Nanotechnology Role for the Production of Clean Fuel E-85 and Petrochemical Raw Materials

Basily, Iskander K.; Shafik, Amira L.; Sarhan, Ali A.; Mohamed, Mona B.

doi:https://doi.org/10.1155/2012/439531

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Abstract Introduction Experimental Materials Discussion Conclusion Acknowledgments References Copyright Related Articles

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Nanomaterials for Energy Production and Storage

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Research Article | Open Access

Volume 2012 | Article ID 439531 | https://doi.org/10.1155/2012/439531

Nanotechnology Role for the Production of Clean Fuel E-85 and Petrochemical Raw Materials

Iskander K. Basily,¹Amira L. Shafik,¹Ali A. Sarhan,¹and Mona B. Mohamed²

Academic Editor: Vaishali R. Shinde

Received21 Jan 2012

Revised14 Apr 2012

Accepted17 Apr 2012

Published20 Jun 2012

Abstract

There have been a number of substantive technical changes that can be described as revolutionary process and evolutionary process. One of these approaches is the use of nanotechnology in the two-stage pyrolysis of petroleum residues of the heavy distillates separated from the Arabian crude oil. Two-stage catalytic pyrolysis technique proved to be an excellent method for the production of unsaturated hydrocarbons (which easily can be converted to alcohol, by addition of H₂O, for the production of E-85, i.e., clean fuel) regardless the type of feed stocks used. Basically, the catalysts are arranged into three large groups; amorphous and crystalline alumino-silicates, alkaline or alkaline earth alumino compounds, and different metal oxides on different catalyst carriers such as Zeolites. The high yield of ethylene (30–40%) brought by different catalysts at temperatures of 700–750°C appear to justify the intensive research work in this field.

1. Introduction

Upgrading of heavy ends for the manufacture of olefins is the main aim of the refineries today. Production of fuel-grade distillate from petroleum residues is a profitable operation for refineries provided that they have necessary technology available. Any processing to convert heavy ends into refined distillates should somewhere include a hydrogen addition step, heteroatom removal step. However, in the two-stage pyrolysis technique, the feed stock can be used without any pretreatment [1–8], regardless of the type of the feed stock used (contaminants are left as pyrolysis residue at the first stage) and the pyrolyzate as then contains high percentage of ethylene and propylene (≈37 wt. % unsaturated) using the normal catalyst. However, when we used the nanocatalyst in the two-stage pyrolysis technique, the unsaturated hydrocarbons reaches ≈85 wt. % in the pyrolyzate yield (i.e., the creative technology is the best protection against uncertainties of the future). Nowadays, scientists do their best to find new sources for clean energy (as the uses of alcohol as it is or as a blend with gasoline 15 vol. % to form E-85).

2. Aim of the Present Work

Obtain unsaturated hydrocarbons from petroleum residues with the help of different types of nanocatalyst and computer program to optimize the pyrolysis parameters of the two-stage reactor.

3. Experimental

An experimental study has been carried out of the effectiveness of some catalysts on the yield and product distribution of the two-stage pyrolysis process. Two topics are discussed.

The first topic is the effectiveness of CaO catalyst on the yield and product distribution of the two-stage pyrolysis of gas-oil, with the intention of the producing ethylene and propylene.

The second topic deals with the two-stage catalytic pyrolysis of light distillates separated from Egyptian crude using nanocatalyst. These catalysts were prepared by different shapes.

Bimetallic colloids can be prepared by simultaneous reduction of two kinds of metal ions with or without the protecting agent or by successive reduction of one metal nuclei of the other.

4. Materials

(A) The feed-stock fraction is the gas-oil supplied by Cairo-Petroleum-Refining and used as it is without pretreatment.(B) The (CaO) catalyst used has been supplied by “Union Carbide”—Tarrytown Technical Center—and composed of Ca⁺⁺ (30-511) Lot number 3358-16, however, the gold nanocatalyst supported on the CaO catalyst and used as powder was supplied by “National Institute Laser Science” (NILES).

5. Procedure

The pyrolysis has been carried out using a batch-type apparatus. A quartz reactor tube (22 mm, 12 mm I'd) was placed horizontally through two separate electric furnaces, and the temperature was controlled by adjusting the electric current of the heaters. Quartz boat containing 0.2 gm of the feed-stock (Gas-Oil) with 1.5 gm of nickel sheet was inserted into the lower -temperature zone with the help of a quartz tube through which argon gas was allowed to flow. The cracked oil and gases produced at the first stage (200–400°C ±5°C) were carried to the second stage (325–500°C ±5°C) by the argon gas to undergo subsequent pyrolysis under the influence of the catalysts bed used.

