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B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering
           Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                     Vol. 2, Issue 5, September- October 2012, pp.364-370
   Adsorption of Chromium on Activated Carbon Prepared from
                        Coconut Shell
             B. Veena Devi*, A.A. Jahagirdar**, M.N. Zulfiqar Ahmed***
        *
         (Department of Chemistry, Dr. Ambedkar Institute of Technology, Bangalore - 560056, India)
        **
          (Department of Chemistry, Dr. Ambedkar Institute of Technology, Bangalore - 560056, India)
           ***
               (Department of Chemistry, HKBK College of Engineering, Bangalore - 560045, India)


ABSTRACT
         Activated carbon was prepared from              environment. In such aqueous waste, Chromium
coconut shell by pyrolysis. It was characterized         (VI) is present as either dichromate (Cr2O7 2-) in
by PXRD, and SEM. Different physical                     acidic environments or as chromate (CrO42- ) in
properties such as bulk density, moisture                alkaline environments.
content, volatile matter content, ash content,           Several treatment technologies have been developed
hardness, decolorizing power, phenol number,             to remove chromium from water and waste water.
iodine number and surface area and porosity              Common methods include chemical precipitation,
were also determined. The activated carbon was           ion exchange, membrane separation, ultrafiltration,
used as adsorbent for the removal of chromium            filtration, elctrocoagulation, solvent extraction,
from an electroplating industry. The effect of           sedimentation,      reverse     osmosis,     dialysis,
various parameters such as adsorbent dosage,             electrodialysis,     adsorption     and     filtration,
particle size, pH,      contact time and stirring        evaporation, cementation, dilution, air stripping,
speed was studied. The studies showed that the           steam stripping, flocculation and chelation [2-6].
activated carbon can be used as a good adsorbent         Reduction and chemical precipitation has
for the removal of hexavalent chromium from              traditionally been the most used method. The most
electroplating industries.                               often used precipitation processes include
Key words - Activated carbon, adsorption,                hydroxide, sulphide, carbonate and phosphate
electroplating industry, hexavalent chromium,            precipitation techniques. The disadvantage of
SEM.                                                     precipitation technique is the production of sludge.
                                                         This process suffers from draw backs like
1. Introduction                                          incomplete removal, requirement of sizable
          Chromium (VI) is highly toxic in nature.       quantities of treatment chemicals and production of
This is due to the fact that one of the reduction        voluminous toxic sludge. It constitutes a solid waste
products of Chromium (VI) is Chromium (V).               disposal problem. A variety of other treatment
Chromium (V) is a known carcinogen and will              technologies were considered and evaluated.
lodge in any tissue to form cancerous growths.           Techniques like ion exchange and adsorption with
There are reports that Chromium (V) is also a factor     products obtained from naturally occurring materials
leading to premature senility in parts of Russia. The    like activated carbon were considered as better
Chromium (VI) is a very strong oxidizing agent           alternatives. The exorbitant cost involved with ion
(therefore very fast in reacting, unlike Chromium        exchange makes it prohibitive for wide application
(III) and likely to form complexes). Chromium (VI)       [7-9].
is not a very stable state when compared to Cr (III).    Coconut shells are available in plenty in tropical
Chronic inhalation of Chromium (VI) compounds            countries. The utilization of this waste material
increases the risk of lung, nasal and sinus cancer.      helps in recycling waste and thus keeping the eco
Severe dermatitis skin ulcer can result from contact     system clean. Mitigation measures based on low
with Chromium (VI) compounds. It can cause mild          cost technologies hold promise of wide applicability
to severe liver abnormalities. Chromium (VI)             in developing countries. This methodology can be
compounds are teratogenic to animals [1].                profitably employed by least developed and
Effluents from electroplating and tannery industries     developing countries in mitigating pollution due to
is a major source of aquatic pollution in India with     the heavy metal ion chromium [10-12].
high chemical oxygen demand (COD), biological
oxygen demand (BOD), and hexavalent chromium.            2. Materials and Methods
In India, there are a large number of tanneries                  The coconut shells were washed with water
scattered all over the country but the main areas of     to remove sticking and lose matter and then sun
their concentration are Tamilnadu, Uttar Pradesh         dried for 5 days (8 hours per day). The dried
and West Bengal. Nearly 80% of these tanneries are       samples were then hammer broken to pieces and
engaged in the chrome tanning processes. Most of         then converted to a powder using a mixer. Three
them discharge untreated wastewater into the             temperature routes were followed for preparing



                                                                                                364 | P a g e
B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering
                Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                          Vol. 2, Issue 5, September- October 2012, pp.364-370
    active carbon by taking known quantities of                  obtained. The residue is reported as ash on
    powdered coconut shell.                                      percentage basis.
    Samples were pyrolysed in a muffle furnace in the
    presence of steam flow. A two step procedure was             2.1.5 Hardness
    followed. Sample was carbonized at 550 0 C for 2                      The percentage of particles passing through
    hours and then a physical activation method was              a screen of 275 mesh was determined. . Then the
    followed for different periods of time. Through the          particles were subjected to hammer force for five
    inspection hole in the muffle furnace door a glass           minutes and then the particles which passed through
    tube was introduced which was connected to a                 a screen of 300 mesh were determined. The
    steam generator. Thus a continuous flow of steam             percentage of particles not broken to fine size was
    was maintained. Three different samples were                 expressed as percentage of hardness.
    prepared and coded as 750S40, 750S100 and
    800S30. The samples 750S40 and 750S100 were                  2.1.6 Decolorizing Power
    prepared by heating the powders to 750 0C and                         Decolorizing power is the ability of
    keeping them at 750 0C for 40 minutes and 100                activated carbon to decolorize a dilute blue colored
    minutes respectively. In case of sample 800S30, the          solution of methylene blue. It is expressed as mg/g.
    powder was heated to 800 0C and then maintained at
    that temperature for 30 minutes.                             2.1.7 Phenol Number
                                                                          100 cm3 of 30 ppm solution of phenol was
    2.1 Characterization of Activated Carbon                     taken in a 250 cm3 leak proof reaction flask. The pH
    Powders                                                      of the solution was adjusted to neutral by adding 0.1
    2.1.1 Bulk Density                                           N NaOH or 0.1 N H2SO4. A known weight of the
             The activated carbon sample were packed             activated carbon powder was added to it. The
    in a previously weighed 25 cm3 specific gravity              solution was equilibrated for 24 hours at room
    bottle by repeatedly tapping the bottle so that              temperature followed by filtration and subsequent
    powder is filled upto the mark. The bottle was               analysis of the filtrate for phenol concentration. The
    weighed again. The difference in the weights gives           concentration of phenol was determined by
    the weight of powder taken in the bottle. The bulk           spectrophotometric analysis for the colour resulting
    density of the powder was calculated using equation          from the reaction of phenol with 4-amino antipyrene
    1.                                                           at a wave length of 600 nm.
                 [(𝑀𝑒𝑖𝑔 𝑕𝑑 π‘œπ‘“ π‘π‘œπ‘€π‘‘π‘’π‘Ÿ π‘‘π‘Žπ‘˜π‘’π‘› 𝑖𝑛 𝑑𝑕𝑒 π‘π‘œπ‘‘π‘‘π‘™π‘’ )
π΅π‘’π‘™π‘˜ 𝑑𝑒𝑛𝑠𝑖𝑑𝑦 =                                             (1)
                                    25
                                                                  2.1.8 Surface area and porosity
    2.1.2 Moisture content
                                                                          The BET surface area of activated carbon
             About one gram of the powdered air dried
                                                                 powder was determined by nitrogen adsorption
    activated carbon powder was taken in a previously
                                                                 desorption method. The instrument used was
    weighed crucible. The crucible was placed in an
                                                                 MICROMERITICS GEMINE 2375. Nitrogen gas
    electric hot air oven maintained at about 110 0 C.
                                                                 was allowed to adsorb on the powder at 77 K. The
    After one hour the crucible is taken out, cooled in a
                                                                 nitrogen adsorption and desorption isotherms were
    desiccator and weighed again. The loss in weight of
                                                                 used to determine parameters like surface area, pore
    the powder reported on percentage basis gives
                                                                 volume and pore size.
    moisture content in the sample.
                                                                 2.1.9 Iodine Number
    2.1.3 Volatile Matter
                                                                           Iodine number is defined as the number of
              About one gram of the powdered air dried
                                                                 milligrams of iodine absorbed by one gram of
    activated carbon powder was taken in a previously
                                                                 activated carbon powder. Iodine solution is prepared
    weighed crucible. The crucible was placed in a
                                                                 by dissolving 13 grams of iodine in 50 cm3 of
    muffle furnace maintained at about 925 0 C. It was
                                                                 glacial acetic acid and then diluting up to the mark
    taken out after exactly 7 minutes. After first cooling
                                                                 in a 1000 cm3 volumetric flask. A known weight of
    in air, the crucible was cooled in a desiccator and
                                                                 the activated carbon powder (about 0.25 g) was
    weighed again. The loss in weight of the powder
                                                                 suspended in 10 cm3 of carbon tetra chloride taken
    reported on percentage basis gives volatile matter
                                                                 in a 250 cm3 conical flask. To this a known volume
    content in the sample.
                                                                 of the prepared iodine solution was added. Similarly
    2.1.4 Ash Content
                                                                 a blank solution was also prepared by taking same
    The residual activated carbon powder from the
                                                                 volumes of carbon tetra chloride iodine solution as
    above step was then heated in a muffle furnace at
                                                                 in the previous case but without the activated carbon
    750 0 C for about half an hour. After first cooling in
                                                                 powder. Both the conical flasks were kept in a
    air, the crucible was cooled in a desiccator and
                                                                 shaking machine for one hour. Then the solution
    weighed again. The heating, cooling and weighing
                                                                 were is rapidly filtered using Whatman filter paper
    cycle was repeated till a constant weight was
                                                                 no. 41. 20 cm3 of the filtrate was transferred into a
                                                                 250 cm3 conical flask. To this 20 ml of 15%



