You are on page 1of 13

Basic nitrogen compounds identification

in a blend of Libyan crudes and in its


middle distillates and Residue

Youssef A. Al Mestiri and Abeer A. Al Shiki

Ras Lanuf Oil and Gas Processing Company


Technical Services Department
Laboratory Section
P.O.Box 1971
Benghazi – Libya
yelmisteri@yahoo.com

Abstract

Basic nitrogen content in naphtha, kerosene, light and heavy gas oils (LGO
and HGO) produced by Ras Lanuf Refinery from a blend of Libyan crudes as
well as the physical and the chemical properties of this crude blend and its
LGO, HGO and residue were determined. Basic nitrogen compounds from this
crude blend and from its LGO, HGO and residue were extracted by
hydrochloric acid, the extracted basic nitrogen compounds were
accompanied with some non basic nitrogen compounds. Separation and
identification of these compounds were achieved by a GC-MS technique. The
basic nitrogen content in naphtha and kerosene is zero ppm whilst in LGO,
and HGO is 13 and 88 ppm respectively, the identified basic nitrogen
compounds are quinoline, isoquinoline, and acridine derivatives and the
accompanied non basic nitrogen compounds are indole derivatives.
Introduction

It has been realized for a long time. The deleterious effect of nitrogen
compounds that naturally occurring in petroleum and distributed in
petroleum distillates.
Environmentally nitrogen compounds are extremely harmful since they
contribute nitrogen oxides emissions and are known to be carcinogenic and
mutagenic in humans and animals [1-3]. Industrially both basic and non-basic
nitrogen compounds reduce the stability and storage stability of petroleum
distillates, by darkening the colour, sediment and odour formation[1,2,4,5],
moreover basic nitrogen compounds are strong inhibitors in various
petroleum processes; cracking, hydrocracking reforming processes and
hydrodesulfurization (HDS) reactions by interacting with the acidic sites of
the catalyst employed causing catalyst poisoning: in this reaction basic
nitrogen compounds are electron pair donor whilst catalyst is electron pair
acceptor [2,5-8]. Non-basic nitrogen compounds inhibition in HDS reactions
has been observed and reported; hydrogenation reduction reaction of these
compounds that take place in HDS and reaction process leading to the
formation of basic nitrogen compounds [8-11] or by a strong adsorption of
non-basic nitrogen compounds over the support surface of the catalyst
[8,12,13].
The aims of this work is to assess quantitatively basic nitrogen content in
naphtha, kerosene, LGO and HGO produced from a blend of Libyan crudes
and extraction, separation and identification of these compounds by GC-MS
technique [14-26].

Experimental

The properties of Libyan crude blend; a 50% Sarir/50% Mesla crudes blend
and its LGO, HGO and residue were attained following ASTM standard
methods whilst the total basic nitrogen content in naphtha and kerosene was
determined following UOP-312 plant control test method and in LGO and HGO
by applying UOP-313 standard method. All the samples were taken from the
Ras Lanuf Refinery.
The extraction of basic nitrogen compounds was performed by a slight
modification of the Hartung and Jewell separation scheme [1].
Prior basic nitrogen compounds extraction; the samples were diluted or
dissolved in the proper solvent as follow, 2.4L raw sample of Libyan
crudes blend were diluted with 600 ml n-heptane, 2L LGO was used
without dilution, 2L HGO sample was dissolved and diluted with 500 ml n-

