Process Analytics in Claus Plants

With the increasing environmental

concerns, sulfur recovery has
become one of the leading issues in
emissions reduction in industry.
For gas processing and refining facilities sulfur recovery requirements
range from 97.5% to 99.8% .
The well known Claus Process with
some form of tailgas cleanup or
special processing capability can meet
this requirements with the help of
high performance process analytics.

Siemens Sensors and Communication, a leader in process analytics, has

proven over decades its competence
to plan, engineer, manufacture,
implement and service analyzer systems for use in Claus plants.
This Case Study provides details about
the Claus process and related analyzer
tasks.

Sulfur recovery
The relatively high sulfur content of
the still available crude oil and natural gas reserves and the more stringent standards for sulfur emissions
from oil, gas, and chemical processing facilities demand reliable and
cost effective technologies for sulfur
recovery. Sulfur recovery refers to
the conversion of hydrogen sulfide
(H2S) as byproduct of natural gas
plants and crude oil refineries to elemental sulfur.
The most common conversion
method is the Claus Process.
Approximately 90 to 95% of recovered sulfur is produced by the Claus
process.
First invented over 100 years ago,
the Claus Process has undergone a
continuous evolution in attempts to
increase the sulphur recovery efficiency of the process.
In the 1930s, a thermal stage was
added to the two catalytic stages,
which increased the recovery efficiency from 95% to approximately
97%. In the 1970s, a hydrogenation/hydrolysis plus amine separation was added to treat the tail gas
from the Claus process. In 1988,
SuperClaus was introduced, which
added a selective oxidation reactor
to the end of the Claus process,
increasing the efficiency to approximately 99%.
Sulfur recovered in Claus plants is
used for manufacturing e. g. of
medicines, cosmetics, fertilizers and
rubber products.
Chemical analysis of the process
streams is required for controlling
and monitoring the Claus process.
Process gas chromatography
together with continuous gas analyzers has proven to be a very reliable and cost efficient method.
Siemens Sensors and Communication provides efficient solutions for
this demanding analysis tasks.

Case Study December 2007

Siemens AG 2007

 Siemens AG 2007

The Claus Process

Claus Process for

H2S removal
Hydrogen sulfide (H2S) is commonly
found in natural gas and products from
oil refineries, especially if the crude oil
contains a lot of sulfur compounds.
Typical sources are
Gas from natural gas fields
Sour refinery gas
Sour water stripper gas
Sour gas from chemical plant
Sour gas from salt production plant
Sour gas from coal gasification
H2S is a smelly, corrosive, highly toxic
gas, which also deactivates industrial
catalysts. Therefore it is converted to
non-toxic and useful elemental sulfur
at almost all locations where it is produced. The process of choice is the
Claus Sulfur Recovery Process.
Most sulfur plants comprise two conversion stages: one non-catalytic, thermal
conversion stage and two or more catalytic conversion stages in series (Fig.1).
The Claus reaction is highly exothermic,
releasing a great deal of heat energy
that can be recovered by generating
steam in heat exchangers following the
conversion stages.

Thermal conversion stage

The H2S containing gas (SWS acid gas,
amine acid gas) is fed to the Thermic
Converter where it is partially oxidized
with air in a reaction furnace at high
temperatures (1000 to 1400 C).
Combustion air is fed to the burner,
with the amount of air controlled to
combust only 1/3 of the H2S to SO2
(reaction 1). 2/3 of the H2S remain unreacted due to lack of oxygen. Additionally air may be fed to combust also
ammonia and hydrocarbons entering
with the acid gas streams.

The furnace acts as a thermal conversion stage, as the high temperature in

the furnace will cause part of the H2S
and SO2 to combine via reaction (2).
Thus sulfur is formed, but some H2S and
SO2 remain unreacted.