                                                                                                       365 | P a g e
B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering
           Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                     Vol. 2, Issue 5, September- October 2012, pp.364-370
potassium iodide and 100 ml of distilled water were       The amount of chromium adsorbed qt was
added. The contents of both the flask were titrated      calculated using equation 3.
against standard sodium thiosulphate using freshly                               πΆπ‘œ – 𝐢𝑑   𝑉
                                                                          π‘žπ‘‘ =                 (3)
prepared starch as indicator. The volume of sodium                                  π‘šπ‘œ
thiosulphate solution consumed in case of both back      where,
and ban titrations was determined. The difference in      Co = initial chromium concentration in mg/L
initial and final concentrations of iodine was           Ct = chromium concentration at time t
determined and from this the iodine number was           mo = mass of activated carbon in g
calculated using equation 2.                             V - Volume of chromium solution in cm3
                    πΌπ‘œπ‘‘π‘–π‘›π‘’ π‘›π‘’π‘šπ‘π‘’π‘Ÿ =                      The effect of adsorbent dosage, particle size, pH,
       π·π‘–π‘“π‘“π‘’π‘Ÿπ‘’π‘›π‘π‘’ 𝑖𝑛 π‘π‘œπ‘›π‘π‘’π‘›π‘‘π‘Ÿπ‘Žπ‘‘π‘–π‘œπ‘› π‘œπ‘“ π‘–π‘œπ‘‘π‘–π‘›π‘’ 𝑖𝑛 π‘šπ‘”       contact time, stirring speed, initial concentration of
                                                   (2)
           π‘Šπ‘’π‘–π‘” 𝑕𝑑 π‘œπ‘“ π‘Žπ‘π‘‘π‘–π‘£π‘Žπ‘‘π‘’π‘‘ π‘π‘Žπ‘Ÿπ‘π‘œπ‘› 𝑖𝑛 𝑔              Cr (VI) and temperature were studied by varying
                                                         any one of the parameters and keeping the other
2.2 X ray Diffraction                                    parameters constant.
        The structural analysis of the activated
carbon powder was determined by PXRD. The                3. Results and Discussions
PXRD pattern was recorded by using Philips PW            3.1 Bulk Density measurements
1051 X-ray diffractometer using Cu KΞ± radiation (Ξ»                Bulk density is an important parameter of
= 1.5405 A0) with Nickel filter at a scanning rate of    powdered solids. The American Water Work
20/minute.                                               Association has set a lower limit on bulk density at
                                                         0.25 gm/ml for activated carbon to be of practical
2.3 FTIR Spectroscopy                                    use. The bulk density values of the prepared are
         The FTIR studies were conducted on              given in table 1 of prepared samples satisfies this
activated carbon sample to determine the various         condition. The bulk density data are in agreement
organic and inorganic groups on the surface. The         with the values reported in literature [13-15].
instrument used to record the FTIR spectrum
Shimadzu with KBr as reference.                              Table 1. Bulk density values of the samples
                                                              Sl.                     Bulk density (g /
2.4 Scanning Electron Microscopy                                        Sample
                                                              No.                     cm3)
        The surface morphology of the activated
                                                               1     750S40           0.2641
carbon samples were studied by scanning electron
                                                               2     750S100          0.2592
microscopy. The SEM micrograph was recorded
                                                               3     800S30           0.2632
using JEOL JSM 5200 instrument.

2.5 Adsorption Studies                                   3.2 Moisture Content
         An adsorbate stock solution of 1000 mg/l                  The moisture content values of the
of Cr (VI) was prepared by dissolving 2.829 g of         prepared activated carbon samples are reported in
potassium dichromate in double distilled water. The      table 2. The commercially available samples contain
stock solution was diluted suitably to get 100, 200,     about 5-8% moisture [16].
300, 400 and 500 mg of Cr (VI) solutions. Batch
adsorption experiments were carried out by shaking         Table 2. Moisture content values of the samples
500 mg of activated carbon with 100 ml of                         Sl.               Percentage
potassium dichromate solution of known                            No. Sample        moisture
concentration in 200 ml Erlenmeyer flasks at                                        content
specified temperatures in a thermostated water bath               1     750S40      5.11
mechanical shaker.                                                2     750S100 5.31
The flasks were removed after the desired contact                 3     800S30      5.21
time. A definite volume (5ml) of the solution was
withdrawn and quickly filtered through Whatmann          3.3 Volatile matter
No.40 filter paper. The filtrates were analyzed using             The coconut shell samples were weighed
UV-Visible spectrophotometer (Hitachi 2000) at a         before and after pyrolysis. Table 3 gives the
wavelength 540 nm using diphenyl carbazide as            percentage conversion values for the samples after
complexing agent. In acidic media some part of           pyrolysis.
chromium (VI) was reduced to the trivalent state.            Table 3. Percentage conversion values for the
Hence Cr (III) is oxidized to Cr (VI) by potassium                      samples after pyrolysis
permanganate and sodium azide. The adsorbed                                                       Percentag
                                                                           Weight      Weight
chromium (VI) was calculated by taking the               Sl.                                      e
                                                                           before      after
difference of initial concentration and final            No Sample                                of
                                                                           Pyrolysi Pyrolysi
chromium concentration in the filtrate.                  .                                        conversio
                                                                           s           s
                                                                                                  n
                                                         1     750S40      300 g       62 g       20.67


