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H
ydrogen plays a critical
role in the production 5.0
of clean fuels, and its
use has increased with the 4.0
Sulphur, wt% max
introduction of low-sulphur
gasoline and diesel fuels. The
3.0 Global
reduction of benzene in gaso-
Global delayed
line via benzene saturation will
also increase hydrogen 2.0 ECA
consumption, as will the trend
toward diesel cetane improve- 1.0
ment and aromatics reduction.
Changes in marine fuel oil
specifications are also expected 0.0
2005 2010 2015 2020 2025 2030
to increase hydrogen demand.
In 2008, MARPOL Annex VI
regulations were passed, setting Figure 1 Bunker fuel oil sulphur specifications
a framework for regional and
global specifications on marine contaminant levels (sulphur
fuel oil quality. These regula- and nitrogen) than the equiva-
tions are expected to further lent straight-run streams.
increase the demand for hydro- Catalyst Hydrotreating these coker
Utilities 1% Hydrogen
gen for desulphurising residual 84% products has also increased
15%
fuel oils and, through the hydrogen consumption.
increase in distillate fuel Hydrocracking has become
demand, to replace residual increasingly important for
fuel oil in marine fuels (see converting heavier crude frac-
Figure 1). tions into high-quality clean
The overall reduction in fuels. Increased reliance on
demand for heavy fuel oils has hydrocracking for clean fuels
encouraged many refiners to production has also led to a
install bottoms upgrading rise in hydrogen consumption.
capacity such as delayed coking A hydrocracking unit is typi-
units. The streams produced by Figure 2 Typical hydrocracker cally the largest hydrogen
coking typically contain higher operating costs consumer in the refinery, and
A P I gr a v i t y
legislation may regulate the
amount of CO2 that can be
generated and may increase the
costs of hydrogen production.
Availability of hydrogen is a
requirement for the production
of clean fuels, and demand for
hydrogen is at an all time high.
Anticipated future trends and
Figure 3 Global crude quality regulations are expected to
further increase hydrogen
hydrogen can account for more lower severity operation is in consumption. At the same time,
than 80% of the units operat- opposition to the increased the production of additional
ing cost (see Figure 2). demand for hydrogen in the hydrogen is expected to become
The quality of crude oil is rest of the refinery and compels more expensive.
gradually declining. Globally, the refiner to obtain hydrogen While it is well understood
crude API gravity is declining from other sources. Some refin- that the ability of a refiner to
and the sulphur content is ers have decided to operate produce clean fuels depends on
gradually increasing (see Figure their catalytic reformer for having sufficient hydrogen,
3). Both of these trends in crude hydrogen production and toler- what many refiners recognise
quality will contribute to ate some octane giveaway in is that optimum use of hydro-
increased hydrogen consump- the gasoline pool. gen will maximise refinery
tion during refining. The use of Many refiners produce or profits.
synthetic crudes derived from purchase hydrogen to have a
oil sands and other unconven- sufficient supply available for Hydrogen network analysis and
tional sources is expected to their refinery. The steam improvements
increase to 2 million b/d by reforming (SR) process is used Refinery hydrogen networks
2020. These synthetic crudes to produce most of the addi- typically interconnect many
will require additional hydro- tional hydrogen required by producers, consumers and
gen to be refined into usable refiners. The cost of the purification units with different
products. hydrogen produced is directly pressures, purities and operat-
One of the major sources of proportional to the feed costs. ing objectives. The network
hydrogen and gasoline pool In the US, most of the hydro- grows with each subsequent
octane is the catalytic reformer. gen is produced in steam refinery project, modified in
The blending of ethanol has methane reforming (SMR) units ways that minimise complexity
reduced the octane require- and the cost is typically tied to and the interruption of existing
ments from other refinery the price of natural gas. units rather than for refinery-
product streams to maintain The production of hydrogen wide optimisation. Hydrogen
the gasoline pool octane; often, by a steam reformer requires production costs and
refiners respond to this situa- significant energy; one tonne of constraints on availability are
tion by reducing the catalytic hydrogen produced requires typically much greater than
reformers severity to produce 3.5 to 4 tonnes of hydrocarbons when the network was first
a lower-octane reformate prod- as feed and fuel. Hydrogen envisioned. All of these factors
uct. However, a lower catalytic production can account for up lead to the conclusion that most
reformer severity typically to 20% of refinery energy operating hydrogen networks
produces less hydrogen. Lower consumption. Additionally, the are not optimised for todays
hydrogen production from a production of hydrogen gener- environment not for the
Catalyst
2%
Change
H2 partial flow piping
pressure 5%
12% Control
improvements
3%
No/low cost
34% Purification
38%
Figure 4 Typical results: summary of benefits was $137 million/y in seven studies
envelope even further, it is one PSA unit. It is possible to potential financial benefits will
possible to consider optimising integrate the two systems also be a function of the value
more than just the hydrogen together by designing a single of hydrogen in a refinery. The
system at one time. There are PSA unit that takes both hydro- potential benefit of improve-
often additional benefits when gen streams as its feed and ments in process performance
several systems are optimised sending the PSA unit tail gas to through hydrogen optimisation
together. For example, when the LPG recovery system in the can be estimated roughly by
designing a refining complex hydrocracker. Since the PSA evaluating current constraints
with new catalytic reforming unit concentrates LPG in the to process performance, refin-
and hydrocracking units, it is tail gas, recovering the LPG ery drivers and refinery
possible to consider the hydro- from the tail gas in the hydroc- economics. Our hydrogen
gen and LPG recovery systems racker recovery system requires management studies generally
at the same time. As standalone less energy and capital than if identify $2 million to $20
designs, each unit would have it was recovered separately in million in annual benefits.