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Catalytic conversion stage

The hot combustion products from the
furnace enter the waste heat boiler and
are partially cooled by generating
steam. The gas is further cooled in the
first sulfur condenser, to condense the
sulfur formed in the furnace, which
is then separated from the gas and
drained to a collection pit.
The gas leaving the sulfur condenser is
heated again to avoid forming liquid
sulfur in the downstream catalyst bed
and enters the first catalytic converter.
There, the remaining H2S reacts with
the SO2 at lower temperatures over a
conversion catalyst (mostly aluminabased) to make more sulfur. Unfortunately the reaction does not go to completion even with the best catalyst.
Typically, about 70% of the H2S and SO2
in the gas will react via reaction (2) to
form sulfur, which leaves the reactor
with the gas as sulfur vapor.
The hot gas is cooled in the second sulfur condenser, where more sulfur is
formed, separated, and drained to the
collection pit. This is usually followed by
one or two more heating, reaction, and
condensing stages to react most of the
remaining H2S and SO2.

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Fig. 1: Generic flowsheet of the Claus Process, simplified

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 Siemens AG 2007

The Claus Process (ctd.)

Tailgas treatment stage

A small amount of H2S and SO2 remains
in the tail gas. The tailgas is routed to
either a Tailgas Cleanup Unit (Modified
Claus Process with Tailgas Cleanup) for
further processing, or to a Tailgas Thermal Oxidizer to incinerate all of the sulfur compounds in the tailgas to SO2
before dispersing the effluent to the
atmosphere.

Claus process versions (selection)

Claus Process versions

Increasingly stringent standards for sulfur emissions have caused further
developments of the Claus Process with
the objective of higher recovery rates.
Table 1 shows a selection.

Analysis Tasks
The continuous development of sulfur
recovery processes has increased the
demand in efficient process analytical
techniques for process and emission
control. Stringent requirements are
placed on the process analyzers and
especially on the tail gas analyzer to
determine process parameter air
demand.
Various measuring points with different
tasks are located along the process
route (Fig. 1 and table 2). The most
important task is the determination of
the concentrations of hydrogen sulphide (H2S) and sulphur dioxide (SO2)
in the desulfurized gas (tail gas, MP 5 in
Fig. 1) and following from this the calculation of the H2S/SO2 ratio.

Claus Process

This original Claus process uses only the catalytic reaction

Modified
Claus Process

This process uses the additional thermal conversion stage where 1/3 of
the H2S is converted to SO2 and S. The modified Claus process is generally
limited to a sulfur recovery efficiency of 94 ... 97%. Higher recovery rates
are achieved by adding a tail gas treatment unit.

Oxygen
Claus Process

This process uses an air/oxygen mixture to reduce the nitrogen content in

the process flow for better plant efficiency.

Super Claus

This process uses a special catalyst material in the last catalytic reactor

Tab. 1: List of Claus Process versions

This ratio is the only parameter for

direct process control through the
amount of combustion air fed to the furnace of the thermal stage. The ratio
should be kept to 2:1 to run the process
at optimum efficiency.
Challenges
There are two major analysis challenges
that must be considered when choosing
the measuring principle of the analyzer:
Other gaseous components may be
present in the sample gas such as
CO2, HC, COS and CS2 with varying
concentration levels.
So the analyzer principle should be
free from cross-interferences.
The sample gas is saturated by sulfur
vapor or even elemtary sulfur may be
produced that may amongst others
block sample lines. So the entire sampling system must be heated to a

Sampling point
Sampling stream

Measuring
Components

Suitable
Siemens Analyzer

Process gas feed

H2S, SO2 , CO2

HC

MAXUM Claus
FIDAMAT 6

Inlet of first catalytic converter

H2S, SO2

MAXUM Claus

Outlet of first catalytic converter

H2S, SO2

MAXUM Claus

Outlet of last catalytic converter

H2S, SO2

MAXUM Claus

Tail gas downstream the last condenser H2S, SO2

COS, CS2
N2, H2O, O2

MAXUM Claus

At the sulfur collection pit

H2S, SO2

MAXUM Claus

Before / at the stack (CEM)

SO2, CO, NOx

O2

ULTRAMAT 6
OXYMAT 6

temperature that prevents reliably

from sulfur condensation.
Solution from one hand
Siemens Process Analytics is able to supply turnkey analyzer systems for Claus
plants including CEM system, along
with planning, engineering, start-up,
commissioning and training services.

