Escolar Documentos
Profissional Documentos
Cultura Documentos
HCl
Electrolysis
Chlorine recovery for
greater sustainability
Six centers of excellence,
global reach
Headquarters
Dortmund
Milan
Houston
ontent
C
04 EPC competence / Process
06 TDI and MDI plants / PU industry
08 Other applications
10 HCl ODC technology
14 Diaphragm technology
18 Service portfolio
thyssenkrupp Industrial Solutions
thyssenkrupp Uhde Chlorine Engineers
04
Proven quality
At thyssenkrupp Uhde Chlorine Engineers
we offer state-of-the-art products that
feature engineering of the highest quality
while taking economic, ecological and
safety considerations into account. The
expertise we have gained in the field of
electrochemical plants is partly the fruit of
long-lasting collaboration with important
industrial partners and customers.
The recovery of chlorine from hydrogen
Added value and chloride or hydrochloric acid has several
complete process chains advantages:
Our proven EPC competence in turnkey
projects is enhanced by the know-how, - Shows general commitment in terms of sustainability
resources and global experience of and therefore ecological responsibility.
thyssenkrupp Industrial Solutions. Our - Makes business independent of chlorine and
business area also offers EDC, VCM hydrochloric acid prices.
and PVC plants where you can use the - Avoids the need to develop traditional chlor-alkali plants
chlorine directly for EDC production. with significantly higher capital expenditure costs.
- Interesting for regions with high chlorine demand or
excess caustic soda (NaOH).
- Eliminates the risks and burden of transporting chlorine.
- No costs related to hydrochloric acid neutralization
or disposal.
EPC competence / Process 05
Process
Cl2 e.g. for TDI or MDI production, Product
many other processes are possible
HCl
By-product
Sale/use
Discharge
Recycle
Diaphragm
ODC
electrolyzer technology
additional O2 needed also produces hydrogen
Chlor-alkali-
HCl Recovery
electrolysis
O2
Natural
gas CO
Steam Phosgene Cl2
HCl absorption
reformer plant
H20
Sulfuric Acid
TDI plant
Nitration MDI plant
HN03
DNT NB
TDA MDA
Toluene
Benzene
Nitric acid plant
NH3
Hydrogenation
Aniline
Ammonia plant
Formaldehyde MDA plant
H2O
H2 N2
MDI complex
Air separation TDI complex
O2 Air
To produce TDI or MDI, chlorine is often Our chlorine recovery processes offer a
generated via chlor-alkali electrolysis – sustainable solution for the recycling of
or even bought elsewhere and transported this excess HCl: Electrolysis of the hydro-
to the plant, if this is possible. In the pro- chloric acid provides an alternative source
duction of isocyanate by phosgenation of of chlorine that can be fed back into the
the appropriate amine, a significant portion process. We can also integrate a process
Products of reaction chlorine is converted to hydrogen for recycling the waste brine (NaCl) from
chloride. This excess HCl often has no TDI/MDI production into the overall plant
further use on site, and selling it is often concept. The combined know-how of
not economically or logistically viable. thyssenkrupp Industrial Solutions regard-
TDI Due to ever-increasing environmental ing related technologies – such as steam
awareness and sensitivity, discharging reforming, ammonia plants, nitric acid
it to waste treatment, which involves plants, or sulfuric acid plants – ensures
additional caustic soda consumption, that we can integrate our HCl and waste
MDI is not a satisfactory solution. brine recycling technologies smoothly
into your processes.
08
HCl recycling –
other process applications
HCl recycling can be implemented However, all processes lead to impurities To close the water balance,
in many production processes, which first need to be dealt with before the several options are available:
including: chlorine can be recovered. Organic residues - HCl purge
- Fumed silica production are quite common, but there can also be - Selling of lean HCl
- PVC production inorganics such as high sulfate levels from - HCl concentration unit
- Chlorination of PVC fertilizer production, metal residues from - Mixed operation with gaseous
- Fertilizer production pickling processes, etc. etc. The fact that and liquid HCl
(e.g. potassium sulfate) HCl often leaves the process in aqueous - Use of lean HCl in other units.
- Metal pickling form poses a challenge all of its own.
to name but a few.
Other applications 09
Sample reference:
Yantai Juli
Laiyang, China
(commissioned 2011)
Capacity: 100,000 t/year of Cl2
HCl ODC technology 11
Minimized energy
consumption with
the ODC process
In addition to the energy savings, the ODC This innovative ODC technology has been
process does not produce hydrogen. This developed and introduced to the market by
is ideal when you do not need hydrogen on thyssenkrupp Uhde Chlorine Engineers and
site for other purposes. Thanks to the inno- its partners Covestro and Industrie De Nora.
vative technology and finely tuned process, The ODC principle is also used in industrial
the chlorine produced via HCl ODC is of a chlor-alkali production, realizing significant
very high purity and can be readily used in energy savings in this field.
subsequent processes.