2
heptane and 1L of residue was dissolved and diluted with 2L 1:1
toluene/xylene mixture.
Basic nitrogen compounds were extracted; from the Libyan crudes blend
sample with 6 x 500 ml 0.1M HCl acid, from each LGO and HGO sample with
5 x 500 ml 0.1M HCl acid and from the residue extracted with 6 x 250 ml
0.1M HCl acid, the acid extract of each sample was extracted with n-heptane
followed by benzene and the resulting acidic aqueous solution was reacted
with concentrated NaOH in presence of 50 ml dichloromethane with vigorous
shaking to raise the pH to 12-13, the liberated basic nitrogen compounds
were extracted from the NaOH solution with 650 ml dichloromethane. The
light-yellow dichloromethane basic nitrogen compounds solution was
evaporated to about 1-2 ml for GC-MS separation and identification of basic
nitrogen compounds.
Basic nitrogen compounds were separated and identified by GC-MS (Thermo
Finnigan Trace GC and Trace DSQ). 2-4 µl of each basic nitrogen compounds
mixture was injected onto the GC fitted with a 30 m, 0.25 mm id, 0.25 μm df
capillary column (5% diphenyl-95% dimethyl polysiloxane), coupled directly
to MS spectrometer detector; operating in electron impact mode at 70 eV,
mass detector gain 1.00 KV, ionization current 100 μA, full scan 40-300 μ.
GC operating temperature was as follows initial temperature was set at 85 оC
for 1 min, ramped 5оC/min up to 200оC at which it was held for 20 min and
finally ramped 5оC/min up to 270оC at which it was held for 5 min.
Injector temperature was 280оC at constant temperature split mode, carrier
gas was helium flow rate 1.0 ml/min; at constant flow. Both MS transfer line
and the ion source temperatures were 250оC. The nitrogen compounds in
each sample were identified by means of a computer matching method,
comparing their spectra with those of the NIST library of mass spectral Data.

Result and Discussions

It is obvious that large volumes of samples and reagent were used to achieve
separation of basic nitrogen compounds from the samples that is to obtain a

3
rather concentrated basic nitrogen compounds mixture suitable for a GC-MS
analysis.
The samples solvents treatment prior basic nitrogen compounds extraction
is; to dilute, to dissolve and to reduce the density of the samples which
facilitate the extraction of basic nitrogen compounds from each sample.
The physical and some of the chemical properties of Libyan crude blend,
LGO, HGO and residue are presented in table 1.
From table 1; the sulfur content increases as the boiling point of the Libyan
crudes blend distillates increases and attain its highest content in residue.
Also basic nitrogen content increases as the boiling point of the distillates
increases; as naphtha and kerosene contain zero ppm of basic nitrogen HGO
contains the highest basic nitrogen content.
GC-MS technique revealed that the extracted basic nitrogen compounds
contain some non-basic nitrogen compounds due to the strong adsorption of
these non-basic nitrogen compounds to the acid. No further attempts were
made to separate the basic nitrogen compounds from the non-basic nitrogen
compounds. The identified basic nitrogen compounds in LGO, HGO and
residue produced from this crudes oil blend do not show any structure
alteration or rearrangement from those identified in the raw crudes blend oil.
All the identified basic nitrogen compounds and the accompanied non-basic
nitrogen compounds are presented in table 2.
Total ion chromatograms of the separated basic nitrogen compounds from
the Libyan crudes blend and its LGO, HGO and residue are shown in figures 1,
2, 3 and 4; the numbers associated with the peaks refer to the identified
basic and non-basic nitrogen compounds in each distillate.

Table 1 Properties of Libyan crude blend, LGO, HGO and residue


Property Method LCB* LGO HGO Residue
Specific gravity @15.6 °C ASTM D-1298 0.8340 0.8192 0.8480 0.9104
Density @15.6 °C ASTM D-1298 0.8336 0.8188 0.8476 0.9099
API gravity (°C) ASTM D-1298 38 41 35 24
Initial boiling point (°C) ASTM D-86 - 207 279 -
Final boiling point (°C) ASTM D-86 - 338 - -
Flash point (°C) ASTM D-93 - 89 - 124
Pour point (°C) ASTM D-97 18 -9 27 41
Cloud point (°C) ASTM D-2500 - -3 - -
Aniline point (°C) ASTM D-611 - 81 94 -
Total Aromatic (wt %) - 9.27 9.30 -
Cetane index ASTM D-976 - 59 - -
Total sulfur (wt %) ASTM D-4294 0.1393 0.0414 0.1372 0.2532

4
Basic nitrogen (wppm) UOP-313 ND 13 88 ND
ND = not determined *Libyan crudes blend

Table 2 Basic and non basic nitrogen compounds identified in


Libyan crude blend, LGO, HGO and residue
Peak No m/z Identified compounds RT. Min Fraction
1 157 Dimethyl quinoline 12.09 LCB, LGO