OXYMAT 6
Fig. 2: Claus plant

Measurements at MP 3, 4 and 5 can be performed with just one Analyzer using sample stream
switching
Tab. 2: Analysis measuring tasks and suitable Siemens analyzers

 Siemens AG 2007

The MAXUM edition II Claus Analyzer

Solution provider for Tail Gas Analysis

MAXUM II Claus Analyzer

MAXUM II Gas Chromatograph
MAXUM Edition II represents the top
technology in process gas chromatography with outstanding features resulting
in a high versatility to solve any given
application task with best possible analytical results at lowest costs:
Multiple analytical tools such as
ovens, detectors, valves etc.
Single and independent dual oven
concept for minimizing the number
of analyzers
Airbath and airless oven to reduce
utility costs
Valveless column switching to reduce
maintenance
Parallel chromatography for fast
analysis, system simplification and
increase of reliability
Complete networking capabilities and
powerful processing software.
MAXUM II Claus Analyzer
for tail gas analysis
Process gas chromatography has generally proven to be a reliable and cost
effective method to solve the demanding task of Claus tail gas analysis.
Especially MAXUM II, because of its double oven concept and outstanding modularized design, can be designed a very
efficient Claus gas analyzer.
The two separately heatable ovens with
airless mass heating (fig. 4) are used to
clearly separate the functionalities
required for the analysis task:
The right oven contains the analysis
system including the separating columns, circuit and detectors,
The left oven contains sample conditioning, calibration media dosing and
the dosing valve. To prevent from
blockages by solid or plastic sulfur the
sample line is purged with nitrogen or
air.

Fig. 3: MAXUM ed. II Claus analyzer

Heated sampling and dosing

Sulfur becomes solid or semiliquid
when the sample temperature
drops below 135 C or rises above
150 C. Therefore the sample temperature must be kept at 145 C
continuously from the sampling
Fig. 4: MAXUM ed. II Claus analyzer, open
point to the analyzer.
(covered by S film)
Steam heated sampling lines (tube-intube technology, Fig. 5) and sample
No UV-lamp, long-time stability,
conditioning components mounted in a
no expensive spare parts regularly
high temperature environment (left
needed
oven) meet this requirement .
High accuracy through use of chromatographic separation (no interferUser Benefits
ences by sulfur, COS, CS2)
Proven technology with high reliabil High reliability because of compreity, long term stability
hensive self diagnosis
Reliable operation through backpurge Extended analysis to other compoto clean analyzer and sample lines in
nents possible such as N2, CO2, COS,
case of temperature drop or power
H 2O
failure and during maintenance
Network with other GCs on plant
Easy operation, remote operation
Very cost efficient
Low maintenance efforts

Fig. 5: Tube-in-Tube technology (left) and isolated sampling lines (right)

 Siemens AG 2007

Siemens Process Analytics at a glance

Products

Siemens Process Analytics

Siemens Process Analytics is a leading
provider of process analyzers and process analysis systems. We offer our global customers the best solutions for
their applications based on innovative
analysis technologies, customized system engineering, sound knowledge of
customer applications and professional
support. And with Totally Integrated
Automation (TIA). Siemens Process
Analytics is your qualified partner for
efficient solutions that integrate process analysers into automations systems in the process industry.
From demanding analysis tasks in the
chemical, oil & gas and petrochemical
industry to combustion control in
power plants to emission monitoring at
waste incineration plants, the highly
accurate and reliable Siemens gas chromatographs and continuous analysers
will always do the job.
Siemens process Analytics offers a wide
and innovative portfolio designed to
meet all user requirements for comprehensive products and solutions.

Our Products
The product line of Siemens Process
Analytics comprises extractive and insitu continuous gas analyzers (fig. 6 to
9), process gas chromatographs (fig. 10
to 13), sampling systems and auxiliary
equipment. Analyzers and chromatographs are available in different versions for rack or field mounting, explosion protection, corrosion resistant etc.
A flexible networking concept allows
interfacing to DCS and maintenance
stations via 4 to 20 mA, PROFIBUS,
Modbus, OPC or industrial ethernet.

