652
The Chemistry and Technology of Petroleum
for regeneration. Typically, during some portions of the year, refinery margins are reduced as a
result of hydrogen shortages.
Multiple hydrotreating units compete for hydrogen—either by selectively reducing throughput,
managing intermediate tankage logistics, or running the catalytic reformer suboptimally just to
satisfy downstream hydrogen requirements. Part of the operating year still runs in hydrogen surplus,
and the network may be operated with relatively low hydrogen utilization (consumption/production)
at 70%–80%. Catalytic reformer off-gas hydrogen supply may swing from 75% to 85% hydrogen
purity. Hydrogen purity upgrade can be achieved through some hydrotreaters by absorbing heavy
hydrocarbons. But without supplemental hydrogen purification, critical control of hydrogen partial
pressure in hydroprocessing reactors is difficult, which can affect catalyst life, charge rates, and/or
gasoline yields.
More complex refineries, especially those with hydrocracking units, also have on-purpose hydrogen production, typically with a steam–methane reformer that utilizes refinery off-gas and supplemental natural gas as feedstock. The steam–methane reformer plant provides the swing hydrogen
requirements at higher purities (92% to more than 99% hydrogen) and serves a hydrogen network
configured with several purity and pressure levels. Multiple purities and existing purification units
allow for more optimized hydroprocessing operation by controlling hydrogen partial pressure for
maximum benefit. Typical hydrogen utilization is 85%–95%.
REFERENCES
Al-Shamma, L.M. and Naman, S.A. 1989. Kinetic study for thermal production of hydrogen from hydrogen sulfide by heterogeneous catalysis of vanadium sulfide in a flow system. International Journal of
Hydrogen Energy 14(3): 173–179.
Arild, V. 2000. Production of hydrogen and carbon with a carbon black catalyst. PCT Int. Appl. No. 0021878.
Balasubramanian, B., Ortiz, A.L., Kaytakoglu, S., and Harrison, D.P. 1999. Hydrogen from methane in a
single-step process. Chemical Engineering Science 54: 3543–3552.
Bandermann, F. and Harder, K.B. 1982. Production of hydrogen via thermal decomposition of hydrogen sulfide
and separation of hydrogen and hydrogen sulfide by pressure swing adsorption. International Journal of
Hydrogen Energy 7(6): 471–475.
Bezler, J. 2003. Optimized hydrogen production—A key process becoming increasingly important in refineries. Proceedings of DGMK Conference on Innovation in the Manufacture and Use of Hydrogen, Dresden,
Germany, October 15–17, p. 65.
Bishara, A., Salman, O.S., Khraishi, N., and Marafi, A. 1987. Thermochemical decomposition of hydrogen
sulfide by solar energy. International Journal of Hydrogen Energy 12(10): 679–685.
Brandmair, M., Find, J., and Lercher, J.A. 2003. Combined autothermal reforming and hydrogenolysis of
alkanes. Proceedings of DGMK Conference on Innovation in the Manufacture and Use of Hydrogen,
Dresden, Germany, October 15–17, pp. 273–280.
Bridge, A.G. 1997. In Handbook of Petroleum Refining Processes, 2nd edn., R.A. Meyers (Ed.). McGraw-Hill,
New York, Chapter 14.1.
Brüschke, H. 1995. Industrial application of membrane separation processes. Pure and Applied Chemistry
67(6): 993–1002.
Brüschke, H. 2003. Separation of hydrogen from dilute streams (e.g. using membranes). Proceedings of DGMK
Conference on Innovation in the Manufacture and Use of Hydrogen, Dresden, Germany, October 15–17, p. 47.
Campbell, W.M. 1997. In Handbook of Petroleum Refining Processes, 2nd edn., R.A. Meyers (Ed.). McGrawHill, New York, Chapter 6.1.
Clark, P.D., Dowling, N.I., Hyne, J.B., and Moon, D.L. 1995. Production of hydrogen and sulfur from hydrogen sulfide in refineries and gas processing plants. Quarterly Bulletin (Alberta Sulfur Research Ltd.),
32(1): 11–28.
Clark, P.D. and Wassink, B. 1990. A review of methods for the conversion of hydrogen sulfide to sulfur and
hydrogen. Alberta Sulfur Research Quarterly Bulletin 26(2/3/4): 1.
Dahl, J. and Weimer, A.W. 2001. Preprints. Division of Fuel Chemistry American Chemical Society 221.
Dalrymple, D.A., Trofe, T.W., and Leppin, D. 1994. Gas industry assesses new ways to remove small amounts
of hydrogen sulfide. Oil & Gas Journal May 23.
Davis, R.A. and Patel, N.M. 2004. Petroleum Technology Quarterly, Spring: 28–35.
