Fuel Sulfur Solutions Page 1 of 3

Fuels for the 21st Century

Changing Fuel Sulfur Solutions

regulations about
fuel sulfur have Within the next few years, European and U.S.
refiners concerned governmental regulations will require refiners to
about what might be significantly lower the sulfur content of gasoline as part
needed to meet them. of the continuing effort to reduce air pollution from
Here are some ideas: gasoline engines. Sulfur is targeted because it
significantly reduces the efficiency of automobile
Make Light Paraffin catalytic converters. Similarly, governments are
Isomerization Units considering, or have recently mandated, changes to
Work for You diesel fuel specifications, again requiring lower sulfur
levels than current specifications. Emissions of SO2 and
Refinerywide other contaminants from fluid catalytic cracking (FCC)
Implications of regenerator and refinery heater stacks continue to be an
Producing Low- issue with refiners throughout the United States and the
Sulfur Fuels rest of the world.
Exploiting Synergy For most refiners, the major source of sulfur in gasoline
between FCC and and diesel fuels comes from components produced by
Feed the FCC unit. Regenerator stack emissions also
Hydroprocessing to contribute significantly to overall stationary-source
Improve Refinery emissions from the refinery. Options for reducing sulfur
Margins and Produce focus on changing crude slates, changing product
Low-Sulfur Fuels fractionation, or treating the FCC feed or products.
The Lower It Goes, Even in light of the new environmental regulations,
the Tougher It Gets which, in most cases, will require increased capital
expenditures, refiners are feeling increased pressure to
Meeting Gasoline
increase profits and return on investment. The
Pool Sulfur and
challenge is to meet the new product requirements and
Octane Targets with
at the same time improve refinery profitability.
the ISAL Process

More on the ISAL Diesel Sulfur Issues

process
Diesel may soon be filling the tanks of our sport utility
FCC Light Cycle Oil: vehicles, light trucks, and passenger cars. With its
Liability or better fuel economy, diesel makes an ideal fuel. But
Opportunity? before diesel displaces gasoline, it must be reformulated
to reduce its emissions.

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Fuel Sulfur Solutions Page 2 of 3

One of the first steps in reformulating diesel will be to

reduce its sulfur content from the current maximum of
500 ppm in the U. S. to probably less than 20 ppm to
meet pending U.S. requirements, and from the current
limit of 350 ppm sulfur to less than 50 ppm to meet
upcoming European requirements

Will this reformulation be sufficient? Automobile and

diesel engine manufacturers dont think so. They
believe that to achieve U.S. market acceptance for light
duty diesel engines, consumers will demand higher
quality diesel similar to what is available in Europe.
As a result, aromatics concentration, cetane, specific
gravity, and distillation are under scrutiny.
Implementation mandates may be just around the
corner!

With increased demand for diesel, you will be under

pressure to find ways of making more high quality
diesel from your existing gasoline oriented refinery.
Flexibility will be essential and UOP has the distillate
technology to provide you with this flexibility.

Maximum Quality Distillate (MQD)

Unionfining is a family of processes that
upgrades difficult diesel blendstocks, such
as light cycle oil, into valuable high-quality
diesel. MQD Unionfining is an integrated
approach that can be tailored to meet your
specific needs and enable you to produce
more high-quality diesel.

The Partial-Conversion Unicracking

process enables you to produce low-sulfur,
high-quality diesel while at the same time
improving FCC yields and reducing FCC
naphtha sulfur so that it can be blended
directly into your gasoline pool. With the
Partial-Conversion Unicracking process,
you now have the flexibility to meet the
demand for more higher-quality diesel
while simultaneously meeting lower
gasoline sulfur requirements.

l Request a copy of Diesel Fuel: Specifications

and Demand for the 21st Century by contacting
UOP at
l

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Fuel Sulfur Solutions Page 3 of 3

l DIESEL@UOP.com
l

file://G:\UOP Communications Group\CD project\nprapapers\fuel_sulfur_solutions.htm 3/19/00

IF YOURE BURNING H2, YOURE BURNING MONEY
Use New H2 Management Techniques to Improve Refinery
Margins and Meet New Fuel Requirements

Alan Zagoria, Gavin P. Towler, and Brian M. Wood

UOP LLC
Des Plaines, Illinois

and

Fred M. Hibbs
UOP Limited
Guildford, U.K.

Prepared for presentation at the

1999 NPRA Annual Meeting
San Antonio, Texas
March 22 25,1999
 IF YOURE BURNING H2, YOURE BURNING MONEY
Use New H2 Management Techniques to Improve Refinery
Margins and Meet New Fuel Requirements

Alan Zagoria, Gavin P. Towler, and Brian M. Wood

UOP LLC
Des Plaines, Illinois

and

Fred M. Hibbs
UOP Limited
Guildford, U.K.

ABSTRACT

One of the most-critical issues in producing low-sulfur fuels is managing the impact of the
new requirements on the refinery hydrogen balance. The combination of low-sulfur fuel
specifications, reduced production of hydrogen in catalytic reformers, and the desire to
process heavier, more-sour crudes make hydrogen management a critical issue. Generating,
recovering, and purchasing hydrogen have a significant impact on refinery operating costs.
More importantly, overall refinery operations may be constrained by the availability of
hydrogen.

New transportation fuel specifications are forcing refiners to look carefully at their
existing hydrogen systems. This situation presents an excellent opportunity to identify ways
to actually increase the refinerys profitability, rather than simply minimizing the negative
impact of the new rules.

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 A methodology has recently been developed for systematically analyzing the refinery
hydrogen balance as a network problem. This methodology provides a means of setting
minimum consumption targets and getting some direction on where network improvements
can be made. It can lower refinery operating costs or new hydrogen plant capacity by
reducing overall hydrogen needs.

UOP has found that combining this methodology with a detailed understanding of the
role that hydrogen plays in hydrogen-consuming processes can increase refinery profitability
far beyond the benefit realized by simply reducing hydrogen costs. Hydrogen, specifically
hydrogen partial pressure, has such a strong impact on profitability because of its effect on
throughput, product quality, conversion, yield, and catalyst life. This paper uses commercial
examples to demonstrate the great potential to increase refinery margins by optimizing,
rather than minimizing, the use of hydrogen in the refinery.

INTRODUCTION

In a typical oil refinery, hydrogen is consumed primarily in hydrotreating and hydrocracking

processes for removal of sulfur and nitrogen, in heavy hydrocarbon cracking, and in
saturation of aromatic compounds. The primary source of hydrogen is by-product hydrogen
from the catalytic reformer. Typically, steam reformers produce any additional hydrogen
required.