A fixed catalyst bed was placed in the second stage by packing the catalyst in layers supported by a quartz wool plug. After a lapse of certain reaction time, the quartz boat is removed, cooled, and weighed to determine the amount of the pyrolyzed residue. The produced gases were collected in a gas burette. The optimum contact tine of the first stage from different experiments was found to be 15 min (the contact time of the feed-stock with the nickel catalyst in the first stage, low-temperature reaction zone). The second stage contact time varied (2.6–3.4 sec).

The pyrolyzate hydrocarbons were analyzed using Gas Chromatography (GC-mass): Agilent 6890 plus Gas chromatograph under the following conditions:

Detector: FID 250°C

Injector: split 1 : 20 250°C, 0.5 mL

Carrier: Ar 3 mL/min.

5°C/min

Oven: 50 → 200.

6. Result and Discussion

The influence of the first stage temperature () in the distribution of hydrocarbon pyrolyzate using gold (Au) nanoparticles as spheres supported on (Cao) catalyst has been illustrated in Figure 1, and the mathematical expressions for the yield of unsaturated hydrocarbons were given for each of the following:

The influence of the second stage temperature () on the distribution of hydrocarbon pyrolyzate using the gold (Au) nanoparticles as spheres supported on the CaO catalyst has been illustrated in Figure 2, and the mathematical expressions for the yield of unsaturated hydrocarbons were given for each of the following:

The influence of the first stage contact time () on the distribution of hydrocarbon pyrolyzate using the gold (Au) nanoparticles as spheres supported on the CaO catalyst has been illustrated in Figure 3, and the mathematical expressions for the yield of unsaturated hydrocarbons were given for each of the following:

The influence of the second stage contact time () on the distribution of hydrocarbon pyrolyzate using the gold (Au) nanoparticles as spheres supported on the CaO catalyst has been illustrated in Figure 4, and the mathematical expressions for the yield of unsaturated hydrocarbons were given for each of the following:

The influence of the catalyst to oil () ratio on the distribution of hydrocarbons pyrolyzate using the gold (Au) nanoparticles as spheres supported on the CaO catalyst has been illustrated in Figure 5, and the mathematical expressions for the yield of unsaturated hydrocarbons were given for each of the following:

Studying the effect of shape of the gold (Au) between (rods, prisms, and spheres) [9–20] nanoparticles supported on CaO catalyst on the distribution of hydrocarbon pyrolyzate produced from two-stage catalytic pyrolysis of the feed stock fraction separated from Egyptian crude oil under the same optimum conditions at which the maximum yield of unsaturated hydrocarbons produced from two-stage catalytic pyrolysis of feed stock fraction using Au-nanoparticles; , , min., sec., cat/oil ratio 1 : 15, it was found that the rod shape nanoparticles have the highest catalytic activity than nanoprisms and nanospheres, that may be due to the presence of different crystalline facets (110) which is absent in nanoshheres and nanoprisms, this facet has higher catalytic properties than others and give the highest yield for total unsaturated hydrocarbons (85.22 wt. %), mainly ethylene (79.41 wt. %) and propylene (5.8 wt. %), while the total unsaturated hydrocarbons using nanoprisms yield 62.28 wt. %, mainly ethylene (51.75 wt. %), and propylene (10.53 wt. %). This confirms that the nanocatalyst with the rod shape is the optimum condition for ethylene production.

Studying the effect of using Pd-Au core-shell and alloy [17, 20–31], supported on the Cao catalyst on the distribution of the hydrocarbon pyrolyzate produced from two-stage catalytic pyrolysis of the feed stock fraction separated from Egyptian crude oil under the same last optimum conditions, with pear in mind that Palladium is used as a catalyst in hydrogenation reactions, when we use Pd-nanoparticles as a core in the catalytic pyrolysis, the total yield of unsaturated hydrocarbons will decrease and give yield (59.48 wt. %) total unsaturated hydrocarbons, mainly ethylene (51 wt. %), and propylene (8.48 wt. %), but the presence of palladium on the surface increases the rate of hydrogenation, contrary to down falling to the yield of the total unsaturated hydrocarbons to give 48.15 wt. %, mainly ethylene (40.2 wt. %), and propylene (7.95 wt. %), and increases the yield of ethane to reach 33.59 wt. % corresponding to 23.17 wt. % of ethane using Pd-Au core-shell.

7. Conclusion

It was found that the maximum yield of unsaturated hydrocarbons using the first catalyst (CaO) is about 54 wt. %, mainly hexene gives 29 wt. %, 12 wt. % ethylene, 12 wt. % aromatics, and ~1 wt. % propylene at the following conditions: , , min, sec and cat/oil ratio () 1 : 25, but by using the gold (Au) nanoparticles supported on the first catalyst, the maximum yield of unsaturated hydrocarbon is about 53 wt. %, mainly 45 wt. % ethylene and 8 wt. % propylene, only without aromatics at the following conditions: , , min, sec, and cat/oil () ratio 1 : 15, so Au-nanoparticles seem to be very selective to these reactions.

