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C7-Electrochemical Processes

SC-EPC

Process Engineering and Energy Technolgy (PEET)-2

Felicitas Berger
Lecture 6: Electrolysis-Part 2
In an experiment 0,03 l Hydrogen were produced
by applying a voltage of 1,95 V
with a current of 1 A over
a time of 300 s. Calculate the energy efficiency !
h= Eproduct/Eelectrical x 100 (%)

h= amount, of substance, mass, volume x caloric value/


VxIxt

h= 3 x 10-5 m3 x 12,745 x 106 J/m3 /


1,95 V x 1 A x 300 s

h= 0.64 m3 x J / V x A x s x m3

h= 0.64 = 64 %
1 4. Electrolysis

4. Electrolysis

Electroplating 19th century Chloralkali plant, 1920

Electrochemical process chemical process

+ yield of Energy per mass of +heat is cheaper than electricity


product -extra energy for aktivation
+high purity of the product barriers
+easy to control reactions -extra costs for catalytic
-extra energy for the over potential materials
-high temperatures required
2 4. Electrolysis

4. Electrolysis
4.3 Chloralkaline process

Chlorine Hydrogen Sodium hydroxide

80 x 106 t/a 65-100 x 106 t/a 65 x 106 t/a

2 NaCl + 2 H2O 2 NaOH + Cl2 + H2


Chlor-Alkali-Elektrolyse
3 Chlor-Alkali-Elektrolyse
➋ Amalgam-Verfahren
➌ Membran-Verfahren 4. Electrolysis
Chlor-Alkali-Elektrolyse

4. Electrolysis
➊ Diaphragma-Verfahren

➋ Amalgam-Verfahren: Prinzip ➌ Membran-Verfahren: Prinzip


4.3 Chloralkaline process
➊ Diaphragma-Verfahren: Prinzip
H2 Cl 2 H2 Cl 2 H2 Cl 2
NaCl−Lsg. Betrieb H 2O NaCl−Lsg.
! A s. Diaphragma-Verfahren
NaOH−Lsg. NaCl−Lsg. ! E
K +
Diaphragma + A ! Salzlösung
Graphit in Anodenraum
K
_
A !K K elementares
+ Hg + A D
Eisen Na Na Na Na
Cl Nickel

Membran
Titan + Titan Titan
Na Na− +
_ H 2O H 2O Cl
_
_ ! Na
Verarmung an Cl durch ! Ausnutzung der hohen Cl _ (
_ _ H 2O _
e e _ e e e
Anoden-Reaktione
Überspannung von HAnolyt
2 an Hg
! M

Hg
Katholyt Anolyt Katholyt
Katholyt Anolyt

NaOH− Lsg. ! Dünnsole strömt durch (Na/H-Potentiale


NaOH−Lsg. (konz.) vertauscht)
NaCl−Lsg. (verd.)
hy
NaOH− Lsg. NaCl−Lsg. (verd.)
NaCl−Lsg.
Diaphragma in Kathodenraum ! Elektrolysezelle: ! vo
! Vermischung mit gebildeter NaOH 2NaCl −→ 2NaHg + Cl2 W
! Diaphragma aus Weiss-Asbest:
! Rückvermischung der NaOH zur separater Amalgamabscheider: be
Na+ - und H2 O-durchlässig !

Anode durch Strömung vermeiden 2Na + 2H2 O −→ 2NaOH + H2 ! A


A früher Graphit, heute Ti-Blech
Diaphragm
(O -Abscheidungprocess Amalgam process Membrane process
!
(Chloratbildung, Sauerstoff- N
2gehemmt) ! Cl2 -freie Natronlauge
abscheidung) K
operational
K Eisen odersince
Stahl 1885 operational since 1892 operational since 1970
!
! ! NaCl-freie (< 0.006 Gew.-% NaCl)
! Elektrolyse nur bis zu geringen N
bis 50%-ige Natronlauge
no new facilities in Ger.
Katholyt: 190 g/l NaCl und 130
!

g/l NaOH
no new facilitiesmöglich
NaOH-Konzentrationen in Ger.
Skizze einer Einfachstanlage clean but expensive
50%T market
= 90 C; U share
! inVUS
= 3.5 - 4.2 o forbidden in Japan s. 1987 50% market share in US
US < 10% market share
Europe 40%

