Title of Invention

"AN IMPROVED PROCESS FOR ADSORPTION AND SUBSEQUENT REDUCTION OF HEXAVALENT CHROMIUM USING FERROUS SAPONITE CLAY TO REMOVE CHROMIUM FROM WATER

Abstract An improved process for adsorption and subsequent reduction of hexavalent chromium using ferrous saponite clay to remove chromium from water An improved process for adsorption and subsequent reduction of hexavalent chromium using ferrous saponite clay to remove chromium from water by reacting aquous dichromate solution with ferrous-saponite clay of formula {Nao.eo K0.40 Ca0.47}[Mg2.o5Fe2+ 3.95](Si 6.45AI-1.55) O2o(OH)4 having particle size in the range of 0.1 to 5 m at temperature 50 to 200°C for the period of 1 to 3 hours, separating the clay by centrifugation and filtration.
Full Text The present invention relates to an improved process for adsorption and
subsequent reduction of hexavalent chromium using ferrous saponite clay to
remove chromium from water.
Background Information
Clean water is one of the most fundamental resources for human kind. In reality
the ground water gets contaminated with various contaminants. Chromium is one
of the very common contaminants, as it is released as effluents from industries of
electroplating, leather tanning, and corrosion protection. Chromium exists in
several valence states. The hexavalent chromium in ground waters is known to
be environmentally hazardous (Blowes, 2002 Science v 295,). Chromium (VI) is
highly toxic and mobile.
Reference may be made to a publication by Taylor et al., 2000, Clays and Clay
Minerals, v48, 648, wherein the hexavalent chromium is reduced by dithionate
clays. The major drawbacks are that Chromium ions are adhered to sodium
dithionate which can be washed of freely and the compilation of inadequate data
in terms of its application.
Reference may be made to a publication by Drljaca et al. 1992, Inorg. Chemistry,
v31, 4894, wherein the trivalent Cr is strongly sorbed by montmorillonite, for the
effective removal of Cr from pollutant environments. The drawback is the
technique deals only with trivalent Cr, which are less toxic compared to the
hexavalent Cr.
References may be made to publication by Kim et al., 2002, Environmental
Geology, v42, 642 wherein the reduction of hexavalent chromium is effected by
wherein the possible reduction of hexavalent chromium is discussed. The draw backs are that they do not describe any technical detail of the conversion and the maximum conversion is about 50 to 60 wt %.
Objects of the invention
The main object of the present invention is to provide an improved methodology for the adsorption and reduction and of hexavalent chromium present in the water which comprises reacting aqueous dichromate solutions with ferrous saponite clays at temperature 50 to 200° C for the period of 1.0 to 3.0 hours.
Another object of the present invention is that ferrous-saponite composed of the formula {Na0.60K0.40Ca0.47} [ Mg2.05Fe2+ 3.95](Si6.45Al1.55) O20(OH)4
Another object of the present invention is that the particle size of the saponite clay is in the range, of 0.1-5 µm
Another object of the present invention is that the clay fraction was separated by centrifuging and filtration.
Another object of the present invention is the simultaneous adsorption and reduction of hexavalent chromium.
Still another object of the present invention is the use of the dichromate solution 0.04 M.
Yet another object of the present invention is the reaction is effected at a temperature in the range of 50 to 200° C for the period of 1 to 3 hours. Summary of the Invention:
The novelty of the present invention lies in the use of natural fine powdered ferrous-saponite for adsorption and reduction of hexavalent chromium, which would help in environmental management. This method provides a very simple procedure, which does not require any expensive chemicals.
The sample has the chemical formula {Nao.eo K0.40 Ca0.47} [ Mg2.05 Fe2+3.95](Si6.45Al1.55) O20(OH)4, indicating presence of only ferrous iron in the sample. When the sample is treated with the 0.04 M potassium dichromate solution at 50 to 200°C for the period of 1 to 3.0 hours, the hexavalent chromium gets simultaneously adsorbed by cationic exchange and converted into a less toxic trivalent chromium. Detailed Description of the Invention:
Accordingly, the present invention provide an improved using tenaus sapanole clay btoun for adsorption and subsequent reduction of hexavalent rhrnminm to nemare chranium from waler
formul Na 0.60 K0.40 Ca0.40 hcmg2.05 Fe2t3.45si6th al .55-020 which comprises, reacting dichromate solutions with ferrpus- saponite clay? at temperature 50 to 20(T C for the penod-bf 1 to 3.0 hours, '^AJ^3 In an embodiment of the present invention the terrous-saponite used is composed of the formula {Nao.60Ko.40Cao.47} [ Mg2.os Fe2+395](Si6 45Ali 55) 02o(OH)4, contains only ferrous iron in the octahedral site.
In another embodiment of the present invention is the simultaneous adsorption and reduction of hexavalent chromium.
In another embodiment of the present invention is that the particle size of the ferrous-saponite clay is in the range of 0.1-5 ^im
In another embodiment of the present invention is that the clay fraction was separated by centrifuging and filtration.
In an another embodiment of the present invention, the concentration of the dichromate solution is 0.04 M.
In another embodiment of the present invention the reaction is effected at a temperature in the range of 50 to 200 °C for 1 to 3.0 hours. Scientific Explanation
In the present invention, we have used natural ferrous-saponite with the chemical formula {Nao.eo K04o Cao.47} [ Mg2.os Fe2+3.95](Si6.45Ali.55) 02o(OH)4> containing only ferrous iron. The sample has been formed at reducing condition. Ferrous-saponite containing Fe (II) can immobilize the chromium on the mineral surface and also reduce Cr (VI) to Cr (III) due to the electron transfer mechanism. Adsorption of hazardous Cr (VI) by the Fe (Il)-containing clay was a prerequisite for the coupled sorption-reduction reaction. The capacity of clays to reduce Cr (VI) are correlated with the ferrous iron content of the clays. When Cr (VI) reduces by Fe(II), 3 mol of Fe(II) need to reduce 1 mol of Cr(VI) to Cr(III). Fe2+(ferrous saponite) + K 2Cr 2O 7 + H+ -» Fe3+ , Cr3+( saponite)
When the temperature is increased beyond 200°C, the ferrous saponite transforms into ferric saponite and the ferric saponite can only adsorp but will not be able to reduce the Cr (VI).
The following examples are given by way of illustration of the present invention and therefore should not be construed to limit the scope of the invention.
Exam ple. 1
Sample preparation and Characterization :
The clay mineral was scooped out from the walls of the amygdales. It is apple green to dull pale green in colour and is soapy to touch. The material was ground in ethanol medium in porcelain mortar to avoid any oxidation during sample preparation and preserved in air tight polythene viols. The chemical composition of the samples was determined by EPMA and Hitachi S-520 SEM in EDAX mode with a filament current of 110 microamperes and an accelerating voltage of 20 kV. Ferrous iron content was separately determined by titrimetric method following the method by Wilson (1960). The composition of the sample is given in the table. 1
Table 1 Chemical composition of the clay samples from the Killari borehole.

