Phosphorus-contained polycondensation type ion-exchange resins | ATI, March 2012
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ATI - Applied Technologies & Innovations
Volume 6 | Issue 1 | March 2012 |pp.10-21
http://dx.doi.org/10.15208/ati.2012.2
Phosphorus-contained polycondensation
type ion-exchange resins
Tulkun Tursunov
Tashkent Institute of Chemical Technology, Uzbekistan
e-mail: [email protected]
postal address: 32, Navoiy str., 100011 Tashkent, Uzbekistan
This work describes synthesis and research of new polycondensation type phosphoruscontained ion-exchange polymers by phosphorylation of polymers received through the
interaction of furfural (accessible and cheap product of hydrolytic and cotton scraping
industry of Uzbekistan) with benzyl bromide (chloride). Furfural and its derivatives possess
high reactionary ability thanks to presence of carbonyl groups, and presence of a heterocyclic
cycle gives to the received polymers high thermal and chemical stability. Polycondensation
reaction kinetics of furfural and benzyl bromide, and phosphorylation reaction of the received
benzyl bromide-furfural polymer were studied. Sorption, kinetic and thermo-chemical
properties of received ion-exchange resins were studied using physico-chemical and chemical
analyses to find out specific objects of practical application. Particularly, sorption and selective
properties of received ion-exchange resins to ions of such metals as copper, nickel, calcium,
magnesium, and uranyl ion were studied. Received results support the application of the
investigated ion-exchange resins in processes of clearing of industrial and waste waters of
hydrometallurgical manufactures.
Keywords: Furfural, benzyl bromide, ion-exchange resin, cation-exchange resin,
polycondensation, sorption, phosphorylation, copper, nickel, calcium, magnesium, uranyl
ion, benzyl bromide-furfural polymer, bromomethyl group, polyethylene polyamine,
potentiometric titration, thermal stability, chemical stability
Introduction
Today ion-exchange polymers, thanks to the valuable properties, have found wide
application in hydrometallurgy, water preparation, in clearing of various industrial
and waste waters of chemical manufactures. In many regions of Uzbekistan,
especially, in Karakalpakstan, water has the raised rigidity of 10-12 mg-ekv/l at
norm of 2.5-7 mg-ekv/l (Pulatov, Tursunov, and Nazirova, 2006). Besides, ionexchange division of ions of some metals, such as molybdenum-reny and others, is
a significant problem to hydrometallurgical manufactures. The annual requirement
of domestic economic industries in ion-exchange polymers makes about fifteen
thousand tons. Nowaday ion-exchange polymers are imported into Uzbekistan
from the CIS countries, and it considerably affects cost of manufactured products.
Therefore, there is an expediency to create the production of ion-exchangers with
orientation to a local source of raw materials.
The basic possibility of this problem solution is working out new or updating of
existing ion-exchange polymers production technologies. Rational use of accessible
substances and secondary material resources will allow organizing manufacturing
of ion-exchange polymers based on stable raw-material base.
Chemical, agricultural, cotton scrape and other industries provide a real rawmaterial base to production of ion-exchange polymers. There are accessible
products, in particular in productions JSC “Navoiazot”, JSC “Maxam-Chirchik”,
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© 2012 Prague Development Center
Phosphorus-contained polycondensation type ion-exchange resins | ATI, March 2012
cotton scrape factories, etc. These industries produce large-tonnage products
which represent perspective raw materials for production of ion-exchange
polymers with good indicators of operational properties. Besides, processing of the
above-stated raw materials in ion-exchange polymers production meets
requirements of ecological efficiency as assume applying low-waste technologies.
Polymers production using the derivatives of furan appears interesting, as the
country possesses huge stocks of vegetative raw materials, including large-tonnage
wastes of cotton processing industry. These raw materials are one of sources of
receiving some chemical compounds, including furfural and its derivatives
(Sherbakov, 1962). High polyfunctionality of furfural caused its use for producing
of polymers possessing universal chemical firmness, increased heat and thermal
resistance (Tursunov and Nazirova, 1985a).
