Introduction

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
H0298 = +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

China building PDH plants, 11 confirmed.

https://sites.google.com/a/intratec.us/intratec-base/home/chemicalprocesses/propylene/propylene-from-propane-via-dehydrogenation-2

Economics advantages
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.

http://www.digitalrefining.com/data/articles/file/221969204.pdf
http://www.cbi.com/images/uploads/tech_sheets/CatofinDehyrogenation-12.pdf

For UOP oleflex,

Purification and reaction
http://base.intratec.us/home/chemical-processes/propylene/propylene-frompropane-via-dehydrogenation
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
http://www.digitalrefining.com/data/articles/file/221969204.pdf
-

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-propanedehydrogenation-part-2

http://www.propylene-propane-markets-2014.com/media/downloads/8-day-onemathew-george-head-of-exports-indian-oil.pdf
http://flowexpertblog.com/2012/11/23/propane-dehydrogenation-part-1-marketsand-prospects/