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DOWEX
Ion Exchange Resins
+
SO3–H+ SO3–H+
styrene CH CH2 ••• CHCH2 ••• ••• CHCH2 •••
divinylbenzene
••• CHCH2CHCH2 ••• ••• CHCH2CHCH2 ••• (1) + N(CH3)3 ••• CHCH2CHCH2 •••
catalyst
+ ClCH2OCH3
(1)
quaternized amine product made by Other Functional Groups. Ion Macroporous (macroreticular) ion
the reaction of trimethylamine with the exchange resins with special exchange resins have pores of a
copolymer after chloromethylation. functional groups have been made for considerably larger size than those of
The Type 1 functional group is the specific applications. Of interest to the the gel type resins with pore
most strongly basic functional group hydrometallurgical industry are a diameters up to several hundred
available and has the greatest affinity variety of resins having chelating Ångstroms. Their surface area may
for the weak acids such as silicic acid ability and which are particularly reach 500 m2/g or higher.
and carbonic acid, that are commonly applicable for the selective exchange Macroporous polymers are generally
present during a water of various heavy metals from alkaline highly cross-linked and therefore
demineralization process. However, earth and alkali metal solutions[2]. exhibit little volume change (swelling).
the efficiency of regeneration of the Polymer Matrix. The structure and Because of the high cross-linkage in
resin to the hydroxide form is porosity of an ion exchange resin are the matrix, the apparent oxidation
somewhat lower, particularly when determined principally by the stability of macroporous resins is
the resin is exhausted with conditions of polymerization of the improved. However, at similar cross-
monovalent anions, such as chloride backbone polymer. Porosity linkages, macroporous resins have
and nitrate. The regeneration determines the size of the species, greater exposure to potential oxidants
efficiency of a Type 2 resin is molecule or ion, that may enter a than gel resins due to their greater
considerably greater than that of Type specific structure and its rate of porosity and surface area.
1. Type 2 functionality is obtained by diffusion and exchange. There also is Poorer regeneration efficiencies,
the reaction of the styrene-DVB a strong interrelationship between the lower capacities and higher
copolymer with equilibrium properties of swelling and regeneration costs are the penalties
dimethylethanolamine. This ionic selectivity. paid for the use of the macroporous
quaternary amine has lower basicity resins. Macroporous resins may be
than that of the Type 1 resin, yet it is For example, a conventional gel type,
styrenic ion exchanger is built on a used as catalysts, particularly in non-
high enough to remove the weak acid polar media where gel resins do not
anions for most applications. The matrix prepared by co-polymerizing
styrene and DVB. In these systems, perform satisfactorily because of their
chemical stability of the Type 2 resins inaccessibility to the reactants.
is not as good as that of the Type 1 porosity is inversely related to the
resins, the Type 1 resins being DVB cross-linking. Gel resins exhibit
favored for high temperature microporosity with pore volumes
applications. typically up to 10 or 15 Ångstroms.
Ion Exchange Regeneration carried out to remove suspended incoming salt solution (feed) is
Technologies solids and resin fines. converted to the corresponding dilute
Counter-Current Regeneration acid. When this acid solution contacts
Ion exchange regeneration the sodium ion, re-exchange of
technology has developed over the Systems. In these systems, the
regenerant is applied in the opposite hydrogen ions for sodium ions occurs
years from the early co-flow and the sodium ions exit the column
regenerated systems to counter-flow direction to the service flow. This has
the advantage of providing better as leakage (Figure 4a). Leakage in
block systems and through to packed counter-flow regeneration is
bed technology, including the Dow water quality (lower ionic leakage),
higher chemical efficiency and substantially reduced as the resin bed
UPCORE* process. Counter-current is predominantly in the regenerated
regeneration systems have reduced reduced waste water. In order to
obtain low leakage levels from a form at the bottom of the vessel
chemical costs, improved water Figure 4b).
quality and less waste volumes counter-flow regenerated resin
compared to traditional co-flow system, the contaminating ions must There are two main types of counter-
regenerated systems. They are also be kept from the effluent end of the current systems:
more productive, utilizing smaller column during re-generation and Blocked Systems. This includes air
vessels, faster regenerations and rinse. This requires avoidance of hold down, water hold down and inert
fewer mechanical failures. conditions that would disrupt the resin mass blocked. The service flow is
bed configuration. Backwash downwards and regeneration upflow.
Co-Current Regeneration System. frequency also must be minimized.
This is the simplest system where a To avoid disturbance of the resin
resin is regenerated in the same The difference between ion leakage polishing zone at the bottom of the
direction as the service flow for co-current and counter-current vessel, the resin bed is held down
(downwards). The vessel has a large regeneration is illustrated in Figure 4. (blocked) during regeneration by air
freeboard to allow expansion of the Re-exchange of the contaminating pressure, water flow or an inert mass
resin bed when backwashing is Na+ ion occurs from the base of the in the top part of the vessel. The
co-flow regenerated bed when the regenerant passes up through the
Figure 4. Ion Leakage: a. Co-flow and b. Counterflow Regenerated Fixed-Bed Column Contractors (H+ Form
Cation Resin; Na+ Removal)
a.