We were the first received and investigated new phosphate cation-exchange resins,
nitrogen-phosphorus containing ion-exchange resins using chemical
transformation of benzyl bromide-furfural polymers (Tursunov and Nazirova,
1985b; 1985c). Validity and perspectives of a choice of furfural as a raw source for
creation ion-exchange polymers is caused by presence in its structure of the
heterocyclic groupings necessary for receiving ion exchangers with the prescribed
properties, namely, thermal and chemical stability, mechanical durability and
radiation stability.
Reaction of polycondensation benzyl bromide with furfural was studied by
chemical and physical methods. Reaction course of polycondensation was
controlled on concentration change of furfural and bromine through certain time
intervals. In parallel removed IR-spectra of reactionary weight from the beginning
of reaction to gel formation. The study has shown that polycondensation of
furfural with benzyl bromide, basically, proceeds at the expense of interaction of
mobile atoms of hydrogen of benzyl bromide aromatic kernel in orto- and pairpositions; and partially for the account bromomethyl groups with aldehyde group
of furfural. The quantity of bromine in an initial stage of reaction made 26% and
decreased by the reaction end to 10-12%. Reduction of the
bromine concentration may also be related to the volatility of the initial monomer.
IR-spectroscopic examination of initial substances, reaction mass and polymer
confirms this point of view. The synthesized polymer was hardened to constant
weight, and then it was phosphorylated (Tursunov and Nazirova, 1978).
Phosphorylation of polymers on a basis
of furfural and benzyl bromide
In search of a convenient method of carrying out of reaction of synthesized
polymer phosphorylation, reaction was organized in the environment of threechloride phosphorus in the presence of aluminium chloride at 50, 60, 700С.
Dependences of degree of polymer transformation on time and temperature were
removed to study a change in the phosphorylation process speed. Kinetics of
reactions was registered by defining the maintenance of the entered phosphorus
and static exchange capacity of end-product. Reaction of polymeranalogous
transformations shows the heterogeneous process presented in this case by
interaction bromomethyl group of polymer with three-chloride phosphorus. The
general speed of heterogeneous reaction in the investigated case can be defined by
diffusion of three-chloride phosphorus or actually speed of one of stages of
© 2012 Prague Development Center
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Applied Innovations and Technologies
Synthesis ion exchangers by chemical transformation of products
of polycondensation of furfural and halogenbenzyls
Phosphorus-contained polycondensation type ion-exchange resins | ATI, March 2012
chemical reaction. Kinetic dependences of reaction speed on time-lg (1-A) =kτ for
film and A=k (τ) for gel kinetics (А - degree of phosphorylation of polymer during
time) were excluded (Tursunov, 2009).
In the analysis of the received kinetic curves it was established that kinetic area,
characteristic for chemical reaction, is observed at А=0.15-0.3. Changes of
constants of phosphorylation reaction speed in dependence on site (А=0.1-0.3, τ
=60 minutes) temperature correspond to the Arrhenius equation (Table 1).
Energy of chemical reaction activation was calculated on a tangent of a straight
line slope based on dependence of -lgK on 1/Т. Limiting influence of gel kinetics
was considered also using linear dependence in coordinates А=f (  ) at А=0.10.3. The magnitude of diffusion activation energy was defined from dependence
 lg D ef . =f(1/Т).
TABLE 1. KINETIC PARAMETERS AT VARIOUS DEGREES OF POLYMER
PHOSPHORYLATION ON A BASIS OF FURFURAL AND BENZYL BROMIDE
Т, 0С
Constant of reaction
speed, К·10-3 sec-1
D 108 , sm2/sek
А=0.1-0.3
Еreac. act.
Еdif. act.