Extractive Continuous Gas Analyzers (CGA)

ULTRAMAT 23
The ULTRAMAT 23 is a cost-effective multicomponent analyser for the
measurement of up to 3 infrared sensitive gases (NDIR principle) plus
oxygen (electrochemical cell). The ULTRAMAT 23 is suitable for a wide
range of standard applications. Calibration using ambient air eliminates
the need of expensive calibration gases.
CALOMAT 6/62
The CALOMAT 6 uses the thermal conductivity detection (TCD) method
to measure the concentration of certain process gases, preferably hydrogen.The CALOMAT 62 applies the TCD method as well and is specially
designed for use in application with corrosive gases such as chlorine.
OXYMAT 6/61/64 The OXYMAT 6 uses the paramagnetic measuring method and can be
used in applications for process control, emission monitoring and quality
assurance. Due to its ultrafast response, the OXYMAT 6 is perfect for
monitoring safety-relevant plants. The corrosion-proof design allows
analysis in the presence of highly corrosive gases.
The OXYMAT 61 is a low-cost oxygen analyser for standard applications.
The OXYMAT 64 is a gas analyzer based on ZrO2 technology to measure
smallest oxygen concentrations in pure gas applications.
ULTRAMAT 6
The ULTRAMAT 6 uses the NDIR measuring principle and can be used in
all applications from emission monitoring to process control even in the
presence of highly corrosive gases.
ULTRAMAT 6 is able to measure up to 4 infrared sensitive components in
a single unit.
ULTRAMAT 6 /
Both analyzer benches can be combined in one housing to form a multiOXYMAT 6
component device for measuring up to two IR components and oxygen.
FIDAMAT 6

The FIDAMAT 6 measures the total hydrocarbon content in air or even in

high-boiling gas mixtures. It covers nearly all requirements, from trace
hydrocarbon detection in pure gases to measurement of high hydrocarbon concentrations, even in the presence of corrosive gases.
In-situ Continuous Gas Analyzer (CGA)
LDS 6
LDS 6 is a high-performance in-situ process gas analyser. The measurement (through the sensor) occurs directly in the process stream,
no extractive sample line is required. The central unit is separated from
the sensor by using fiber optics. Measurements are carried out in realtime. This enables a pro-active control of dynamic processes and allows
fast, cost-saving corrections.
Fig. 7: Product scope Siemens Continuous Gas Analyzers

Fig. 6: Series 6 gas analyzer (rack design)

Fig. 8: Series 6 gas analyzer (field design)

Fig. 9: LDS 6 in-situ laser gas analyzer

 Siemens AG 2007

Siemens Process Analytics at a glance

Products (continued) and Solutions

Fig. 10: MAXUM edition II Process GC

Process Gas Chromatographs (Process GC)

MAXUM edition II MAXUM edition II is very well suited to be used in rough industrial environments and performs a wide range of duties in the chemical and petrochemical industries and refineries.
MAXUM II features e. g. a flexible, energy saving single or dual oven concept, valveless sampling and column switching, and parallel chromatography using multiple single trains as well as a wide range of detectors
such as TCD, FID, FPD, PDHID, PDECD and PDPID.
MicroSAM
MicroSAM is a very compact explosion-proof micro process chromatograph. Using silicon-based micromechanical components it combines
miniaturization with increased performance at the same time.
MicroSAM is easy to use and its rugged and small design allows mounting right at the sampling point. MicroSAM features drastically reduced
cycle times, provides valveless sample injection and column switching
and saves installation, maintenance, and service costs.
SITRANS CV
SITRANS CV is a micro process gas chromatograph especially designed
for reliable, exact and fast analysis of natural gas. The rugged and compact design makes SITRANS CV suitable for extreme areas of use, e.g. offshore exploration or direct mounting on a pipeline.
The special software "CV Control" meets the requirements of the natural
gas market, e.g. custody transfer.
Fig. 13: Product scope Siemens Process Gas Chromatographs

Our solutions
Fig. 11: MicroSAM Process GC

Analytical solutions are always driven

by the customers requirements. We
offer an integrated design covering all
steps from sampling point and sample
preparation up to complete analyser
cabinets or for installation in analyser
shelters (fig. 14). This includes also signal processing and communications to
the control room and process control
system.

Fig. 12: SITRANS CV Natural Gas Analyzer

Fig. 14: Analyzer house (shelter)

We rely on many years of world-wide

experience in process automation and
engineering and a collection of specialized knowledge in key industries and
industrial sectors. We provide Siemens
quality from a single source with a function warranty for the entire system.
Read more in "Our Services.

