USOO6187826B1

(12) United States Patent (10) Patent No.: US 6,187.826 B1

Viscardi et al. (45) Date of Patent: Feb. 13, 2001

(54) DEVICE AND METHOD FOR THE 3,429.807 2/1969 Burgess.

REGENERATION OF MIXED ON 3,711,401 1/1973 Hamilton et al. ...................... 210/34
EXCHANGE RESIN BEDS 3,933,631 * 1/1976 Adams ............ ... 210/34
4.017,262 * 4/1977 Small et al. . 23/253 R
(75) Inventors: Carlo Felice Viscardi; Marina 4.299,922 * 11/1981 Holl et al. ... 521/26
Ausonio, both of Milan; Mauro 4,622,141 11/1986 Salem ....... ... 210/189
Parenti, Triulzi, all of (IT) 5,019,542 * 5/1991 Bento ... ... 502/25
5,322,934 6/1994 Kneller ................................... 534/16
(73) Assignee: Dibra S.p.A., Milan (IT) 5,863,438 1/1999 Katzakian et al. ................... 210/674
(*) Notice: Under 35 U.S.C. 154(b), the term of this FOREIGN PATENT DOCUMENTS
patent shall be extended for 0 days.
(21) Appl. No.: 09/125,461 27 O3 044 7/1978 (DE).
28 OO 194 7/1979 (DE).
(22) PCT Filed: Feb. 13, 1997
(86) PCT No.: PCT/EP97/00670 * cited by examiner
S371 Date: Aug. 19, 1998
Primary Examiner-David W. Wu
S 102(e) Date: Aug. 19, 1998 Assistant Examiner Tanya Zalukaeva
(87) PCT Pub. No.: WO97/30788 (74) Attorney, Agent, or Firm Nixon & Vanderhye
PCT Pub. Date: Aug. 28, 1997 (57) ABSTRACT
(30) Foreign Application Priority Data Equipment and procedures for regenerating ion exchange
Feb. 20, 1996 (IT) .............................................. MI96AO314 resin mixed beds, used for the desalination of water or of
(51) Int. Cl." .............................. C08J 5/20; B01D 24/00; aqueous Solutions from industrial processes (process
CO2F 1/42 Solutions), that use two columns: the first treatment column
(52) U.S. Cl. ............................ 521/26; 210/674; 210/284; (C1), containing a mixed bed of ion exchange resins, in
210/296 which the cation eXchange resins are regenerated, and a
(58) Field of Search ............................... 521/26; 210/674, Second column (C2) into which the anion exchange resins
210/284, 296 are transferred and regenerated, to be then reintroduced from
the bottom into the above mentioned first column (C1),
(56) References Cited where they rise through the cation eXchange resins and
intimately mix with the anionic exchange resins.
U.S. PATENT DOCUMENTS
2,461.506 2/1949 Daniel. 8 Claims, 1 Drawing Sheet
U.S. Patent Feb. 13, 2001 US 6,187.826 B1

I) AR INT
II) DEIONIZED WATER INIST
III) HC1 INLRT
IW) INLET OF SOLUTION TO BE DESALINATED
V) NaOH NET
WI) TRANSFER OPENING OF THE ANION EXCHANGER

FIGURE
 US 6,187.826 B1
1 2
DEVICE AND METHOD FOR THE the final desalination of water to be fed to steam-boilers in
REGENERATION OF MIXED ON thermoelectric or thermonuclear power Stations.
EXCHANGE RESIN BEDS The most widely used process for Small or medium sized
units is the internal regeneration. In this latter case the
This application is a 35 U.S. C. S371 of PCT/EP97/ 5 reagents for regeneration of the anion and the cation
OO670 filed Feb. 13, 1997. eXchangers enter the column from the top and bottom
This invention concerns a new device for regenerating respectively, either Simultaneously or at different times
mixed beds of ion exchangers used for the desalination of (regeneration of the anionic exchanger is normally carried
water or aqueous Solutions deriving from industrial pro out first), while the exhausted regenerating Solutions are
cesses (process Solutions) and the method of carrying out collected from the same discharge line provided with
this regeneration. devices (strainers) able to retain the portion of resin situated
The technique of desalination by means of mixed beds of near the interface between the resins.