2 171 Ethyl-methyl quinoline 13.57 LCB, LGO


3 171 Trimethyl quinoline 14.61 LCB, LGO, HGO
4 159 Trimethyl indole 16.44 LCB, HGO
5 173 Tetramethyl indole 17.07 LCB, HGO, R
6 185 1,2-Dimethyl-5,6-dihydro-4H- 17.56 LCB, LGO, HGO
pyrrolo[3,2,1-ij]quinoline
7 187 Pentamethyl indole 18.52 LCB, LGO, HGO
8 211 7-ethyl-1,2,3,4-tetrahydroacridine 21.45 LCB, LGO
9 213 6-methyl-2-(2-thienyl)-1H-indole 24.83 LCB, LGO
10 207 Ethyl acridine 26.35 all
11 221 Trimethyl benzoisoquinoline 30.01 all
12 251 1,2,3,4,7,8,9,10-octahydro-12-methyl 31.49 LCB, HGO
benzoacridine
13 251 1,2,3,4,8,9,10,11-octahydro-7-methyl 34.17 LCB, HGO
benzoacridine
14 221 2,3,4-trimethyl benzoquinoline 34.83 LCB, HGO
R = Residue RT. Min = Retention time in minutes

Figure 1. Total ion chromatogram of nitrogen compounds in crude blend

Figure 2. Total ion chromatogram of nitrogen compounds in LGO

5
Figure 3. Total ion chromatogram of nitrogen compounds in HGO

Figure 4. Total ion chromatogram of nitrogen compounds in the residue

The identified basic nitrogen compounds in Libyan crudes blend and in its
LGO, HGO and residue were C2- to C3-methyl quinolines, ethyl-methyl
quinoline, ethyl acridine, ethyl hydroacridine, C1-alkyl benzohydroacridine, C2-
alkyl dihydro pyrrolo-quinoline, C3-methyl benzoquinoline and C3-methyl
benzoisoquinoline. The non-basic nitrogen compounds accompanied the
extracted basic nitrogen compounds were indole derivatives; C3- to C5-methyl
indoles and 6-methyl-2-(2-thienyl)-1H-indole.
Figures 5-8 are reproduced mass spectra of C2-methyl, ethyl-methyl and
C3-methyl quinolines and 1,2-dimethyl-5,6-dihydro-4H-pyrrolo[3,2,1-
ij]quinoline; molecular ion peaks of these quinoline derivatives appear at m/z
157, 171, 171 and 185 whilst the base ion peaks appear at m/z 157, 170, 171
and 185 respectively.

Figure 5. Dimethyl quinoline mass spectrum

6
Figure 6. Ethyl-methyl quinoline mass spectrum

Figure 7. Trimethyl quinoline mass spectrum

Figure 8. 1,2-dimethyl-5,6-dihydro-4H-pyrrol[3,2,1-ij]quinoline mass spectrum

Figures 9, 10, 11 and 12 are reproduced mass spectra of substituted alkyl


hydroacridine and alky acridine; these are 7-ethyl-1,2,3,4-tetrahydroacridine,
ethyl acridine, 1,2,3,4,7,8,9,10 - Octahydro - 12- methylbenzoacridine and
1,2,3,4,8,9,10,11- Octahydro -7- methylbenzoacridine; molecular ion peaks
of these hydroacridine and acridine derivatives appear at m/z 211, 207, 251
and 251 whilst the base ion peaks appear at m/z 196, 206, 251 and 251
respectively.

Figure 9. 7-ethyl-1,2,3,4-tetrahydroacridine mass spectrum

7
Figure 10. Ethyl acridine mass spectrum

Figure 11. 1,2,3,4,7,8,9,10-Octahydro-12-methylbenzoacridine mass spectrum

Figure 12. 1,2,3,4,8,9,10,11-Octahydro-7-methylbenzoacridine mass spectrum

Figures 13 and 14 are reproduced mass spectra of both


trimethylbenzoisoquinoline and 2,3,4-trimethylbenzoquinoline the molecular
ion peaks of these two compounds appear at m/z 221 whilst the base ion
peaks appears at m/z 221 for trimethylbenzoisoquinoline and 220 for 2,3,4-
trimethylbenzoquinoline.