 Siemens AG 2007

Siemens Process Analytics at a glance

Solutions (continued) and Services

Our solutions ...

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Analyzer networking for

data communication
Engineering and manufacturing of process analytical solutions increasingly
comprises "networking". It is getting a
standard requirement in the process
industry to connect analyzers and
analyzer systems to a communication
network to provide for continuous and
direct data transfer from and to the
analysers.
The two objectives are (fig. 16):
To integrate the analyzer and
analyzer systems seamless into the
PCS / DCS system of the plant
and
To allow direct access to the analyzers
or systems from a maintenance
station to ensure correct and reliable
operation including preventive or
predictive maintenance (fig.15).
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Siemens Process Analytics provides networking solutions to meet the demands

of both objectives.

Our Services
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Fig. 15: Communication technologies

Siemens Process Analytics is your competent and reliable partner world wide
for Service, Support and Consulting.
Our rescources for that are
Expertise
As a manufacturer of a broad variety
of analyzers, we are very much experienced in engineering and manufacturing of analytical systems and
analyzer houses.
We are familiar with communication
networks, well trained in service and
maintenance and familiar with many
industrial pro cesses and industries.
Thus, Siemens Process Analytics owns
a unique blend of overall analytical
expertise and experience.

Global presence

With our strategically located centers

of competence in Germany, USA,
Singapore, Dubai and Shanghai, we
are globally present and acquainted
with all respective local and regional
requirements, codes and standards.
All centers are networked together.

Fig. 17: Portfolio of services

 Siemens AG 2007

Siemens Process Analytics at a glance

Services, continued

Our Services ...

Service portfolio
Our wide portfolio of services is segmented into Consulting, Support and
Service (fig. 17 to 18). It comprises
really all measures, actions and advises
that may be required by our clients
throughout the entire lifecycle of their
plant. It ranges from site survey to
installation check, from instruction of
plant personnel to spare part stock management and from FEED for Process
Analytics (see below) to internet-based
service Hotline.
Our service and support portfolio
(including third-party equipment) comprises for example:
Installation check
Functionality tests
Site acceptance test
Instruction of plant personnel on site
Preventive maintenance
On site repair
Remote fault clearance
Spare part stock evaluation
Spare part management
Professional training center
Process optimisation
Internet-based hotline
FEED for Process Analytics
Technical consullting
FEED for Process Analytics
Front End Engineering and Design
(FEED) is part of the planning and engineering phase of a plant construction or
modification project and is done after
conceptual business planning and prior
to detail design. During the FEED phase,
best opportunities exist for costs and
time savings for the project, as during
this phase most of the entire costs are
defined and changes have least impact
to the project. Siemens Process Analytics holds a unique blend of expertise in
analytical technologies, applications
and in providing complete analytical
solutions to many industries.

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Fig. 18: Portfolio of services provided by Siemens Process Analytics

Based on its expertise in analytical technology, application and engineering ,

Siemens Process Analytics offer a wide
scope of FEED services focused on analysing principles, sampling technologies,
application solutions as well as communication system and given standards (all
related to analytics) to support our clients in maximizing performance and
efficiency of their projects.
Whether you are plant operators or
belong to an EPC Contractor you will
benefit in various ways from FEED for
Process Analytics by Siemens:
Analytics and industry know how
available, right from the beginning
of the project
Superior analyzer system performance with high availability
Established studies, that lead to
realistic investment decisions
Fast and clear design of the analyzer
system specifications, drawings and
documentation
Little project management and
coordination effort, due to one
responsible contact person and
less time involvement

Additional expertise on demand,

without having the costs, the effort

and the risks of building up the capacities
Lowest possible Total Costs of Ownership (TCO) along the lifecycle regarding investment costs, consumptions,
utilities supply and maintenance.

 Siemens AG 2007

Case Study
Siemens Process Analytics - Answers for industry

If you have any questions, please contact your local sales representative or any of the contact addresses below:
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Phone: +49 721 595 3829

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E-mail:

Phone: +1 713 939 7400

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E-mail: [email protected]

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www.siemens.com/processanalytics

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Siemens AG

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Subject to change