ion exchanger resins, described for the first time in 1951 This System is less costly but has two significant disad
(U.S. Pat. No. 2.578,937), is now widely used for the Vantages:
production of very low ion content water: among the most 15 1) the interface between the resins must be exactly
important applications are the production of Steam-boiler maintained at the level of the discharge line, otherwise
feed water and water for the electronic and pharmaceutical a part of the anionic exchanger will be Saturated by the
industries. acid used for the regeneration of the cationic exchanger
Another application of mixed bed processes concerns the or, Vice versa, a part of the cationic exchanger will be
desalination of process Solutions containing non-ionic Saturated by the base used for the regeneration of the
organic compounds, as, for example, molecules of pharma anionic exchanger.
ceutical or foodstuffs interest. What characterizes mixed bed This fact implies that it is not possible to handle a mixed
processes is the fact that water or the Solution to be desali bed with quantities of cationic resin different from those of
nated is percolated through an intimate mixture of a cation the original design and that each variation of Volume of the
eXchanger and an anion eXchanger. 25 cationic resin, either due to the normal Swelling occuring
Mixed bed treatment allows the reduction of the residual during regeneration or to a possible loSS of resin, will have
Saline content of treated water to quite lower levels as negative effects on the following performance of the bed;
compared with desalination through Separate beds of two ion 2) even if the level of the interface is maintained at the
eXchangers, in fact, whereas in the case of Separate beds, the level at which the discharge line has been installed,
fraction of ions removed is limited by the equilibrium value there will always be a certain mixing between the two
corresponding to the maximum degree of regeneration of the regenerating liquids or between one regenerating liquid
ion eXchangers and hardly exceeds 99%, in the case of a and the barrier water, in a Substantial Volume around
mixed bed there are no theoretical limits to the fraction of the interface between the resins.
ions removed. Both problems 1 and 2 cause incomplete regeneration of
Furthermore, whereas during the treatment, for example, 35 that portion resins which is near to the interface; it means
through Separate beds of cationic and anionic exchangers that a part of the anionic resin will be saturated with the
connected in Series, the pH of the treated Solution falls to cationic resin regeneration liquid and Vice versa. This
very low levels in the column containing the cationic resin, implies a lower exchange capacity in the regenerated resins
in the mixed bed pH remains near to neutral. This charac at equal Volumes and consumption of regenerating liquid;
teristic allows, for example, the desalination of Solutions of 40 furthermore, the portion of Saturated anionic resin will
pH sensitive molecules. release Sulphate or chloride ions and the portion of Saturated
Opposed to these advantages, the regeneration of mixed cationic resin will release Sodium ions, So affecting the
beds after use is unfortunately till now much more complex quality of water produced in the Successive desalination
and costly than with Separate beds, because the cation process (see e.g. G. J. Crits, Ion Exchange, Technology of
eXchangers and the anion eXchangers must be separated 45 Mixed Beds, Ultrapure Water, November, 1984).
before regeneration, which is carried out with acids and These disadvantages can be reduced by introducing into
baseS respectively and then they must be homogeneously the mixed bed, other than the two ion exchange resins, an
remixed after regeneration. inert Separator consisting, for example of inert Small beads
Separation and regeneration of exhausted mixedbeds has with an intermediate density between those of the two resins.
been described for the first time in U.S. Pat. No. 2,771,424 50 During hydraulic classification, the Separator positions
(1956). A monography of recent processes was reported by itself between the two resins distancing them from the Zone
B. Coulter, Ultrapure Water, November, 1987. where mixing of the two regeneration reagents takes place.
In all regeneration processes, the resins are separated by In this way, the partial Saturation of the anionic resin is
hydraulic classification by utilizing the different densities reduced as well as the criticality of the level of the cationic
and granulometries of the two exchangers. 55 resin, but the desalination capacity per unit volume of bed
Once Separated, the resins can be regenerated in the same will be inferior because the inert Separator occupies a
column which contained the mixed bed (internal portion of the column Volume.
regeneration) or one or both of them can be transferred into On the contrary, external regeneration eliminates all of the
one or more different columns where regeneration is carried problems related to imperfect Separation of the regenerating
out (external regeneration); they are then mixed in a special 60 reagents in Such Way assuring greater eXchange efficiency,
mixer (or even in the column used for the regeneration of the an improved degree of purity of the treated water and better
cation exchanger) and then transferred into the column used repeatability of the desalination process: a recent mixed bed
for the mixed bed. Another possibility consists in transfer process with external regeneration is, for example, described
ring Said resins, after regeneration, into the column used for in U.S. Pat. No. 4,472.282.