The Au nanocatalyst with rods shape gives the maximum yield of ethylene (which can be converted easily to ethyl alcohols which is used as E-85 clean fuel) from petroleum residues.

Acknowledgments

The authors would like to thank Professor Yehya Badr (Chairman of National institute of laser research) for financial support; they also thank Professor Ashraf El-Naggar for the support and discussions for the GC-mass spectrometer.

References

I. K. Basily, S. T. El-Shaltawy, and B. S. Mostafa, “The catalytic pyrolysis of the Egyptian bitumen for industrial production raw material,” Journal of Analytical and Applied Pyrolysis, vol. 76, no. 1-2, pp. 24–31, 2006.
View at: Publisher Site | Google Scholar
I. K. Basily and K. Thamer, “Pyrolysis products dependence on the nature of heavy hydrocarbon feedstock,” Applied Catalysis, vol. 73, pp. 125–133, 1991.
View at: Publisher Site | Google Scholar
I. K. Basily and N. N. Ibraheam, “Two-stage pyrolysis of heavy residues: feedstock versus yield,” Fuel, vol. 72, no. 2, pp. 161–164, 1993.
View at: Google Scholar
M. Itoh, T. Suzuki, Y. Tsujimoto, K. I. Yoshii, Y. Takegami, and Y. Watanabe, “Two-stage pyrolysis of heavy oils. 3. Pyrolysis of tar-sand bitumens. Relation between ethylene yield and structural characteristics of heavy oils,” Fuel, vol. 62, no. 1, pp. 98–102, 1983.
View at: Google Scholar
I. K. Basily, E. Souaya, and N. N. Ibraheem, “Gas-liquid chromatographic determination of the gaseous products of the two-stage pyrolysis of heavy oils,” Microchemical Journal, vol. 38, no. 3, pp. 283–294, 1988.
View at: Google Scholar
I. K. Basily, E. Ahmed, and N. Nashed, “Factors affecting the yields produced from the two-stage pyrolysis of Egyptian bitumen,” Journal of Analytical and Applied Pyrolysis, vol. 17, no. 2, pp. 153–167, 1990.
View at: Google Scholar
I. K. Basily, “Metal-catalyzed two-stage pyrolysis 2. Role of different catalysts in the production and composition of ethylene/propylene-enriched gases,” Journal of Analytical and Applied Pyrolysis, vol. 32, pp. 213–219, 1995.
View at: Publisher Site | Google Scholar
I. K. Basily, E. Ahmed, and N. N. Ibraheam, “Upgrading heavy ends into marketable products. New concepts and new catalysts for two-stage catalytic pyrolysis,” Journal of Analytical and Applied Pyrolysis, vol. 32, pp. 221–232, 1995.
View at: Google Scholar
I. Hussain, S. Graham, Z. Wang et al., “Size-controlled synthesis of near-monodisperse gold nanoparticles in the 1–4 nm range using polymeric stabilizers,” Journal of the American Chemical Society, vol. 127, no. 47, pp. 16398–16399, 2005.
View at: Publisher Site | Google Scholar
J. H. Chen, J.-N. Lin, Y. M. Kang, W. Y. Yu, C. N. Kuo, and B. Z. Wan, “Preparation of nano-gold in zeolites for CO oxidation: effects of structures and number of ion exchange sites of zeolites,” Applied Catalysis A, vol. 291, no. 1-2, pp. 162–169, 2005.
View at: Publisher Site | Google Scholar
J.-N. Lin and B.-Z. Wan, “Effects of preparation conditions on gold/Y-type zeolite for CO oxidation,” Applied Catalysis B, vol. 41, no. 1-2, pp. 83–95, 2003.
View at: Publisher Site | Google Scholar
M. Tréguer-Delapierre, J. Majimel, S. Mornet, E. Duguet, and S. Ravaine, “Synthesis of non-spherical gold nanoparticles,” Gold Bulletin, vol. 41, no. 2, pp. 195–207, 2008.
View at: Google Scholar
G. C. Bond, C. Louis, and D. T. Thompson, Catalysis by Gold, vol. 6 of Catalytic Science Series, 2006.
View at: Publisher Site
C. J. Murphy, T. K. Sau, A. M. Gole et al., “Anisotropic metal nanoparticles: synthesis, assembly, and optical applications,” The Journal of Physical Chemistry B, vol. 109, no. 29, pp. 13857–13870, 2005.
View at: Publisher Site | Google Scholar
J. Perez-Juste, I. Pastariza-Santos, L. Liz-Marzan, and P. Mulvaney, “Gold nanorods: synthesis, characterization and applications,” Coordination Chemistry Reviews, vol. 249, no. 17-18, pp. 1870–1901, 2005.
View at: Publisher Site | Google Scholar