А=0.5
Еdif. act.
kJ/mol
50
60
70
0.633
0.765
0.919
0.37
0.46
1.40
40.28
28.64
50.04
On the basis of the received experimental data it is possible to draw a conclusion
that polymer phosphorylation reaction on a basis furfural and benzyl bromide
proceeds with sufficiently high degree of transformation; speed of process
phosphorylation is defined in an initial stage (А=0.3) and limited by kinetic area of
chemical reaction. Further process of transformation degree increasing is
characterized by penetration of three-chloride phosphorus deep into polymer
grains, i.e. diffusion in granules of polymer (Table 1) becomes a limiting stage of
process. On the basis of experimental data for reaction phosphorylation polymer
on the basis of benzyl bromide and
furfural the following optimum conditions are
accepted: τ =7.0-7.5 hours, Т=700С, molar parity of benzyl bromide to furfural 2:1. Table 2 shows the basic properties of received cationites.
Except phosphorylation the synthesized polymer on a basis furfural and benzyl
bromide, we also conducted reaction of its amination for the purpose of receiving
anion-exchanger containing high-basic groups. Polymer was aminated by
trimethylamine. Concentration influence of trimethylamine, temperatures,
durations of reaction and dependence of properties anion-exchange resin on a
parity of benzyl bromide and furfural in a reactionary mix (Tursunov,
Zajnutdinova, and Nazirova, 1999) were studied.
Polymer amination was made after its preliminary swelling in organic solvents.
Studying of influence of reaction
temperature to polymer transformation degree
was made at 20,0 30, 400С. The obtained data testify that optimal amination
temperature is 20 С. Research of influence of trimethylamine quantity on size of
anion-exchange resin exchange capacity showed that the maximum degree of
amination of polymer is reached at 4 multiple surplus of amine.
Duration of amination varied in the range of 2-6 hours. 6 hours were accepted as
optimal time of amination. Speed of amination substantially depends on degree of
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© 2012 Prague Development Center
Phosphorus-contained polycondensation type ion-exchange resins | ATI, March 2012
crosslinking polymer: the more strongly polymer is sewed, the more slowly process
of diffusion proceeds and longer time for reaction end is required.
TABLE 2. PHYSICAL AND CHEMICAL PROPERTIES OF SYNTHESIZED IONITES
Dampness
Specific volume of bulked up
ion-exchange resin
Static exchange capacitance
on 0.1 N solutions of:
caustic soda
muriatic acid
sodium chloride
Chemical stability. Static
exchange capacity of ionexchange resin on 0.1 N
solution of NaOH after
treatment by solutions:
5 N solution of H2SO4
5 N solution of NaOH
5 N solution of HNO3
Sorption ability to ions:
Н-form
copper
nickel
uranyl
Na- form
copper
nickel
uranyl
ОН- form
copper
Unit of
measure
Phosphate cationexchange resin
Amphoteric ionexchange resin
Aminated benzyl
bromide-furfural
polymer
40
3.2-3.5
%
ml/g
15-20
3.2-3.4
14-17
2.8
3.8-7.5
0.8
3.6
4.0
-
3.2-3.4
6.7-7.3
6.8-7.7
6.75-7.68
3.56
365
3.62
3.3
3.1
-
1.2-2.6
1.2-2.0
200-350
1.76-3.08
2.0-3.74
300-450
-
1.8-2.0
2.5-2.7
80-100
2.8-3.0
3.1-3.3
220
2.5-2.8
2.2
mg-ecv/g
1.5-2.0
mg-ecv/g
mg-ecv/g
Research shows that with furfural concentration increase in a reactionary mix the
size of exchange capacity and swelling capacity of anion-exchange resin go down.
At using 1 mole furfural to 1.5 moles benzyl bromide the size of exchange capacity
reaches 3.5 mg-ekv/g. The preliminary results shows possibility of anion-exchange
resins synthesis using polymer amination on a basis furfural and benzyl bromide.
Synthesis of nitrogen-phosphorus contained ion-exchange resins
As a polymeric matrix for introduction of phosphate groups we used anionexchanger, synthesized by polycondensation polyethylenepolyamine (PEPA),
furfural and benzyl bromide. Table 3 shows properties of the anion-exchanger.