the mixed bed and mixing them therein. 65 On the other hand, transferring the resins involves, as has
The external regeneration procedure requires a much already been pointed out, complex equipments and trouble
more complex plant, and is therefore normally used only for Some handling of the same and long overall regeneration
 US 6,187.826 B1
3 4
times, thus making this method economically feasible only A further object of this invention is the method described
for the treatment of big volumes of water, already with a below for the preparation of a mixed bed of ion exchangers,
very low Salt content. characterized by great homogeneity. This process does not
Consequently, the equipment complexity is justified only require the use of air for mixing the resins and is applicable
for big plants and Such operational work and long regen to units with external regeneration.
eration times are only acceptable when infrequent regenera The simplicity and versatility of the plant object of this
tion cycles (see e.g. B. L. Coulter, art. cit.) are required. invention, make it usable even for Small or medium sized
Another critical point in all mixed bed processes is the applications and even in processes which require frequent
homogeneous mixing of the ion eXchange resins once the regeneration, for the first time rendering possible, and
regeneration is carried out. It is well known that the quality economic, to obtain purified water with a purity degree
of water produced and the working capacity of the bed, similar to those obtained by the best units with external
largely depend on the quality of the mixing which must be regeneration, even when Starting from well-water or even
as homogeneous as possible (see e.g. E. G. Baeva et al., from Sea-water.
Development of a System for Mixing Ion Exchangers, The mixed bed obtained by the method and the plant
Teploenergetika, 1968). 15 object of this invention, is furthermore able to reduce
In the devices known in the State of the art, mixing is inorganic and organic ionic impurities to extremely low
always obtained by fluidizing the bed by counter-washing levels in aqueous Solutions of neutral organic products (for
with water and then blowing air from the bottom of the example, molecules of pharmaceutical interest and their
column. This method is also applied in external regeneration intermediates or Sugar Solutions or food products).
units, with the Sole difference that in the latter case, mixing The Scope and advantages of the device and the method
is Sometimes effected in a special apparatus instead of in the according to the invention are reached with the character
column dedicated to the mixed bed. istics listed respectively in independent claims 1 and 6.
Mixed beds obtained by this procedure can be, and Advantageous applications of the invention appear in the
usually are, lacking in homogeneity: in general, the upper dependent claims.
part of the bed consists almost exclusively of the lighter 25 Substantially, according to the invention, two columns are
anionic resin and the lower part almost eXclusively of the foreseen: a first treatment column containing the mixed bed
cationic resin (data concerning lack of homogeneity in of ion exchange resins, in which the cation exchange resins
mixed beds are given by Baeva and S. Fisher, Trouble are regenerated after the treatment/desalination process, and
Shooting in Mixed Bed Ion Exchange, Ultrapure Water, then a Second column into which the anion exchange resins
July-August, 1992). Only the central portion contains both are transferred and regenerated, to be then reinserted at the
resins mixed in quantities approaching the optimal ratio; bottom of the first column where they rise through the cation
however, if, for example, transparent columns are used, a eXchange resins present therein, intimately mixing them
Simple optical analysis shows that even in this portion, Selves With these, to give a reconstituted homogeneous
homogeneity is not optimal: relatively large portions (of the mixed bed.
order of 0.5 L in a 40 L bed) in which cation exchangers 35 Further characteristics of the invention will be made clear
prevail, alternate with Zones of the same size in which anion by the detailed description which follows, which refers to
eXchangers prevail. one of its purely exemplary forms, therefore not limitative,
In conclusion, available mixed bed techniques at the and which is illustrated in the annexed FIG. 1, in which:
current State of the art, have disadvantages as compared to FIG. 1 is a scheme of the device for the regeneration of
the conventional treatment with two or more Separate beds, 40 fluidized beds according to the invention.
which are tied on the one hand to greater plant and opera Referring to this figure, the device object of this
tional complexity (above all if external regeneration is used) invention, consists Substantially of two columns, one of
and on the other hand to high handling costs and, as a which, indicated by C1 is dedicated to contain the mixedbed
consequence, are competitive for the production of ultrapure and to the regeneration of the exhausted cationic exchanger.