H+ Resin
b.
resin and out of a collector system in 1. Dissolved solids are removed to exchange resins where both types of
the middle part of the vessel. the extent of the alkalinity in the exchange occur simultaneously:
Packed Bed Systems. These may raw water by passing the raw RH+ + ROH- + C+A- !RC+ RA- + H2O
be up-flow service with down-flow water through a bed of weak acid
cation resin in the hydrogen form. The choice of the ion exchange
regeneration or down-flow service system for demineralization depends
with up-flow regeneration, such as the The 100 percent utilization of
regenerant acid that is an the water quality desired,
Dow UPCORE system. operating and capital economics and
characteristic of this process
Semi-Continuous and Continuous. decreases operating costs and composition of the raw water.
Semi-continuous and continuous greatly minimizes the waste Condensate Polishing. Single or
contactors operate as intermittently disposal problem. A weak acid mixed bed ion exchange resins are
moving packed beds as typified by cation resin creates no free used in deep bed filter demineralizers
the Higgins contactor[3] or as fluidized mineral acidity in the effluent when for reduction of particulate matter and
staged (compartmented) columns regenerated at a level of not more dissolved contaminants in utility
such as the Himsley contactor[4-6]. than 105-110 percent of the power plant condensates.
Flow is counter-current and their use theoretically required amounts for
is in increased resin utilization and Ultra Pure Water. Ultra pure water
the cations picked up. (UPW) is essential to the proper
high chemical efficiency. Commercial
installations include those for 2. Chloride anion dealkalizing fabrication of integrated circuit boards
phosphoric pickle acid recovery, involves passing the raw water in the semiconductor industry. As the
water softening and ammonium through a Type 2 anion exchange degree of integration becomes
nitrate recovery. resin that is in the chloride form to increasingly more complex, the
remove alkalinity. semiconductor industry requires
Resin Applications Demineralization. Ion exchange higher levels of water purity. Single
demineralization[7] is a two step beds, mixed beds and also reverse
Water Softening. Water softening process involving treatment with both osmosis are used in the production of
accounts for the major tonnage of cation and anion exchange resins. ultra pure water.
resin sales. Hard waters, which Water is passed first through a Nitrate Removal. Ion exchange is
contain principally calcium and column of strong acid cation used for the removal of nitrates from
magnesium ions, cause scale in exchange resin that is in the nitrate polluted waters[8]. Strong base
power plant boilers, water pipes and hydrogen form (RH+) to exchange the anion exchange resins operating in
domestic cooking utensils. Hard cation in solution for hydrogen ions: the chloride ion form (salt solution
waters also cause soap precipitation regenerated) have been successfully
which forms an undesirable gray curd RH+ + C+ !RC+ + H+
used for this service.
and a waste of soap. Water softening where C+ represents common
involves the interchange of hardness cations, for example, Ca2+, Mg2+ and Waste Treatment. Radioactive.
for sodium on the resin. Typically, Na+. This effluent is passed to a Radiation waste systems in nuclear
hard water is passed through a bed of column of anion exchange resin in the power plants include ion exchange
a sodium cation exchange resin and hydroxide form R OH–) to replace systems for the removal of trace
is softened. anions in solutions with hydroxide: quantities of radioactive nuclides from
water that will be released to the
2RNa+ + Ca2+ !R2Ca2+ + 2Na+ ROH– + A– !RA– + OH– environment. The primary resin
Regeneration of the exchanger where A– represents common anions, system used is the mixed bed.
involves the passage of a fairly for example, Cl–, SO42– and NO3–. Chemical Processing – Catalysis.
concentrated (8-12 percent) solution The hydrogen ions from the cation Since ion exchange resins are solid,
of sodium chloride through the resin. resin neutralize the hydroxide ions insoluble (but reactive) acids, bases,
R2Ca2+ + 2Na+ !2RNa+ + Ca2+ from the anion resin: or salts, they may replace alkalis,
Dealkalization. Many industrial H+ + OH– !H2O acids and metal ion catalysts in
processes require that hardness and The net effect is the removal of hydrolysis, inversion, esterification,
alkalinity be removed from a raw electrolytes and a yield of purified hydration or dehydration,
water before the water is used in the water. polymerization, hydroxylation and
process. Two main processes epoxidation reactions. The
Alternatively, the impure water may advantages of ion exchange resins as
involving ion exchange are used for be passed through an intimately
dealkalizing: catalysts include easy separation
mixed bed of cation and anion from the products of reaction,
repeated reuse, reduction of side glucose and fructose, mixed bed Bibliography
reactions and lack of need for special polishing and color removal. In [1] B. A. Adams and E. L. Holmes, J. Soc.
alloys or lining of equipment. deashing, a bed of strong acid cation Chem. Ind. 54,1-6T (1935).