Phosphorylation of anion-exchange resin was made by three-chloride phosphorus
in the presence of waterless chloride aluminium (Turobjonov et al., 2005).
Studying of dependence of anion-exchange resin phosphorylation degree on
process duration, at molar parity of three-chloride phosphorus and three-chloride
aluminium 4:2, showed that optimal time of phosphorylation of anion-exchange
resin is 6-7 h. Thus the polymer contains 9% of Р corresponding to exchange
capacity of 3 mg-ekv/g of a caustic sodium solution. Spectral examination showed
© 2012 Prague Development Center
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Applied Innovations and Technologies
Parameters
Phosphorus-contained polycondensation type ion-exchange resins | ATI, March 2012
that in a spectrum-1 of phosphorylated anion-exchange resin there were strips in the-1
field of 750 sm corresponding to P-C-communication, and 2250-2230 sm
corresponding to Р(О)(ОН)2 group. Deformation fluctuations in the field of 825805 sm-1 are connected with 1,2,3,4-replacement
in benzene ring. Strips of
absorption in the field of 900, 650, 1150 sm-1 are connected with fluctuations of
primary and secondary amines which are identical to the same strips of absorption
in a spectrum non-phosphorylated anion-exchanger. Valence
vibrations of -C-N=
amine linkage are shown in the field of 1220-1230 sm-1. However, presence in the
same area of absorption strips of РО2Н2 groups complicates their interpretation.
On the basis of data of the element analysis, alkalimetric titration, the IRspectroscopy, etc. we can assert that synthesized polymeric ampholyte contains in
the structure except amino groups also phosphate groups. The basic physical and
chemical properties of the received polymeric ampholyte are shown in the Table 2.
TABLE 3. THE BASIC PHYSICAL AND CHEMICAL INDICATORS OF ANION-EXCHANGE RESINS
Parameters
Unit of
measure
Dampness
Static exchange capacitance on 0.1 N
solutions of:
NaCl
HCl
HNO3
H2SO4
Specific volume of bulked up anionexchange resin in OH-form
Oxidability of a filtrate
Chemical stability. Static exchange
capacitance of ion-exchange resin on
0.1 N solution of HCl after boiling
during 30 minute by solutions:
5 N solution of NaOH
5 N solution of H2SO4
Thermal stability. Static exchange
capacitance of anion-exchange resin
on 0.1 N solution of HCl after boiling in
water during 20 hours
%
mg-ecv/g
Anion-exchange resins on a basis of
PEPA, furfural and:
benzyl chloride
benzyl bromide
13
11
ml/g
mg-О2/g
mg-ecv/g
mg-ecv/g
1.0-1.1
4.5
4.35
5.63
1.8-2.0
1.5-2.0
4.8
4.85
5.82
2.5-2.8
3.0-5.0
2-5
4.5
4.3
4.2-4.22
4.8
4.4
4.2-4.3
To find specific objects of practical application there were studied sorptive and
operational properties of the received ion-exchange resins.
Research of properties in phosphorus-containing
ion-exchange resins
Cationites with phosphorus-containing groups represent a class of the selective
sorbents capable to display both of ion-exchange and complexing properties. The
presence of three functional groups, two acid hydroxyls and phosphoryl oxygen is
characteristic to phosphorus-containing cation-exchange resins. In subacid and
alkaline environments, at absence of complexing metals for these cation-exchange
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© 2012 Prague Development Center
Phosphorus-contained polycondensation type ion-exchange resins | ATI, March 2012
resins, usual dissociation with an exchange of cations is typical. Speed of exchange
reactions for one-and bivalent ions on phosphate cation-exchange resins is less
than on sulfonic acid and on carboxylated cation-exchange resins; i.e. speed of
reaction falls from strong - to weak dissociate: SO3Н>РO(OН)2>СOOН. Data in
the+Table 2 testify that the size of exchange capacity makes 6 mg-ekv/g on ions
Na from alkaline solutions, and 0.8 mg-ekv/g from the neutral ones. Considering
that the size of exchange capacity of phosphate cation-exchange resins depends on
рН environment and the initial form of ion-exchange groups, there
was examined
the sorption ability of synthesized cation exchange resin on Са2 + ions in Na- and2
H-forms
(Table 2). From the table it is clear that the exchange capacity on ions Са
+
in the H-form - 0.8-1.0 mg-ekv/g - is slightly inferior to capacity in the Na-form
- 3 mg-ekv/g. influence of рН on size of exchange capacity was investigated by the
method of potentiometric titration. The curve of potentiometric titration had 2
excesses that testifies to presence in structure of cation-exchange resin functional
groups with various degree of dissociation. Seeming constants of ionogenic groups
dissociation, found from the titration curves, correspond to рК-3.4, рК-7.5 (Table
4).