water or of proceSS Solutions with very low ionic content, 45 The other, indicated by C2, is dedicated to the regeneration
only in the case of Solutions with already Very low Saline of the exhausted anionic exchanger, Said columns being
content, usually lower than that found in well water. joined according to the diagram in FIG. 1. In the device of
On the other hand, Separate bed processes are not nor FIG. 1 in which the salient characteristics are shown, the
mally usable to produce water or process Solutions with a open and close type valves are indicated with the term V, the
conductivity of less than 0.5 uS/cm. Consequently, the 50 regulation valves with the term VR and the circulation pump
production of water with very low conductivity (that is less with the term P.
than 0.5 uS/cm, preferably less than 0.25 uS/cm or even 0.08 The functioning of the device of the invention substan
puS/cm, Such as for example for thermonuclear plants) nor tially follows the operations described below.
mally requires two treatment Steps, in which only the Second Initially, the anionic exchange resin is loaded into column
is carried out with a mixed bed. 55 C2 and the cationic exchange resin into column C1. Both of
Furthermore, internal regeneration processes are normally the exchange resins are regenerated Separately and accord
used for Small mixed beds and as has been previously Stated, ing to the Supplier's instructions (for example, for the
they are rather unsatisfactory, even for the quality of the regeneration of the anionic exchanger a strong base is used,
deionized water produced in each Successive phase. usually sodium hydroxide at 4% w/w, whereas for the
It is to the Subject of this invention a new device for the 60 regeneration of the cationic exchanger, a strong acid is used,
regeneration and mixing of ion eXchangers resins in a mixed normally hydrochloric acid at 8 to 12% w/w or Sulphuric
bed and method for operating it. This handling is much acid at the same concentration).
Simpler in comparison to the units with external regeneration For the cation exchanger, the acid Solution is fed to C1
of the present State of the technology, it maintains all of their through Valve V4, Simultaneously discharging the exhausted
advantages and even increases their performance, in par 65 regenerating Solution through valve V5 and regulating VR4
ticular thanks to the greater homogeneity of the mixed bed to maintain the liquid just above the level of the resin.
obtained by said method. Similarly, for the anion eXchanger, the alkaline Solution is
 US 6,187.826 B1
S 6
fed to C2 through V6, discharging the exhausted regener below the transfer opening of the anion exchanger (indicated
ating solution through V7 and regulating VR5 to maintain by A in FIG. 1): valve V13 can be opened (partially or
the liquid just above the level of the resin. completely) to reach the maximum flow without excessive
After regeneration, the ion exchangers are thoroughly loss of load in the anion resin bed in C2.
washed with deionized water through the same hydraulic When all of the anion exchanger is transferred into C2, the
circuits. Upon completion of the washing (which can be Step is terminated by Stopping the pump P and closing the
determined on the basis of the conductivity of the eluate or Valves which were opened at the beginning of the transfer.
on the total volume of water used), both resins are counter The technicians can then proceed with emptying exceSS
washed with the flow recommended by the Supplier for an water from the columns and with the regeneration of the ion
expansion of between 25% and 100% of the initial volume, eXchangers by the procedure which has already been
supplying deionized water through valves V8 and V9 described.
respectively and first discharging the air and then the water In a variant of the invention, before the Separation of the
through valves V10 and V11 respectively. At the end of this resins is Started, a quantity of 4-12% W/W hydrochloric acid,
phase, the counter-washing is continued in C2, whereas it is greater than that required for the regeneration of the cation
stopped in C1 by closing V8 and V10. 15 eXchanger, is fed into the mixed bed in C1. In this case, after
The cation exchange resin bed in C1 is again fluidized by the Separation, there will be no need to regenerate the cation
opening valves V12 and V13, starting the pump P and eXchanger.
regulating the valve VR1 to obtain the flow necessary to Apart from an increased acid consumption, this variant
expand the bed of cation exchange resin up to 200%-400% brings an easier and more complete Separation of the ion
of its initial volume. Valves V9 and V11 are then closed and eXchangers and is often advantageous in cases of desalina
V1 is opened to pressurize the columns. tion of concentrated Solutions of organic molecules.