One or more hydrogen headers form the distribution system that supplies hydrogen to
the consuming processes. Hydrogen-rich purge gases from the consuming processes are
either returned to this distribution system or burned as fuel. A complex series of makeup
and recycle compressors is required to move the hydrogen through the network. As the
hydrogen vented from one process is used as makeup to another, the pressure and purity
typically fall; hence, the distribution system often includes cascades of hydrogen from high
purity to low purity. Hydrogen purification processes such as pressure-swing adsorption
(PSA) and membrane separation, which upgrade the hydrogen purity of these offgasses, are
often added to the hydrogen distribution system.

In the past, refiners have rarely been limited in their production capacity or product
slate by the availability of hydrogen. However, current trends in the refining industry are
reducing the availability of hydrogen to the point where most refiners are concerned about
their future hydrogen balance. The specifications for low-sulfur fuels require increased
hydrogen consumption in hydrotreaters. At the same time, limits on the aromatics content
of gasoline and the requirements for oxygenates have led to lower severity in the catalytic

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reformer and so less hydrogen is produced in this unit. The use of heavier crude oils and
more bottom-of-the-barrel processing increase the hydrogen demand in hydrocracking and
heavy oil hydrotreating units.

Traditionally, refiners would have met this increased demand by increasing hydrogen
plant production (turning up production or revamping existing equipment), building a new
hydrogen plant, purchasing hydrogen from outside suppliers, or increasing recovery of
hydrogen that was going to fuel by installing new hydrogen purification capacity. These
options are all expensive because they require large capital outlays or high operating costs
or both. As a result, refiners are interested in the lower-cost alternative of optimizing and
revamping the hydrogen distribution network. Table 1 shows typical operating and capital
cost implications of these alternatives for meeting increased hydrogen demand.

Table 1. Typical Costs to Meet Additional H2 Requirements

Capital Cost, Operating Cost, Total Cost,

Options $/SCFD $/M SCF $MM/yr
Turn-up H2 plant 0 2 7
Expand H2 plant 0.2 1.0 2.1 8 - 10
Build new H2 plant 1 1.9 9
Add new H2 purification 0.1 0.4 0.5-1.0 24
Purchase over-the-fence H2 0 15 3 - 17
Modify the H2 network 0.1 0 0.3
Based on 10 MM SCFD additional capacity and 25%/year capital charges. Operating cost for
new purification includes debit for the heating value of hydrogen not going to fuel.

Many refiners are inclined to avoid capital investment in hydrogen production facilities
because the hydrogen plant is regarded as a utility and not a profit center. Over-the-fence
supply may be cost-effective in some cases, but it inevitably makes the refinery critically
dependent on an external supplier. Although the addition of purification capacity is usually
an attractive option, it involves complex decisions such as:

Which stream or streams to recover?

Which recovery technology to use?
What inlet and outlet pressures to use?
What trade-off to make between product purity, recovery, and capital cost?

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The complexity of the problem has created a need for systematic methods and tools for
hydrogen management.

PREVIOUS WORK

Alves and Towler1 proposed a method for analyzing refinery hydrogen networks that is
analogous to the well-established pinch analysis method for heat integration. The hydrogen
pinch method they describe requires collecting hydrogen balance data around individual
process units (sinks and sources) and generating a hydrogen purity diagram. In Figure 1, the
stream hydrogen purity is plotted against the gas flow rate as two composite streams, one
representing the hydrogen sources and the other representing the demands of the hydrogen
consumers (sinks). From this plot a purity surplus diagram, as described by Alves and
Towler2 and illustrated in Figure 2, is generated. The surplus must be zero or greater at all
points on this curve. If the surplus were negative, then some unit would not receive all the
hydrogen it needs or would receive hydrogen at a lower purity than required. If the surplus
at any point is negative, then hydrogen production from the swing unit (usually a hydrogen
plant) must be increased to make more pure hydrogen, thus shifting the curve to the right.
This diagram can be used to set targets for the minimum hydrogen consumption in the
network. The target is the hydrogen flow rate from the swing producers that creates a
purity surplus pinch, that is, a purity at which the surplus is zero. The hydrogen pinch
method can also provide guidance in selecting which offgas streams are most suitable for
recovery.

Although the hydrogen pinch method can identify network modifications that reduce
hydrogen consumption, the pinch method cannot be directly used to design the actual
network, because the pinch method specifies only the network as a whole, not flows
between the various process units. Another limitation of the method is that the feed flow,
feed composition, and performance of all purification units must be known before the
analysis begins, because the purifiers must be treated as a process unit and included in the
composite curves. Designing the network requires more-detailed models of the real network
and its components.

REDEFINING THE PROBLEM

Applying hydrogen pinch analysis and a network model is sufficient to substantially reduce
overall hydrogen requirements and the related compression costs. However, a more-
powerful approach is to look at the role hydrogen plays in the hydroprocessing units,

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because hydrogen significantly affects the performance of hydrotreaters and hydrocrackers.
What every refiner is really concerned about is increasing refinery profitability. Modifying
the hydrogen network to reduce hydrogen requirements without considering the impact of
hydrogen on the overall refinery does not maximize refinery profitability. Therefore, the
hydrogen network analysis must be expanded to consider the overall refinery, including the
hydroprocessing processes, catalytic reforming processes, and refinery economics.

The hydrogen pinch method assumes that the purity of hydrogen (makeup plus recycle)
fed to the reactor of every consuming process remains constant. Although this assumption
simplifies network analysis, significant process and economic benefits can be obtained by
varying the hydrogen partial pressure in hydroprocessing reactors. The key to this approach
is to understand its effects on process performance. Although the hydrogen saved by
network optimization can be valuable, using the hydrogen more effectively within the
refinery provides a greater impact on profitability than simply minimizing its consumption.

Increasing the hydrogen partial pressure in a process improves conversion, yield,

product quality, catalyst life, or throughput. Depending on the specific network, these
factors may or may not affect the overall hydrogen consumption in the refinery. If one of
these factors is constraining the overall refinery, then the increased costs of the hydrogen
system are usually inconsequential compared to the economic benefits realized. UOP has
developed detailed process models that can be used to determine the relationship between
reactor hydrogen partial pressure and process performance.

On the supply side of the hydrogen balance, the catalytic reforming process and its
economics should also be considered. Typically, the economics of the gasoline pool, not
hydrogen requirements, govern the desired severity of the reformer. The reformer feed rate
and severity are not normally adjusted to meet hydrogen demand. However, when major
changes in the hydrogen balance are anticipated and capital expenditures of some kind are
required, the catalytic reformer may be a cost-effective source of additional hydrogen.
Process revamps to increase naphtha charge rate or hydrogen yield may be a practical
alternative to increasing hydrogen plant capacity.

INCREASING PROFITABILITY WITH HYDROGEN

Optimizing the use of hydrogen in the refinery consists of three major steps. First, the
network itself is optimized. Second, existing hydrogen purification is modified, or new
purification capacity is added, if appropriate. Third, process changes are made that improve

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5
refinery gross margin. Because the process changes require redesign of the hydrogen
network, the analysis becomes iterative.

