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Alkaline Chloride

electrolysis plants
Superior membrane
process

tk

A company
of ThyssenKrupp
Technologies
Uhde
2 Table of contents

3 Company profile

4 Uhde’s remarkably long experience

6 The Uhde membrane process

8 The only membrane cell of its kind

10 Current through bipolar electrolyser

12 The advantages of a modular concept

14 There is even more in for you

15 Technical data

16 Solutions through innovations

18 Additional Uhde Process Features

19 Services for our customers

The sodium chloride crystal.


It consists of tiny cubes tightly
bound together.
Similar to the Uhde single
element technology.
This modular concept has
a significant number of
advantages. Find out more
about these benefits and one
of the world’s leading suppliers
of chlorine plants.
Company profile 3
Uhde and De Nora group
to collaborate on electrolysis

Engineering offices
and headquarters
of Uhde in Dortmund,
Germany.

To date, the Dortmund-based Uhde and De Nora intend to Uhde was founded in 1921 and
engineering contractor with its combine their technologies and is now part of the ThyssenKrupp
highly specialised workforce of expertise in research and devel- group. The company employs
around 3,500 and its interna- opment, in order to provide 3,500 persons around the
tional network of subsidiaries their worldwide alkali chlorine world. Its main field of activity,
and branch offices, has suc- industry customers with even alongside chlorine alkali elec-
cessfully completed over 2,000 better performance in the fields trolysis, being in the
projects throughout the world. of planning, design, construc- engineering and construction of
tion and after-sales service for plants for fertilisers, organic
Uhde can offer more than 250 electrolysis plants. It is our chemicals, polymers, oil and
different processes covering target to optimise the relevant gas technology and pharma-
many different sectors of the technologies and to reduce ceuticals.
chemical industry. even further the energy con-
sumption. Since 1923, De Nora has been
In the field of chlorine technology Uhde and De Nora have expe- one of the world leaders in the
Uhde and De Nora established rience stretching back over development of new technolo-
beginning of 2001 a Joint decades in this field and have gies and industrial processes,
Venture to cooperate in the field constructed over 135 reference particularly for the alkaline
of electrolysis technology. plants around the world. They chlorine industry. The company
This cooperation will be based now have subsidiaries on all employs a total of 650 staff, with
on the foundation of two joint continents. 350 in Italy and 300 abroad.
companies domiciled in Milan/
Italy and mentioned below: Our plant construction business
in this technological field will
Uhdenora Technologies S.r.l. in future be handled by Uhde
Uhdenora S.p.A. of Dortmund, Germany and
Uhdenora S.p.A. of Milan.
The new italian company will be
managed by Uhde.
This cooperation will further
improve our service for our cus-
tomers in this highly competitive
market.
4 Uhde’s remarkably
long experience

Uhde has more than The first processes used to Today both the diaphragm and Until today Uhde’s know-how is
manufacture chlorine and the amalgam processes have based on the combined efforts
caustic soda involved the become obsolete for new of these three companies in the
40 years of experience
electrolytic splitting of salt installations as they have a research and development of
(sodium chloride) and were higher energy consumption and this technology.
in the designing and introduced to Germany in 1890 are less environmentally friendly. Since 1998 Uhde is the sole
in the form of the ”Griesheim” They have been replaced by the owner of this know-how and
construction of chlorine/ diaphragm cell and to the USA latest development in chlorine/ continues to put great effort in
in 1897 in the form of the caustic soda technology: the the further development of the
”Castner-Kellner” cell which membrane process. Uhde membrane cell technology.
caustic soda plants.
worked on a mercury/amalgam
basis. In 1973 when the first commer- In December 2000, Uhde and
Our more than 150 cial membranes became avail- Gruppo de Nora of Milano, Italy
In the 1980s the manufacture able, Hoechst AG, Bayer AG and agreed on the foundation of
plants throughout the of chlorine using these two Uhde GmbH began research Uhdenora Technologies S.r.l. to
processes reached maximum and development work on the further optimise the technology
capacity producing approx. 35 membrane technology. and to reduce even further the
world have an overall
million tpa. More than 80 of the This process is not just energy energy consumption. The
plants involved were built by efficient, it also produces entrepreneurial management of
production capacity in Uhde. consistently high-quality caustic the joint company lays with
soda, is environmentally friendly, Uhde.
excess of 9 million tpa and extremely safe.