                                                                                                     366 | P a g e
B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering
              Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                        Vol. 2, Issue 5, September- October 2012, pp.364-370
2       750S10    300 g       65 g        21.67          3.7 Phenol Number
        0                                                          It is the amount of activated carbon
3       800S30    300 g       68 g        22.67          required for 90% removal of phenol. This indicates
                                                         the ability to remove taste and odor. It is expressed
From table 3, it can be noticed that the yield of        as mg/g.
pyrolyzed carbon is around 20%. The samples used             Table 7. Phenol number values of the samples
for the study contain substantial quantity of volatile            Sl. No. Sample        Phenol number
matter.                                                           1           750S40           27
                                                                  2           750S100          31
3.4 Ash Content and Ash analysis                                  3           800S30           37
         Table 4 gives the values of percentage ash
content of the samples.                                  3.8 Surface area, pore volume and pore size
   Table 4. Percentage ash content of the samples                 Table 8 gives the values of BET surface
    Sl. No. Sample           Percentage ash              area, pore volume and pore size values of the
                             content                     samples.
    1         750S40         1.42                          Table 8. BET surface area, pore volume and pore
    2         750S100        1.54                                     size values of the samples.
    3         800S30         1.37                                             BET          Total
                                                                                                   Average
                                                         Sl.                Surface         pore
                                                                Sample             2               pore size
From table 4, it can be seen that the ash content in     No.               area (m /      volume
                                                                                                      (Γ…)
activated carbon samples is low. The low ash                                   g)         (cm3 /g)
content    makes activated carbon an attractive           1     750S40        695         0.38781    17.88
candidate for adsorption studies. The ash content of      2    750S100        730         0.40734    18.78
commercial samples is around 2% (133,134). If ash         3     800S30        790         0.44082    19.82
content is high it will interfere with pore structure
development and hence adsorption will be less.           The above results show that surface area of
                                                         activated carbons is in agreement with other studies.
3.5 Ash analysis                                         Average pore volume of 0.4 cm3 /g suggests good
         The ash obtained from various samples was       pore structure development. The BET surface area
mixed well and its analysis was conducted. Table 5       increases with increase in temperature of activation,
gives the composition of the various components in       soaking time and porosity as well. Increase in
the ash.                                                 surface area results in an increase in chromium
      Table 5. Ash analysis data for the samples         adsorption. This can be explained as due to the
          Sl. No. Substance Percentage                   increases in the number of adsorption sites.
          1.        SiO2         18.3
          2.        K 2O         0.99                    3.9 Iodine Number
          3.        CaO          0.95                             Table 9 gives the values of the iodine
          4.        MgO          8.92                    number of the samples. The iodine numbers of
          5.        P2O5         0.09                    activated carbons prepared in this investigation lies
          6.        Na2O         70.75                   between 480-700. This is quite comparable with the
          7.        Fe2O3        1.22                    values reported by other workers. The iodine
                                                         numbers reported by other workers lies between 550
3.6 Hardness                                             – 850 . Generally, higher the iodine number, greater
         The activate carbon powder should possess       is the sorption capacity. ASTM D 4607 describes
sufficient mechanical strength to withstand the          the procedure for determining the iodine number.
abrasion resulting from continuous use. The              The iodine number recommended as a minimum by
commercial samples have hardness in the range of         the American Water Works Association for a carbon
80-90%, where as prepared samples possess 90-98          to be used in removal low molecular weight
% hardness.                                              compounds is 500. The two factors that determine
Decolorizing power                                       good iodine number are activation temperature and
Table 6 shows the values of decolorizing power of        dwell time. At 800 0 C even a dwell time of 30
the samples.                                             minutes is sufficient. For lower temperatures dwell
 Table 6. Decolorizing power values of the samples       time of more than one hour is required. Hence
         Sl. No. Sample       Decolorizing               samples 750S100 and 800S30 conform to these
                                Power                    specifications. The sample 750S40 has an under
                                                         developed pore structure. From figure 1, it can be
                                                         observed that the iodine number increases as the
         1        750S40      66                         temperature of activation increases. This suggests
         2        750S100     68                         that surface area has increases in terms of
         3        800S30      69                         microscopic pores. Iodine adsorption is usually


                                                                                                367 | P a g e
B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering
                     Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                               Vol. 2, Issue 5, September- October 2012, pp.364-370
          associated with micro pores because of the small
          size of iodine molecule.
              Table 9. Iodine number values of the samples
                 Sl. No.   Sample       Iodine Number
                 1         750S40            478
                 2         750S100           562
                 3         800S30            682

                                  Variation of Iodine Number in S samples

                            800

                            700                                                 682

                            600
                                                          562
                                                                                      Figure 6 SEM micrograph of sample after adsorption of
            Iodine Number




                            500
                                      478

                            400
                                                                                      chromium
                            300
                                                                                      3.2 Adsorption Equilibrium Studies
                            200
                                                                                      3.2.1 Effect of Adsorbent Dosage
                            100
                                                                                               Figure 7 shows the effect of adsorbent
                             0
                                  750S40              750S100               800S30    dosage on the removal of chromium. It is clear from
                                                     samples                          the figure that as the adsorbent dosage increases, the
           Figure 1. Variation of iodine number of the samples                        adsorption also increases. This is due to fact that an
          3.10 X-Ray Diffraction Studies                                              increase in adsorbent dosage increases the number
          Figure 2 shows the PXRD profile of the powdered                             of active sites available for adsorption. Optimum
          sample. The PXRD pattern shows the presence of                              removal of chromium (about 94%) was achieved for
          amorphous carbon in the sample. The crystalline                             an adsorbent dosage of 2 g of the adsorbent. Beyond
          phases of Si, KCl, Fe, Zn are also present. The                             the optimum dosage, the adsorption negligible
          peaks in the PXRD profile correspond to those                               increase in adsorption occurred.
          reported in the literature for activated carbon.                                                                            Dosage of Carbon and Removal of Cr

                                                                                                                    100

                                                                                                                    90

                                                                                                                    80
                                                                                        Amount of Cr romoved in %




                                                                                                                    70

                                                                                                                    60

                                                                                                                    50

                                                                                                                    40

                                                                                                                    30

                                                                                                                    20

                                                                                                                    10

                                                                                                                     0
                                                                                                                              0.5 g            1.0 g                      1.5 g    2.0 g

           Figure 2. PXRD profile of activated carbon sample                                                                                           Amount of carbon


                                                                                                                          Figure 7. Effect of adsorbent dosage
          3.11 Scanning Electron Microscopy Studies
                   Figures 5 and 6 show the SEM
                                                                                      3.2.2 Effect of Particle Size
          micrographs of the sample before and after
                                                                                                Various particle sizes of carbons were used
          chromium coating. The porosity is less in case of
                                                                                      to conduct experiments to determine % removal of
          figure 6 compared to that in case of figure 5 which                         chromium at 25 0C at an initial concentration of 200
          indicates the adsorption of chromium in the pores of                        mg /dm3 . The removal of chromium at different
          the sample.
                                                                                      particle sizes illustrated that removal rate increases
                                                                                      as the particle size decreases. As can be seen from
                                                                                      figure 8 that the adsorption increases as the particle
                                                                                      size decreases. The relatively higher adsorption rate
                                                                                      as the particle size decreases is due to the increase in
                                                                                      surface area. There is a tendency as fine particles
                                                                                      exhibit lesser time to equilibriate in shorter time.




