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3 (2014), 629-633
http://dx.doi.org/10.14233/ajchem.2014.16055
REVIEW
Cationic Polyacrylamide: Synthesis and Application in Sludge Dewatering Treatment
Received: 16 July 2013; Accepted: 25 September 2013; Published online: 30 January 2014; AJC-14603
Cationic polyacrylamide (CPAM) were used extensively in water treatment, enhanced oil recovery and sludge dewatering. The review
summarized the synthesis methods research progress of cationic flocculants. Four groups of synthesis technologies of cationic copolymers
were reviewed, including aqueous solution polymerization, dispersion polymerization, inverse emulsion polymerization and photo initiated
polymerization. Furthermore, the paper reviewed that the application of cationic flocculants in sludge dewatering treatment. Based on
these reviews, the future research perspectives of synthesis and application on cationic flocculants in sludge dewatering treatment were
proposed.
weight14. Above these two synthesis methods were without is more important that cationic degree can be easily controlled
using extensively in the industrialization production. The most through copolymerization16. Based on the above advantages,
important CPAM synthesis method was free radical copolyme- this technology was widely used in European and American
rization method, the basic reaction of polymerization usually countries. Table-1 presents the research of aqueous solution
expressed as Fig. 1. In recent years, free radical polymerization polymerization at present.
method included four different synthesis technologies as follows: From previous studies, there was still a problem that
aqueous solution polymerization, dispersion polymerization, reactivity ratio between acrylamide and other monomers have
inverse emulsion polymerization and photo initiated polymeri- a big difference (For example: rAM = 1.0, rDMDAAC = 0.69), which
zation. can lead to increase reaction mechanism complicated17,18. In
this way, it was difficult to acrylamide monomer complete
CH3 polymerization, CPAM with high purity is very necessary
n(CH2)2=CH–CONH2 + CxHyNCl
Initiator
CH2 C
consider for the techology. Due to biotoxicity, the technology
Solution n of aqueous solution polymerization had been gradually given
CxHy up in China.
N
+ Dispersion polymerization: Fig. 3 presented the techno-
Cl
- logical process of dispersion polymerization. It showed that
acrylamide and a double bond of quaternary ammonium
Fig. 1. Basic reaction of CPAM polymerization
dissolving in the saline solution was different from aqueous
solution polymerization19,20. Finally, the discrete form of small
Aqueous solution polymerization: Fig. 2 presented the polymer particles were precipitated down.
technological process of aqueous solution polymerization. It
showed that acrylamide, cationic monomer and initiator dissol-
Saline solution Initiator, N 2
ving in the water were induced polymerization by adjusting
the pH, temperature, time and additives. Finally, CPAM colloid
products was obtained. AM, a double bond of
quaternary ammonium
The discrete form of Purification
small polymer particles
TABLE-1
AQUEOUS SOLUTION POLYMERIZATION OF CATIONIC POLYACRLAMIDE
Raw materials Initiator Temperature Results Ref.
The dependency of initial polymerization rate on 34
AM,
4,4'-azobis-4- cyanovaleric acid 30-90 ºC monomer and initiator concentrations at 50 ºC were
acrylonitrile
1.16 ± 0.01 and 0.52 ± 0.03, respectively
PDA can be obtained higher intrinsic viscosity the 35
Inorganic: K2S2O8 and NaHSO3,
AM, Inorganic: 25-30 ºC, preparation of different cationic degree products
organic: 2,2'-azobis (2-
DMDAAC organic: 55-60 ºC should pay attention to optimizing according to
amidinopropane)-dihydro chloride
different monomer ratio.
TABLE-2
DISPERSION POLYMERIZATION OF CATIONIC POLYACRLAMIDE
Raw materials Solution Initiator Stabilizer Results Ref.
Varying the salt concentration could
2,2'-azobis [2-(2-inidazolin-2-yl) Poly(acryloylxyethyl
(NH4)2SO4 affect the morphology and
AM, DMC propane]- dihydro chloride (VA- trimethyl ammonium 36
or NaCl molecular weight of the resultant
044) chloride) (PDAC)
copolymer particles significantly.
The product particle size range of 4-
2,2'-azobis(2-methyl Poly(acryloyloxyethyl
AM, 7 µm are more than PAM particle 37,
(NH4)2SO4 propionamidine) dihydrochloride trimethyl ammonium
AODBAC size through the same method 38
(AIBA) chloride) (PAOTAC)
polymerization.
Poly(dimethylaminoethyl
2,2'-azobis (2-amidinopr opane)- The molecular weight of PDMC
AM, DMC NaCl methacrylate methyl 39
dihydro chloride (V-50) formed was 1.5 × 105-7.0 × 105
chloride) (PDMC)
AODBAC = Acryloyloxyethyl dimethylbenzyl ammonium chloride
Vol. 26, No. 3 (2014) Cationic Polyacrylamide: Synthesis and Application in Sludge Dewatering Treatment: A Review 631
From previous studies, there were also some shortcom- Aqueous solution Initiator, N2
Drying and
grinding
ings for this technology. The main problem was that the polymer
products were low concentration and poor stability. Moreover, AM, Cationic Polymerization Cutting
due to high monomer prices, cationic quaternary ammonium monomer colloid formation granulation
obstacle for large scale application in the industrial production Fig. 5. Technological process of photo initiated polymerization
all over the world.