NaOH (100%) and help Comparative energy consumption figures

kWh/t NaOH Conversion factor: 1 t steam ≈ 400 kWh


make Uhde unique in
3 600 _

its field.
3 200 _

2 800 _

2 400 _

2 000 _

Mercury process Diaphragm process Membrane process

DC-power Steam consumption for concentration of the NaOH to 50 %


5

The SADAF plant


in Saudi Arabia,
which has a capa-
city of 250,000 tpa
NaOH (100%).
This plant went on
stream in 1997
and is one of the
largest membrane
plants in the world.
6 The Uhde membrane process
All from one hand

Uhde is the only

contractor able to

supply complete
Brine
Brine Brine
plant complexes
Filtration
Filtration Purification

from one hand.

The Uhde know-how for the


membrane process covers all
the process units as shown
in the diagram as well as vari-
ous downstream and utilities
Brine Clarification Chlorine
supply units.
and Precipitation Compression
A modern chlorine plant is
equipped with a brine circulation
system which is specially desi-
gned for the membrane techno-
logy. The higher sodium chloride
Cl2
depletion in the membrane cells
means that the recycle rate and
the amount of equipment
needed are significantly lower Salt storage Brine Chlorine
than in a mercury plant with the and Handling Saturation Treatment
same capacity. The plant has
an additional brine preparation
process which uses polishing
filters and ion exchangers to
ensure that higher quality brine
enters the membrane cells.

The chlorine leaves the cells with


the depleted brine. If high-purity Anolyte Membrane
chlorine is required (e.g. for a Dechlorination Electrolysis
downstream VCM plant), hydro-
chloric acid can be added to the
feed brine to reduce the oxygen
content in the chlorine product.
NaOCl-
Solution

Chlorate Transformer/
Decomposition Rectifier
7

Chlorine Absorption Bleaching Lye


and Safety System
Cl2
Tailgas

Chlorine Once the wet chlorine gas is


cooled and filtered it can be fed
directly to the consumer plant
(e.g. a hydrochloric acid plant).
In other cases, it is dried and
Chlorine Chlorine Chlorine
Dry compressed before being fed to
Liquefaction Storage Evaporation
Chlorine the consumer plant (e.g. a VCM
plant) or before being liquefied
for storage in tanks.

Cl2 Tailgas Chlorine


The membrane process also
involves a catholyte circulation
H2 Hydrogen system. A part stream of the
product NaOH 32% is recycled
Hydrogen from
as catholyte inlet to the mem-
Steam-Reformer
Hydrogen brane cells. Before inlet, it is
Treatment diluted by demineralised water
to NaOH 30%. The produced
caustic soda can be concentra-
ted and fed to a crystallisation
unit if necessary.
Circulation
Hydrogen is a valuable by-pro-
duct of the process and can be
supplied to hydrogen consum-
Catholyte Caustic Caustic ers, such as hydrochloric acid
NaOH plants or hydrogen plants, once
and Cooling Dilution
32 % it has been cooled and filtered.

Caustic Caustic 50 %
Concentration

The Uhde membrane


process providing all
units from one single
source.
8 The only membrane cell of its kind:
The single element

The single element


One of the most significant
Anode half shell
factors affecting the operating
PTFE frame gasket
costs of a chloralkali plant
Discharge pipe
is its on-stream time which is
Membrane
particularly dependent upon
the reliability of the materials
and the robust construction of
Cathode half shell
the cell.

Sealing cord This is especially true in the


case of membrane electrolysis
units in which the relatively
sensitive membrane plays the
central role.

The single cell element, other-


wise known as the single ele-
ment, is based on an optimal
combination of the ideal mate-
rials for the job and simple
maintenance.

The anode half shell is made


completely from titanium and the
The single element comprises cathode half shell from nickel.
an anode half shell, a cathode The seal system comprises a
half shell, a membrane and PTFE frame gasket and goretex
a sealing system with external
flanges. sealing cords. The external
steel flanges, which have elec-
trically insulated bolting with
spring washers, guarantee
that the single element has no
leakages for the whole service
life.

Functional description
Pure brine enters the anode
half shell via an external tube
and a nozzle and is distributed
across the whole width via an
internal feed pipe.