TABLE 4. EXCHANGE CAPACITIES OF RECEIVED CATION-EXCHANGE RESINS
Functional group
Phosphorylated
benzyl bromidefurfural polymer
Exchange capacities
рК1
The
Static on Calculated, calculated on
theoretical,
0.1 N
under the
curves of
mg-ecv/g solution of maintenance potentiometric
NaOH,
(%) of sulfur titration, mgmg-ecv/g
and
ekv/g
phosphorus,
mg-ekv/g
рК2
4.84
4.5-5.2
5.0-5.5
5.5-5.6
-
7.8
4.8
6.8-7.5
5.0-5.5
6.5-7.5
3.4
7.6
СН
O
СН2 Р
Phosphorylated
benzyl bromidefurfural polymer
with the
subsequent
oxidation
О
ОН
СН
O
ОН
СН2 Р О
ОН
Presence of ionogenic groups in structure of received cation-exchange resin was
also investigated by IR-spectroscopical method. In the IR-spectrum of phosphate-1
cation-exchange resin there are strips of absorption in the
field of 750 sm
corresponding to P-C-linkage, in the area of 1250-2560 sm-1 they correspond to-1
Р(О)(ОН) group. There are also strips of absorption in the field of 750 sm
corresponding to СН2-Р(ОН)2 group. Deformation fluctuations in the field of
825-805 sm-1 are connected with 1,2,3,4 substitution in benzene ring.
Absence of characteristic strips of absorption in the field of 1670-1685 sm-1
testifies on exhaustion of aldehyde group of furfural. Thus, structure of ionexchange resins received by phosphorylation of polymer synthesized on the basis
of benzyl bromide and furfural, can be presented as in the Figure 1.
© 2012 Prague Development Center
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Applied Innovations and Technologies
Cation-exchange
resins
Phosphorus-contained polycondensation type ion-exchange resins | ATI, March 2012
FIGURE 1. ION-EXCHANGE RESINS DELIVERED BY: RECEPTION OF BENZYL BROMIDE-FURFURAL
POLYMER (I); PHOSPHORYLATION OF BENZYL BROMIDE-FURFURAL POLYMER (II); AMINATION OF BENZYL
BROMIDE-FURFURAL POLYMER (III), PHOSPHORYLATION OF ANION-EXCHANGE RESIN ON THE BASIS OF
PEPA, FURFURAL AND BROMIDE BENZYL
+
C H2 N (C H ) B r3 2
CH
O
N(C H3 )3
(II)
C H 2 Br
C
(I)
O
O
H
P C l3
С Н 2 Br(Cl)
(III)
C H2 P (O )(O H)2
CH
PEPA +
CH 2 Br(Cl )
NH
C H2
C H2
N
HC
O
NH C H2 C H2 N
(IV)
C H2 C H2 NH
O
C H2 C H2 NH
P C l3
CH2 P (O )(OH)2
NH
C H2
C H2
N
HC
NH C H2 C H2 N
C H2 C H2 NH
O
C H2 C H2 NH
Research of kinetic properties of cation-exchange resin
The research of properties on ion-exchange resins with various functionality
showed that speed of establishment of ion-exchange balance is substantially
defined by speed of diffusion of ions deep into grains of ion-exchange resin. Speed
of an establishment of sorption balance also depends on degree of dissociation of
acid (basic) groups of ion-exchange resins. Phosphate ion-exchange resins on
kinetic properties concede to sulfonic
acid ion-exchange resins. We investigated
kinetics an exchange of ions Na+→Са2+ on received phosphate cation-exchange
resin (Tursunov, Mirkamilov, and Nazirova, 1995). For comparison we examined
properties of phosphate cation-exchange resin KF-1.