Figure 13. Trimethyl benzoisoquinoline mass spectrum

8
Figure 14. 2,3,4-trimethyl benzoquinoline mass spectrum

Non-basic nitrogen compounds are shown in figures 15, 16, 17 and 18 these
are C3, C4 and C5 methyl indole and 6-methyl-2-(2-thienyl)-1H-indole (a non-
basic nitrogen compound containing sulfur), the molecular ion peaks of these
indole derivatives appear at m/z 159, 173, 187 and 213 and the base ion
peaks appear at m/z 158, 173, 186 and 213 respectively.
The mass spectrum of 6-methyl-2-(2-thienyl)-1H-indole shows an M + 2 ion
peak of about 4% of the abundance of the main molecular ion peak that is a
typical of 32
S containing compound.

Figure 15. Trimethyl indole mass spectrum

Figure 16. Tetramethyl indole mass spectrum

Figure 17. Pentamethyl indole mass spectrum

9
Figure 18. 6-methyl-2-(2-thienyl)-1H-indole mass spectrum

The mass spectra of these compounds show a loss of the stable HCN (m/z 27)
neutral molecule; a typical fragmentation pattern of nitrogen compounds.

Conclusion
Basic nitrogen compounds accompanied with some non-basic nitrogen from
Libyan crudes blend and from its LGO, HGO and residue were successfully
separated and identified as well the basic nitrogen content in naphtha,
kerosene, LGO and HGO were quantitatively determined.
The identified basic nitrogen compounds are quinoline, isoquinoline,
benzoquinoline, benzoisoquinoline, acridine, benzohydroacridine and
hydroacridine derivatives and the identified non-basic nitrogen compounds
are indole derivatives.
The identified basic and non-basic nitrogen compounds are thermally
stable through the refining processes of the Libyan crudes blend.
The nitrogen compounds which identified in residue are only trapped
basic nitrogen molecules.
Acknowledgement

We are grateful to Ras Lanuf refinery operation staff for collecting and
providing the samples. The preparation of the reagent by the special analysis
lab of Ras Lanuf is gratefully acknowledged.

Reference

[1] Hartung, G. K., and Jewell, D. M., "Carbazoles, phenazines and


dibenzofuran in petroleum products; methods of isolation, separation and
determination" Analytica Chimica Acta., V. 26, 514-527, 1962.

10
[2] Mao, J., Pacheco, R. C., Traficante, D. D., and Rosen W.,
"Identification and characterization of nitrogen compounds in Brazilian
diesel oil by particle beam I.c.-m.s", Fuel, V. 74, 880-887, 1995.
[3] Poveda Jaramillo, J. C., Molina Velazco, D. R., and Baldrich, C.,
"Semiquantitative analysis of thiophenic compounds in light cycle oil using
13
C NMR spectroscopy", Fuel, V. 83, 337-342, 2004.
[4] Worstell, J. H., Daniel, S. R., and Fruenhoff, G., "Deposit formation in
liquid fuels. The effect of selected nitrogen compounds on diesel fuel",
Fuel, V. 60, 485-487, 1981.
[5] Qi, J., Yan, Y., Fei, W., Su, Y., and Dai, Y., "Solvent extraction of nitrogen
compounds from catalytically cracked diesel oil by metal ion complexation",
Fuel, V. 77, 255-258, 1998.
[6] Furimsky, E., and Massoth, F. E., "Deactivation of hydroprocessing
catalysts ", Catalysis Today, V. 52, 381-495, 1999.
[7] Girgis, M. J., and Gates, B. C., “Reactivities, reaction networks, and
kinetics in high-pressure catalytic hydroprocessing", Ind. Eng. Chem. Res., V.
30, 2021-2058, 1991.
[8] Laredo, C. G., Leyva, S., Ma. A. R., Mares, T., Castillo J., and Luis Cano, J.,
"Nitrogen compounds characterization in atmospheric gas oil and light cycle
oil from a blend of Mexican crudes", Fuel, V. 81, 1341-1350, 2002.
[9] Nagai, M., and Kabe, T., "Selectivity of molybdenum catalyst in
hydrodesulfurization, hydrodenitrogenation, and hydrodeoxygenation: Effect
of additives on dibenzothiophene hydrodesulfurization", Journal of Catalysis,
V. 81, 440-449, 1983.
[10] Odebunmi, E. O., and Ollis, D. F., "Catalytic hydrodeoxygenation:
III. Interactions between catalytic hydrodeoxygenation of m-cresol and
hydrodenitrogenation of indole", Journal of Catalysis, V. 80, 76-89, 1983.
[11] Morrison, T. R., and Boyd, N. R., (1971) "Organic Chemistry", 2 nd edition,
tenth printing., Allyn and Bacon, page 1081.
[12] Yang, S. H., and Satterfield, C. N., "Catalytic hydrodenitrogenation of
quinoline in a trickle-bed reactor. Comparison with vapor phase reaction",
Ind. Eng. Chem. Process. Des. Dev., V. 23, 11-19, 1984.

