Removal of Chlorinated Organic Solvents By Various Zeolite

Supported Nano Metallic/Bimetallic Catalysts

Chlorinated organic solvents have various industrial applications, such as in detergents, paints,
glues and pesticides (2) as well as a degreasing agent (3). Removal of carcinogenic COSs
such as TCE by Adv. Oxidation processes (ISCO in particular) has been studied using
homogenous Fenton reagent. Several other techniques, such as in situ air stripping, in situ
bioremediation, enhanced solubilization flushing and permeable reactive barriers have also
been considered, but ISCO has been found to be more efficient. (2) (5)

Potassium Permanganate, Calcium Peroxide, ozone and Fenton reagent has been proposed as
oxidants, Fenton reagent having more reactivity toward COS (2). While conc. Fenton reagent is
much effective, its transport is dangerous, and its performance is pH dependent. Recently, SPC
has been considered as a safer and efficient alternative. It is solid, hence easier to transport,
cheaper, nontoxic, can be used in wider pH range. (1) as its introduction in system increases
the pH which has a buffering effect against decreasing pH latter in the process. (3)
n-ZVI with and without zeolite support has been used in Fenton processes as a support and
catalyst for generation of hydroxyl ions. Zerovalent Fe is a efficient catalyst for COS oxidation,
as it increases the generation of OH ions by increasing the generation of Fe2+.(2) Although it
may agglomerate, resulting in decrease in catalytic ability. By including a second metal, such as
Ni increase the catalytic activity and stability of catalyst. (1)

Several supports has been used for catalysts, such as CA, starch, graphene oxide, C-n-tubes,
silica etc. For Fe-Cu bimetallic catalysts, PAN fibers and iron-copper and aluminum clays have
also been considered as support for catalytic activity (3). A novel support may be the use of
zeolite (natural)(1), with a Al/Si ratio of 1.56 (2)

Two major approaches for incorporation of heterogenous catalysts on zeolite sheet are Ion
exchange method and hydrothermal method, the latter being lesser efficient. Z-nZVI-Cu was
prepared by adding ferrous sulfate heptahydrate and copper sulfate heptahydrate along with 0.5
gm of aluminosilicates in 300ml of ultrapure water. For 60 min of agitation, solution was filtered
and sodium borohydride was added to get black particles of catalyst. (3)
Z-nZVI-Ni was prepared by adding ferrous sulfate heptahydrate and nickel chloride hexahydrate
were dissolved in 250 ml of ethanol and water in 2:1 ratio. Natural zeolite was added in the
solution maintained at pH : 4 and mixed via sonication and mech agitation for 50 mins. Process
takes place in Nitrogen environment. In the end, black particles were vacuum filtered and
washed with water and ethanol. (1)

Surface morphologies were obtained by SEM and TEM. Particle size, pore size and surface
area were obtained by BET method. (1) Natural Zeolite has a smooth surface, while the Z-nZVI-
Cu, Z-nZVI and nZVFe has abrasive surfaces (3).

Standard solution of TCE was prepared by mixing pure TCE with miliQ water with moderate
stirring for 60 min. in absence of light. TCE and catalyst were vigorously stirred together for 60
min, with adding SPC. TCE was degraded in a glass reactor (6 X 9 cm), maintained at 20 C with
magnetic stirring. Sample were analyzed by HPLC, gas Chromatography, TOC analyzer and UV
Detector. KI was used as scavenging agent. Inductively coupled plasma Mass spectrometer
was used to measure leaching of Ni and Fe. (1).

Same procedure was also repeated for probe testing, by using NB (OH probe) and carbon CT
(O2 probe) instead of 1,1,1-TCA and TCE, when Z-n-ZVI was tested as support. FID detector
was used for measurement of NB. (2). Also, iron particles may subject to aggregation due to
oxide layer formation, which can be reduced by suitable support layer, such as zeolite, and by
addition of a second metal. This non-aggregation increases the surface area of nZVI particles.
This surface area was decreased after use. n-ZVI particles have amorphous-like structure. (2).
nZVI could not completely remove the COS, but removed more 1,1,1-TCA then TCE.
Performance of nZVI can be improved significantly (from 39% degradation of TCE to 99%) by
adding reducing agents (such as hydroxylamine and Ascorbic acid (4)), which enhanced the
generation of reactive oxygen species. (2)