Table 5 shows resulted sizes of static exchange capacity and value of factor of
distribution;
they provide quantitative characteristic of equilibrium distribution of
ions Са2+ between solutions and cation-exchange resin.
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© 2012 Prague Development Center
Phosphorus-contained polycondensation type ion-exchange resins | ATI, March 2012
TABLE 5. VALUE OF EXCHANGE CAPACITY AND DISTRIBUTION FACTOR
AT SORPTION IONS OF СА2+ WITH CATION-EXCHANGE RESINS
Cation-exchange resin
Obtained cation-exchange
resin
KF-1
Static exchange capacitance,
mg-ecv/g
3.96
Coefficient of distribution Кd
Na+→ Са2+, ml/g
198
4.2
210
From Table 5 data it is visible that received cation-exchange resin does not
concede on sorption ability to polymerized cation-exchange resin KF-1.
TABLE 6. FACTORS OF DIFFUSION FOR IONS СА2 + ON CATION-EXCHANGE RESIN IN THE NA-FORM
Са2+
Contact time,
sec
120
300
600
900
Investigated cation-exchange
resin
Bt
t
D , sm2/s
0.0025
0.002
0.002
0.003
3.26
3.26
3.26
4.89
КF-1 (gel structure)
Bt
t
0.004
0.0026
0.0038
0.0038
D , sm2/s
6.5
3.9
4.89
6.1
The important kinetic characteristic of process is the diffusion factor in ionexchange resin. From Table 6 data it is visible that sizes of factors of diffusion are
constant.
The constancy of values of factors of diffusion confirms limiting
role of diffusion
in particles of cation-exchange resin at an exchange of ions Na+→Са2+. Thus, the
received results testify that investigated phosphate cation-exchange resin on
sorption and on kinetic properties does not concede phosphate cation-exchange
resin KF-1.
Research of thermal stability of received
phosphate cation-exchange resin
Thermal stability of received ion-exchange resins was investigated on air and in
water; the differential-thermal analysis was used also. Thermal stability was
monitored on change of exchange capacity, swelling capacity, weight loss in ionexchange resin, filtrate oxidability. Heating of phosphate cation-exchange resin in
the H-form in water within 30 hours at temperature of boiling of water slightly
reduced size of exchange capacity. It is obviously connected with process of
thermal dephosphorylation representing hydrolysis reaction. Thus, one can judge
on thermal stability of cation-exchange resin considering an increase of acidity of a
water extract. Aqueous extracts of phosphate cation-exchange resin after heat
treatment had slightly acid reaction (рН of filtrate 4.3-4.8). The size of exchange
capacity at all cation-exchange resins decreased for 1%. Swelling capacity samples
did not vary; hence, essential changes in structure cation-exchange resin did not
© 2012 Prague Development Center
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Applied Innovations and Technologies
Diffusing ion
Phosphorus-contained polycondensation type ion-exchange resins | ATI, March 2012
occur. Thermostability
in water phosphate cation-exchange resin was studied also
at 150-1800С. Change of properties of cation-exchange resin after heat treatment
was compared to change of properties of phosphate cation-exchange resins of the
RF polycondensation and SF polymerization types. The size of exchange capacity
at synthesized cation-exchange resin after heat treatment decreased for 8-10%
whereas at RF cation-exchange resin in the same conditions it decreased almost
for 65-85%, and at SF on 8%. Thermal stability of cation-exchange resins on air
was investigated using of thermogravimetric analysis method. Results of researches
showed that heating curves of examineed cation-exchange resin are characterized
by two endothermic peaks. The first endothermic peak at 100-1400С brings
dehydration of cation-exchange resin. Eliminating of functional groups at all
examinees
cation-exchange resin begins at temperature of an order from 2004500С (the second endothermic peak). The skeleton of received cation-exchange
resin is steady against temperature action. At their heating to 1000 0С within 30
minutes the loss in weight reach 40-60 %.