11
[13] Dong, D., Jeong, S., and Massoth, F. E., "Effectg of nitrogen compounds
on deactivation of hydrotreating catalyst by coke" Catalysis Today, V. 37,
267-275, 1997.
[14] Wiwel, P., Knudsen, K., Zeuthen, P., and Whitehurst, D., "Assessing
compositional changes of nitrogen compounds during hydrotreating of typical
diesel range gas oils using a novel pre concentration technique coupled with
gas chromatography and atomic emission detection", Industrial &
Engineering Chemistry Research, V. 39, 533-540, 2002.
[15] Briker, Y., Ring, Z., Lacchelli, A., McLean, N., "Miniaturized method for
separation and quantification of nitrogen species in petroleum distillate",
Fuel, V. 82, 1621-1631, 2003.
[16] Ellis, J., and Korth, J., "Removal of nitrogen compounds from
hydrotreated shale oil by adsorption on zeolite", Fuel, V. 73, 1569-1573,
1994.
[17] Nwadinigwe, C. A., and Maduka, C. M., "A quantitative assessment of the
classes of nitrogenous compounds in light crudes", Fuel, V. 72, 1139-1143,
1993.
[18] Jewell, D. M., Weber, J. H., Bunger, J. W., Plancher, H., and Latham, D. R.,
"Ion-exchange, coordination, and adsorption chromatographic separation of
heavy-end petroleum distillates", Analytical Chemistry, V. 44, 1391-1395,
1972.
[19] Helm, R. V., Latham, D. R., Ferrin, C.R., and Ball, J. S., "Identification of
carbazole in Wilmington petroleum through use of gas-liquid chromatography
and spectroscopy", Analytical Chemistry, V. 32, 1765-1767, 1960.
[20] Okuno, I., Latham, D. R., and Haines, W. E., "Type analysis of nitrogen in
petroleum using nonaqueous potentiometric titration and lithium aluminum
hydride reduction", Analytical Chemistry, V. 37, 54-57, 1965.
[21] Drobon, M., Bernasconi, C., "Nitrogen compounds in light cycle oils:
identification and consequences of ageing", Fuel, V. 68, 1067-1074, 1989.
[22] Severin, D., and David, T., "Separation and analysis of hetero
compounds from middle distillates", Pet. Sci. Technol., V. 19, 469-479, 2001.
[23] Maowen, Li., Larter, S. R., Stodaart, D., "Liquid chromatography
separation scheme for pyrrole and pyridine nitrogen aromatic heterocycle

12
fractions from crude oils suitable for rapid characterization of geochemical
samples", Analytical Chemistry, V. 64, 1337-1344, 1992.
[24] Schmitter, J. M., Ignatiadis, I., Arpino, P.J., Guiochon, G., " Selective
isolation of nitrogen bases from petroleum", Analytical Chemistry, V. 55,
1685-1688, 1983.
[25] Dorbon M, Ignatiadis I, Schmitter JM, Arpino PJ, Guiochon G, Toulhoat H,
Huc A., "Identification of carbazoles and benzocarbazoles in coker gas oil and
influence of catalytic hydrotreatment on their distribution", Fuel, V. 63, 565-
570, 1984.
[26] Maowen, Li., Bernard, F., Bowler, J., and Larter, S. R., Clegg, H., Wilkes,
H., and Horsfield, B., "Dimethylcarbazoles in crude oils comment on liquid
chromatographic separation schemes for pyrrole and pyridine nitrogen
aromatic heterocycle fractions from crude oils suitable for rapid
characterization of geochemical samples", Analytical Chemistry, V. 69. 3128-
3129, 1997.

13