41b

Large-scale hydrogen plants. Uhde and UOP’s experience

John Larsen, Dr. Marcus Michel and Jan Zschommler (Uhde)

Dr. Michael Whysall and Dr. Stefaan Vanheertum (UOP)

Prepared for presentation at the 2003 Spring Meeting, New Orleans March 30-April 03

Copyright © John Larsen, Marcus Michel and Jan Zschommler (Uhde)

Michael Whysall and Stefaan Vanheertum (UOP)

AIChE shall not be responsible for statement or opinions contained in these papers or printed in its publications
ABSTRACT

With reference to a recent project Uhde and UOP will outline the evolution of their
respective hydrogen generation and purification technologies and how they have been
combined to meet demand for ever larger capacity hydrogen plants. Concentrating on
large-scale hydrogen plants, the presentation will discuss issues of design, efficiency and
reliability as well as control system integration, project scheduling and overall
economics. The importance of integration of hydrogen generation and hydrogen
purification will be highlighted as well as the co-operation between hydrogen generation
and purification plant designers, customers and suppliers. Future trends will be outlined.

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 Large Scale Hydrogen Plants. Uhde and UOP’s Experience
by John Larsen, Dr. Marcus Michel and Jan Zschommler (Uhde)
Dr. Michael Whysall and Dr. Stefaan Vanheertum (UOP)

Sincrudos de Oriente’s (SINCOR) oil upgrader complex in José, Venezuela, started up in 2001. This
upgrader complex produces 180,000 bpsd of low-sulfur syncrude from an extra heavy crude oil, which is
highly viscous at ambient temperature. A pipeline transports the crude oil, diluted with light distillate, about
600 kilometers from the Orinoco Belt to Sincor’s upgrader complex on the coast. The distillate is recovered
in José and recycled via pipeline to the source.

Below is a simplified block diagram of the Sincor Upgrader process scheme. The block diagram shows how
the HMU’s fit into Sincor’s overall process schemes.

Diluent Diluent
Commercial
Diluent
Production
Straight Run Gas Oils Naphtha Phase
Distillate
Light Vacuum Gas Oil Hydro-
Diluted
Desalter CDU treater
Extra
Heavy
Crude Oil VDU Light
Ends Syn- Export
crude
Medium &
Heavy
Vacuum Mild
Gas Oil Hydro-
cracker
Rich Amine Amine
Lean Am ine Regeneration Sulfur Gas Re-
Recovery covery Unit Refinery
Sour W ater Sour W ater Hydrogen
Unit Offgas
Stripper
Light Coker Hydrogen
Stripped W ater to W aste Gas Oil Heavy Manuf. Unit Natural Gas
Vacuum Coker
W ater Treatm ent Unit
Residue Gas Oil
Delayed
Coking Unit Coke Export or Local Sales
Sulfur Export or Local Sales

Source: Sincor, Venezuela

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The plants’ hydrogen supply must be highly reliable because the plant is highly integrated and hydrogen
cannot be stored economically. Loss of hydrogen would lead to a shut down of the entire $5 billion
upgrader facility and has to avoided. Therefore, having two independent HMU’s greatly increases the
probability that the hydrogen supply will never be completely lost. Other plant reliability features include:
• Reformer fans and BFW pumps equipped with dual steam turbine/electric drives.
• Two-out-of-three voting for all emergency trips
• Reformer tubes, outlet manifold system, and process gas coolers design very conservatively
• Two 14-adsorber PSA units, with extra safeguards against PSA valve malfunction, including multiple
operating modes.

The complex requires 200,000 Nm3/h or high purity (99.9 volume percent) hydrogen for hydro-processing
of the medium and heavy vacuum gas-oil and the heavy coker gas-oil. For the generation of this hydrogen
Uhde supplied Sincor with a two hydrogen manufacturing units (HMU’s). Each train includes a down-fired
reformer and a Polybed™ pressure swing adsorption (PSA) unit. Uhde’s top fired reformer design with the
unique cold outlet manifold was chosen. A high-alloy liner shields the manifold’s refractory lining from the
hot gas. Consequently, the reformer’s tube-to-manifold connections are as reliable as any other carbon steel
pipe connections in the plant.

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Each reformer in this HMU is the size of the ammonia industry’s largest reformers. Table 1 compares one
of the Sincor reformers with that of Qafco III’s reformers. Qafco III produces 1,500 mtpd of ammonia.
Equipment downstream of the reformer includes a process gas cooler, a high temperature carbon monoxide
shift reactor, a cooling train, and a (PSA) unit.

Table 1 Comparison Sincor and Qafco Reformers

Uhde Steam Reformer Design

Inlet manifold
Comparison Hydrogen Ammonia
Comparison reformer reformer
Burner
(Sincor) (QAFCO III)
Reformer
tubes
T proc. out [°C] 850 820

p proc. out [bara] 33.7 39.5

n tubes [-] 264 240

Catalyst
grid
Flue gas V flue gas [Nm3/h] 285,000 185,000
Outlet
manifold
Refractory Q abs. Ref. [MW] 101 83
system
lining

Q abs. Conv. [MW] 100 65

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The HMU is based on two large-scale hydrogen reformers with capacities of 100,000 Nm3/h each, designed
according to the proprietary Uhde steam reformer technology.

The project was awarded to Uhde in 1998 and executed in the following time frame:
start of negotiations May 1998

effective date of contract with Uhde Oct. 1998

effective date of subcontract with UOP Feb. 1999

end of basic engineering April 1999

start erection Feb. 2000

end of detail engineering Aug. 2000

start commissioning Aug. 2001

handover to client Nov. 2001

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It needs to be noted that this time schedule was not particularly tight. The client dictated the dates in order
to integrate with the much larger projects of the rest of the upgrader. If it had been for the HMU only, Uhde
would consider an overall duration in the range of 2 to 2,5 years for this type of project.

The typical flow scheme for an Uhde designed hydrogen plant incorporates a process condensate recovery
system, which re-uses the process condensate in the process and avoids vapor emissions from the treatment
of the condensate. This process has been in operation for more than ten years.

FL/PR Dr. Michel 30.06.2001 Z:\DAT\FL_FF2K\FOLIEN\Powerpo.int\Wasserstoff\_Standardpräsentation\hydrogen page 19 PRW-017 04/01

Flow Scheme Hydrogen Plant

Fuel Steamreformer
Steam reformer

Steam export
De-
De-
sulphurisation
sulphurisation

Processgas
gas
1
Process
2 3 4 5 6 cooler
cooler

Hydrogen
Feed
Combustion air
BFW

Convection
Convectionbank
bankcoils
coils HT-shift PSA
PSA
1 Steam generator HT-shift
Steam generator
2 Steam superheater
Steam superheater
3 Feed / steam preheater
Feed / steam preheater
4 Feed preheater
Feed preheater
5 Condensate partial evaporator
Condensate partial evaporator
6 Combustion air preheater C.W. Process water
Combustion air preheater reuse

The following diagram highlights another design criterion which Uhde always considers when designing a
hydrogen unit with a tailor-made fit for a specific client: the ratio between operating expenditures (OpEx)
and capital expenditures (CapEx).

The OpEx/CapEx-ratio is plotted over the feedstock cost in US$/MMBTU. For a given plant design one
can calculate the ratio between the OpEx and the CapEx, where the OpEx are based on a net present value
calculation for 10 years. According to Uhde experience, typical hydrogen plant designs will be arranged in
a more or less linear manner along the indicated dotted line.

There is always a trade-off between the cost factors OpEx and CapEx, e.g. on order to achieve very low,
competitive consumption figures that lead to low OpEx one has to install equipment for optimal heat
recovery that leads to an increased CapEx.

To give a practical example: the operator of plant 1 will spend during 10 years of operation 4 times as much
on operating cost as he will spend on the initial investment. The reason for this high ratio is the high gas
price at the specific location of plant 1. Obviously, this scenario calls for a design for low consumption
figures.