Figure 5 SEM micrograph of sample before adsorption of
chromium

                                                                                                                                                                   368 | P a g e
B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering
                                    Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                                              Vol. 2, Issue 5, September- October 2012, pp.364-370
                                    particle size and % Cr removal
                                                                                    point charge (pHzpc) which lies between the two
                                                                                    values. The pHzpc is a point at which the adsorbent
               120
                                                                                    surface groups either acidic or basic no longer
               100
                                                                                    contribute to the pH of the solution. Maximum
                                                                                    adsorption of Cr (VI) ions at lower pH has been
               80
                                                                                    reported [17, 18].
% Cr removal




               60                                                                                                                                        Effect of pH on Cr removal for S samples

                                                                                                                                      100                                                                     90
               40
                                                                                                                                      90                                                                      80
                                                                                                                                      80                                                                      70
               20
                                                                                                                                      70
                                                                                                                                                                                                              60




                                                                                                                       % Cr removal
                                                                                                                                      60
                0                                                                                                                                                                                             50
                                                                                                                                      50
                     0        50        100         150          200   250    300
                                                                                                                                                                                                              40
                                                  mesh no.                                                                            40
                                                                                                                                                                                                              30
                                                                                                                                      30
                                                                                                                                                                                                              20
                            Figure 8. Effect of particle size on adsorption                                                           20

                                                                                                                                      10                                                                      10

                                                                                                                                          0                                                                   0
                         3.2.3 Effect of pH                                                                                                   0      1           2    3      4        5        6      7   8

                                   The effect of pH on the adsorption of                                                                                                    pH


                         chromium by activated carbon was studied at pH
                         values of 1 to 7. 0.5g of activated carbon was                                                                            750S40,         750S100,        800S30
                         suspended in 100 ml of solution which contained 80                                                                       Figure 9. Efect of pH on adsorption
                         mg of chromium per liter. Different pH conditions
                         were maintained by adding HCl and acetic acid-             3.2.4 Effect of contact time on Adsorption
                         sodium acetate buffer. The adsorption of chromium                   Adsorption experiments were conducted as
                         was determined after an equilibration time of one          a function of contact time and the results are shown
                         hour at a stirring speed of 200 rpm.                       in figure 10. The rate of Cr (VI) binding with
                         pH influences the adsorption of Cr(VI) ions on the         adsorbent was greater in the initial stages, then
                         adsorbate as it affects the solubility of metal ions       gradually decreased and remained almost constant
                         and hence the electrostatic binding of ions. From          after an optimum period. After 60 minutes the
                         figure 9, it is evident that at lower pH between 2 and     adsorption reaches an optimum value of 92%. This
                         3 the adsorption is maximum. This could be                 is because initially a large number of vacant sites are
                         attributed to the high concentration of H+ ions at         available for adsorption and after some time the
                         lower pH values which neutralizes the negatively           remaining sites may be difficult to occupy due to
                         charged adsorbate Cr2O72- ions. The decrease in the        repulsive forces between adsorbate ions on the solid
                         adsorption efficiency at higher pH can be attributed       and in the solution. Similar results have been
                         to increase in the concentration of OH- ions which         reported by other investigators.
                         hinder the diffusion of Cr (VI) ions.                                                                                                       Effect of time on Adsorption
                         The process of adsorption of metal ions on the                                                  30
                         adsorbent involves the binding of metal ions by
                                                                                      Amount of Cr on adsorbate (mg)




                         electrostatic forces of attraction. The surface of the                                          25


                         adsorbent is positively chargede and hence                                                      20

                         negatively charged Cr2O72- ions are held by
                                                                                                                         15
                         electrostatic forces of attraction.
                         It has been suggested that the mechanism for metal                                              10

                         adsorption is due to the acidic functional C=O                                                         5
                         groups on the adsorbent surface. The presence of
                                                                                                                                0
                         oxygen functional groups make the adsorbent                                                                  0                     50              100                150            200    250

                         surface negatively charged and therefore a repulsive                                                                                                    time in minutes

                         electrostatic interaction between the adsorbent and                                                          Figure 10. Effect of contact on adsorption
                         the anion where as for a cation the negatively
                         charged group enhances the electrostatic interaction       3.2.5 Effect of Stirring Speed
                         with the negatively charged surface of the adsorbent                The effect of the agitation of the
                         mainly through carboxylic ligands.                         sorbent/sorbate system in chromium adsorption was
                         According to the fig, the rates of adsorption are          monitored at low, medium and high- agitation
                         weak with low values of pH (<2). Between 2 and 3           speeds (80, 100, 120, 150, 200 rpm). The results are
                         the rates of absorption increase rapidly. This is due      shown in figure 11.
                         to the surface charge of the metal, which is strongly      0.5 gm of adsorbent and 50 ml of the solution
                         related to the pH of the solution. Maximum                 containing 100 mg/l of chromium at pH 3 was
                         adsorption capacity is observed in the pH range 2 to       agitated between 90 and 210 rpm. Maximum of
                         3. This indicates that the pH corresponds to the zero      97.77 % chromium removal was achieved at 200



                                                                                                                                                                                                     369 | P a g e
B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering
           Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                     Vol. 2, Issue 5, September- October 2012, pp.364-370
rpm. The effect of chromium adsorption on low and                                    1200H, 1500H and IRN97H, J. Hazard. Mater.
high agitation speed was observed. An increase in                                    102 (2/3) (2003) 257–275.
adsorption was observed from 66.66 % to 97.77 %,                               6.    D. Petruzzelli, R. Passino, G. Tiravanti, Ion
when the agitation speed was increased from 90 to                                    exchange process for chromium removal and
                                                                                     recovery from tannery wastes, Ind. Eng. Chem.
200 rpm. Due to agitation, proper contact was                                        Res. 34 (1995) 2612–2617.
developed between metal ion in solution and the                                7.    D. Mohan, K.P. Singh, V.K. Singh, Trivalent
binding sites, which promoted effective transfer of                                  chromium removal from wastewater using low
adsorbate ions onto the adsorbent sites.                                             cost activated carbon derived from agricultural
                                      Effect of Stirring Speed
                                                                                     waste material and activated carbon fabric cloth,
                                                                                     J. Hazard. Mater. 135 (2006) 280–295.
                 120                                                           8.    C.P. Huang, M.H.Wu, Chromium removal by
                                                                                     carbon adsorption, J.Water Pollut. Contr. Fed.
                 100
                                                                                     47 (10) (1975) 2437–2446.
                 80
                                                                               9.    C.P. Huang, M.H.Wu, The removal of
  % Cr removal