H+
Anode
Membrane
ODC
HCl O2
Acid condensate outlet
Anode Cathode
HCl
filtration
Anolyte O2 + Catholyte
system HCl acidic system
12.5 % H2O Waste
HCl
gas water /
HCl reuse
absorption
H20 Cl2 NaOH
HCl
Lean 12.5 % HCl Waste gas NaOCl
HCl storage dechlorination dechlorination
Chlorine
Cl2*
treatment
* to consumer
Sample reference:
CUF-QI
Estarreja, Portugal
(commissioned 2008)
Capacity: 40,000 t/year of Cl2
Diaphragm technology 15
All cell elements consist of a bipolar graphite The process was developed jointly by the
electrode separated by a special PVC or former Hoechst AG and Bayer AG as well as
PVC/PVDF diaphragm. The individual cell thyssenkrupp Uhde Chlorine Engineers.
elements are assembled similar to a filter- Collaboration between Covestro (formerly
press-type bipolar electrolyzer. In order to Bayer MaterialScience AG) and thyssenkrupp
improve gas discharge, the electrodes are Uhde Chlorine Engineers continues today.
provided with a large number of vertical
slots. The individual electrodes are fitted
into frames made of synthetic material
resistant to hydrochloric acid and chlorine.
Cl-
H+
Diaphragm
Anode Cathode
2 Cl- gCl2 + 2 e- 2 H+ + 2 e- g H2
2 HCl g Cl2 + H2
Diaphragm technology 17
HCl HCl
17 % 17 %
HCl diaphragm
Anolyte electrolysis Catholyte
system HCl HCl system
HCl 23 % 21 %
filtration
Cl2 H2
HCl
gas HCl
absorption HCl Hydrogen
17 % cooling
H20
H2*
Lean HCl HCl Cl2 Hydrogen
dechlorination H2SO4 scrubbing
HCl storage
Na2SO4
Cl2*
NaOCl
* to consumer
HCl absorption and treatment absorption is usually applied for weak HCl gases the heat balance of the process is maintained
If deployed in conjunction with MDI/TDI plants, and includes the deployment of tray or packed using heat exchangers. A partial stream of the
the process starts with anhydrous hydrogen columns. With an adiabatic absorption process 17 wt.% acid feedstock is diverted from the
chloride gas which is conditioned in the absorp- it is not possible to produce more highly concen- catholyte recycle, re-concentrated with hydrogen
tion unit. The dissociation of HCl gas in water or trated hydrochloric acid. chloride to approx. 28–37 wt.% in the absorption
weak HCl solution is a strong exothermic reac- unit, and then fed back to both electrolyte cycles.
tion. In general, hydrochloric acid in a concen- Electrolyzer with
tration range between 28 to 37 % is required. anolyte and catholyte recycles Product treatment
There are two different options: isothermal or The concentrated aqueous hydrochloric acid is Once the wet chlorine gas has been cooled and
an adiabatic absorption. The above process flow fed to the anolyte system and to the catholyte filtered, it is either fed directly to the downstream
diagram shows an isothermal HCl absorption system. The process has hydrochloric acid consumer, or dried and compressed before
process, which is used for the production of recycles for anolyte and catholyte. The two either being directly routed back to the chlorine
hydrochloric acid feeds with a higher concentra- compartments receive aqueous acid feeds of consumer to close the chlorine recycle loop, or
tion. Here, either demineralized water or 17 wt.% different concentrations, the anode compart- liquefied for storage in tanks.
hydrochloric acid is used as an absorbent in a ment approx. 23 wt.% and the cathode compart-
falling-film column to produce hydrochloric acid ment approx. 21 wt.%. Chlorine and hydrogen Hydrogen is a valuable by-product of the process
with a concentration of up to 37 wt.%. It is con- are generated inside the cell. Depleted hydro- and can be supplied to hydrogen consumers,
tinuously removed and stored after filtration, chloric acid with a concentration of 17 wt.% such as hydrogenation plants, once it has been
which includes e.g. active carbon filters to adsorb leaves both compartments of the cell. cooled and scrubbed with caustic soda.
organics. A stripping column is used to remove
the impurities within the HCl absorption unit. The anolyte acid flows through the anode cham-
The stripper waste gas contains the majority of bers connected in parallel and the catholyte acid
the organic compounds and chlorine. It needs to flows similarly through the cathode chambers.
be treated in a scrubber, for example. Adiabatic Any solid impurities are retained by filters, while
18
Worldwide service –
everything from a single
source
Our ongoing aim is to enter into long-term partnerships
with our customers. Therefore, our world-leading tech-
nologies and solutions for high-efficiency electrolysis
plants are rounded off by a comprehensive service portfolio
to meet all your operational needs – wherever in the world
your plant may be located.
Long-term partnership
If you want a plant that fulfills the highest possible efficiency and safety standards
throughout its service life, we are just the partner you need. Our modular service portfolio
will provide ongoing support in minimizing power consumption and maximizing plant
availability, safety and product quality – so you can achieve your goal of becoming a
best-in-class producer.
Element Membrane
Full service – Manufacturer Supplier
maximum service,
minimal downtime
Logistics
The challenge in electrolyzer Partner
maintenance is to minimize
downtime and ensure work thyssenkrupp
undertaken is of the highest Customer Uhde Chlorine
quality. This is where our Engineers
full-service package comes Coating
into play. Your main benefits: Supplier
a single point of responsibility,
our comprehensive expertise
and experience, and our highly Assembly
Partner Leasing
qualified service technicians.
of Elements
Spare Parts
Supplier
Service portfolio 19
Spare parts
The innovative design of our electrolyzers
ensures necessary maintenance activities
are kept to a minimum. However, if your
plant is to run economically, efficiently and
reliably, it is vital to use nothing but our
certified and carefully tested spare parts
when components have to be replaced.
We use proven supply chains to minimize
delivery times.