Sorption of ions of metals
For phosphate cation-exchange resins various types of linkage of metal with
ionogenic groups of ion-exchange resin are characteristic: ionic, mixed ioniccoordination and purely coordination. The communication type is defined by
ability of this or that metal to formation donor-acceptor complexes and degree
dissociation of ion-exchanger.
TABLE 7.SORPTION OF CATIONS OF METALS BY PHOSPHATE CATION-EXCHANGE RESIN
0.1 N
solution
NaOH
NaCl
CaCl2
CuSO4
CuSO4
CuSO4
NiSO4
NiSO4
NiSO4
NiSO4
CoSO4
CoSO4
CoSO4
UO2(NO3)2
UO2(NO3)2
UO2(NO3)2
рН of
solution
13
8.13
6.5
4.8-5.0
11
7.6
10
8
4.5
Н-form
Sorbed,
mg-ecv/g
6.6-7.6
0.8-1.0
1.1-1.2
1.2-1.3
2.64-2.7
1.1-1.2
2.0-2.1
2.0-2.05
150-200
Na-form
Coefficient of рН of solution
Sorbed,
distribution, ml/g
mg-ecv/g
184
11.5
120
6.5
3.57-3.6
66
4.8-5.0
1.75-1.8
733
11
3.08-3.1
2.35
1.0-1.1
20
2.25
1.0
84
3.8
3.6
7.6
2.0
10
3.75-3.8
35
2.36
0.8-0.9
3.18
2.4
8
2.65
300
2.02
95-100
3.12
240-250
4.5
450
There was interest to study such properties of received phosphate cation-exchange
resin as sorption ability to ions of copper, nickel, calcium, sodium, cobalt and
uranyl; to study influence of various factors on process sorption of these cations,
and also their mechanism of sorption with application of the IR-spectroscopical
analysis. Therefore, interaction of cation-exchange resin in Na- and H-forms with
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© 2012 Prague Development Center
Phosphorus-contained polycondensation type ion-exchange resins | ATI, March 2012
salt solutions of copper sulfate, nickel, cobalt, chloride sodium, calcium and nitrate
of uranyl were examined. Results of researches are shown in Table 7 (Tursunov,
Gabrielyan, and Suhinina, 1974).
Data in Table 7 testify on influence nature of cation on its sorption. It is found
that investigated cations are unequally sorbed by cation exchange resin; on ability
to sorption they can be located in the following number:
UO22+ > Ni2+ > Cu2+ > Co2+ > Na+
TABLE 8. DESORPTION OF IONS OF METALS FROM CATION-EXCHANGE RESIN
Desorbing
cation
calcium
copper
nickel
cobalt
uranyl-ion
Sorbed,
mg-ecv/g,
ml/g
3.57
3.08
3.6
1.4
450
Н2О
0.2
0.06
0.56
0.2
0.0
Desorbing solution
2 N solution of H2SO4 and
2 N NaHCO3
2.9
2.7
2.83
0.9
396
Desorbed,
mg-ecv/g,
ml/g
3.1
2.76
3.39
1.1
396
Spectrum of ion-exchange resin saturated with uranyl ion shows a sharp reduction
of intensity of fluctuations in phosphorus-oxygen connection. The same picture is
observed in spectra of cation-exchange resin saturated with copper and nickel ions.