                                                                                     chromium(VI) from dilute aqueous solution by
                 60                                                                  activated carbon, Water Res. 11 (8) (1977) 673–
                                                                                     679
                 40
                                                                               10.   C. Selomulya, V. Meeyoo, R. Amal,
                 20
                                                                                     Mechanisms of Cr(VI) removal from water by
                                                                                     various types of activated carbons, J.
                  0                                                                  Chem.Technol. Biotechnol. 74 (2) (1999) 111–
                       0         50          100           150     200   250
                                                                                     122.
                                           Stirring Speed in rpm
                                                                               11.   S.J.T. Pollard, G.D. Fowler, C.J. Sollars, R.
    Figure 11. Effect of stirring speed on adsorption                                Perry, Lowcost adsorbents for waste and
                                                                                     wastewater treatment: a review, Sci. Tot.
                                                                                     Environ. 116 (1992) 31–52.
4. Summary and Conclusions                                                     12.   D. Mohan, K.P. Singh, Granular activated
         Activated carbon was successfully prepared                                  carbon, in: J. Lehr, J. Keeley, J. Lehr (Eds.),
by pyrolysis. The results indicated that the                                         Water Encyclopedia: Domestic, Municipal, and
adsorption capacity depends upon the pore size,                                      Industrial Water Supply and Waste Disposal,
surface area and temperature of activation of the                                    Wiley/Interscience, New York,2005.
activated carbon. At pH 3, the adsorption was found                            13.   N.K. Lazaridis, C. Charalambous, Sorptive
to be maximum. The activated carbon can act as a                                     removal of trivalent and hexavalent chromium
good adsorbent for the adsorption of chromium from                                   from binary aqueous solutions by composite
                                                                                     alginate–goethite beads, Water Res. 39 (18)
industrial effluents such as electroplating industries.
                                                                                     (2005) 4385–4396.
                                                                               14.   S.Gueu, B.Yao, K.Adouby and G.Adoβ€”Heavy
Acknowledgements                                                                     Metals removal in aqueous solution by activated
        BVD and AAJ are thankful to the Principal                                    carbons prepared from coconut shell and seed
and management of Dr. AIT, Bangalore for                                             shell of the palm treeβ€”Journal of applied
encouragement and support. MNZA acknowledges                                         Sciences 6(13); 2789-2793, 2003
the support rendered by the Principal and                                      15.   Karuppanna Periaswamy and Chinnaiya
management of HKBK College of Engineering,                                           Namasivayam--Process         development       for
                                                                                     removal and recovery of cadmium from waste
Bangalore.
                                                                                     water by a low cost adsorbent: Adsorption rates
                                                                                     from equilibrium studiesβ€”Ind. Eng. Res. 1994,
References                                                                           33, 317-320
                 1.        D.E. Kimbrough, Y. Cohen, A.M. Winer, L.            16.   Giles.C.H. and Nakhwa S.N.,--Studies in
                           Creelman, C.A. Mabuni, Critical assessment of             Adsorption.XVI-The measurement of specific
                           chromium in the environment, Crit. Rev.                   surface areas of finely divided solids by solution
                           Environ. Sci. Technol. 29 (1) (1999) 1–46.                adsorptionβ€”J.Appl. Chem.,12,June, 1962, 266-
                 2.        J.W.     Paterson,    Wastewater      Treatment           273.
                           Technology, Ann Arbour Science, Michigan,           17.   Min Gyu Lee, Gyeougheam Yi, Byoung Joon
                           1975, pp. 43–58.                                          Ahu and Felicity Roddickβ€”Conversion of Coal
                 3.        S. Rengaraj, K.-H. Yeon, S.-H. Moon, Removal              fly adh into zeolite and heavy metal removal
                           of chromium from water and wastewater by ion              characteristics of the productsβ€”Korean Journal
                           exchange resins, J. Hazard. Mater. 87 (1–3)               of Chem. Engg.β€”17(3), 325-331 (2000).
                           (2001) 273–287.                                     18.   Parinda Suksabye , Paitip Thiravetyan ,
                 4.        S. Rengaraj, K.-H. Yeon, S.-Y. Kang, J.-U. Lee,           Woranan Nakbanpote , Supanee Chayabutr--
                           K.-W. Kim, S.-H. Moon, Studies on adsorptive              Chromium removal from electroplating
                           removal of Co(II), Cr(III) and Ni(II) by IRN77            wastewater by coir pithβ€”online publicationβ€”
                           cation-exchange resin, J. Hazard. Mater. 92 (2)           Elsevier,doi 10.1010-2006.07.18
                           (2002) 185–198.
                 5.        S. Rengaraj, C.K. Joo, Y. Kim, J. Yi, Kinetics of
                           removal of chromium from water and electronic
                           process wastewater by ion exchange resins:



                                                                                                                      370 | P a g e

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Coconut coir dust ion exchange resins for removal of ni2+ ion
Coconut coir dust ion exchange resins for removal of ni2+ ionCoconut coir dust ion exchange resins for removal of ni2+ ion
Coconut coir dust ion exchange resins for removal of ni2+ ion
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  • 1. B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.364-370 Adsorption of Chromium on Activated Carbon Prepared from Coconut Shell B. Veena Devi*, A.A. Jahagirdar**, M.N. Zulfiqar Ahmed*** * (Department of Chemistry, Dr. Ambedkar Institute of Technology, Bangalore - 560056, India) ** (Department of Chemistry, Dr. Ambedkar Institute of Technology, Bangalore - 560056, India) *** (Department of Chemistry, HKBK College of Engineering, Bangalore - 560045, India) ABSTRACT Activated carbon was prepared from environment. In such aqueous waste, Chromium coconut shell by pyrolysis. It was characterized (VI) is present as either dichromate (Cr2O7 2-) in by PXRD, and SEM. Different physical acidic environments or as chromate (CrO42- ) in properties such as bulk density, moisture alkaline environments. content, volatile matter content, ash content, Several treatment technologies have been developed hardness, decolorizing power, phenol number, to remove chromium from water and waste water. iodine number and surface area and porosity Common methods include chemical precipitation, were also determined. The activated carbon was ion exchange, membrane separation, ultrafiltration, used as adsorbent for the removal of chromium filtration, elctrocoagulation, solvent extraction, from an electroplating industry. The effect of sedimentation, reverse osmosis, dialysis, various parameters such as adsorbent dosage, electrodialysis, adsorption and filtration, particle size, pH, contact time and stirring evaporation, cementation, dilution, air stripping, speed was studied. The studies showed that the steam stripping, flocculation and chelation [2-6]. activated carbon can be used as a good adsorbent Reduction and chemical precipitation has for the removal of hexavalent chromium from traditionally been the most used method. The most electroplating industries. often used precipitation processes include Key words - Activated carbon, adsorption, hydroxide, sulphide, carbonate and phosphate electroplating industry, hexavalent chromium, precipitation techniques. The disadvantage of SEM. precipitation technique is the production of sludge. This process suffers from draw backs like 1. Introduction incomplete removal, requirement of sizable Chromium (VI) is highly toxic in nature. quantities of treatment chemicals and production of This is due to the fact that one of the reduction voluminous toxic sludge. It constitutes a solid waste products of Chromium (VI) is Chromium (V). disposal problem. A variety of other treatment Chromium (V) is a known carcinogen and will technologies were considered and evaluated. lodge in any tissue to form cancerous growths. Techniques like ion exchange and adsorption with There are reports that Chromium (V) is also a factor products obtained from naturally occurring materials leading to premature senility in parts of Russia. The like activated carbon were considered as better Chromium (VI) is a very strong oxidizing agent alternatives. The exorbitant cost involved with ion (therefore very fast in reacting, unlike Chromium exchange makes it prohibitive for wide application (III) and likely to form complexes). Chromium (VI) [7-9]. is not a very stable state when compared to Cr (III). Coconut shells are available in plenty in tropical Chronic inhalation of Chromium (VI) compounds countries. The utilization of this waste material increases the risk of lung, nasal and sinus cancer. helps in recycling waste and thus keeping the eco Severe dermatitis skin ulcer can result from contact system clean. Mitigation measures based on low with Chromium (VI) compounds. It can cause mild cost technologies hold promise of wide applicability to severe liver abnormalities. Chromium (VI) in developing countries. This methodology can be compounds are teratogenic to animals [1]. profitably employed by least developed and Effluents from electroplating and tannery industries developing countries in mitigating pollution due to is a major source of aquatic pollution in India with the heavy metal ion chromium [10-12]. high chemical oxygen demand (COD), biological oxygen demand (BOD), and hexavalent chromium. 2. Materials and Methods In India, there are a large number of tanneries The coconut shells were washed with water scattered all over the country but the main areas of to remove sticking and lose matter and then sun their concentration are Tamilnadu, Uttar Pradesh dried for 5 days (8 hours per day). The dried and West Bengal. Nearly 80% of these tanneries are samples were then hammer broken to pieces and engaged in the chrome tanning processes. Most of then converted to a powder using a mixer. Three them discharge untreated wastewater into the temperature routes were followed for preparing 364 | P a g e
  • 2. B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.364-370 active carbon by taking known quantities of obtained. The residue is reported as ash on powdered coconut shell. percentage basis. Samples were pyrolysed in a muffle furnace in the presence of steam flow. A two step procedure was 2.1.5 Hardness followed. Sample was carbonized at 550 0 C for 2 The percentage of particles passing through hours and then a physical activation method was a screen of 275 mesh was determined. . Then the followed for different periods of time. Through the particles were subjected to hammer force for five inspection hole in the muffle furnace door a glass minutes and then the particles which passed through tube was introduced which was connected to a a screen of 300 mesh were determined. The steam generator. Thus a continuous flow of steam percentage of particles not broken to fine size was was maintained. Three different samples were expressed as percentage of hardness. prepared and coded as 750S40, 750S100 and 800S30. The samples 750S40 and 750S100 were 2.1.6 Decolorizing Power prepared by heating the powders to 750 0C and Decolorizing power is the ability of keeping them at 750 0C for 40 minutes and 100 activated carbon to decolorize a dilute blue colored minutes respectively. In case of sample 800S30, the solution of methylene blue. It is expressed as mg/g. powder was heated to 800 0C and then maintained at that temperature for 30 minutes. 2.1.7 Phenol Number 100 cm3 of 30 ppm solution of phenol was 2.1 Characterization of Activated Carbon taken in a 250 cm3 leak proof reaction flask. The pH Powders of the solution was adjusted to neutral by adding 0.1 2.1.1 Bulk Density N NaOH or 0.1 N H2SO4. A known weight of the The activated carbon sample were packed activated carbon powder was added to it. The in a previously weighed 25 cm3 specific gravity solution was equilibrated for 24 hours at room bottle by repeatedly tapping the bottle so that temperature followed by filtration and subsequent powder is filled upto the mark. The bottle was analysis of the filtrate for phenol concentration. The weighed again. The difference in the weights gives concentration of phenol was determined by the weight of powder taken in the bottle. The bulk spectrophotometric analysis for the colour resulting density of the powder was calculated using equation from the reaction of phenol with 4-amino antipyrene 1. at a wave length of 600 nm. [(𝑀𝑒𝑖𝑔 𝑕𝑑 π‘œπ‘“ π‘π‘œπ‘€π‘‘π‘’π‘Ÿ π‘‘π‘Žπ‘˜π‘’π‘› 𝑖𝑛 𝑑𝑕𝑒 π‘π‘œπ‘‘π‘‘π‘™π‘’ ) π΅π‘’π‘™π‘˜ 𝑑𝑒𝑛𝑠𝑖𝑑𝑦 = (1) 25 2.1.8 Surface area and porosity 2.1.2 Moisture content The BET surface area of activated carbon About one gram of the powdered air dried powder was determined by nitrogen adsorption activated carbon powder was taken in a previously desorption method. The instrument used was weighed crucible. The crucible was placed in an MICROMERITICS GEMINE 2375. Nitrogen gas electric hot air oven maintained at about 110 0 C. was allowed to adsorb on the powder at 77 K. The After one hour the crucible is taken out, cooled in a nitrogen adsorption and desorption isotherms were desiccator and weighed again. The loss in weight of used to determine parameters like surface area, pore the powder reported on percentage basis gives volume and pore size. moisture content in the sample. 2.1.9 Iodine Number 2.1.3 Volatile Matter Iodine number is defined as the number of About one gram of the powdered air dried milligrams of iodine absorbed by one gram of activated carbon powder was taken in a previously activated carbon powder. Iodine solution is prepared weighed crucible. The crucible was placed in a by dissolving 13 grams of iodine in 50 cm3 of muffle furnace maintained at about 925 0 C. It was glacial acetic acid and then diluting up to the mark taken out after exactly 7 minutes. After first cooling in a 1000 cm3 volumetric flask. A known weight of in air, the crucible was cooled in a desiccator and the activated carbon powder (about 0.25 g) was weighed again. The loss in weight of the powder suspended in 10 cm3 of carbon tetra chloride taken reported on percentage basis gives volatile matter in a 250 cm3 conical flask. To this a known volume content in the sample. of the prepared iodine solution was added. Similarly 2.1.4 Ash Content a blank solution was also prepared by taking same The residual activated carbon powder from the volumes of carbon tetra chloride iodine solution as above step was then heated in a muffle furnace at in the previous case but without the activated carbon 750 0 C for about half an hour. After first cooling in powder. Both the conical flasks were kept in a air, the crucible was cooled in a desiccator and shaking machine for one hour. Then the solution weighed again. The heating, cooling and weighing were is rapidly filtered using Whatman filter paper cycle was repeated till a constant weight was no. 41. 20 cm3 of the filtrate was transferred into a 250 cm3 conical flask. To this 20 ml of 15% 365 | P a g e