S. Link and M. El-Sayed, “Shape and size dependence of radiative, non-radiative and photothermal properties of gold nanocrystals,” International Reviews in Physical Chemistry, vol. 19, no. 3, pp. 409–453, 2000.
View at: Publisher Site | Google Scholar
M. S. Chen and D. W. Goodman, “Structure-activity relationships in supported Au catalysts,” Catalysis Today, vol. 111, no. 1-2, pp. 22–33, 2006.
View at: Publisher Site | Google Scholar
R. Narayanan and M. A. El-Sayed, “Shape-dependent catalytic activity of platinum nanoparticles in colloidal solution,” Nano Letters, vol. 4, no. 7, pp. 1343–1348, 2004.
View at: Publisher Site | Google Scholar
M. Ahmadpour and N. Mostoufi, “Catalyst wetting efficiency in trickle-bed reactors at high pressure,” Chemical Engineering Science, vol. 50, no. 15, pp. 2377–2389, 1995.
View at: Publisher Site | Google Scholar
R. S. Sonawane and M. K. Dongare, “Sol-gel synthesis of Au/TiO₂ thin films for photocatalytic degradation of phenol in sunlight,” Journal of Molecular Catalysis A, vol. 243, no. 1, pp. 68–76, 2006.
View at: Publisher Site | Google Scholar
M. Haruta and M. Date, “Advances in the catalysis of Au nanoparticles,” Applied Catalysis A, vol. 222, no. 1-2, pp. 427–437, 2001.
View at: Publisher Site | Google Scholar
Y. Lizuka, T. Tode, T. Takao et al., “A kinetic and adsorption study of CO oxidation over unsupported fine gold powder and over gold supported on titanium dioxide,” Journal of Catalysis, vol. 187, no. 1, pp. 50–58, 1999.
View at: Publisher Site | Google Scholar
M. M. Schubert, S. Hackenberg, A. C. Van Veen, M. Muhler, R. J. Behm, and V. Plzak, “CO oxidation over supported gold catalysts—“Inert” and “active” support materials and their role for the oxygen supply during reaction,” Journal of Catalysis, vol. 197, no. 1, pp. 113–122, 2001.
View at: Publisher Site | Google Scholar
J. Chou, N. R. Franklin, S. H. Beack, T. M. Jaramillo, and E. W. McFarland, “Gas-phase catalysis by micelle derived Au nanoparticles on oxide supports,” Catalysis Letters, vol. 95, no. 3–5, pp. 107–111, 2004.
View at: Publisher Site | Google Scholar
S. H. Overbury, L. Ortiz-Soto, H. G. Zhu, B. Lee, S. Dai, and M. D. Amiridis, “Comparison of Au catalysts supported on mesoporous titania and silica: investigation of Au particle size effects and metal-support interactions,” Catalysis Letters, vol. 95, no. 3-4, pp. 99–106, 2004.
View at: Publisher Site | Google Scholar
B. Hammer and J. K. Norskov, “Why gold is the noblest of all the metals,” Nature, vol. 376, no. 6537, pp. 238–240, 1995.
View at: Google Scholar
V. Subramanian, E. E. Wolf, and P. V. Kamat, “Catalysis with TiO₂/gold nanocomposites. effect of metal particle size on the fermi level equilibration,” Journal of the American Chemical Society, vol. 126, no. 15, pp. 4943–4950, 2004.
View at: Publisher Site | Google Scholar
C. Wang, C. Kan, J. Zhu et al., “Synthesis of high-yield gold nanoplates: fast growth assistant with binary surfactants,” Journal of Nanomaterials, vol. 2010, Article ID 969030, 2010.
View at: Publisher Site | Google Scholar
J. P. Deng, C. Wu, C. H. Yang, and C. Y. Mou, “Pyrene-assisted synthesis of size-controlled gold nanoparticles in sodium dodecyl sulfate micelles,” Langmuir, vol. 21, no. 19, pp. 8947–8951, 2005.
View at: Publisher Site | Google Scholar
S. Schimpf, M. Lucas, C. Mohr et al., “Supported gold nanoparticles: in-depth catalyst characterization and application in hydrogenation and oxidation reactions,” Catalysis Today, vol. 72, no. 1-2, pp. 63–78, 2002.
View at: Publisher Site | Google Scholar
G. Walther, D. J. Mowbray, T. Jiang et al., “Oxidation of CO and H₂ by O₂ and N₂O on Au/TiO₂ catalysts in microreactors,” Journal of Catalysis, vol. 260, no. 1, pp. 86–92, 2008.
View at: Publisher Site | Google Scholar

Copyright

Copyright © 2012 Iskander K. Basily et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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