Inverse emulsion polymerization: Fig. 4 presented the purity product and less investment. Moreover, low activation
technological process of inverse emulsion polymerization. It energy of reaction could be fastly initiated polymerization at
shows that acrylamide, cationic monomer dissolving in the room temperature. The researches of photo initiated polymeri-
aqueous solution were added to water-insoluble organic solvent zation at present were as follows: Seabrook and Gillert28 studied
that be conducted in water-in-oil emulsion, inverse emulsion that classical free-radical polymerization kinetics provided an
polymerization would be occured in the presence of initiator. acceptable quantitative description for this system, even though
the rate of coefficients controlling aqueous-phase polymeri-
Aqueous solution Initiator, N2
zation of acrylamide were very sensitive to change in solvency
during polymerization. The initiation rates with all three photo-
AM, Cationic Water-insoluble Polymerization
initiators were proportional to the absorption at 254 nm wave-
monomer organic solvent emulsion formation length of the Hg lamp28. Liu et al.29 researched that cationic
Fig. 4. Technological process of inverse emulsion polymerization polyacrylamide P(AM-DMC) had been synthesized by the
metal halide lamp irradiation. The reaction process was stable
Vanderhoff first proposed inverse emulsion polymerization and it could obtain good solubility and high molecular weight
method in 1962, after inverse emulsion polymerization had products. So it was considered that the technology of inverse
become one of the important methods for polymer production24. emulsion polymerization was worthy of study and exploration
The synthesis technology had easily obtained higher molecular in actual production.
weights and fast reaction rates25. Moreover, the chance of Application in sludge dewatering treatment: In recent
implosion in oil phase had been greatly reduced because of years, CPAM known as sludge dewatering agent, had been
the easy control of reaction system26. Meanwhile, the range of used in activated sludge dehydration in municipal wastewater
molecular weight was narrow with the smoothly reaction. treatment plant, which may remove the water contained in the
Table-3 presented the research of dispersion polymerization activated sludge30. The flocculation mechanism that the surface
at present. adsorption water of activated sludge particles was separated
From previous studies, it was difficult to control emulsifi- out through charge neutralization and adsorption bridging31.
cation and oil-water separation. Moreover, the operate process Fig. 6 showed the mechanism of the sludge dewatering with
was complicated and the equipments utilization ratio was low27. CPAM. Cationic polyacrylamide could play an important role
Up to now, the technology of inverse emulsion polymerization in sludge dewatering, micro-polluted source water, even indus-
was not widely used in China. trial water treatment32. It showed that the charge neutralization
Photo initiated polymerization: Fig. 5 presented the and the adsorption/bridging mechanisms played an important
technological process of photo initiated polymerization. It role in sludge dewatering performance.
showed that acrylamide, cationic monomer dissolving in the Table-4 showed the application situation of CPAM in
water were induced by photo radiation. Finally, CPAM colloid sludge dewatering treatment. Generally, the organic polymeric
products had been obtained. sludge dewatering agent was effective application in sludge
Photo initiated polymerization had received more and dewatering treatment, due to characteristics of CPAM with
more attention in recent years. The synthesis technology had linear molecular chain and positive charge group and large
many advantages such as simple operation, easy control, height specific surface area. In the process of sludge dewatering treat-
ment, there were only a few dosages in concentrator. Moreover,
TABLE-3
RESEARCH ON INVERSE EMULSION POLYMERIZATION OF CATIONIC POLYACRYLAMIDE
Temp. Initiator and mass Mass fraction of
Raw materials Results Ref.
(ºC) fraction monomer (%)
Greater compressive yield stress was achieved for the
(NH4)2S2O8/NaHSO3
AM, MADQUAT 30 30 strong flocs produced by copolymer prepared in inverse 40
= 2:1
microemulsion than produced by that in solution.
AM The formulations with 3000 ppm of initiator were the
Ammonium
Dimethylaminoethyl most interesting of all copolymer compositions since they
50 persulphate (APS) 25 41
acrylate methyl presented very high conversions and their viscosities were
and NaHSO3
chloride (Q9) higher than commercial copolymer solutions.
While PDA is mixed with alum as flocculating agent, the
Initiator: m(K2S2O8)/
AM, DMDAAC 40 33 optimum dosages for alum and PDA are 25 mg/L and 4. 42
m(NaHSO4) = 5:1
16 mg/L.
MADQUAT = 2-(Methacryloyloxy) ethyltrimethyl ammonium chloride
632 Jiang et al. Asian J. Chem.
TABLE-4
APPLICATION OF CPAM IN SLUDGE DEWATERING TREATMENT
Factory Reagent dosage (g/kg) Effect Ref.
Specific consumption of flocculant amounting to 5.4 g/kg of dry solids of
Small-scale waste water
Polymer organic flocculant, 8 sludge (calculated value) under identical operational conditions proves to 43
treatment plant, Czech
be the best economical option.
Tangjiatuo Wastewater Minimum filter cake moisture content and turbidity of 63.5% and 2.95
P(AM-DAC-DMC), 1.0 44
Treatment Plant, China NTU were achieved.
Both of fractal dimensions arrived at maximum values (D1= 1.19, D2 =
Beijing Wastewater
CPAM CZ-8698, 9.36-15.61 1.41), at the optimalpolymer dosage which meant that the flocs formed at 45
Treatment Plant, China
this dosage had the coarsest surface and most compact structure.
Coagulation
Water
Water
Water
AM bone
Water
Activated sludge