its own LPG recovery system the reformer. An additional In seven studies, UOP identi-
and produce moderate- purity benefit of the integration is that fied a total of $137 million in
hydrogen to be purified/recov- a PSA unit product bypass can annual benefits. A third of the
ered (reformer net gas and now be integrated with the opportunities identified were
hydrocracker flash gas). The hydrocracker to enable optimi- no/low-cost changes and the
reformer net gas contains the sation of the hydrocracker remainder required capital
recoverable LPG and hydrogen, make-up purity a degree of projects (all with a simple
while the recoverable hydrogen freedom that would not other- payback of less than two years).
and LPG are found in the purge wise exist. While 38% of the opportunities
and flash gas streams of the for improvement came from
hydrocracker. Hydrogen network adding or improving hydrogen
LPG recovery is much more improvements purification capacity, a much
efficient in the hydrocracker The potential for improving broader scope of evaluation is
than in the reformer because hydrogen efficiency is esti- required to achieve these bene-
the gas stream has a lower mated by evaluating the fits. Operating changes and
hydrogen concentration. Also, hydrogen-containing streams better management of hydro-
it is more cost effective to proc- currently going to fuel, flare gen partial pressure targets
ess both hydrogen streams in and hydrogen plant feed. The were important, as well as
30
and the low-pressure flash
25 gases of the RDS unit. The
Product
20 high-pressure vent gas was
15 scrubbed of H2S and throttled
10 Tail gas down to the steam reformers
5
PSA2 feed pressure, and the low-
PSA1 pressure vent was compressed
0
1 3 5 7 9 11 13 15 17 19 21 23 1 3 5 7 9 11
to match the steam reformers
Time of day, hours feed pressure. Figure 6 shows
the overall flow scheme.
Various revamps have taken
Figure 5 Comparison of two identical PSA units loaded with different adsorbents place to meet the refinerys
increasing needs for hydrogen
between adsorbent layers. This improvements as trends over the years (see Table 2).
presented an opportunity to recorded by the distributed
replace the existing adsorbent control system. The new Phase 2: first revamp of steam
with higher-performance adsorbents in PSA1 enabled it reformer PSA
adsorbent to provide higher to produce more hydrogen The first plant expansion saw
recovery and capacity. from the same or less feed. total hydrogen production
After reloading with higher- increased from 55 million scfd
performance adsorbents, the Case study 2: phased revamps to 70 million scfd. The initial
previously identical PSA1 and A large residuum desulphuri- capacity increase was achieved
PSA2 units for their respective sation (RDS) facility in the through debottlenecking of the
SMR units were in operation Americas was designed using steam reformer and SMR PSA
side-by-side with advanced hydrogen make-up from a unit to increase hydrogen
and original adsorbents in steam reformer hydrogen plant output by 18% from 55 million
service. PSA1 demonstrated a with a product flow of 55 scfd to 65 million scfd. The
capacity increase of 10% over million scfd. The hydrogen SMR PSA units debottleneck-
the original adsorbent (still plant employed a large ten-bed ing was achieved through a
installed in PSA2) as well as a PSA unit that removed essen- process redesign and changes
2% increase in hydrogen tially all impurities, including to the control system software,
recovery. nitrogen, from the steam with essentially no hardware
Figure 5 shows these reformers effluent. modifications. Reducing the
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