STEP 1. NETWORK OPTIMIZATION

Hydrogen-related field data for each consuming and producing unit are used to generate the
composite curves, hydrogen purity surplus curve (pinch diagram), and a detailed hydrogen
network model of the existing refinery. The surplus curve is used to generate a target
hydrogen consumption. The detailed hydrogen network model is used to find modifications
to the network (connections and cascades) that will bring consumption down to the target
level. Usually, these modifications can be made without any major capital projects.

STEP 2. IMPROVED PURIFICATION

Modifying the feed flow, feed composition, performance, or recovery of existing

purification equipment changes the target hydrogen consumption and therefore may be a
relatively low-cost way to reduce hydrogen consumption below the target calculated in the
network optimization step. New purification reduces the target in the same way that
modifying existing purification does. The capital cost of the purification must be justified by
the hydrogen savings, and the hydrogen lost in the purifier waste stream must be justified by
the reduction in hydrogen makeup requirements.

Many choices must be made in selecting an improved purification scheme. Guidance on

which streams should be recovered can be found in the hydrogen purity surplus curve (pinch
diagram). Selecting between membrane and PSA systems requires a series of trade-offs in
capital cost, purity, recovery, and flexibility. Because operating pressures have a very strong
impact on purifier performance, selecting the optimum feed and tail gas pressures requires
trade-offs in capital cost and performance of the purifier relative to compression cost. Once
a PSA or membrane system is chosen, variations of the purifier process, in essence trade-
offs of recovery vs. purity and recovery vs. capital cost, must still be considered.

STEP 3. PROCESS MODIFICATIONS

Modifying the hydrogen partial pressure in the reactor may significantly affect the
performance of the hydroprocessing unit. Detailed process models predict the effect of
changing partial pressure on conversion, yield, throughput, product quality, and catalyst life.
The economic impact of these changes is determined by a refinerywide economic model.

AM-99-08
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 Increasing the hydrogen partial pressure may or may not increase the overall hydrogen
requirements of the network, depending on the location of the process on the pinch diagram
and other factors. Even if overall hydrogen requirements do not increase, network
modifications must be made, and so the whole design process becomes iterative. Analysis
will show that the economic benefit of some process changes more than justifies increasing
the overall hydrogen demand.

TOOLS REQUIRED

To effectively maximize refinery profits through hydrogen management, the following

analytical tools are required:

Calculation of hydrogen pinch curves and target hydrogen consumption.

Detailed model of the hydrogen network: calculation of flows and purity to each
unit, including the purifier.
Detailed process models of hydroprocessing units: estimate performance as a
function of hydrogen partial pressure.
Detailed models of membrane and PSA purification processes: estimate
performance and capital cost as a function of feed flow, feed composition, pressure
levels, and various process options.
Refinerywide economic model: calculate impact of changing yields, product quality,
and throughput on refinery gross margin. This model is usually implemented using
linear programming (LP) techniques.

COMMERCIAL EXAMPLES

LARGE ASIA-PACIFIC REFINERY

These hydrogen management methods can be illustrated by an example based on a study

performed for a refinery in the Asia-Pacific area. The hydrogen study was part of a
refinerywide consulting study. The base case (current operation) is shown in Figure 3. The
customers stated objective was to reduce the direct operating costs associated with
hydrogen production. UOP recommended adopting the broader objective of increasing
overall refinery profitability.

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 The hydrogen plant production in the base case (current operation) is only slightly
greater (3% of total hydrogen plant production) than the target value based on the pinch
analysis. Hydrogen is lost to the vent only from HT 10 and the membrane nonpermeate
(Figure 3). Therefore, hydrogen demand can be reduced only slightly unless the feed to the
purification unit (membrane) or the performance of the purification unit are modified. A
detailed network model was used to identify the network modifications that are required to
reduce hydrogen requirements to the target value. Only minor piping modifications were
required.

An analysis of the refinerywide LP economic model and detailed process models

showed a great benefit from increasing the hydrogen partial pressure in two
hydroprocessing units (HT 4 and HT 10 ). This increase in partial pressure results in more
production of high-value distillates through greater conversion with the existing reactors
and catalyst. The existing run length was maintained. Network improvements were
therefore identified to provide higher purity in these two reactors with the lowest possible
hydrogen production requirements. Because changing the purity in these reactors makes the
previously optimized network suboptimal, network improvements were made to reduce the
overall hydrogen production requirements.

Various options to improve the network were developed (Table 2). Each has a
different impact on hydrogen requirements and refinery profit.

Case 1 shows the improvements that could be achieved by applying the basic hydrogen
pinch methodology (that is, modifying connections and purification only). The total savings
reported in this table includes the costs of additional compression power, membrane
replacement, and additional hydrogen as well as the value of increased distillate production.
Although the savings realized in Case 1 are significant, improving overall refinery
profitability has much more potential.

Case 2 includes additional hydrogen purification capacity along with network

optimization.

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 Table 2. Summary of Alternative Network Modifications

H2 Savings, Total Savings, Capital Cost,

Case Description Nm3/hr* $MM/yr** $MM
Base Current operation 0
1 Network optimization only 1,300 0.5 < 0.05
2 Network optimization & 1,950 0.7 0.7
purification
3 Process improvement, no (21,660) 2.8 < 0.05
network optimization
4 Process improvement, network (5,640) 8.1 3.1
optimization & purification
5 Process improvement, easy (3,470) 4.3 < 0.05
optimization only
* A negative number in the H2 savings column indicates that overall hydrogen requirements
increased.
** Savings include incremental cost of hydrogen + compression costs + increase in overall
refinery margin as determined by the refinery LP model. The refinery margin is increased by
increasing the amount of distillate produced in hydrotreaters HT 10 (Cases 3 to 5) and HT 4
(Cases 3and 4).

In Case 3, the hydrogen purity (partial pressure in the reactors) in the two units is
increased without changing the hydrogen distribution system by simply increasing purge
flows. Although this increase in hydrogen purity improves process performance, it also
tremendously increases hydrogen demand and sends so much purge gas to fuel that the
refinery fuel balance may be upset. Therefore, this solution is not practical.

Case 4 represents optimizing the hydrogen distribution system, including new

purification capacity, after incorporating the process changes to the two reactors.
Additional purification was clearly warranted in this case to reduce the amount of hydrogen
lost to fuel from the purge of these two reactors. All of the trade-offs in operating
conditions and processing schemes described earlier for both PSA and membrane systems,
were considered. For this particular application, the most cost-effective solution is
membrane process with compression of the hydrogen product. Figure 4 shows the trade-off
between purifier capacity (capital cost) and hydrogen savings. The capital costs shown for
Case 4 reflect the estimated installed capital cost of the new membrane and compressor.