(Formula Removed)
Number of ions are calculated on the basis of 22 O, ignoring H2O+ . Example.2
XRD studies:
For powder diffraction study, the ground sample was sieved through 40 micron filter to obtain uniform sized material. Less than 2 micron clay fraction was separated by centrifuging and filtration. Air dried and ethylene glycol treated samples mounted on low back-ground quartz plate were subject X-ray diffraction study. The diffraction patterns were obtained by Philips diffractometer and Siemens D-5000 powder diffractometer with HOPG graphite monochromator. Air dried sample exhibits a strong d (001) line at 1.54 nm and weak lines at 0.510nm, 0.378nm, and 0.308 nm. These correspond to (002), (003), (004) and (005) Bragg reflections
respectively. These data are in good agreement with the published data of saponite (JCPDS card No.29-1491), with unit cell parameters a=0.52 nm, b=0.92 nm and c=1.54 nm. XRD patterns of randomly oriented samples show d (060) value of 0.1532 ±0.0005 nm yielding bo = 0.9275 ± 0.002 nm. Example 3
For chromium-adsorption measurements, clay sample was taken in a 15 mi centrifuge tube, to which 0.04 M potassium dichromate solution was added. The contents were agitated for 1 to 3 hour, and subsequently heated to 200°C. The suspended particles were dried and analyzed for determining the valence- state of adsorbed chromium adopting XPS method. XPS measurements were conducted with Kratos XPS Axis 165 spectrometer equipped with a hemispherical energy analyzer. The non-monochromatized Mg-Kct X-ray source (hv = 1253.6 eV) was operated at 5 kV and 15 mA with pass energy of 80 eV, and an increment of 0.1 eV. The samples were out gassed for several hours in the XPS chamber to minimize air contamination to sample surface. In order to overcome the charging problem, charge neutralizer of 2 eV was applied and the binding energy of C Is core level (B.E.=284.6 eV) of adventitious hydrocarbon was taken as standard. The obtained XPS spectra were fitted using a non-linear square method with the convolution of Lorentzian and Gaussian functions after the polynomial background subtraction from the raw spectra.
The narrow scan of Cr 2p for the Killari saponite treated with dichromate solution is show two weak peaks at binding energies 587.9 eV (0.2 of the total Cr) and 577.7 eV corresponding to Cr (VI) and very strong peaks at 585.6 eV (0.8 of the Total Cr) and 576.0 eV (0.78 of total Cr) corresponding to Cr (III) are observed. It is clear from the intensity of the peaks in Fig. 1, that the clay sample not only adsorbs the Cr(VI), but also reduces it by about 80 % to Cr (III). It is also observed that the ferrous iron in the clay sample has got oxidized to ferric state following the treatment with dichromate solution. The samples treated with dichromate solutions show two peaks for Fe 2p3/2 at 710.9 eV and 713.0 eV , which are ascribed to Fe2+ and Fe3+ oxidation states. Similarly the two Cr 2p3/2 peaks observed are attributed to Cr3+ and Cr6+oxidation states. The XPS studies on the Killari saponite shows that it is capable of reducing Cr (VI) to Cr (III). The ferrous saponite in Deccan Flood basalts could be useful in environmental management in areas affected by Cr(VI) effluents.
The Main advantages of the present invention are
1. A simpler method for the removal of toxic chromium from water
2. It basis for utilization of ferrous saponite in environmental management.
3. The conversion of Cr (VI) to Cr (III) is quantified by the peak area intensity.
4. Work-up procedure is very simple.
5. The present method does not involve any expensive chemical and hence economical.
6. The present method is environmentally safe.