A downcomer plate uses the


9

Cathode half shell

Foam

Anode half shell

Functional description
Pure brine enters the anode
half shell via an external tube
and a nozzle and is distributed
across the whole width via an
internal feed pipe.
Baffle plate
A downcomer plate uses the
gas lift effect to create a high
degree of internal brine circula-
tion ensuring ideal distribution
with uniform density and
temperature.
A baffle plate is arranged in
the upper section of the anode
half shell and has the following
3 basic functions:
Contact strip

● The brine and the chlorine


are fed to the upper end of
the anode half shell ensuring
that this section is completely
supplied with brine for a proper
function of the membrane.
● The chlorine is separated
from the brine behind the Downcomer plate

baffle plate in a kind of


„separation zone“, so that
the chlorine gas and the brine
can leave the single element
in a homogeneous flow
through the discharge pipe.
● The gas lift effect also causes
circulation around the baffle
plate ensuring uniform distri-
bution here too.

A similar method involving a feed


pipe is used to distribute caustic
soda in the cathode half shell.
Feed pipe
The products, hydrogen and
Feed pipe
caustic soda (32%), also
leave the single element via a
discharge pipe.
Discharge
Due to the fact that there is
only a small difference in the
caustic soda concentration at
the inlet and at the outlet and
that hydrogen and caustic soda
are more easily separated the
cathode half shell does not
have a downcomer and a baffle
plate.
10

1.+2.

Principle of the
current flow
through the bipolar
stack of single
elements.
Current through bipolar electrolyser 11

Membrane

Anode

1.

A direct and short current path


ensures low ohmic drop
Cathode and ideal current
distribution.

Plate conductor

The single elements are 2.


arranged in series to form an
Contact strip
electrolyser. A parallel connec-
tion is used on the electrolyte
and product side whilst the
serial configuration is used for
the electrical side. The electro-
lysis current (direct current) is
fed across contact strips from
the cathode half shells to the
anode half shells of the adjacent
single elements in the electro-
lyser. Internal plate conductors
arranged in the half shells ensure
uniform current distribution
to the anodes and cathodes.

Single elements are assembled


and tested in the workshop
outside the cell room where
they can be stored for months.
In case of maintenance of a
single element from the cell
room it can be quickly and
easily replaced by another one
taken from the stores.
12

Connection of the
inlet and outlet
pipes to each
individual element
and to the power
supply.
The advantages of a modular concept 13

The bipolar membrane electroly-


ser is a modular concept, that
has a number of advantages
including low investment costs,
low energy consumption and a
long service life.
The single elements are sus-
pended in a frame and are
pressed against each other by
a clamping device to form a
„bipolar stack“. Slight pressure
by spring loaded pressure bolts
is exerted on the stack prior
to start-up to ensure optimal
electrical contact between the
elements. In contrast to con-
ventional electrolysers with a
filter press design, no heavy-
duty pressers or track rods are
needed to seal the electrolyser.
The elements are all sealed
individually beforehand which
leads to increased operational
reliability.

All the elements are connected Below: The single Top: Bipolar membrane electrolyser,
to the inlet and outlet headers element rack: pictured here in the cell room at BAYER
Each element Uerdingen: we see 6 bipolar electrolysers
arranged underneath the elec- can be exchanged with a total of 158 single elements in each
trolyser by flexible, transparent individually electrolyser (79 elements forming a stack).
PTFE tubes (see picture). The
tubes with smaller cross-sec-
tions ensure that a constant
stream of electrolyte is supplied
to the half-shells, whilst the
Single element
tubes with larger cross-sections
(corrugated hoses) carry the Contact strip
chlorine gas with anolyte and
hydrogen gas with catholyte
away from the cell. This fail-safe
connection system can be used
External flexible
to check each individual cell for hose-connections
Cell rack
proper functioning by observing for the inlet and
outlet of fluids,
the colour and flow of the Header
located underneath
product streams in these tubes. the electrolyser.

