The Application of Selective Ion Exchange Resins in Environmental Technology

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The Application of Selective Ion Exchange Resins
in Environmental Technology

• Recycling Exhibition, Istanbul
• July 1st, 2005

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Abbreviation
IX Ion Exchange(r)
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Content
General Overview on IX-Applications in
Environmental Technology
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2
Special IX-Products for the use in Environmental
Technology
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General Overview on IX-Applications in
Environmental Technology
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5
Overview on IX-Applications in Environmental
Technology
end of pipe waste water treatment lt---
polishing filters remediation of ground water
purification of potable water recycling
technology recycling of water, chemicals,
metals, ... process integrated environmental
technology lt--- help making processes more
efficient purification of air remediation of
soil lt--- in situ adsorption
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Example 1 Recycling of Rinse Water at
PCB-Industry
regenerants
rinsewater recycle plant
demin plant
fresh water
IX
IX
IX
IX
anion
cation
gravel
anion
cation
gravel
adsorber
printed circuit board production
regenerates
Ca(OH)2, Na2S, ...
polishing
precipitation plant
purge
IX
gravel
selective
waste water
Cu(OH)2, CuS, ... Sludge
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Example 2 Recycling of Sulfuric Acid by Acid
Retardation
H2O
2nd fraction H2O, FeSO4 , H2SO4
c
Fe
H2O, recycled
H2SO4
H2SO4 Pickling Bath
H2SO4
FeSO4
IX
V
f2
f1
5 H2SO4, 5 g/L FeSO4
anion
1st fraction H2O, FeSO4
waste water
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Example 3 Recycling of Hydrazine for
Synthesis-Step
H2O
educts
solvent
regenerant rinse water
HCl produced as by-product
distillation column
product isolation
anion
IX
1 HCl , 30 H2N-NH2
reactor (organic synthesis)
phase separation
Cl - waste water
recycled 64 H2N-NH2
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Example 4 Recycling of Hydrochloric Acid
Pickling Bath
spent HCl replacement
Regenerant H2O
Fe
HCl , FeCl4 -
HCl, Fe 2 -
HCl Pickling Bath
15 to 20 HCl lt 5g/L FeCl2
anion
IX
Fe 2, Cl- HCl
recycled HCl
flocculant production
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Example 5 Recycling of Rhodium Catalyst
Olefin
recycled organic solvent
H2
selective
Olefin Hydration Process
Solvent Purification
Product Recovery
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Rh on IX
Rh - catalyst
Hydrated Product
Catalyst Synthesis
Furnace
elemental Rh
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Example 6 Recycling of Zn/Ni Electrolyte for
Surface Plating
raw Fe - coil
Zn/Ni-coated Fe - coil
Regenerants H2SO4, NaOH, H2O
e-
Fe
-

Zn/Ni
Zn 2, Ni 2, Fe 2
Zn 2, Ni 2, Fe 3
e-
selective
Zn/Ni electrolyte, pH 3.5
IX
recycled electrolyte
Zn 2, Ni 2,
waste water
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Example 7 Recycling of Cobalt for
Co-doped-Polymer Production
educts
regnerants 1) HCl 2) NaOH
product separation
product isolation
water treatment
H2O, Co2, ...
reactor
Co-doped polymer
H2O, HCl
waste water
concentrated aqueous CoCl2 soln.
CoCl2-make up tank
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Example 8 Recycling of Brine for Chloroalkaline
Electrolysis
NaHCO3 / NaOH
CaCO3, MgCO3
NaCl
Precipitation
Solid/Liquid Separation
fresh NaCl dissolution
Regneration 1) HCl 2) NaOH
Brine - Cycle
Cl2
Excess Cl2- Removal
Electrolysis
CaCl2, MgCl2
20 NaCl
pure 30 NaCl
NaOH
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Other Examples for IX-Applications in Recycling
Technology
Applied Processes - recycling of silver from
fotographic laboratory waste - recycling of
phosphoric and chromic acid - recycling of
Molybdenum catalyst - recycling of Cr(III)
electrolytes - recycling of Co or Ni-electrolytes
(removal of Zn) - recycling and conditioning of
nuclear reactor process water circuits -
recycling of solid nuclear waste -
.... Processes for Investigation - recycling
of waste hydraulic oil - recycling of metal
working liquids - recycling of fish farm water -
...
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Special IX-Products for the use in Environmental
Technology
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Common Types of Ion Exchangers
CH2 - N(CH3)2H Cl
SO3 Na
weakly-basic-resin (WBA) (e.g. Lewatit MP 62)
Strongly-acidic-Resin (SAC) (e.g. Lewatit S 100)
CO2 Na
CH2 - N(CH3)3 Cl
weakly-acidic-resin (WAC) (e.g. Lewatit CNP 80)
strongly-basic-resin-type 1 (SBA1) (e.g. Lewatit
M 500)
CH2 - N(CH3)2CH2-CH2-OH Cl
strongly-basic-resin-type 2 (SBA2) (e.g. Lewatit
M 600)
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Examples for Selective Ion Exchangers
CH2-CO-ONa
CH2 - SH
CH2 - N
CH2-CO-ONa
Thiole-Resin (IONAC SR 4)
IDA-Resin (Lewatit TP 207)
O