- Asbestos! - mercury!
➊ Diaphragma-Verfahren: Prinzip
4 4. Electrolysis

4. Electrolysis H2 Cl 2
4.3 Chloralkaline process NaCl−Lsg. Betrieb
K + A ! Sa

Diaphragma
+
Eisen Na Na Titan

_ H 2O H 2O Cl
_
_ ! V
e e
Katholyt Anolyt A
NaOH− Lsg. ! D
NaCl−Lsg.
D
! V
Diaphragm process: The Partition aus
! Diaphragma is made out of asbestos covered
Weiss-Asbest:
polymers. The Cathode +consists of iron, the anode of tinanium, the ! R
Na - und H2 O-durchlässig
electrolyte, konzentrated sodium chloride solution is filled to the anode A
container. ! A früher Graphit, heute Ti-Blech
(C
(O- 2 -Abscheidung gehemmt)
Cathode:2H2O + 2e 2H2 + 2OH- Anode:2Cl- Cl2 + 2e- ab
! K Eisen oder Stahl
!
➊ Diaphragma-Verfahren: Prinzip
5 4. Electrolysis

4. Electrolysis H2 Cl 2
4.3 Chloralkaline process NaCl−Lsg. Betrieb
K + A ! Sa

Diaphragma
+
Eisen Na Na Titan

_ H 2O H 2O Cl
_
_ ! V
e e
Katholyt Anolyt A
NaOH− Lsg. ! D
NaCl−Lsg.
D
! V
Unwanted side reactions aus Weiss-Asbest: Cl2 +
at the anode:
! Diaphragma Anode:2Cl- 2e-
+
Na - und H2½O-durchl ässig
! R
2 OH- O2 + H2O + 2e-
A
! A früher Graphit, heute Ti-Blech
Cl2 + 2 OH- ClO- + Cl- + H2O (C
(O2 -Abscheidung gehemmt)
ab
6ClO- + 3H2O 2 ClO3- + 4 Cl- + 6 H+ + 1,5 O2 + 6 e-
! K Eisen oder Stahl
!
6 4. Electrolysis
H2 Cl 2
4. Electrolysis
H 2O NaCl−Lsg.
4.3 Chloralkaline process

Graphit K A
_
+
Na Cl Titan
Na Na
+

_
_ e
e

Hg
Katholyt Anolyt

NaOH− Lsg. NaCl−Lsg. (verd.)

Amalgam process: The Partition is made out of mercury, which also


forms the cathode material. The anode consists of tinanium, the
electrolyte, konzentrated sodium chloride solution is filled to the anode
container.

Cathode: Na+ + xHg. NaHgx Anode:2Cl- Cl2 + 2e-


7 4. Electrolysis
H2 Cl 2
4. Electrolysis
H 2O NaCl−Lsg.
4.3 Chloralkaline process

Graphit K A
_
+
Na Cl Titan
Na Na
+

_
_ e
e

Hg
Katholyt Anolyt

NaOH− Lsg. NaCl−Lsg. (verd.)

Almost no side reaction are observed, because OH- cannot enter the
anolyte. The sodium-amalgam is rinsed with water in a seperate
container. Pure sodium hydroxide is formed.
Overall: 2 NaCl + xHg Cl2 + 2NaHgx

Reaction in the Katholyte: 2NaHgx + 2 H2O 2 NaOH + H2 + Hgx


8 4. Electrolysis

4. Electrolysis
4.3 Chloralkaline process
9 4. Electrolysis

4. Electrolysis H2 Cl 2
4.3 Chloralkaline process NaOH−Lsg. NaCl−Lsg.

K + + A
Nickel Na Na Titan

Membran
_
_ H 2O Cl _
e e
Katholyt Anolyt

NaOH−Lsg. (konz.) NaCl−Lsg. (verd.)

Membran process: The Partition is made out of a


perfluorsulfonate/perfluorocarboxylate membrane. The Cathode
consists of nickel, the anode of tinanium, the electrolyte, konzentrated
sodium chloride solution is filled to the anode container.

Cathode:2H2O + 2e- 2H2 + 2OH- Anode:2Cl- Cl2 + 2e-


mbran-Verfahren: Einzelzelle∗
10 4. Electrolysis

4. Electrolysis
4.3 Chloralkaline process
A Ti mit TiO2 /RuO2 -Deckschicht
K Ni Purification steps needed for the Kathoden− H2 Cl 2
Kanal Anoden−

membrane process NaOH


Kanal

uleitungen usw. aus Teflon (PTFE) NaCl

Anodenhalbraum mit Einbauten (Bleche zum Wasser Salz

verdünnte

Umlauf) Sole

Natronlauge
Solesättigung

Rohsole
elektr.
Kontakte
H2
Fällung Fällmittel Cl 2
Cl2 -Blasen, Ausleitung gelöst in NaCl
Entchloren