The Chemistry and Technology of Petroleum
for regeneration. Typically, during some portions of the year, refinery margins are reduced as a
result of hydrogen shortages.
Multiple hydrotreating units compete for hydrogen—either by selectively reducing throughput,
managing intermediate tankage logistics, or running the catalytic reformer suboptimally just to
satisfy downstream hydrogen requirements. Part of the operating year still runs in hydrogen surplus,
and the network may be operated with relatively low hydrogen utilization (consumption/production)
at 70%–80%. Catalytic reformer off-gas hydrogen supply may swing from 75% to 85% hydrogen
purity. Hydrogen purity upgrade can be achieved through some hydrotreaters by absorbing heavy
hydrocarbons. But without supplemental hydrogen purification, critical control of hydrogen partial
pressure in hydroprocessing reactors is difficult, which can affect catalyst life, charge rates, and/or
gasoline yields.
More complex refineries, especially those with hydrocracking units, also have on-purpose hydrogen production, typically with a steam–methane reformer that utilizes refinery off-gas and supplemental natural gas as feedstock. The steam–methane reformer plant provides the swing hydrogen
requirements at higher purities (92% to more than 99% hydrogen) and serves a hydrogen network
configured with several purity and pressure levels. Multiple purities and existing purification units
allow for more optimized hydroprocessing operation by controlling hydrogen partial pressure for
maximum benefit. Typical hydrogen utilization is 85%–95%.
REFERENCES
Al-Shamma, L.M. and Naman, S.A. 1989. Kinetic study for thermal production of hydrogen from hydrogen sulfide by heterogeneous catalysis of vanadium sulfide in a flow system. International Journal of
Hydrogen Energy 14(3): 173–179.
Arild, V. 2000. Production of hydrogen and carbon with a carbon black catalyst. PCT Int. Appl. No. 0021878.
Balasubramanian, B., Ortiz, A.L., Kaytakoglu, S., and Harrison, D.P. 1999. Hydrogen from methane in a
single-step process. Chemical Engineering Science 54: 3543–3552.
Bandermann, F. and Harder, K.B. 1982. Production of hydrogen via thermal decomposition of hydrogen sulfide
and separation of hydrogen and hydrogen sulfide by pressure swing adsorption. International Journal of
Hydrogen Energy 7(6): 471–475.
Bezler, J. 2003. Optimized hydrogen production—A key process becoming increasingly important in refineries. Proceedings of DGMK Conference on Innovation in the Manufacture and Use of Hydrogen, Dresden,
Germany, October 15–17, p. 65.
Bishara, A., Salman, O.S., Khraishi, N., and Marafi, A. 1987. Thermochemical decomposition of hydrogen
sulfide by solar energy. International Journal of Hydrogen Energy 12(10): 679–685.
Brandmair, M., Find, J., and Lercher, J.A. 2003. Combined autothermal reforming and hydrogenolysis of
alkanes. Proceedings of DGMK Conference on Innovation in the Manufacture and Use of Hydrogen,
Dresden, Germany, October 15–17, pp. 273–280.
Bridge, A.G. 1997. In Handbook of Petroleum Refining Processes, 2nd edn., R.A. Meyers (Ed.). McGraw-Hill,
New York, Chapter 14.1.
Brüschke, H. 1995. Industrial application of membrane separation processes. Pure and Applied Chemistry
67(6): 993–1002.
Brüschke, H. 2003. Separation of hydrogen from dilute streams (e.g. using membranes). Proceedings of DGMK
Conference on Innovation in the Manufacture and Use of Hydrogen, Dresden, Germany, October 15–17, p. 47.
Campbell, W.M. 1997. In Handbook of Petroleum Refining Processes, 2nd edn., R.A. Meyers (Ed.). McGrawHill, New York, Chapter 6.1.
Clark, P.D., Dowling, N.I., Hyne, J.B., and Moon, D.L. 1995. Production of hydrogen and sulfur from hydrogen sulfide in refineries and gas processing plants. Quarterly Bulletin (Alberta Sulfur Research Ltd.),
32(1): 11–28.
Clark, P.D. and Wassink, B. 1990. A review of methods for the conversion of hydrogen sulfide to sulfur and
hydrogen. Alberta Sulfur Research Quarterly Bulletin 26(2/3/4): 1.
Dahl, J. and Weimer, A.W. 2001. Preprints. Division of Fuel Chemistry American Chemical Society 221.
Dalrymple, D.A., Trofe, T.W., and Leppin, D. 1994. Gas industry assesses new ways to remove small amounts
of hydrogen sulfide. Oil & Gas Journal May 23.
Davis, R.A. and Patel, N.M. 2004. Petroleum Technology Quarterly, Spring: 28–35.