CH2-P-ONa
CH2 - N
ONa
H
AMPA-Resin (Lewatit TP 260)
Methyl-Glucamine-Resin (Lewatit MK 51 )
SH
_
CNH
CH2 - N
CH2 - N(CH2-CH2-CH3)3Cl
...
H
Tripropylamine-Resin (IONAC SR 7)
Thiurea-Resin (Lewatit TP 214)
Chelating Resins
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Selectivity Series Comparison
SAC- v. IDA Resin
SAC-Resin
SO3 Na
Ba2 gt Pb2 gt Sr2 gt Ca2 gt Ni2 gt Cd2 gt Cu2 gt
Co2 gt Zn2 gt Fe2 gt Mg2 gt Mn2 gt Alkalis gt H
CH2-CO-ONa
IDA-Resin (Chelating Resin)
Cu2gt Hg2 gt Pb2 gt Ni2 gt Zn2 gt Cd2 gt Co2gt
Fe2 gt Mn2gt Ca2 gt Mg2 gt Sr2 gt Ba2 gtgtgt
Alkalis gt H
- IDA has higher Selectivity for Transitient
Metals Earth Alkali than for Alkalies -
Selectivity for Earth Alkali/Transition Metals in
Opposite Order
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Summary
- Ion exchangers play an important rule in
recycling technology - Numerous individual
solutions have been realised and work properly -
Special opportunities are offered by so called
selective IX - Wide range of LEWATIT resins
from LANXESS are available to cover
interesting applications in recycling technology
You are kindly welcome to discuss your recycling
application with us at the ÖKOTEK stand in hall 7
/ A2 or contact directly our ÖKOTEK collegues at
0212 482 02 42
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Backup
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Challanges for IX-Applications in Environmental
Technology
high removal rates to match emission limits and
product specifications high selectivity to
remove pollutants / impurities under
sophisticated operating conditions inert and
robust materials no secondary pollution by
decomposition processing with low energy and
chemical consumption, low secondary waste
production easy to operate
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Benefit of Selectivity in IX Applications
remove ions even from solutions with a high
concentration of competing ions (e.g. gt 15
NaCl or cCa 1000 cNi) remove certain ions in
presence of weak complexing agents (eg.
aliphatic amines, carboxylic acids, glycine,
...) work in non-conventional pH-ranges
(e.g. remove Hg or Au, Pt, ... from 15 HCl)
fast kinetics due to high driving forces no
dumping by competing ions ) (e.g. dumping of
NO3- by SO42-) capacity of filter is
exhausted by target impurity only ) (e.g.
UO2(CO3)34- from ground water loads without
competition with SO42-)
) explanation of capacity increase dumping
effect
a
b
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Motivation to Use Ion Exchangers in Separation
Technology
high selectivity driven by both selective
chemical reactions and molecular sieve effects
(e.g. higher selectivity than membrane
technology) diverse products with different
selectivity, kinetics, stability and mechanical
properties (many options to realise tailor made
solutions) low rest concentrations after
treatment feasible (ppm --gt ppb ---gt ppt
(?)) fixed bed filters are easy to operate
(e.g. easier then wet oxidation) low energy
consumption (e.g. compared to evaportion)
resistant against suspended solids (e.g. more
resistant than liquid/liquid extraction) inert
and robust materials of construction
) different particle sizes different grades of
crosslinking different pore size
distributions .... -gt MDS TP207
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Examples for Selective Solvent Doped Ion
Exchangers
D2EHPA
D2EHPA doped resin (Lewatit OC 1026)
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Examples for Selective Metal Doped Ion
Exchangers
CH2-CO-ONa
produced for HAsO42- removal
FeO(OH)
CH2 - N
CH2-CO-ONa
IDA-Resin, Iron doped (Lewatit S 7267)
produced for F- removal
SAC-Resin, Zriconia doped (UNITIKA UR 3700 S)
CH2-CO-O
proposed to be used for NH3 removal
CH2 - N
Zn
CH2-CO-O
IDA-Resin, Zinc doped (Lewatit TP 207)
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Overview on Types of IX-Products
common IX-resins
selective IX-resins
IDA AMPA Thiurea ...
chelating type special types metal doped
type solvent doped type
acidic strongly basic mixed
basic acidic weakly basic
type 1 type 2
Thiole Glucamine ...
FeO(OH) Zr ..
D2EPA ..
variations in crosslinking, beads- and pore-
sizes, type of polymer, ...
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Types of IX-Products
selective for
transitient metals gt earth alkali gt alkali
IDA AMPA thiurea
chelating type special types metal doped
type solvent doped type
transitient metals gt earth alkali gt alkali
precius metals gt transistient metals
thiole glucamine
precious metals gt other transistion metals boron,
special oxo-Anions (Ge, Ga, ...)
FeO(OH) Zr Zn
Arsenate, special oxo-anions Fluoride, .. NH3, ..
D2EPA
In, Zn, Sn, Sb, Bi ... gt Cu, Co, Ni, ...
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Selectivity Series Comparison OC 1026 - v.
IDA Resin
OC 1026
Ti4 gt Fe3 gt In3 gt Sn2/4 gt Sb3 gt Bi3 gt VO2
gt Be2 gt Al3 gt Zn2 gt Pb2 gt Cd2 gt Ca2 gt Mn2
gt Cu2 gt Fe2 gt Co2 gt Ni2 gt Mg2 gt Cr3 gtgtgt
Alkalis gt H
CH2-CO-ONa
IDA-Resin (Chelating Resin)
Cu2 gt Hg2 gt Pb2 gt Ni2 gt Zn2 gt Cd2 gt Co2gt
Fe2 gt Mn2gt Ca2 gt Mg2 gt Sr2 gt Ba2 gtgtgt
Alkalis gt H
- Selective resins have different selectivity
series - Different applications possible