Purification. Purification by ion resin is typically followed by a bed of
[2] D. C. Kennedy, Chem. Eng., (Dune 16,
exchange is used to remove weak base anion resin. The resins 1980).
contaminating acids, alkalis, salts or used are macroporous, as their large
porous structure allows syrup [3] U.S. Pat. 3,580,842 (May 25, 1971), I.
mixtures from non-ionized or slightly R. Higgins (to Chemical Separations
ionized organic or in-organic components to move freely into the
Corporation).
substances. Examples include formic bead.
acid removal from 50 percent Chromatographic Separation. [4] Can. Pat. 980,467 (Dec.. 23, 1975), A.
Himsley (to Himsley Engineering).
formaldehyde solutions, removal of Chromatographic separation is a
amines from methanol, removal of manufacturing process using ion [5] U.S. Pat. 3,549,526 (Dec. 22, 1970), H.
iron from steel pickling operations, exchange resins to separate one Brown.
purification of aluminum bright dip dissolved component from another. It [6] U.S. Pat. 3,551,118 (Dec. 29,1970), F.
baths and removal of iron in the is applied in the sugar industry for the L. D. Cloete and M. Streat (to National
purification of hydrochloric acid[9]. purification of compounds such as Research Development Corporation,
Metal Extraction, Separation and sucrose, glucose, fructose, London).
Concentration. In aqueous or solvent oligosaccharides, sorbitol and [7] W. J. Weber, Jr., “Physicochemical
mixtures containing large amounts of mannitol. It can be used to separate Processes for Water Quality Control” in
contaminants and small amounts of a salt from glycerol and in purifying Ion Exchange, Wiley Interscience, New
desired solute, ion exchange resins amino acids and various organic York, 1972, Chapter 6.
can be used to selectively isolate and acids. Most industrial chromatography
[7] S. B. Applebaum, Demineralixation by
concentrate the desired solute, for today utilizes simulated moving bed Ion Exchange, Academic Press, Inc.,
example, the recovery of uranium (SMB) technology to minimize solvent New York, 1968.
from sulfuric acid leach solution with use, leading to a significantly reduced
cost of operation when compared to [8] M. Sheinker and J. Cudoluto, Public
strong base anion resins. Other Works, 71 (Dune 1977).
specific chelating resins can be used traditional batch chromatography.
[9] K. A. Kraüs and G. E. Moore, J Am.
for metals recovery such as copper, Pharmaceuticals and
Chem. Soc. 71, 3263 (1949).
nickel, cobalt and precious metals. Fermentation. Ion exchange resins
Desiccation. Ion exchange resins, are useful as carriers for medicinal [10] C. E. Wymore, Ind. Eng. Chem. Prod.
materials and in slow release Res. Deu. 1, 173 (1962).
particularly strong acid cation
exchange resins in the dry state, are applications. In some cases, the ion
useful as desiccants[10]. Ion exchange exchange resin has the medicinal
resins show their greatest capability affect desired, for example,
as desiccants in the drying of Cholestyramine, a dried and ground
hydrophobic solvents, for example, strong base anion resin used to bind
hydrocarbons and chlorinated bile acids for reducing blood
hydrocarbons. cholesterol. Ion exchange resins also
are used in a variety of fermentation
Sugar Separations and Purifications. and biotechnology processes, such
Ion exchange resins are used as an as the isolation and purification of
integral part of corn syrup, high- lysine, streptomycin and neomycin
fructose corn syrup (HFCS) and other similar antibiotics.
processing and other starch based
syrups. In sucrose processing, the
resins are often used for softening
feed streams, recovering sugar from
molasses streams, or decolorization.
They are also used in the production
of non-nutritive sweeteners such as
sorbitol or mannitol. Resins and
adsorbents are used in four major unit
processes in corn sweetener
processing: deashing,
chromatographic separation of
Dow Liquid Separations Offices.
For more information call Dow Liquid Separations:
Lenntech
info@lenntech.com
info@lenntech.com Tel.
Tel. +31-152-610-900
+31-152-610-900
www.lenntech.com
www.lenntech.com Fax.
Fax.+31-152-616-289
+31-152-616-289
WARNING: Oxidizing agents such as nitric acid attack organic ion exchange resins under certain conditions. This could lead to anything from
slight resin degradation to a violent exothermic reaction (explosion). Before using strong oxidizing agents, consult sources knowledgeable in
handling such materials.
NOTICE: No freedom from any patent owned by Seller or others is to be inferred. Because use conditions and applicable laws may differ from
one location to another and may change with time, Customer is responsible for determining whether products and the information in this
document are appropriate for Customer’s use and for ensuring that Customer’s workplace and disposal practices are in compliance with
applicable laws and other governmental enactments. Seller assumes no obligation or liability for the information in this document. NO
WARRANTIES ARE GIVEN; ALL IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE
EXPRESSLY EXCLUDED.