AM-99-08
9
Clearly, the capital project in Case 4 pays out quickly. The modified network for this case is
shown in Figure 5.

Because the improved network requires a capital project, an additional optimization

was carried out to identify a low-capital solution that would capture the benefit of the
process improvements but could be implemented immediately. In Case 5, only the purity in
HT 10 is increased, because too much venting was required to increase the purity in HT 4.
The only modifications are simple network modifications such as varying flows and
connections. This option still improves profitability over the base case, and network-only
improvement (Case 1) requires negligible investment and can be implemented until the new
purification unit can be installed.

This study demonstrates that solely minimizing hydrogen consumption does not
maximize refinery profitability. Figure 6 represents this case study from a hydrogen-
consumption point of view. The left bar shows the hydrogen savings benefit of improving
the network only (Case 1). The middle bar shows the benefit of improved network plus new
purification (Case 2), and the right bar shows the result of process optimization (Case 4). If
a refiner is concerned only with minimizing hydrogen consumption, Case 2 would be the
best he could do because it is at target, and purifying more hydrogen does not reduce
hydrogen consumption. From a hydrogen-consumption point of view, the proposed process
changes are clearly a bad idea. However, the real benefit of hydrogen management is
derived from viewing it as a means to increase refinery profit. When the options are judged
based on overall refinery economics (Figure 7), the profit improvement achieved by
combining network analysis with process know-how and refinerywide economics is far
superior (more than $7 MM/year) to the option selected based on network analysis alone.

EUROPEAN REFINERY

Summarizing the results of the hydrogen management study of a much-simpler European

refinery demonstrates that the previous example is not an isolated case. The refiners
primary concern here was reducing future hydrogen plant requirements as new fuel
specifications come into effect. Figure 8 shows that a suboptimal solution would have been
selected if process concerns and refinerywide economics were not considered. Process
improvements can increase profitability by an additional $1.2 MM over network analysis

AM-99-08
10
alone. In addition, 29 MM SCFD of potential additional hydrogen production was made
available through revamps of the existing catalytic reformers. The increased hydrogen
production results from both increasing naphtha charge rate and reducing reactor pressure.

IMPLEMENTING THE H2 NETWORK MODEL

WITHIN A REFINERY LP MODEL

Linear programming, a mathematical technique that has been used to optimize the operation
of refinery and petrochemical complexes for more than 30 years is the method used by most
refiners to make economic decisions. The refinery LP model includes simplified process
models that include, for example, product yields and properties, utility consumption rates,
unit capacity limits, and blending rules. Hydrogen is typically modeled on an extremely
simplistic basis. Until now, refinery hydrogen systems have commonly been modeled by
assuming fixed hydrogen purities for each process stream. Makeup and vent flows do not
change with makeup purity. The LP forces a hydrogen material balance so that excess
hydrogen ends up in the fuel system and hydrogen shortages force increased production in
the hydrogen plant.

The application of pinch analysis to refinery hydrogen management has highlighted the
need for more-rigorous LP modeling. The refinery hydrogen network and all other aspects
of the refinery operation should be optimized simultaneously. To achieve overall optimum
refinery operation, new insights and an understanding of the refinery hydrogen network
problem need to be incorporated into the conventional LP model of the refinery complex.

The results from optimizing the refinery hydrogen network obtained to date by LP
modeling have confirmed many of the old heuristic rules of refinery hydrogen management,
for example, that hydrocrackers should be fed high-purity hydrogen and low-purity
hydrogen streams are best used as hydrogen plant feedstock. New insights, particularly with
respect to the optimum use of the medium-purity hydrogen streams, have also been
obtained. Hydrogen management and the individual process units can thus be optimized at
the same time. Addressing the hydrogen network within the LP model ensures that the
hydrogen management study is not carried out in isolation from the overall refinery
optimization.

AM-99-08
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 CONCLUSION

Improved hydrogen management offers the refiner a means of not only cost-effectively
meeting the increased hydrogen demands of low-sulfur fuels, but also improving
profitability. The hydrogen pinch methodology can provide significant savings in hydrogen
production and compression costs. However, benefits far in excess of what hydrogen pinch
alone can achieve are realized by considering the effect of hydrogen on hydroprocessing
performance and using increased overall refinery profitability instead of reduced hydrogen
consumption as the objective. This approach takes into account the effect of hydrogen
partial pressure on throughput, yield, product quality, and catalyst life in critical reactors.
The methodology described in this paper has been tested on a number of refineries and has
delivered significant profit improvement in every case.

REFERENCES

1. J.J. Alves, and G.P. Towler, Design of Refinery Hydrogen Networks, workshop
presented at UMIST PIRC Hydrogen Consortium meeting, Manchester, April 1998.
2. J.J. Alves, and G.P. Towler, Analysis and Design of Refinery Hydrogen Distribution
Systems submitted to Ind. Eng. Chem. Res., in preparation.

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 Figure 1. H2 Composite Curves
100
95
90
85
H2 Purity, %

80
75
70
65
60 Sources
Sinks
55
50
0 5,000 10,000 15,000 20,000 25,000 30,000
Gas Flow Rate, mol/hr
UOP 3125-1

Figure 2. H2 Purity Surplus Curve

100
95
90
85
H2 Purity, %

80
75
70
65
60
55
50
0 50 100 150 200 250 300
H2 Surplus, mol/hr
UOP 3125-2

AM-99-08
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 Figure 3. Initial H2 Network

Isom Fuel
HT 1
Reformer 1 HT 2
HT 3

HT 4

HT 5 Fuel
H2 Plant 1
HT 6 HT 7

Reformer 2 HT 8
Nonpermeate
Permeate
Membrane Fuel

HT 9 HT 10 Fuel
H2 Plant 2

HT 11
UOP 3125-3

Figure 4. Relationship of Capital Investment

and H2 Savings
25,000

20,000
H2 Saved, Nm3/hr

15,000

10,000

5,000

0
0 .5 1.5 2.0 2.5 3.0 3.5 4.0 4.5
Total Capital Investment, $MM
UOP 3125-5

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 Figure 5. Revamped H2 Network

Isom Fuel
HT 1
Reformer 1 HT 2
HT 3
New Increased Reactor Purity
Membrane HT 4 Fuel
Fuel
HT 5 Fuel
H2 Plant 1
HT 6 HT 7

Reformer 2 HT 8
Nonpermeate
Permeate
Membrane Fuel
Increased Reactor Purity
HT 9 HT 10 Fuel
H2 Plant 2

HT 11
UOP 3125-4

Figure 6. Hydrogen Savings

10
H2 Saved, % of Base Case

-5

-10

-15
Improved New Process
Network Purification Optimization

UOP 3125-6

AM-99-08
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 Paper No. 37e

Selection and Revamp of Hydrogen Purification Processes

Michael Whysall and Kathy Ward Picioccio

UOP LLC, Des Plaines, Illinois

Prepared for presentation at the

1999 AIChE Spring Meeting,
Houston, Texas,
March 13-18,1999
Session: Refinery Hydrogen Management

Copyright 1998, UOP LLC

Unpublished

AIChE shall not be responsible for statements or opinions

contained in papers or printed in its publications.
 ABSTRACT

Increased demand for lighter fuels and products, a desire for higher-performance products, and an
insistence on more environmentally acceptable products require refiners to alter processing conditions
and technologies so that they can successfully meet the demands of todays society. Although all of
these demands relate to product slate or quality, they also have a significant impact on a valuable but
often overlooked refinery by-product: hydrogen, which is important as both a commodity and a reactant
in the total refinery.

The hydrogen balance in a typical refinery is straightforward: hydrogen supplied by the feedstock leaves
in the products, by-products, and wastes. In the 1950s, catalytic reforming provided refiners with a
relatively pure hydrogen stream as a by-product of normal refining practice. Refiners had a ready-made
source of hydrogen, which could be used as a reagent in the chemistry of their refining schemes. In the
1990s, increasingly demanding product specifications require more hydrogen content in the products as
well as removal of contaminants.

To avoid investing in a new hydrogen-producing plant, a refiner with a tight hydrogen balance needs to
consider three main issues:
Maximizing the hydrogen yield from the refinery with particular attention to the primary source: the
catalytic reformer.
Determining the hydrogen required to produce increasing amounts of high-performance products.
Considering the hydrogen management technologies required to convey hydrogen from the source
to the user under the most-appropriate conditions.

This paper compares the three processes for the recovery and purification of hydrogen: adsorption using
pressure swing adsorption, permeation using semi-permeable membranes and cryogenics.
The paper then addresses improvements that have been made to existing equipment to increase
hydrogen production by either debottlenecking units to increase throughput or increasing hydrogen
recovery to improve the hydrogen balance in refineries.
 INTRODUCTION

Although the balance of the hydrogen content in a refinerys feed and products is fundamental to the
ultimate product slate that can be achieved, refiners are not entirely left to the whims of Mother Nature to
restrict their product slates. In todays refinery, the desired hydrogen content of the products is achieved
almost exclusively by reaction. The modern oil refinery consists of several processing operations that
either produce or consume molecular hydrogen. Thus, in a practical sense, hydrogen management is the
collection of hydrogen from the producers and the distribution of that hydrogen to the consumers. The
distribution of the hydrogen often involves purification to ensure the efficient operation of the
consuming operations.

Selection of an appropriate hydrogen management technology is crucial to fully utilizing hydrogen

sources and hydrogen-rich off-gas streams. The selection of this technology is especially true when the
primary source of hydrogen is a catalytic reformer and the continuing drive to greater yields of high-
quality products makes the refinery hydrogen balance tight.

When a catalytic reformer is the primary source of hydrogen in a refinery, the technology used to purify
the hydrogen source as well as recover hydrogen from off-gas streams for redistribution to consumers
clearly plays a crucial role in the refinery material balance. The selection of the appropriate hydrogen
purification technology is intimately related to the hydrogen source and the final use of the hydrogen.

HYDROGEN PURIFICATION TECHNOLOGIES

The purity of the hydrogen available to consumers can have a significant effect on the design and
operation of the consuming units which is generally a hydro-processing unit. The three main hydrogen
purification technologies used in refineries are pressure swing adsorption (PSA), selective permeation
using polymer membranes, and cryogenic separation. Each of these processes is based on a different
separation principle, and consequently, the process characteristics differ significantly. Selecting the
appropriate hydrogen purification technology depends not only on the economics, but also on such
project considerations as process flexibility, reliability, and ease of future expansion. This paper reviews
the purification process characteristics and equipment as well as other project considerations for these
technologies. General selection guidelines are presented along with process integration that takes
advantage of the complementary characteristics of the three processes.

PSA Process

POLYBED PSA units for hydrogen purification are based on the ability of adsorbents to adsorb more
impurities at high gas-phase partial pressure than at low partial pressure. This UOP process has been in
commercial operation since 1966 for various refinery and petrochemical applications Nearly 600 units are
on-stream worldwide. Impurities are adsorbed in an adsorber at high partial pressure and then desorbed
at low partial pressure. The impurity partial pressure is lowered by swinging the adsorber pressure from
the feed pressure to the tail gas pressure and by using a high-purity purge gas. Hydrogen is recovered at
high pressure and purity. Although cyclic, multiple absorbers are used to provide constant product and
tail-gas flows. Commercial units normally use between 4 and 12 absorbers. More absorbers are used to
provide higher hydrogen recovery or to increase capacity.

The driving force for the separation is the difference in impurity partial pressure between the feed and tail
gas. A minimum pressure ratio of approximately 4:1 between the feed and tail-gas pressure is usually
required for hydrogen purification. However, the absolute pressure of the feed and tail-gas is also
important, particularly for hydrogen recovery. In refinery applications, the feed pressure is usually in the
range of 200 to 500 psig, but more important than the feed pressure is the tail-gas pressure. The optimum
tail-gas pressure is as low as possible. Because vacuum is normally avoided, tail-gas pressures of 5 to 10
psig are typically used when high hydrogen recovery is desired. For refinery feed, the PSA tail-gas is
frequently compressed from this low pressure to fuel-gas pressure. For steam reformer operation, the
PSA tail-gas is normally used at a pressure of 5 psig in low-pressure burners.

Hydrogen is essentially not adsorbed in the PSA process and is available at close to feed pressure: the
typical pressure drop between the feed and product battery limits is less than 10 psi. The two key
advantages of the PSA process are its ability to remove impurities to any level and to produce a high-
purity high-pressure hydrogen product. The purity of the hydrogen product from a PSA unit is typically
in excess of 99 vol-% and frequently 99.999 vol-%. Removal of CO and CO 2 to a volume level of 0.1 to
10 ppm is common and readily achieved.

Membrane Process

POLYSEPTM membrane systems are based on the difference in permeation rates between hydrogen and
impurities across a gas-permeable polymer membrane. Permeation involves two sequential mechanisms:
the gas-phase component must first dissolve into the membrane and then diffuse through it to the
permeate side. Different components have different solubility and permeation rates. Solubility depends
primarily on the chemical composition of the membrane and diffusion on the structure of the membrane.
Gases can have high permeation rates as a result of high solubility, high diffusivity, or both. The driving
force for both solution and diffusion is the partial pressure difference across the membrane between the
feed and permeate sides. Gases with higher permeability, such as hydrogen, enrich on the permeate side
of the membrane, and gases with lower permeability enrich on the non-permeate side of the membrane
because of the depletion of components with high permeability.
The first fraction of the gas to permeate through the membrane consists primarily of the components
with the highest permeability. As a larger fraction of the feed gas is allowed to permeate, the relative
amount of the components with lower permeability increases in the permeate stream.
In hydrogen separations, higher purity hydrogen is associated with lower recovery, and lower purity
hydrogen is associated with higher recovery. The effect of hydrogen purity on recovery is much more
dramatic with membrane systems than with PSA or cryogenics units. A fairly small change in hydrogen
purity can change the recovery significantly. (Figure 1)

Figure 1
Hydrogen Recovery vs Product Purity
M em b r a n e S y s t e m s

100

Pressure ratio 5:1

98
Hydrogen Purity, %

96
Pressure ratio 2.5:1

94

92
40 50 60 70 80 90 100
Hydrogen Recovery, %

Higher hydrogen recovery also requires that more membrane area be provided. The membrane area
required when feed composition and system pressure levels are fixed increases exponentially at high
hydrogen recovery. The performance of a specific membrane system, that is, the recovery versus the
product purity for a given feedstock, is primarily dependent on the ratio of feed to permeate pressure and
is largely independent of the absolute pressure level. However, the area requirement is inversely
proportional to the feed pressure. Hence, compressing the feed gas rather than the permeate, even
though the permeate flow is smaller, is often preferable when the objective is to achieve the required
pressure ratio.

Cryogenic Process

Cryogenic units are based on the difference in boiling temperatures (relative volatility) of the feed
components. Hydrogen has a high relative volatility compared with hydrocarbons. The process
condenses the required amount of feed impurities by cooling the feed stream against the warming
product and tail-gas streams in brazed aluminum multi-pass heat exchangers. The refrigeration required
for the process is obtained by Joule-Thomson refrigeration, which is derived from throttling the
condensed liquid hydrocarbons. Additional refrigeration, if required, can be obtained by external
refrigeration packages or by turbo expansion of the hydrogen product.

The partial condensation process is normally applied to hydrogen-hydrocarbon separations. The feed
needs to be pretreated to remove water and other components that could freeze in the system. The
pretreated feed at high pressure, 300 to 1,200 psig, is cooled against a stream leaving the cryogenic unit to
a temperature at which the majority of the C 2+ hydrocarbons condense. The two-phase stream is sent to
a separator where the hydrogen-methane vapor stream is taken overhead and further cooled to a
temperature low enough to give the desired hydrogen purity. The cooled stream is fed to another
separator, and the hydrogen product is taken overhead. Before leaving the cryogenic unit, the hydrogen
is heated by heat exchange against the hydrogen-methane from the first separator and the feed. The
liquid methane from the second separator is expanded to a suitable pressure so that it will vaporize
against the hydrogen-methane stream from the first separator. Additional cooling is provided by
expanding part of the C 2+ hydrocarbons product, if necessary.

Thus, the cryogenic unit typically splits the feed into three products: a high purity hydrogen stream, a
methane-rich stream at fuel gas pressure, and a C 2+ hydrocarbons product, which may be two phase. By
using additional separators, additional products, such as ethane-propane and LPG streams, can also be
produced. If the feed stream does not contain sufficient hydrocarbons to achieve the necessary cooling
by the Joule-Thomson effect alone, then additional refrigeration can be provided by expansion of the
hydrogen product or a package refrigeration system, normally at 5 to -40F.

TECHNOLOGY SELECTION CRITERIA

The most-appropriate choice of hydrogen purification technology depends on both performance criteria
(hydrogen recovery and feed and product conditions) and operational requirements (flexibility,
reliability, feed pretreatment and by-product recovery). These factors are summarized for each of the
three technologies previously discussed in Tables 1 and 2. The PSA process requires relatively high
hydrogen purity feeds

Table 1
Process Considerations for Hydrogen Purification Technology

Factors PSA Membrane Cryogenic

Minimum feed H 2, % 50 15 15

Feed pressure, psig 150 - 1,000 200 - 2,000 200 - 1,200

 H2 purity, % 99.9+ 98 max. 97 max.

H2 recovery, % up to 90 up to 97 up to 98

CO + CO2 removal Yes No No

H2 product pressure Approximately feed Much less than feed Approximately feed

Table 2
Operational Considerations for Hydrogen Purification Technology

Factors PSA Membrane Cryogenic

Feed pretreatment No Yes Yes

Flexibility Very high High Average

Reliability High High Average

By-product recovery No Possible Yes

Ease of expansion Average High Low

(typically above 50 vol-%) at moderate pressures but delivers a high-purity product with little pressure
drop and good hydrogen recovery from the feed. PSA units are particularly well suited for purifying
catalytic reformer hydrogen for use in hydro-processing units. The high purity of the hydrogen from a
PSA unit helps maintain a high recycle gas purity in the hydro-processing unit and the small pressure
drop across the PSA avoids excessive recompression duties.

Membrane systems need to operate under sizeable pressure drop to deliver moderately pure hydrogen
(typically 90 to 95 vol-%) at low pressure but with high recovery. Such systems are more suited to
recovering hydrogen from high-pressure purge gases.

The performance of cryogenic units is similar to that of membrane systems except that the hydrogen
pressure loss is much less. The cryogenic process is most attractive when the hydrogen content of the
feed is low (30 to 50 vol-%), when the expansion of hydrocarbons provides the necessary cooling
without external refrigeration.

Cryogenic units allow the simultaneous recovery of by-products, such as ethane and methane. However,
they are handicapped by poorer reliability and flexibility and require significant feed pretreatment.
Although the cryogenic process is thermodynamically the most-efficient hydrogen purification
processes, the PSA process is the most commonly selected hydrogen purification technology, despite its
lower hydrogen recovery. This lower hydrogen recovery is more than compensated for by the flexibility
of operation, the high reliability, and the ability of the adsorption process to produce high-purity, high-
pressure hydrogen. If higher hydrogen combined with by-product recovery is needed the integration of a
PSA unit with a cryogenic unit can provide the required high-purity hydrogen at high overall recovery.
This subject is described in the paper by Pacalowska, Whysall and Narasimhan.
 PSA REVAMPS

Recently, many refineries and chemical plants have faced a hydrogen shortage. Revamping existing PSA
units for additional hydrogen capacity is an option that offers attractive economics. Many PSA units
continue to operate today at original design capacities and performance. Since their original design, a
number of developments have increased both capacity and performance. Cycle modifications have
demonstrated increases in capacity in excess of 15%, and new adsorbents offer better performance.

To increase the recovery of hydrogen in a PSA unit several co-current depressurization steps are made to
transfer the hydrogen that is present in the voids to another adsorber, which is at a lower pressure, either
on the purge step or during repressurization back to feed pressure. Adding to the number of
depressurization and repressurization (equalization) steps increases the hydrogen recovery, but the
amount of adsorbent required to keep the impurities trapped also increases (Figure 2).