Valve V12 is closed then valve V14, which changes the The device and the method object of this invention, are
flow of pumped water from C1 to C2, is opened simulta very useful in the pharmaceutical field, for example, because
neously to V3, which causes the anionic resin to be trans they consent to reduce the amount of inorganic and organic
ferred from C2 to C1. 25 ionic impurities to extremely low levels in aqueous Solutions
In this way, the flow of water pumped through V14 pushes of drugs and of diagnostics agents. Among these, it is
the fluidized bed of the anion exchanger through V3 and into Worthwhile to mention compounds of non-ionic type, Such
column C1 where the anionic resin, which is lighter than the as, for example, iodinated contrast agents for radiography or
cationic resin, rises through the fluidized bed of the cation paramagnetic contrast agents for magnetic resonance imag
eXchanger mixing itself intimately with it. ing (MRI), products which often must be administered in
When the anion exchanger has been transferred into C1, particularly high concentrations and for which an high
the pump P is stopped, valves V13, V14 and V3 are closed degree of purity is essential.
and the fluidized mixed bed, just obtained after the transfer Among the neutral iodinated contrast agents for
of the anion exchanger from C2 to C1, is compacted by radiography, the following can be, by way of an example,
rapidly discharging water through valve V5. Valve V5 is 35 mentioned iopamidol, iomeprol, ioheXol, ioverSol, iopentol,
closed when the level of water in the column is just a little iopromide, iOXilan, iotriside, iobitridol, iodixanol, iofratol,
above the level of the resin. iotrolan, iodecimol, iopirol, iopiperidol.
The mixed bed obtained by this process results extraor Among the neutral paramagnetic contrast agents for MRI
dinarily homogeneous as compared with those obtained by particularly preferred resulted to be the gadolinium complex
known methods (such as, for example, counter-washing with 40 of 10-(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane-1,
water and blowing air into the bottom of the column). The 4,7-triacetic acid (gadoteridol).
two resins are found to be homogeneously mixed for at least The following examples are intended to illustrate the best
80% of the column length (preferably for at least 90%); experimental conditions in which to apply the method,
minimal non-homogeneous residual Zones are observed only subject of the invention.
at the top of the column. 45
EXPERIMENTAL SECTION
At this point, column C1 contains the regenerated mixed
bed onto which the Solution to be desalinated can be loaded EXAMPLE 1.
(through V4); the resulting desalinated water (ultra-pure
water or desalinated Solution of organic compounds) is In a device according to the preceding description and to
collected through valve V16. When the conductivity of the 50 FIG. 1, the columns C1 and C2, which have effective
desalinated solution is above the level of acceptability Volumes (measured from the Support plate to the height of
established for the type of occuring purification, or when a the feed distributor) of 36 and 22 L, were loaded respec
predetermined Volume of Solution has been treated, the tively with 12 L of Sulphonic cation exchanger Rohm &
desalination phase is stopped and the Separation of the resins Haas Amberjet(R) 1200 Na and with 22 L of strong anion
is begun for the regeneration of the Same. 55 exchanger, type I Rohm & Haas Amberjet(R) 4200 Cl. The
To this effect, column C1 is filled with water, through V8 ion exchangers were regenerated respectively with 26 kg
for example, closing V1 and venting the air through V10; HCl 10% w/w at a flow of 40 L/h and with 135 kg of sodium
when the column is full, V10 is closed and valves V1,V2, hydroxide 4% w/w at a flow of 90 kg/h. Both of the ion
V15, and V12 are opened; the pump P is started and valve eXchangers were then washed with deionized water until the
VR1 is gradually opened. In this way, the mixed bed in C1 60 eluate conductivity fell below 50 uS/cm. Then the anion
is fluidized and the lighter anionic resin gradually Separates eXchanger was transferred to C1 and mixed with the cation
out, above the cationic resin. When the flow, regulated by eXchanger according to the method Subject of this invention.
VR1 is increased, the upper part of the anionic fluid bed To the mixed bed so prepared, were fed 100 L of a solution
reaches the resin transfer line and begins to pass over into of 1.3 kg (22 mol) of NaCl in 100 L of water (conductivity
column C2 through valve V2, together with the flow of 65 28,000 uS/cm) at a rate of 100 L/h.
fluidization water. Valve VR1 is gradually opened to give the The conductivity of the treated water was, at the
flow necessary to expand the cation exchanger to a level just beginning, a little less than 1 uS/cm but rapidly fell, becom
 US 6,187.826 B1
7 8
ing stable, at 0.1 uS/cm until 80 L of water had been treated. treated water and of capacity before exhaustion, at equal
The conductivity then rose very rapidly until it went out of reagent consumption.
the limit of the instrument (3,000 uS/cm) indicating that the EXAMPLE 3
bed was exhausted.