  • 3. B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.364-370 potassium iodide and 100 ml of distilled water were The amount of chromium adsorbed qt was added. The contents of both the flask were titrated calculated using equation 3. against standard sodium thiosulphate using freshly πΆπ‘œ – 𝐢𝑑 𝑉 π‘žπ‘‘ = (3) prepared starch as indicator. The volume of sodium π‘šπ‘œ thiosulphate solution consumed in case of both back where, and ban titrations was determined. The difference in Co = initial chromium concentration in mg/L initial and final concentrations of iodine was Ct = chromium concentration at time t determined and from this the iodine number was mo = mass of activated carbon in g calculated using equation 2. V - Volume of chromium solution in cm3 πΌπ‘œπ‘‘π‘–π‘›π‘’ π‘›π‘’π‘šπ‘π‘’π‘Ÿ = The effect of adsorbent dosage, particle size, pH, π·π‘–π‘“π‘“π‘’π‘Ÿπ‘’π‘›π‘π‘’ 𝑖𝑛 π‘π‘œπ‘›π‘π‘’π‘›π‘‘π‘Ÿπ‘Žπ‘‘π‘–π‘œπ‘› π‘œπ‘“ π‘–π‘œπ‘‘π‘–π‘›π‘’ 𝑖𝑛 π‘šπ‘” contact time, stirring speed, initial concentration of (2) π‘Šπ‘’π‘–π‘” 𝑕𝑑 π‘œπ‘“ π‘Žπ‘π‘‘π‘–π‘£π‘Žπ‘‘π‘’π‘‘ π‘π‘Žπ‘Ÿπ‘π‘œπ‘› 𝑖𝑛 𝑔 Cr (VI) and temperature were studied by varying any one of the parameters and keeping the other 2.2 X ray Diffraction parameters constant. The structural analysis of the activated carbon powder was determined by PXRD. The 3. Results and Discussions PXRD pattern was recorded by using Philips PW 3.1 Bulk Density measurements 1051 X-ray diffractometer using Cu KΞ± radiation (Ξ» Bulk density is an important parameter of = 1.5405 A0) with Nickel filter at a scanning rate of powdered solids. The American Water Work 20/minute. Association has set a lower limit on bulk density at 0.25 gm/ml for activated carbon to be of practical 2.3 FTIR Spectroscopy use. The bulk density values of the prepared are The FTIR studies were conducted on given in table 1 of prepared samples satisfies this activated carbon sample to determine the various condition. The bulk density data are in agreement organic and inorganic groups on the surface. The with the values reported in literature [13-15]. instrument used to record the FTIR spectrum Shimadzu with KBr as reference. Table 1. Bulk density values of the samples Sl. Bulk density (g / 2.4 Scanning Electron Microscopy Sample No. cm3) The surface morphology of the activated 1 750S40 0.2641 carbon samples were studied by scanning electron 2 750S100 0.2592 microscopy. The SEM micrograph was recorded 3 800S30 0.2632 using JEOL JSM 5200 instrument. 2.5 Adsorption Studies 3.2 Moisture Content An adsorbate stock solution of 1000 mg/l The moisture content values of the of Cr (VI) was prepared by dissolving 2.829 g of prepared activated carbon samples are reported in potassium dichromate in double distilled water. The table 2. The commercially available samples contain stock solution was diluted suitably to get 100, 200, about 5-8% moisture [16]. 300, 400 and 500 mg of Cr (VI) solutions. Batch adsorption experiments were carried out by shaking Table 2. Moisture content values of the samples 500 mg of activated carbon with 100 ml of Sl. Percentage potassium dichromate solution of known No. Sample moisture concentration in 200 ml Erlenmeyer flasks at content specified temperatures in a thermostated water bath 1 750S40 5.11 mechanical shaker. 2 750S100 5.31 The flasks were removed after the desired contact 3 800S30 5.21 time. A definite volume (5ml) of the solution was withdrawn and quickly filtered through Whatmann 3.3 Volatile matter No.40 filter paper. The filtrates were analyzed using The coconut shell samples were weighed UV-Visible spectrophotometer (Hitachi 2000) at a before and after pyrolysis. Table 3 gives the wavelength 540 nm using diphenyl carbazide as percentage conversion values for the samples after complexing agent. In acidic media some part of pyrolysis. chromium (VI) was reduced to the trivalent state. Table 3. Percentage conversion values for the Hence Cr (III) is oxidized to Cr (VI) by potassium samples after pyrolysis permanganate and sodium azide. The adsorbed Percentag Weight Weight chromium (VI) was calculated by taking the Sl. e before after difference of initial concentration and final No Sample of Pyrolysi Pyrolysi chromium concentration in the filtrate. . conversio s s n 1 750S40 300 g 62 g 20.67 366 | P a g e
  • 4. B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.364-370 2 750S10 300 g 65 g 21.67 3.7 Phenol Number 0 It is the amount of activated carbon 3 800S30 300 g 68 g 22.67 required for 90% removal of phenol. This indicates the ability to remove taste and odor. It is expressed From table 3, it can be noticed that the yield of as mg/g. pyrolyzed carbon is around 20%. The samples used Table 7. Phenol number values of the samples for the study contain substantial quantity of volatile Sl. No. Sample Phenol number matter. 1 750S40 27 2 750S100 31 3.4 Ash Content and Ash analysis 3 800S30 37 Table 4 gives the values of percentage ash content of the samples. 3.8 Surface area, pore volume and pore size Table 4. Percentage ash content of the samples Table 8 gives the values of BET surface Sl. No. Sample Percentage ash area, pore volume and pore size values of the content samples. 1 750S40 1.42 Table 8. BET surface area, pore volume and pore 2 750S100 1.54 size values of the samples. 3 800S30 1.37 BET Total Average Sl. Surface pore Sample 2 pore size From table 4, it can be seen that the ash content in No. area (m / volume (Γ…) activated carbon samples is low. The low ash g) (cm3 /g) content makes activated carbon an attractive 1 750S40 695 0.38781 17.88 candidate for adsorption studies. The ash content of 2 750S100 730 0.40734 18.78 commercial samples is around 2% (133,134). If ash 3 800S30 790 0.44082 19.82 content is high it will interfere with pore structure development and hence adsorption will be less. The above results show that surface area of activated carbons is in agreement with other studies. 3.5 Ash analysis Average pore volume of 0.4 cm3 /g suggests good The ash obtained from various samples was pore structure development. The BET surface area mixed well and its analysis was conducted. Table 5 increases with increase in temperature of activation, gives the composition of the various components in soaking time and porosity as well. Increase in the ash. surface area results in an increase in chromium Table 5. Ash analysis data for the samples adsorption. This can be explained as due to the Sl. No. Substance Percentage increases in the number of adsorption sites. 1. SiO2 18.3 2. K 2O 0.99 3.9 Iodine Number 3. CaO 0.95 Table 9 gives the values of the iodine 4. MgO 8.92 number of the samples. The iodine numbers of 5. P2O5 0.09 activated carbons prepared in this investigation lies 6. Na2O 70.75 between 480-700. This is quite comparable with the 7. Fe2O3 1.22 values reported by other workers. The iodine numbers reported by other workers lies between 550 3.6 Hardness – 850 . Generally, higher the iodine number, greater The activate carbon powder should possess is the sorption capacity. ASTM D 4607 describes sufficient mechanical strength to withstand the the procedure for determining the iodine number. abrasion resulting from continuous use. The The iodine number recommended as a minimum by commercial samples have hardness in the range of the American Water Works Association for a carbon 80-90%, where as prepared samples possess 90-98 to be used in removal low molecular weight % hardness. compounds is 500. The two factors that determine Decolorizing power good iodine number are activation temperature and Table 6 shows the values of decolorizing power of dwell time. At 800 0 C even a dwell time of 30 the samples. minutes is sufficient. For lower temperatures dwell Table 6. Decolorizing power values of the samples time of more than one hour is required. Hence Sl. No. Sample Decolorizing samples 750S100 and 800S30 conform to these Power specifications. The sample 750S40 has an under developed pore structure. From figure 1, it can be observed that the iodine number increases as the 1 750S40 66 temperature of activation increases. This suggests 2 750S100 68 that surface area has increases in terms of 3 800S30 69 microscopic pores. Iodine adsorption is usually 367 | P a g e
  • 5. B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.364-370 associated with micro pores because of the small size of iodine molecule. Table 9. Iodine number values of the samples Sl. No. Sample Iodine Number 1 750S40 478 2 750S100 562 3 800S30 682 Variation of Iodine Number in S samples 800 700 682 600 562 Figure 6 SEM micrograph of sample after adsorption of Iodine Number 500 478 400 chromium 300 3.2 Adsorption Equilibrium Studies 200 3.2.1 Effect of Adsorbent Dosage 100 Figure 7 shows the effect of adsorbent 0 750S40 750S100 800S30 dosage on the removal of chromium. It is clear from samples the figure that as the adsorbent dosage increases, the Figure 1. Variation of iodine number of the samples adsorption also increases. This is due to fact that an 3.10 X-Ray Diffraction Studies increase in adsorbent dosage increases the number Figure 2 shows the PXRD profile of the powdered of active sites available for adsorption. Optimum sample. The PXRD pattern shows the presence of removal of chromium (about 94%) was achieved for amorphous carbon in the sample. The crystalline an adsorbent dosage of 2 g of the adsorbent. Beyond phases of Si, KCl, Fe, Zn are also present. The the optimum dosage, the adsorption negligible peaks in the PXRD profile correspond to those increase in adsorption occurred. reported in the literature for activated carbon. Dosage of Carbon and Removal of Cr 100 90 80 Amount of Cr romoved in % 70 60 50 40 30 20 10 0 0.5 g 1.0 g 1.5 g 2.0 g Figure 2. PXRD profile of activated carbon sample Amount of carbon Figure 7. Effect of adsorbent dosage 3.11 Scanning Electron Microscopy Studies Figures 5 and 6 show the SEM 3.2.2 Effect of Particle Size micrographs of the sample before and after Various particle sizes of carbons were used chromium coating. The porosity is less in case of to conduct experiments to determine % removal of figure 6 compared to that in case of figure 5 which chromium at 25 0C at an initial concentration of 200 indicates the adsorption of chromium in the pores of mg /dm3 . The removal of chromium at different the sample. particle sizes illustrated that removal rate increases as the particle size decreases. As can be seen from figure 8 that the adsorption increases as the particle size decreases. The relatively higher adsorption rate as the particle size decreases is due to the increase in surface area. There is a tendency as fine particles exhibit lesser time to equilibriate in shorter time. Figure 5 SEM micrograph of sample before adsorption of chromium 368 | P a g e