However, considerable reduction of intensity of this strip for cation-exchange
resin saturated with an uranyl ion in comparison with ion-exchange resin saturated
with nickel and copper ions indicates on participation of phosphoryl oxygen (P=O) in formation of intracomplex connection of an uranyl ion with Р=О group
of cation-exchange resin which has a following structure:
HO
R
O
UO2
P
O
2+
O
O
OH
P
R
Reduction of intensity of fluctuations of P-OH groups R for cation-exchange
resin, containing ions of copper, nickel and sodium, appears with the reduction of
© 2012 Prague Development Center
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Applied Innovations and Technologies
Studying of influence of the ionic form of cation-exchange resin on absorption of
examinees cation-exchange resins showed that Na-form ion-exchange resin (Table
7) possesses larger sorption ability in comparison with the hydrogen form. Also
there was investigated influence of рН environment to sorption of ions of metals
by cation-exchange resin.
The data (Tables 7 and 8) testify that received cation-exchange resin possesses
enough high sorption and desorption ability to ions of examined metals. To find
out mechanism of sorption of specified metals’ cations the IR-spectra of cationexchange resin (saturated with copper and nickel ions) in H- and Na-form were
examined.
Phosphorus-contained polycondensation type ion-exchange resins | ATI, March 2012
quantity -1of P-OH groups having deformation fluctuations in the range of 21002600 sm . It means that ions of copper, nickel, sodium are absorbed by cationexchange resin, basically, at the expense of formation of ionic-coordination
connection of a following structure:
HO
R
O
P
O
O
Me
2+
OH
P
O
R
where, Me2+ - Ni2+, Cu2+, Na+.
Conclusion
The study suggests new way of receiving of polymer with halogen methyl group
through polycondensation of furfural with halogenbenzyl (bromide benzyl). The
polymer can be used as a polymeric matrix in synthesis of ion-exchange polymers.
The mechanism of formation and structure of the specified polymer were studied.
It is established that the polymer contains up to 10-12% of bromine. Reaction of
polymeranalogous transformations of the received polymer were studied: by
phosphorylation of polymer there was synthesized new, earlier not described
phosphate cation-exchange resin with exchange capacity of 6 mg-ekv/g. There
were investigated basic kinetic laws of reaction of the polymer phosphorylation
depending on temperature. Energy of activation and a constant of process speed at
initial and final stages of phosphorylation reaction were calculated. It is established
that at А>0.5 a diffusion deep into polymer grains is a limiting stage in
phosphorylation process. New heat-resistant anion-exchange resin, containing
highly basic groups, was synthesized by polymer amination of trimethylamine.
Optimum conditions of synthesis anion-exchange resin were defined.
The new method was developed for synthesis of phosphorus-nitrogen containing
ion-exchange resins - using phosphorylation of anion-exchange resin on a basis
polyethylenepolyamine, furfural and halogenbenzyls. It was established that
synthesized ampholytes possess sufficient high sorption and complexing ability in
relation to ions of copper, nickel, uranyl both from sour and alkaline solutions.
It was established that received ion exchangers are characterized by the raised
stability to thermal and chemical influences in water and on air. Kinetic
characteristics of the received cation exchangers were investigated. It was
established that cation exchange resins on speed of an exchange of ions
Na+→Ca2+ do not concede a well-known polymerization sulfonic cation KU-2-8
and phosphate cation-exchange resin KF-1.
There were studied sorption and complexing characteristics of received ionexchange resins among metals: copper, nickel, cobalt, and uranyl-ion, depending
on pH-environment, the ionic form of ion-exchange resin, concentration of the
investigated cation-exchange resins. It was shown that copper, nickel, cobalt and
an uranyl-ion by phosphate cation-exchange resin sorbs at the expense of an ionic
exchange and partially at the expense of formation of coordination bonds with
ionogenic group of cation-exchange resin.
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© 2012 Prague Development Center
Phosphorus-contained polycondensation type ion-exchange resins | ATI, March 2012
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© 2012 Prague Development Center
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Applied Innovations and Technologies
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