In order to have a measure of the total capacity up to Desalination of a concentrated Solution of N,N'-bis
Saturation of the ion eXchangers, feeding of the Saline (2,3-dihydroxypropyl)-5-(hydroxyacetyl)
Solution was continued until the end and the eluate was methylamino-2,4,6-triiodo-1,3-benzene
collected in a second fraction. Then the mixed bed was dicarboxamide
washed with deionized water to a conductivity of 100 A) Solution of N,N'-bis(2,3-dihydroxypropyl)-5
tuS/cm, Still collecting the eluate in fraction 2. (hydroxyacetyl)methylamino-2,4,6-triiodo-1,3-benzene
The total capacity of the anion and cation eXchangers was dicarboxamide.
determined by dividing the molar quantity of eXchanged 90 kg of N,N'-bis(2,3-dihydroxypropyl)-5-
ions by the Volume of the anion and cation eXchangers. The (hydroxyacetyl)-methylamino-2,4,6-triiodo-1,3-benzene
molar quantity was obtained deducting from the total quan dicarboxamide obtained by the procedure described in EP
tity of Sodium chloride fed, respectively, the total quantity of 15 185130 were suspended in 400 L of deionized water and
chloride ions determined with silver nitrate in fraction 2 and heated under reflux. 310 g of 30% w/w sodium hydroxide
the difference between the total quantity of chloride ions and were added to the Suspension. It was then heated to 120° C.
the free acidity titrated with caustic Soda. under Sealing conditions and this temperature was main
The total capacity of the anion exchanger resulted to be tained for 1 hour. It was then cooled to 50° C. and 7.7 kg of
0.84 mol/L (referred to the exchanger volume in the form of 30% w/w sodium hydroxide were added gradually cooling
chlorine) and that of the cation exchanger 1.7 eq/L (referred to 40 C. over 2 hours. After a further 4 hours at 40 C., it
to the exchanger volume in the form of Na), in accordance was cooled to 20 C. and pH was adjusted to 5.5 with
with what declared from the ion exchanger manufacturer. hydrochloric acid. The solution obtained was loaded onto
The effective capacity of the mixed bed (defined as the 160 L of absorbent resin R&H Amberlite 1600, feeding the
quantity of ions fixed before the conductivity rises above 0.5 25 eluate to a nanofiltration unit equipped with a Desal DK4040
uS/cm) resulted to be 17.6 eq., which, when referred to the membrane. When the loading was completed, the resin was
quantity of anion exchanger corresponds to 0.8 eq/L. This washed with 800 L of water at 40 C. collecting the eluate
value is very high, in fact better than that foreseen on the in the tank of the nanofiltration unit. During elution or at the
basis of the data supplied by Rohm & Haas for a unit which end of it, the nanofiltration unit was Started and the operation
continued until the volume of the Solution in the unit was
uses separate beds (Amberjet 4200 Cl co-flow engineering reduced to about 200 L. At the same time, the elimination of
data). the greater part of Sodium chloride contained in the eluted
EXAMPLE 2 Solution was also obtained.
For purposes of comparison, the same ion exchangers The obtained concentrated solution of N,N'-bis(2,3-
from Example 1 were loaded into two separate columns, 35 dihydroxypropyl)-5-(hydroxyacetyl)methylamino)-2, 4,6-
regenerated in the same conditions, counter-washed and triiodo-1,3-benzene-dicarboxamide, which will from now
washed with deionized water to the same final conductivity. on be referred to as Solution A, contains 80 kg of the desired
The two columns were joined in Series in Such a way that product, about 0.05 mol/L of organic ionic impurities
the anion exchanger followed the cation exchanger. (aromatic carboxylic acids) and 0.03 mol/L of inorganic
A Solution of Sodium chloride in water in the same 40 salts (prevalently NaCl)
quantities as in Example 1 was fed to the two columns at a B) Desalination of solution A.
rate of 100 L/h. 200 kg of Solution A at 40% w/w were fed at a rate of 40
The conductivity of the treated water was initially a little L/h to the same unit of Example 1, filled with the same
less than 50 uS/cm, but rose moving up to 100 and then to quantities of the same ion exchangers, which were previ
300 uS/cm up to 70 L of treated water (pH alkaline). The
45 ously regenerated by the same method of example 1.