  • 6. B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.364-370 particle size and % Cr removal point charge (pHzpc) which lies between the two values. The pHzpc is a point at which the adsorbent 120 surface groups either acidic or basic no longer 100 contribute to the pH of the solution. Maximum adsorption of Cr (VI) ions at lower pH has been 80 reported [17, 18]. % Cr removal 60 Effect of pH on Cr removal for S samples 100 90 40 90 80 80 70 20 70 60 % Cr removal 60 0 50 50 0 50 100 150 200 250 300 40 mesh no. 40 30 30 20 Figure 8. Effect of particle size on adsorption 20 10 10 0 0 3.2.3 Effect of pH 0 1 2 3 4 5 6 7 8 The effect of pH on the adsorption of pH chromium by activated carbon was studied at pH values of 1 to 7. 0.5g of activated carbon was 750S40, 750S100, 800S30 suspended in 100 ml of solution which contained 80 Figure 9. Efect of pH on adsorption mg of chromium per liter. Different pH conditions were maintained by adding HCl and acetic acid- 3.2.4 Effect of contact time on Adsorption sodium acetate buffer. The adsorption of chromium Adsorption experiments were conducted as was determined after an equilibration time of one a function of contact time and the results are shown hour at a stirring speed of 200 rpm. in figure 10. The rate of Cr (VI) binding with pH influences the adsorption of Cr(VI) ions on the adsorbent was greater in the initial stages, then adsorbate as it affects the solubility of metal ions gradually decreased and remained almost constant and hence the electrostatic binding of ions. From after an optimum period. After 60 minutes the figure 9, it is evident that at lower pH between 2 and adsorption reaches an optimum value of 92%. This 3 the adsorption is maximum. This could be is because initially a large number of vacant sites are attributed to the high concentration of H+ ions at available for adsorption and after some time the lower pH values which neutralizes the negatively remaining sites may be difficult to occupy due to charged adsorbate Cr2O72- ions. The decrease in the repulsive forces between adsorbate ions on the solid adsorption efficiency at higher pH can be attributed and in the solution. Similar results have been to increase in the concentration of OH- ions which reported by other investigators. hinder the diffusion of Cr (VI) ions. Effect of time on Adsorption The process of adsorption of metal ions on the 30 adsorbent involves the binding of metal ions by Amount of Cr on adsorbate (mg) electrostatic forces of attraction. The surface of the 25 adsorbent is positively chargede and hence 20 negatively charged Cr2O72- ions are held by 15 electrostatic forces of attraction. It has been suggested that the mechanism for metal 10 adsorption is due to the acidic functional C=O 5 groups on the adsorbent surface. The presence of 0 oxygen functional groups make the adsorbent 0 50 100 150 200 250 surface negatively charged and therefore a repulsive time in minutes electrostatic interaction between the adsorbent and Figure 10. Effect of contact on adsorption the anion where as for a cation the negatively charged group enhances the electrostatic interaction 3.2.5 Effect of Stirring Speed with the negatively charged surface of the adsorbent The effect of the agitation of the mainly through carboxylic ligands. sorbent/sorbate system in chromium adsorption was According to the fig, the rates of adsorption are monitored at low, medium and high- agitation weak with low values of pH (<2). Between 2 and 3 speeds (80, 100, 120, 150, 200 rpm). The results are the rates of absorption increase rapidly. This is due shown in figure 11. to the surface charge of the metal, which is strongly 0.5 gm of adsorbent and 50 ml of the solution related to the pH of the solution. Maximum containing 100 mg/l of chromium at pH 3 was adsorption capacity is observed in the pH range 2 to agitated between 90 and 210 rpm. Maximum of 3. This indicates that the pH corresponds to the zero 97.77 % chromium removal was achieved at 200 369 | P a g e
  • 7. B. Veena Devi, A.A. Jahagirdar, M.N. Zulfiqar Ahmed / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.364-370 rpm. The effect of chromium adsorption on low and 1200H, 1500H and IRN97H, J. Hazard. Mater. high agitation speed was observed. An increase in 102 (2/3) (2003) 257–275. adsorption was observed from 66.66 % to 97.77 %, 6. D. Petruzzelli, R. Passino, G. Tiravanti, Ion when the agitation speed was increased from 90 to exchange process for chromium removal and recovery from tannery wastes, Ind. Eng. Chem. 200 rpm. Due to agitation, proper contact was Res. 34 (1995) 2612–2617. developed between metal ion in solution and the 7. D. Mohan, K.P. Singh, V.K. Singh, Trivalent binding sites, which promoted effective transfer of chromium removal from wastewater using low adsorbate ions onto the adsorbent sites. cost activated carbon derived from agricultural Effect of Stirring Speed waste material and activated carbon fabric cloth, J. Hazard. Mater. 135 (2006) 280–295. 120 8. C.P. Huang, M.H.Wu, Chromium removal by carbon adsorption, J.Water Pollut. Contr. Fed. 100 47 (10) (1975) 2437–2446. 80 9. C.P. Huang, M.H.Wu, The removal of % Cr removal chromium(VI) from dilute aqueous solution by 60 activated carbon, Water Res. 11 (8) (1977) 673– 679 40 10. C. Selomulya, V. Meeyoo, R. Amal, 20 Mechanisms of Cr(VI) removal from water by various types of activated carbons, J. 0 Chem.Technol. Biotechnol. 74 (2) (1999) 111– 0 50 100 150 200 250 122. Stirring Speed in rpm 11. S.J.T. Pollard, G.D. Fowler, C.J. Sollars, R. Figure 11. Effect of stirring speed on adsorption Perry, Lowcost adsorbents for waste and wastewater treatment: a review, Sci. Tot. Environ. 116 (1992) 31–52. 4. Summary and Conclusions 12. D. Mohan, K.P. Singh, Granular activated Activated carbon was successfully prepared carbon, in: J. Lehr, J. Keeley, J. Lehr (Eds.), by pyrolysis. The results indicated that the Water Encyclopedia: Domestic, Municipal, and adsorption capacity depends upon the pore size, Industrial Water Supply and Waste Disposal, surface area and temperature of activation of the Wiley/Interscience, New York,2005. activated carbon. At pH 3, the adsorption was found 13. N.K. Lazaridis, C. Charalambous, Sorptive to be maximum. The activated carbon can act as a removal of trivalent and hexavalent chromium good adsorbent for the adsorption of chromium from from binary aqueous solutions by composite alginate–goethite beads, Water Res. 39 (18) industrial effluents such as electroplating industries. (2005) 4385–4396. 14. S.Gueu, B.Yao, K.Adouby and G.Adoβ€”Heavy Acknowledgements Metals removal in aqueous solution by activated BVD and AAJ are thankful to the Principal carbons prepared from coconut shell and seed and management of Dr. AIT, Bangalore for shell of the palm treeβ€”Journal of applied encouragement and support. MNZA acknowledges Sciences 6(13); 2789-2793, 2003 the support rendered by the Principal and 15. Karuppanna Periaswamy and Chinnaiya management of HKBK College of Engineering, Namasivayam--Process development for removal and recovery of cadmium from waste Bangalore. water by a low cost adsorbent: Adsorption rates from equilibrium studiesβ€”Ind. Eng. Res. 1994, References 33, 317-320 1. D.E. Kimbrough, Y. Cohen, A.M. Winer, L. 16. Giles.C.H. and Nakhwa S.N.,--Studies in Creelman, C.A. Mabuni, Critical assessment of Adsorption.XVI-The measurement of specific chromium in the environment, Crit. Rev. surface areas of finely divided solids by solution Environ. Sci. Technol. 29 (1) (1999) 1–46. adsorptionβ€”J.Appl. Chem.,12,June, 1962, 266- 2. J.W. Paterson, Wastewater Treatment 273. Technology, Ann Arbour Science, Michigan, 17. Min Gyu Lee, Gyeougheam Yi, Byoung Joon 1975, pp. 43–58. Ahu and Felicity Roddickβ€”Conversion of Coal 3. S. Rengaraj, K.-H. Yeon, S.-H. Moon, Removal fly adh into zeolite and heavy metal removal of chromium from water and wastewater by ion characteristics of the productsβ€”Korean Journal exchange resins, J. Hazard. Mater. 87 (1–3) of Chem. Engg.β€”17(3), 325-331 (2000). (2001) 273–287. 18. Parinda Suksabye , Paitip Thiravetyan , 4. S. Rengaraj, K.-H. Yeon, S.-Y. Kang, J.-U. Lee, Woranan Nakbanpote , Supanee Chayabutr-- K.-W. Kim, S.-H. Moon, Studies on adsorptive Chromium removal from electroplating removal of Co(II), Cr(III) and Ni(II) by IRN77 wastewater by coir pithβ€”online publicationβ€” cation-exchange resin, J. Hazard. Mater. 92 (2) Elsevier,doi 10.1010-2006.07.18 (2002) 185–198. 5. S. Rengaraj, C.K. Joo, Y. Kim, J. Yi, Kinetics of removal of chromium from water and electronic process wastewater by ion exchange resins: 370 | P a g e