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 FL 13 .0 6.20 02 Z:\DAT\FL\FL _W OR K\Ko nfere nze n\20 02 _a kt\02 _0 6_ 12_KU _Fertilise r_Symposium\Papers\Master\Master-Fertilise r-Symposiu m pa ge 5

Process Design Criteria

OpEx *
CapEx
5.0
Designfor
Design forlow
low
Plant 1
consumption
consumption
4.0 Sincor
Plant 3
Plant 4
3.0

* Operating expenditures
vs. capital expeditures,
2.0 based on a 10 years
net present value
calculation

Designfor
Design forlow
low
1.0
investment
investment

0 1.0 2.0 3.0

Feed stock cost [US$ / MMBTU]

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Ratio of operating expenditures OpEx and capital expenditures CapEx

Much the opposite is true for the Sincor HMU design: the gas price is extremely low, and therefore the
most important cost factor for the client is the initial investment.

Before starting with the design work for a new hydrogen project, this graph and the principle behind it is
always considered to determine the design objective that will provide best value for the client. And as
demonstrated by the four example plants displayed, Uhde can provide a client with solutions for the whole
range of possible design cases.

Over a period of more than 25 years UOP has made continuous improvements to its Polybed technology
which has led to even larger capacity units and significant reductions in capital costs (Figure II).

Figure II PSA Product Capacity Milestones

PSA Product Capacity Milestones

300000 ?
250000
/h)
Nm³/h)
H2 Product ((Nm³

200000 > 12-bed

200.000
150000
12-bed
100000 fast cycle
12-bed 113.000
50000 71.000
10-bed
0 47.000
1975 1985 1995 2001 2005

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Prior to the Sincor project, PSA units with 10 or 12 adsorbers handled similar large hydrogen production
capacities. UOP’s studies for Sincor compared the operability, capital cost, and reliability of 14-adsorber
systems with these existing systems and chose the 14-adsorber system.

Figure III shows the 28 adsorbers in the two HMU trains.

Sincor PSA Units

UOP 4072-8

Also an evaluation of purifying the feed from the two steam reformers with a single PSA unit was made.
Although this option was technically viable and offered cost advantages, UHDE and UOP opted for two
separate PSA units in order to be consistent with the overall two-train plant concept. Although PSA
reliability is extremely high, UOP included several other features in the Sincor units to enhance their
reliability, including a back-up valve-header on the product side of each unit. If a valve malfunctions, the
valves in this back-up header take over and the PSA continues to operate in a 14-adsorber cycle, which is
the most efficient operating mode.

The 14-adsorber cycle has four adsorbers in the adsorption mode while the others are either reducing or
increasing the pressure in three pressure equalization steps, or on desorption (impurity removal) mode.
With the selected cycle either five or six adsorbers are supplying tail gas to the reformer-fuel mixing drum.
This operating regime provides very smooth flows of product hydrogen and reformer fuel gas. It also
optimizes hydrogen recovery. The tail-gas from the PSA units supply 75 percent of the steam reformers’
heat requirements. Automatic capacity and self-tuning algorithms ensure a steady flow of tail gas to the fuel
header. Sincor can turn down each unit to 40 percent of its design rate and maintain constant product purity
and hydrogen recovery. The product hydrogen contains less than 10 ppm by volume of carbon oxides,
which is critical for the lifetime and performance of the hydro-processing catalysts.

Within a PSA unit, the only moving parts are the switching valves. If a valve or an instrument fails, each
PSA unit can either bring the back-up valve header into operation or change to a 12-adsorber cycle. In
either case the PSA unit continues to process the same feed flow. The steam reformer furnace is not
affected and the hydrogen production falls only slightly.

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For Sincor, the feedback from the smart positioners indicates the position of each switching valve. This
arrangement simplifies cabling, input/output modules and junction boxes since all the signals are analog.

The tail gas from each adsorber vessel varies in composition during the cycle and flows through a mixing
drum to dampen the variation. Precise temperature control in the steam reformer furnaces is achieved
during all operating modes of the PSA units. In earlier PSA designs, a control valve on the fuel gas header
to the reformer compensated for pressure variations. In the Sincor units, any pressure change in the mixing
drum automatically adjusts internal steps within the PSA unit, so that the flow into the drum is constant.
The advantages of this control system are a lower tail gas pressure drop and a higher hydrogen recovery
rate.