Fe and Ni nano particles (1.5-3 nm), quasi-spherical in shape (2), were highly distributed on
zeolite surface. TEM of used catalyst showed no aggregation in case of bimetallic catalysts. N2
adsorption desorption showed highly uniform pore size and EDX elemental analysis showed
significant iron content in Fe-Ni composite. FTIR-spectra with wavenumber 280 to 4000 cm
confirmed the existence of Z-nZVI-Ni. (1) Spherical shape of bimetallic Nano particles was also
observed in case of Fe-Cu.
Degradation of TCE was compared with Z-nZVI-Ni, Z-nZVI-Cu and with SPC and catalysts.
Adsorption of TCE by Z-nZVI-Ni increased with increase in Ni Concentration. But increase in
nickel concentration beyond 10% doesnt show any significant increase in performance, due to
decreasing exposure of iron particles. (1) . Other catalysts, including nZVI-Cu, Z-nZVI, nZVI,
nZV-Ni, and zeolite showed lesser adsorption and degradation of TCE as compared to Ni-Fe
composite catalyst.
Using only SPC for degradation showed weak performance, but with Ni-Fe composite catalyst,
almost all TCE was degraded. (1). Pseudo 1st order model was used to study reaction kinetics. It
was found that rate constant for Z-nZVI-Ni was several times higher than for iron-copper, nano
iron, and zeolite supported nano iron catalysts. (1). 250 ppm was used as ideal loading for Fe-Ni
catalyst and 200 ppm for Fe-Cu catalyst (3). Maximum TCE Degradation was obtained at 10 mM
conc. of SPC for Z-nZVI-Ni and 1mM conc. for Z-nZVI-Cu.

Oxygen species involved in TCE degradation are OH, O2H, O2- and SO4- . OH radical is the most
active ROS. NB was used as probe for OH identification testing. NB degradation increases in
case of zeolite supported catalysts, indicating more generation of OH radicals. NB degradation
can be further increased by adding reducing agents. (4) Addition of reducing agent also decreases
the scavenging effects of other radicals, as tested with TBA and Chloroform.
It was confirmed by ESR that Z-nZVI-Ni effectively activated SPC. ESR also showed that zeolite
has minimum role in TCE Degradation. Generation of OH radicals was increased, due to more
surface area and active sites. Leaching of Fe and Nickel was also slowed down due to addition
of nickel in the catalyst composite. Z-nZVI-Ni and Z-nZVI-Cu have exceptional ability to produce
OH radicals in the system under consideration, which are the major reactive oxygen species
responsible for TCE degradation (4). Z-nZVI-Ni also exhibited highest removal of TOC.
Effect of different chelating agents such as oxalic acid, citric acid monohydrate, glutamic acid,
ethylene-diamine-tetra-acetic acid (EDTA) and L-Ascorbic acid on TCE degradation in SPC
system catalyzed by bimetallic catalysts were studied. Oxalic acid shows best results, while Citric
acid monohydrate and glutamic acid also increased the COS degradation upto a certain conc.
limit, while EDTA and L-Ascorbic acid had adverse effect. TCE degradation was inhibited in
presence of TBA and chloroform scavengers, even when the system was chelating agent
modified. Oxalic acid also leads to complete mineralization of COS. (5)
Anions present in the groundwater also have significant effects on TCE removal. Chloride ion and
HCO3- decreases the TCE degradation due to scavenging effect, while SO42- had negligible effect
for Z-nZVI system. Addition of reducing agents mitigates the effect of anions, and increase the
degradation of TCE at all pH. (4)

Bibliography:
1. Efficient Catalytic Degradation of TCE in SPC system catalyzed by Ultrafine
heterogenous Z-nZVI-Ni Composite (Elsevier 2016)

2. Degradation of chlorinated organic solvents in aqueous percarbonate system

using zeolite supported nano zero valent iron (Z-nZVI) composite (Springer 2016)

3. Efficient transformation of trichloroethylene activated through sodium

percarbonate using heterogeneous zeolite supported nano zero valent
iron-copper bimetallic composite (Elsevier 2016)

4. Role of reactive oxygen species and effect of solution matrix in trichloroethylene

degradation from aqueous solution by zeolite-supported nano iron as
percarbonate activator (Springer 2016)

5. The Effect of Chelating Agents on Enhancement of 1,1,1-Trichloroethane and

Trichloroethylene Degradation by Z-nZVI-Catalyzed Percarbonate Process
(Springer 2016)