Between 20 and 80 elements Busbars


can be connected to form a
stack. Several of these stacks
connected in series create a
membrane electrolyser.
Outlet hoses

Inlet hoses
14 There is even more in for you

Cell room
crane

Product main
headers for Cl2+H2

Single elements
Pressure plates

Cell headers for


Cl2 + anolyte
and H2 + catholyte

The Uhde design of the cell room has been A number of electrolysers Each electrolyser is equipped
(the number being determined with a control and instrument
by the production capacity) unit for adjusting the amount of
optimised to ensure simple maintenance,
are set up side by side and electrolytes and with shut-off
electrically connected in parallel. valves.
minimal space requirement and low investment A rectifier supplies one or more
of the electrolysers with direct A header system is attached to
costs. It has been standardised to a large extent current and they can be easily the front side of the electrolysers
serviced by disconnecting the for distributing the electrolytes,
rectifier or by the individual or for collecting the products.
and is shown in detail in a 3D computer model
circuit breakers and isolating
switches.
(PDMS).
The pipelines, which are used
for supplying the single ele-
ments with brine and caustic
soda and discharging the
chlorine, caustic soda and
hydrogen, are arranged under-
neath the electrolyser such
that the single elements can
be easily replaced.
Technical data 15

Operating data Product quality Power Consumption per metric ton NaOH

U [V] E[kWh]
Current density up to 6 kA/m2 Caustic soda solution
3,2_ _2300
Power consumption see graph NaOH 32 % (wt.)
Cell temperature 88 - 90° C NaCl < 30 ppm
3,0_ _2200

Service life : Gaseous chlorine


2,8_ _2100
anode coating > 8 years Cl2 > 98 % (vol.)
cathode coating > 8 years O2 0.6-1.5 % (vol.)
2,6_ _2000
membranes > 4 years H2 < 0.05 % (vol.)
gaskets > 4 years
2,4_ _1900
metal elements > 10 years Hydrogen
Active area per element 2.72 m2 H2 > 99.9 % (vol.)
2,2_ _1800
_

0 1 2 3 4 5 6 7 i [kA/m2]
16 Solutions through innovations

Single element technology High material quality Membrane stability Individual seal system
The single element can be The anode half shell (Ti), catho- The membranes in the cell Each single element is sealed
replaced quickly and easily. de half shell (Ni), gaskets and elements are fixed between using a flange, bolting and
Elements are assembled tubes (PTFE) are all made two electrodes using spacers. PTFE gaskets. Each cell
in the electrolyser workshop, from corrosion-resistant The electrode spacing can be element is tested prior to
where leakage tests are material and guarantee the optimally adapted to each operation to ensure that it is
carried out. cell elements a maximum membrane type using spacers 100% leakproof. Costly
service life. The electrolyser with the appropriate thick- pressing systems, such as
These features ensure: headers are long service life ness. those used in electrolysers
● highest possible operational components and are made with a filter press design, are
reliability from PVC/FRP or titanium on not necessary.
● easy maintenance the anode side and from
● cost-optimised membrane PP/FRP on the cathode side.
replacement and electrode
recoating according to
schedule
● no additional investments
needed for back-up electro-
lysers
● minimal loss of production
17

Bipolar arrangement Modular construction High current densities State-of-the-art technology


The bipolar arrangement The modular construction of Single-element cells can be The single-element techno-
allows the voltage of each the single element electroly- operated at a current density logy and the alkali-chloride
single element to be precisely sers allows the cell room to of up to 6 kA/m2. This permits technology are under costant
monitored. Faults can be be configured in a number low investment cost and low development and are contin-
spotted immediately and of different ways. space requirement for a cell ually being adapted to meet
consequent damage avoided. The electrolysers can have up room. increasing demands. This
Uhde has been using the to 160 elements, whilst there ensures that our technology
bipolar cell arrangement for is no limit to the number of No stray currents is always state-of-the-art and
over 20 years and has much electrolysers permitted in always at the head of its field.
more experience in this field each cell room. Consequently, Stray currents are hardly The third cell generation is
than most of its competitors. different cell rooms can be detectable, even in the largest now in operation and is
realised for different capacities, electrolysers which can have compatible with previous
areas of application and oper- up to 160 cell elements. This generations. Older elements
ations etc. whilst the same is attributable to the fact that can be modernised during
cell type is used in all cases. the electrolyte enters and remembraning and recoating
Existing cell rooms can also leaves the cells via long tubes processes.
be easily expanded. which are situated outside
the cell and which act as
insulators.
18 Additional Uhde process features