Filtration Rückstand
Salzsäure

Kathodenhalbraum
H
ohne Einbauten
Chlorat− Feinreinigung
zersetzung
Salzsäure
trom in Reihe durch Module Anolyt
Elektrolyse
Wasser
Leitblech
Vol.-%) H2 Cl 2 NaOH

toffstrom parallel durch Zellbatterie


Kühlen Kühlen Kühlen
NaOH

ktive Fläche pro Element: 5 m2 Trocknen Konzentration

Kompression Kühlen
ch
ndlich Verflüssigung Lagern
NaOH− NaCl−
Zuleitung Zuleitung
h
Verdampfen

Wasserstoff Chlor NaOH

Abb. Fa. Uhde Membranprozess


Chlor-Alkali-Elektrolyse

11
➌ Membran-Verfahren 4. Electrolysis

4. Electrolysis
4.3 Chloralkaline process
➋ Membran-Verfahren (Foto)

Montage der Module eines bipolaren Uhde BM 2.7 Elektrolysiers

(Quelle: Fa. Thyssen-Krupp Electrolysis GmbH, ehem. Uhde/Thyssen-Krupp, DeNora)

Filme: 4+5 und 6. Generation


12 4. Electrolysis

4. Electrolysis
4.4 Production of metals

Metals with a high Redox potential can be electropurified out of


aqueous solutions containing the metalsalt. The get deposited at the
cathode of an electrolytic cell.

Gold, silver, copper, lead, tin, nickel, cobald, chrome and zinc are
produced by electrolysis.
13 4. Electrolysis

4. Electrolysis
4.4 Production of metals

Cathode: Zn2+ + 2e- Zn


Anode: SO42- + Pb
PbSO4 + 2 e-

Zinc is electropurified aut of acidic zinc sulfate solutions. It is deposited


at an aluminium cathode, whereas the sulfate forms insoluble
leadsulfate precipitates at the anode.
14 4. Electrolysis

4. Electrolysis
4.5 Electroplating

Zinc, nickel, silver and other metals are also used as material for
electroplating of a variety of metals like copper, steel, iron and others.
The surface of the carrier metal is altered by that process and proprties
like hardness, luster or corrosion resistance can be changed.
15 4. Electrolysis

4. Electrolysis
4.5 Electroplating
16 4. Electrolysis

4. Electrolysis
4.5 Electroplating

The mass of a plated or recovered metal can be calculated by using the


faraday laws:

m = M x Q / z x F or m = M x I x t / z x F

M= molecular weight (g/mol)


z = amount of charge per mole of converted substance
F = Faradaic constant (C/mol or A x s/mol)
Q = charge (C)
I = current (A)
t = time (s)
17 4. Electrolysis

4. Electrolysis
4.5 Electroplating

The thickness of the coat or layer thickness s (m) can be calculated by


including the density of the material r (kg/m3) and the area of the
surface A (m2) that will be plated:

m=r x Axs m=MxIxt/zxF

M= molecular weight (g/mol)


z = amount of charge per mole of converted substance
F = Faradaic constant (C/mol or A x s/mol)
Q = charge (C)
I = current (A)
t = time (s)
Bathroom fittings with an area surface of 0,5 m2
are plated with nickel at 50 A for 2 hours.
The density of Nickel is 8910 kg/m3.

m=r x Axs m=MxIxt/zxF


m=r x Axs m=MxIxt/zxF

r x Axs=MxIxt/zxF
s=MxIxt/r x A xF

s=
58,6934 g/mol x 50 A x 7200 s / 8910 kg/m3 x 0,5 m2 x 2 x 96485 As/mol

s = 24,5 µm
18 4. Electrolysis

4. Electrolysis
4.5 Electroplating

Cutlery is often plated with silver in a Silvernitrate bath and a silver


anode Bathroom fittings can be plated with chrome or even platinum,
automoblile parts can be plated by nickel, zinc or chrome.
19 4. Electrolysis

4. Electrolysis
4.6 Anodization

Anodization is a process,
used to thicken th
eprotective oxide layer,
found on many metals,
like aluminium or
titanium.
20 4. Electrolysis

4. Electrolysis
4.6 Anodizing

The metal that should be anodized, forms the anode. Oxygen is formed
and reacts with the metal. At the cathode Hydrogen is formed.

Anode:2 H2O O2 + 4e- + 4 H+ Cathode:2 H+ + 2e- 2H2


chemical: 3 O2 + 4 Al 2Al2O3
21 4. Electrolysis

4. Electrolysis
4.7 Fused salt electrolysis

Anode: O2- + 4 e- ½ O2

Cathode: Al3+ + 3e- Al

Metals with a low Redoxpotential can be purified out of their salts by


fused salt electrolysis in the absence of water. The salts are heated, the
metal ions leave the cristall and are attracted by the cathode, were they
are reduced and form the liquid metal that can be recovered.