Figure 2
Relationship between Hydrogen Recovery and Adsorbent Quantity

140
Relative Adsorbent Quantity, %

130

120

110

100

90
87 88 89 90 91
Hydrogen Recovery, %

In an existing unit, the quantity of adsorbent is fixed, but reducing the number of co-current
depressurization steps, which effectively frees up adsorbent capacity, allows significant increases in the
feed rate to the PSA unit and only a small decrease in hydrogen recovery. Capacity increases of up to
40% have been achieved by this type of revamp. The maximum capacity increase is normally set by
hydraulics limitations: frequently by the pressure drop over the hydrogen product valves. Development
in the last 10 years has resulted in a new generation of adsorbents with superior mass transfer
characteristics. Using these adsorbents can give either an increase in capacity or hydrogen recovery. In
some cases the loss in hydrogen recovery as a result of reducing the co-current depressurization steps
can be largely compensated for by replacing part of the original adsorbent charge.
 PSA AND MEMBRANE INTEGRATION FOR DEBOTTLENECKING

In 1983, a large atmospheric residuum desulfurization (ARDS) unit was commissioned. The hydrogen
make-up for this plant came from a steam reformer with a product flow of 55 MM SCFD; the
purification of the steam reformer effluent used a 10-adsorber PSA unit. As designed, the feed gas to the
steam reformer was mainly natural gas supplemented with the high-pressure vent and the low-pressure
flash gases from the ARDS unit. The flow scheme is shown in Figure 3.

Figure 3
Original Refinery Flow Balance

HP Vent LP Flash
90% Hydrogen 60%Hydrogen
2,000 psig 500 psig

Steam PSA ARDS

Reformer

55 MM SCFD

In 1987, a plant expansion was undertaken, and the target hydrogen capacity was increased from 55 to
80 MM SCFD. The first capacity increase was achieved by debottlenecking the steam reformer and its
associated PSA unit to increase the capacity by 18%, from 55 to 65 MM SCFD. This increase was
achieved through a process redesign, required reprogramming of the control software and essentially no
hardware changes.

The high-pressure vent stream at over 2,000 psig was routed to a membrane system. The hydrogen
product was delivered to the suction of the hydrogen make-up compressor. This change added a further
5 MM SCFD of hydrogen to the refinery balance.

A second PSA unit was proposed to purify the low-pressure flash gas from the ARDS unit combined
with the non-permeate from the membrane unit and to deliver the product to the suction of the make-up
compressor. This change would have increased the amount of available hydrogen to the desired 80 MM
SCFD. Implementation of this change is still pending. The revamped scheme is shown in Figure 4.
 Figure 4
Revamped Refinery Flow Balance

Membrane
5 MM SCFD Recovered Hydrogen

PSA

Fuel

Steam PSA ARDS

Reformer

65 MM SCFD
10 MM SCFD Recovered Hydrogen

SUMMARY

As the product slate of refineries shifts further toward lighter products with enhanced performance and
cleaner properties to meet environmental considerations, the more important effective hydrogen
management becomes. Careful consideration should be given to the purification and utilization of the
hydrogen produced from existing units before the additional investment in a steam reforming hydrogen
plant is considered.

Catalytic reforming is still often the main supplier of hydrogen in a refinery. The technology is
continually evolving to produce increasingly higher yields of hydrogen, although for the low-pressure
CCR Platforming process, the hydrogen yield is approaching the theoretical maximum. By applying
hydrogen management technologies and by carefully selecting the appropriate hydrogen purification
technology, refiners can make efficient use of the hydrogen contained in the crude.

REFERENCE

Pacalowska, B., Whysall, M., and Narasimhan, M. V. Improve Hydrogen Recovery from Refinery
Offgases, Hydrocarbon Processing , Nov. 1996.
 Figure 7. Potential Profit Improvement
10.0

8.0 Process Improvements

Profit, $MM/yr

6.0

4.0

2.0
Network Only

0
0 1 2 3
Investment, $MM
UOP 3125-7

Figure 8. Potential Profit Improvement

for Second Refinery
5.0
Process Improvements
4.0
Profit, $MM/yr

3.0 Network Only

2.0

1.0

0
0 1 2 3
Investment, $MM
UOP 3125-8

AM-99-08
16
 PROCESS PLANTS & SYSTEMS

POLYBEDTM PSA SYSTEMS

FOR GAS EXTRACTION AND PURIFICATION

The Pressure Swing Adsorption (PSA) process is based

on the principle that adsorbents are capable of selectively
adsorbing impurities.The impurities are adsorbed in a
fixed-bed adsorber at high pressure and desorbed by
swinging the adsorber from the feed to the tail gas
pressure and by using a high-purity purge. Typically the
desired component is not adsorbed and is recovered at
high purity.

UOPs Polybed PSA system offers:

J High reliability (greater than 99.8% on-

stream time)
J Minimal manpower requirements due to
automatic operation, which can include
automatic start-up, capacity control, tail gas
control, switchover, pressure control, and
product purity control
J Reduced equipment costs and enhanced
performance based on high performance
adsorbents and advanced PSA cycles
J Lower operating and equipment costs for
downstream process units due to the avail-
ability of a high-purity product gas
J Flexibility to process more than one feed- OPERATION
stock and maintain product purity and
recovery during changing conditions UOPs Polybed PSA systems are designed to be safe,
efficient, and economical.
J Minimal feed pretreatment and utility
requirements A PSA system operates as a batch process; however,
J Adsorbents last for the life of the mechani- multiple adsorbers operating in a staggered sequence
cal equipment (more than 30 years) are used to produce constant feed, product, and tail gas
flows. Regardless of the number of adsorber vessels, all
J Reduced plot requirements, fast delivery
Polybed systems follow the five-step pressure-swing
times, and low installation costs based on
cycle shown next. The brown area represents the impu-
the modular design
rities, and the blue area the product.
J Worldwide service and support
 STEP 1 ADSORPTION
The feed gas enters an adsorber at a high
pressure, impurities are adsorbed, and high-
purity product is produced. Flow is normally
in the upwardly direction. When an adsorber
has reached its adsorption capacity, it is taken
off-line, and the feed automatically switched
to a fresh adsorber.
STEP 2 CO-CURRENT DEPRESSURIZATION
To recover the product trapped in the adsor-
bent void spaces, the adsorber is co-currently
(in the direction of feed flow) depressurized.
The product gas withdrawn is used internally
to repressurize and purge other adsorbers.
STEP 3 COUNTER-CURRENT
DEPRESSURIZATION
At the conclusion of the co-current depressur-
ization step, the adsorbent is partially regener-
ated by counter-currently depressurizing the
adsorber to the tail gas pressure, and thereby
rejecting the impurities.
Tail Gas
STEP 4 PURGE
Purge
The adsorbent is purged with a high-purity
stream (taken from another adsorber on the co-
current depressurization step) at a constant
pressure to further regenerate the bed.
STEP 5 REPRESSURIZATION
The repressurization gas is provided from the
co-current depressurization step and a slip-
stream from the product. When the adsorber
has reached the adsorption pressure, the
cycle has been completed, and the vessel is
ready for the next adsorption step.
1999 UOP LLC. All rights reserved
This information is not to be taken as a warranty or representation for which UOP
assumes legal responsibility nor as permission or recommendation to practice any
patented invention without a license. It is offered solely for your consideration.
UOP 3150-5 899PPS5A
COMMERCIAL EXPERIENCE
Since commercialization in 1966, UOP has provided over
Product
650 PSA systems in more than 60 countries. These sys-
tems have found application in the refining, petrochemi-
cal, polymer, steel, and power generation industries. The
Polybed PSA system has demonstrated exceptional eco-
nomic value in many applications, such as recovery of
hydrogen from refinery off-gases, recovery of monomers
Feed
in polyolefin plants, extraction of hydrogen from gasifica-
tion syngas, purification of helium for industrial gas use,
adjustment of synthesis gas for ammonia production,
To next purification of methane for petrochemicals production,
vessel
and H2/CO ratio adjustment for syngas used in the manu-
facture of oxo-alcohols.
Feed conditions typically range from (7 to 70 kg/cm2g)
(100 to 1,000 psig), with concentrations of the desired
component from 30 to 98+ mol %. System capacities
range from less than 1 to more than 350 MM SCFD (less
than 1,100 to more than 390,000 Nm3/h).
UOP:
J Optimizes the integration of PSA technology
within your plant
J Continually improves existing technology to
meet your changing process needs
J Develops new applications to meet your new
challenges
J Provides ongoing technical services and sup-
port after startup.
J Keeps you informed on the latest develop-
ments and advancements in our technology
through seminars and conferences
J Provides revamp services
Tail Gas
FOR MORE INFORMATION
For more information, contact your UOP representative or
UOPs Process Plants and Systems group at:
Telephone: 1-847-391-1347
Fax: 1-847-391-2469
uop TM
UOP L L C
25 East Algonquin Road
Des Plaines, IL 60017-5017 USA

POLYSEPTM MEMBRANE SYSTEMS FOR
GAS EXTRACTION AND PURIFICATION
Polysep systems combine state-of-the-art composite
membrane technology with advances in polymer sci-
ence, a combination that results in membranes that are
fundamentally different from others. The Polysep family
of separation polymers offers a range of separation
characteristics (permeability, selectivity, and contaminant
resistance) that allow the design of an optimum system
to fit a given process need.
Polysep membrane systems are modular units contain-
ing either hollow fiber or spiral wound membrane ele-
ments.
J Hollow fiber elements consist of fibers wound
helically around a perforated hollow tube
through which the non-permeate gas is removed.
The desirable, or permeate, gas will collect
inside the fiber and exit as product.
J Spiral wound elements consist of several leaves.
Each leaf contains two membrane sheets that are
separated by a permeate channel spacer of rigid
and porous material. The membrane leaves are
wound around a perforated hollow tube through
which the permeate gas is removed as product.
The membranes are well supported by the element
structure, resulting in excellent mechanical integrity and
Hollow Fiber Membrane
PROCESS PLANTS & SYSTEMS
Spiral Wound Membrane
Feed Non-permeate
Permeate
Feed Non-permeate
Feed Spacer
Membrane
Permeate Spacer
Membrane
Feed Spacer
flow distribution. The elements are housed in pressure
tubes, which are in turn mounted on a skid in series or
parallel configurations depending upon feed gas volume
and product requirements. High membrane packing
density (high surface area per volume) minimizes sys-
tem size and cost.
UOP Polysep membrane systems offer:
J Ease of installation and maintenance
Modular design and shop fabrication permit com-
pact design, yet membrane elements are oriented
for ease of maintenance. Testing of components
before delivery allows for faster start-ups.
J Minimal manpower requirements
Automatic operation features, which can include
automatic start-up, capacity control, product
purity control, and auto depressurization, require
no special operator consideration. The system
design permits easy turn-up and turn-down with-
out ongoing operator attention to capacity.
J High reliability
Historical operating data indicates minimum
unscheduled shutdowns for these systems. This
record of more than 99.8% on-stream time is
due to reliability features that include:
- Minimal feed pretreatment and utility
requirements
- Proven valve and instrument designs
 - Unique turn-down capability, which limits the
risk of condensation in the membrane system
during reduced feed rate operation
- High resistance to contaminants
J Future expandability by adding modules or skids.

PROCESS DESCRIPTION
The separation of a gas mixture by membranes is effected
by the differences in permeation rates of various gases
through the polymeric membrane. The more permeable
gas (for example, hydrogen) is enriched on the permeate
side of the membrane, while the less permeable gas
enriches on the feed side of the membrane. The membrane
separation of these gases is a pressure driven process and UOP provides:
requires a high feed pressure. The product stream (perme-
ate) is produced at a lower pressure by taking a pressure J Unparalleled international experience in project
drop across the membrane. The non-permeate stream is development, engineering, fabrication, and technical
available at essentially feed pressure. support
J Flexibility in project execution
The membrane process is continuous, and produces per-
meate and non-permeate streams at constant flow, pres- J Membrane systems optimized within customer
sure, and purity. requirements
J Worldwide sourcing to meet local requirements
EXPERIENCE J Shop fabricated skid-mounted systems for fast on-
In their primary application, Polysep systems produce site installation and short start-ups.
high-purity hydrogen from a variety of feed sources, such J Products and services within ISO-9001 certification
as high-pressure vents and purge streams from hydropro-
J On-going technical support after plant start-up
cessing, methanol, and ammonia plants. Other proven
applications are H2/CO syngas ratio adjustment, CO
purification, and CO2 removal from natural gas. In addi-
tion to stand-alone systems, Polysep membranes have
been installed in combination with UOPs Polybed PSA
and Isosiv adsorption technologies, and UOPs Amine
Guard, Benfield, and Selexol absorption technolo-
FOR MORE INFORMATION
gies to meet unique plant or project needs. For more information, contact your UOP representative,
or UOPs Process Plants and Systems group at:

Telephone: 1-847-391-1347
Fax: 1-847-391-2469

uop TM

1999 UOP LLC. All rights reserved

This information is not to be taken as a warranty or representation for which UOP
UOP L L C
assumes legal responsibility nor as permission or recommendation to practice any 25 East Algonquin Road
patented invention without a license. It is offered solely for your consideration. Des Plaines, IL 60017-5017 USA
UOP 3150-7 899PPS5C