We claim :
1. An improved process for adsorption and subsequent reduction of hexavalent chromium using ferrous saponite clay to remove chromium from water which comprises, reacting aquous dichromate solution with ferrous-saponite clay of formula {Na0.60 K0.40 Ca0.47}[Mg2.05Fe2+ 395KSi 6.45AI1.55) O20(OH)4 having particle size in the range of 0.1 to 5 m at temperature 50 to 200°C for the period of 1 to 3 hours, separating the clay by centrifugation and filtration.
2. A process as claimed in claim 1 wherein the concentration of the dichromate solution is 0.04 M.
3. An improved process for adsorption and subsequent reduction of hexavalent chromium using ferrous saponite clay to remove chromium from water substantially as herein described with reference to examples accompanying this specification.

Documents:

272-del-2003-abstract.pdf

272-del-2003-claims.pdf

272-del-2003-complete specification (granted).pdf

272-del-2003-correspondence-others.pdf

272-del-2003-correspondence-po.pdf

272-del-2003-description (complete).pdf

272-del-2003-drawings.pdf

272-del-2003-form-1.pdf

272-del-2003-form-13.pdf

272-del-2003-form-19.pdf

272-del-2003-form-2.pdf

272-del-2003-form-3.pdf

272-del-2003-form-4.pdf

272-del-2003-form-5.pdf

272-del-2003-pa.pdf


Patent Number 242191
Indian Patent Application Number 272/DEL/2003
PG Journal Number 34/2010
Publication Date 20-Aug-2010
Grant Date 18-Aug-2010
Date of Filing 12-Mar-2003
Name of Patentee COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH
Applicant Address RAFI MARG NEW DELHI-110001,INDIA
Inventors:
# Inventor's Name Inventor's Address
1 G. PARTHASARATHY NATIONAL GEOPHYSICAL RESEARCH INSTITUTE, HYDERABAD-500 007, A.P.INDIA
2 B.SREEDHAR INDIAN INSTITUTE OF CHEMICAL TECHNOLOGY, HYDERABAD-500 007, A.P.INDIA
3 B.M. CHOUDARY INDIAN INSTITUTE OF CHEMICAL TECHNOLOGY, HYDERABAD-500 007, A.P.INDIA
PCT International Classification Number B01J 20/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA