Since 1930, paraffin dehydrogenation for production of olefins has been used. Eg: catalytic dehydrogenation of butanes by a chromia-alumina catalyst to produce butenes, and in 1980 by Houdry to produce isobutylene from isobutene. However, recent shale boom coupled with increased demand for propene has made on purpose propene production an attractive process to invest in.
Propene from Propane Dehydrogenation
Basic Chemistry
C3 H 8 ⇔ C 3 H 6 + H 2
ΔH0298 = +124 kJ/mol
PDH (propane dehydrogenation process) produces propene through converting
propane into propene in the presence of a catalyst under high temperature. The reaction favours high temperature and low pressure. To mitigate thermal cracking side reactions, it is usually operated between 580 oC to 650oC and slightly below atmospheric pressure.
The average yield of PDH is 85 wt% of propane is converted to propene.
Source of raw material (propane)
Recovered from propane rich-liquefied petroleum gas streams from natural
gas processing plants. Smaller amounts as by-products of petroleum refinery operation from hydrocracking and fluidized catalytic cracking.
Opportunities
Constant growing propylene need and declining propylene supply (mainly
as byproducts) from traditional sources (Fluidised catalytic cracking & olefin cracking) created imbalance in supply and demand. Exploitation of shale gas causes decline in price of propane, the raw material for Propane Dehydrogenation. (currently looking at 1.06 US dollars per Gallon) Decline in propane price increases usage of propane as feedstock in steam crackers. This shift to lighter feedstock produces less propene so it reduces propene availability in the market, making it favorable to use Propane Dehydrogenation. Combination of low-cost propane with high priced propylene creates advantage for on purpose production of propylene through dehydrogenation process Profitability lies heavily on price differential between propane and propene.
Competitors
8 projects announced in US, capacity over 3m tons
According to the forecast from the US Energy Information Administration (EIA), in
2035, about half of the natural gas production in the US will be from shale gas. This, along with the increasing trends in both propylene demand and propane supply, makes the PDH process an attractive chemical route to evaluate, not only in the US, but also in China, where feedstock propane imported from Middle East is available at low prices, allowing attractive margins for PDH processes. Intratec | Technical Analysis Source: US Energy Information Administration (EIA) AOE2012 15
Synthesis Routes 4) Fluidised Bed Dehydrogenation (FBD) from Snamprogetti/Yarsubtez
5) PDH from Linde/BASF
Main differences between the technologies are the type of catalyst and regeneration methods used, reactor design and operating conditions.
‘The purification and reaction section consists of four radial-flow reactors, charge and interstage heaters, and a reactor feed-effluent heat exchanger. It also comprises cooling, compression and drying of reaction effluent as well as the Continuous Catalyst Regenerator (CCR) unit.’
Product recovery Reactor effluent (hydrogen-rich stream) separated from hydrocarbon stream in a cryogenic system to regain 85-93% hydrogen purity. The hydrocarbon liquid stream then undergoes a selective hydrogenation unit to eliminate diolefins and acetylenes. Then, product mixture goes into a deethanizer to remove light hydrocarbons and hydrogen traces from selective hydrogenation in order to create a recycle stream of unreacted propane without impurities back to the reactor.
Finally, propene and propane are separated in the propane-propene splitter, with propene acquired as a vapour and propane as a liquid which gets recycled back to the reactor. Challenges faced
- Energy intensive process due to endothermic nature of dehydrogenation
reaction. - Propane consumption of a PDH plant typically makes up for more than 80% of all operating cost and more than 60% of the cost of production. - Catalyst deactivation caused by coke formation on catalyst surface needs to be burned off with air or oxygen. - Following more and more startup of PDH, price of propylene is likely to decline.
Sustainability
Growing global demand for propene so propene production on purpose
helps fill that gap. Shale gas exploitation in US leads to low feedstock cost. Middle East produces abundance of propane so price differential between propene and propane makes it sustainable.
Safety and Environmental concerns
Operates at high temperature (over 540 oC)
Working with propane and propene which will be flammable. PDH produces H2 as a by-product which can be used as fuel for the propane dehydrogenation reaction. http://www.slideshare.net/intratec/propylene-production-via-propane- dehydrogenation-part-2