Pressurised cell operation External caustic circulation Brine acidification Chlorine drying tower
The robust design and excel- Uhde strongly recommends Feed brine can be acidified to The Uhde chlorine drying
lent tightness of the cells that the membrane electrol- improve the Cl2 gas quality. tower is part of our range of
allows that they can be oper- ysers are operated with exter- The potential risk of destroy- proprietary equipment. One
ated at pressures of up to nal circulation loops for the ing membranes by over-acidi- particular feature of the tower
200 mbar g. Blowers for Cl2 caustic soda solution and with fication is eliminated in the is the fact that sulphuric acid
and H2 are not necessary as a heat exchanger. This will al- cell element by the internal consumption is at its lowest
air cannot be sucked into the low plant operators to optimi- cell design (downcomer plate) when the ultimate humidity of
Cl2 or H2 lines. se the temperature of the cells which provides effective mix- the chlorine is at its lowest.
Each electrolyser is equipped at any load and to cool down ing within the cells. This is achieved by the two-
with safety valves for Cl2 and electrolysers in the event stage design which is housed
H2 to ensure safe plant of shutdowns thus avoiding in a single tower thus saving
operation. This safety device the production of off-spec. Waste gas dechlorination space and investment cost.
is exclusive to Uhde. caustic soda. Any plant using gaseous or
Operate with a large volume liquid chlorine, must comply
of caustic soda solution makes with stringent environmental
the plant not sensitive to short regulations. The waste gas
disturbances e. g. to the dechlorination unit is an es-
demineralised water supply. sential feature in this respect
and the Uhde design ensures
that chlorine cannot enter the
environment under any oper-
ating conditions.
Services for our customers 19

Uhde is dedicated to providing Uhde provides more than the


their customers with a wide spectrum of services associated
range of services and to with an EPC contractor from the
supporting them in their efforts initial feasibility study, to financ-
to succeed in their line of ing and project management
business. right up to the commissioning
With our worldwide network of of units and grass-root plants.
subsidiaries, affiliated companies,
experienced local representatives Our large portfolio of services
and first-class backing from our ● Feasibility studies/Technology
head office, Uhde has the ideal selection
qualifications to achieve this ● Project management
goal. ● Arranging financing schemes
between customers, partners,
We at Uhde place particular im- ● Financial guidance based on
operators and our specialists.
portance on getting together intimate knowledge of local
This enables our
with the customers at an early laws, regulations and tax
customers to benefit from
stage to combine their ambition procedures
the development of new
with our experience. ● Environmental studies
technologies and the
Whenever necessary we give ● Basic/Detail engineering
exchange of trouble-
potential customers the oppor- ● Utilities/Offsites/Infrastructure
shooting information.
tunity to visit operating plants ● Procurement/Inspection/
and to personally evaluate such Transportation services
We like to cultivate our
matters as process operability; ● Civil works and erection
business relationships
maintenance and on-stream ● Commissioning
and learn more about the
time. We aim to build our future ● Training of operating personnel
future goals of our
business on the confidence our ● Plant operation/Plant
customers. Our after-sales
customers place in us. maintenance
service includes regular
consultancy visits which keep
The policy of our Uhde group For more information contact
the owner informed about latest
and our subsidiaries is to one of the Uhde offices near
developments or revamping
ensure utmost quality in the you or see Internet:
possibilities. The direct delivery
implementation of our projects. www.thyssenkrupp.com/uhde
of spare parts has always been
Our head office and subsidiaries
part of the after-sales service
worldwide work to the same Further information on this
provided by Uhde.
quality standard, certified DIN / subject can be found in the
Uhde stands for tailormade
ISO 9001 / EN29001. following video:
concepts and international com-
We remain in contact with our The market is never wrong
petence.
customers even after project The success story of our
Competence that is based an
completion. Partnering is our Single-Element Technology
more than 79 plants worldwide
byword.
Process control
featuring membrane techno-
By organising and supporting The video is available free of
system configuration. logy.
technical symposia, our Chlorine charge in English, in VHS, PAL
Symposium for example, we or NTSC from:
promote active communication Public Relations,
Mrs Klimeck
Tel.: +49 2 31 5 47-20 43
Fax: +49 2 31 5 47-26 28

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