conductivity then went out of the limit of the instrument The eluate line was equipped with a conductivity analyser
(3,000 uS/cm) indicating that the deionizer was exhausted. and also with a photometer to measure the absorbance at 280
AS in the previous example, in order to have a measure of nm, to detect the presence of organic Substances in the
eluant.
the total capacity up to Saturation of the ion exchangers, 50 The eluate was discarded until its absorbance began to
feeding of the Saline Solution was completed the eluate was rise rapidly, indicating the presence of the organic product in
collected in a Second fraction. question.
Then the in series beds were washed with deionized water
From this moment, the eluate was collected in a tank up
to a conductivity of 100 uS/cm still collecting the eluate in to exhaustion of Solution A.
fraction 2. 55 During the collection of this fraction which contains the
Whereas the total capacity of the exchangers, determined greater part of the organic product, the conductivity
by the same method as in Example 1, resulted practically remained below 0.1 uS/cm.
identical to that of Example 1, the effective bed capacity When Solution A was finished, the mixed bed was washed
(defined in this case as the quantity of ions fixed before the with 30 L of water at the same flow rate and then again with
conductivity rises above 400 uS/cm) resulted to be 0.68 60 150 L of water at a flow rate of 100 L/h always collecting
eq/L. the eluate in the same tank of the product fraction.
This value is near to that expected, based on data Supplied Even during this phase, the conductivity of the eluate
by Rohm & Haas for a separate bed unit like the one in this remained very low.
example (Amberjet 1200 Na co-flow engineering and The fraction corresponding with the desalinated product,
Amberjet 4200 Cl co-flow engineering). 65 which is free from chloride ions and carboxylic acids, was
The considerable advantages assured by the unit of concentrated by evaporation to a Viscous residue containing
Example 1 appear evident, both in terms of quality of the 15% of water. The product was then isolated in a practically
 US 6,187.826 B1
10
pure form (99%) by the addition of absolute alcohol at reflux exchange resins, contained in a first treatment column (C1)
temperature, followed by cooling and filtration. the device comprising:
EXAMPLE 4

Regeneration of the Mixed Bed after Treatment of means for the Separation of the anion eXchange resins
the Organic Solution of Example 3. from the cation exchange resins in Said first column
The mixed bed to be regenerated was counter-washed (C1) by fluidizing the mixed bed of resins which allows
with 10 L of water. The water level was lowered to just water to enter first column (C1) from the bottom, so
above the level of the resin and then, through the feed-line that the lighter anion resins shift themselves on top of
were fed, firstly 60 kg of 8.5% w/w HCl at a flow rate of 40 the cation resins,
kg/h and then 200 kg of deionized water, the first 30 L at the means for the transfer of the anion eXchange resins into a
Same flow rate and the remainder at a rate of 150 kg/h. second treatment column (C2) which column is in fluid
The cation and anion exchangers were then Separated and communication with the first column (C1) by a conduit
the anion exchanger transferred to column 2, according to 15
including a transfer opening (A) in the first column
the description of this invention: the Separation was found to (C1), at a level above that of the mixed bed, a conduit
be easy and clean-cut. connecting said opening (A) to the Second column
The anion eXchanger was regenerated, washed and then (C2), intercepted by a valve (V2), and further compris
retransferred to column C1 where it was mixed with the
cation eXchanger, exactly as described in Example 1. ing means for expanding the cationic resin in the first
column (C1) up to a level just below said opening (A);
EXAMPLE 5 means for the regeneration of the cation exchange resins
DeSalination test equal to that described in directly in the first column (C1);
Example 3 on the regenerated mixed bed of 25 means for the regeneration of the anion exchange resins in
Example 4 the Second column (C2) transferring the regenerated
As a confirmation of the repeatability and reliability of the anionic resins from the Second column (C2) to the first
method object of this invention, the complete regeneration column (C1) and preparing a homogeneous reconsti
cycle according to Example 4 and desalination of a Solution tution of the mixed resins and fluidizing the bed by
prepared according to point B of Example 3, were repeated pumping water into the Second column (C2);
42 times without significant functional anomaly and with the Said regeneration means consisting of an acid Solution fed
Same desalination efficiency.
