on this fluid, in which mixtures with JP-8 were discussed. In the near future, we will report measurements done with the ADC on blends of CSK with JP-8 and also additional property measurements (density, speed of sound, and viscosity). The thermochemical data generally follow the same trends as the volatility data.
’ AUTHOR INFORMATION Corresponding Author
*E-mail:
[email protected].
’ ACKNOWLEDGMENT A Professional Research Experience Program undergraduate fellowship is gratefully acknowledged by E.B. We acknowledge the Propulsion Directorate of the Air Force Research Laboratory, Wright Patterson Air Force Base, for the samples of fuel measured in this effort. We also acknowledge helpful discussions with Robert Hendricks of NASA and Liat Cinamon of Evogene, Ltd. ’ REFERENCES (1) Muzzell, P. S. L.; Freerks, R.; McKay, B.; Terry, A.; Sattler, E. Properties of Fischer-Tropsch (FT) blends for use in military equipment. SAE Paper No. 2006-01-1702, 2006. (2) Daggett, D. L.; Hendricks, R. C.; Walther, R.; Corporan, E. Alternate fuels for use in commercial aircraft, NASA/TM-2008-214833, ISABE-2007-1196; 2008. (3) Bruno, T. J.; Baibourine, E.; Lovestead, T. M. Comparison of synthetic isoparaffinic kerosene turbine fuels with the composition explicit distillation curve method. Energy Fuels 2010, 24, 3049–3059. (4) Daggett, D.; Hadaller, O.; Hendricks, R.; Walther, R. Alternative fuels and their potential impact on aviation (Prepared for the The 25th Congress of the International Council of the Aeronautical Sciences), NASA-TM-2006-214365, 2006. (5) Bruno, T. J.; Ott, L. S.; Smith, B. L.; Lovestead, T. M. Complex fluid analysis with the advanced distillation curve approach. Anal. Chem. 2010, 82, 777–783. (6) Bruno, T. J.; Ott, L. S.; Lovestead, T. M.; Huber, M. L. The composition explicit distillation curve technique: relating chemical analysis and physical properties of complex fluids. J. Chromatogr. 2010, A1217, 2703–2715. (7) Bruno, T. J.; Ott, L. S.; Lovestead, T. M.; Huber, M. L. Relating complex fluid composition and thermophysical properties with the advanced distillation curve approach. Chem. Eng. Technol. 2010, 33 (3), 363–376. (8) Bruno, T. J. Improvements in the measurement of distillation curves - part 1: a composition-explicit approach. Ind. Eng. Chem. Res. 2006, 45, 4371–4380. (9) Bruno, T. J.; Smith, B. L. Improvements in the measurement of distillation curves - part 2: application to aerospace/aviation fuels RP-1 and S-8. Ind. Eng. Chem. Res. 2006, 45, 4381–4388. (10) Bruno, T. J. Method and apparatus for precision in-line sampling of distillate. Sep. Sci. Technol. 2006, 41 (2), 309–314. (11) Smith, B. L.; Bruno, T. J. Advanced distillation curve measurement with a model predictive temperature controller. Int. J. Thermophys. 2006, 27, 1419–1434. (12) Smith, B. L.; Bruno, T. J. Improvements in the measurement of distillation curves: part 3 - application to gasoline and gasoline þ methanol mixtures. Ind. Eng. Chem. Res. 2007, 46, 297–309. (13) Smith, B. L.; Bruno, T. J. Improvements in the measurement of distillation curves: part 4- application to the aviation turbine fuel Jet-A. Ind. Eng. Chem. Res. 2007, 46, 310–320. 1856
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