through a valve (V4), and the exhausted Solution after
EXAMPLE 6 regeneration is discharged through a valve (V5) the
35 Second consisting of an alkaline Solution fed through a
DeSalination of a Solution of the non-ionic organic
complex of Gadolinium of 10-(2-hydroxypropyl)-1, valve (V6), and the exhausted Solution after regenera
4,7,10-tetraazacyclododecane-1,4,7-triacetic acid. tion is discharged through a valve (V7);
100 kg of an aqueous Solution containing 25 kg of the means for the transfer of the regenerated anionic resins
compound in question, (Solution A"), obtained by the method 40 from the second column (C2) to the first column (C1)
described in patent application EP 292689, was fed at a rate comprising a conduit intercepted by a valve (V3),
of 40 L/h to the same unit of Example 1, filled with the same which joins Said columns in the region of their respec
quantities of the same ion exchangers, previously regener tive bases and water pumped in the Second column (C2)
ated according to the same method of Example 1. which transfers the bed of anionic resins into the
45
The eluate line was equipped with a conductivity analyser second column (C1) where it rises through the fluidized
and also with a photometer to measure the absorbance at 280 bed of the cationic resins mixing itself intimately with
nm, to detect the presence of organic Substances in the them.
eluate.
The eluate was discarded until its absorbance began to 2. Method of regenerating mixed beds of ion exchange
rise rapidly, indicating the presence of the organic Substance 50 resins, comprising cation eXchange resins and anion
in question. exchange resins, contained in a first treatment column (C1)
From this moment the eluate was collected in a tank until having a top and a bottom, Said method comprising the
the Solution was finished. following Successive Steps;
During the collection of this fraction which contains the 55 (1) separating the anion exchange resins from the cation
greater part of the organic product, the conductivity exchange resins in the first column (C1) by introducing
remained below 0.1 uS/cm. water from the bottom of the first column (C1), to
When Solution A was finished, the mixedbed was washed fluidize the mixed bed So that the lighter anionic resins
with 30 L of water at the same flow rate and then finally with rise above the cationic resins,
300 L of water at a flow rate of 100 L/h, always collecting 60
the eluate in the same tank of the product fraction. (2) transferring the anionic resins from the first column
Even during this phase, the conductivity of the eluant (C1) to the Second column having a top and bottom
remained very low and the fraction corresponding to the (C2) through a conduit connecting Said first column
desalinated product was shown to be free from chloride ions. (C1) and Second column (C2), the conduit positioned at
What is claimed is: 65 a higher level than that defined for the mixed bed and
1. A device for the regeneration of mixed beds of ion expanding the cationic resin bed in the first column
eXchange resins, including cation exchange resins and anion (C1) to a level just below that of the transfer line;
 US 6,187.826 B1
11 12
(3) regenerating the cation exchange resin directly in the ducing into the first column (C1) of an acid Solution in
first column (C1) by introducing an acid Solution and in quantities greater than those necessary for the regeneration
discharging the exhausted Solution, maintaining the of Said cationic resins.
liquid level just above that of the resins; 5. The method according to claim 4 wherein the acid
(4) regenerating the anion exchange resin in the Second solution contains 8% to 12% w/w hydrochloric acid or
column (C2); Sulfuric acid.
(5) to the first column (C1) and preparing a homogeneous 6. The method according to claim 2, wherein the anionic
reconstitution of the mixed resins and fluidizing the bed resins are regenerated in column 2 (C2) by introducing an
by pumping water into the Second column (C2) to push alkaline Solution and discharging exhausted Solution while
the bed of anionic resins through a conduit with valves maintaining the liquid level just above the level of the resins.
and through the bottom of the first column (C1) where 7. The method according to claim 4, wherein the alkaline
the bed of anionic resins rises through the fluidized bed solution contains 4% w/w sodium hydroxide.
of cationic resins mixing intimately with them. 8. The method according to claim 2, wherein after
3. The method according to claim 2, in which the cation 15
regeneration, the resins are washed with deionized water and
eXchange resins are regenerated prior to Separating the anion counter-washed with deionized water thereby reaching an
eXchange resins from the cation exchange resins. expansion of 25% to 100% of their initial volume.
4. The method according to claim 2, wherein the regen
eration of the cation eXchange resins takes place by intro k k k k k