“ DYNAMIC and EQUILIBRIUM STUDIES on ADSORPTION of

Cr(VI) IONS onto BINARY BIO-POLYMERIC BEADS of

CROSS LINKED ALGINATE and GELATIN “

J.Bajpai
Bose Memorial Research Laboratory, Department of Chemistry, India
accepted 30 January 2004

0505-7323 Kemal ARAT

Cr(VI) Applications

The major industries including water pollution by chromium are:

• mining,
• leather tanning,
• steel fabrication
• textile dyeing,
• electroplating,
• aluminum conversion coating operations,
• plants producing industrial inorganic chemicals and pigments.
 It is applied for example for metal surface refinery and in
alloys. Stainless steel consists of 12-15% chromium.
Chromium metal is applied worldwide in amounts of
approximately 20,000 tons per year. The metal industry
mainly discharged trivalent chromium. Chromium(VI) in
industrial wastewaters mainly originates from leather tanning
and painting.
Chromium compounds are applied as pigments, and 90%
of the leather is tanned by means of chromium compounds.
Wastewater usually contains about 5 mg/L of chromium.
Chromium may be applied as a catalyser, in audio and video
production and in lasers. Chromite is the starting product for
inflammable material and chemical production.
Cr(VI) is a toxic ion that causes:
• Cancer
• Epigastric pain
• Nausea
• Vomitting
• Severe Diarrhea
• Hemorrhage
Cr(VI) ion removal operations:
• Filtration
• Chemical precipitation
• Ion exchange adsorption
• Electro deposition
• Membrane systems
• Evaporation
• Reverse osmosis
• Biosorption
Alginate:
 Structure
 Properties Gelatin:
 Uses  Structure
 Properties
 Uses
Experimental materials :
• Sodium alginate
• Gelatin (acid processed)
• Potassium dichromate (absorbate-K2Cr2O7)
• Calcium chloride (cross linking agent for alginate)
• Gluteraldehyde (cross linking agent for gelatin)
• Triple distilled water
etc…
Preparation of bio-polymeric beads

Sodium alginate (0.4g)

Gelatin (1g)
CaCI2(0.05M) gluteraldehyde

Gelatin-alginate beads overnight

24 hours

Crosslinked Gelatin-alginate beads

Adsorption experiment

0.2 g bio-polymeric beads

3 hours

20 ml 245 mg/dm3
K2Cr2O7

pH=6.0
0.001 M KNO3 ionic strength
Results :
 Langmuir Isotherms
 Freundlich isotherms
 Modified freundlich isotherms
 Lagergreen equation
 Adsorption measurement with time intervals
Langmuir isotherms

Ce=equilibrium concentration

K=adsorption coefficient

a=coefficient

as=adsorped amount
at saturation
Freundlich isotherms
Modified Freundlich isotherms
Lagergreen equation
 Freundlich isotherm

120

100
Absorbed Cr(IV) mg/g x102

80

60

40

20

0
0 10 20 30 40 50 60 70

Ce (mg/dm3) x103
Adsorption measurement with time intervals

C,C0 = Concentration

k1 = rate constant
t = time

Lagergreen equations
Factors affecting adsorption :
 Solid to liquid ratio
 Effect of pH
 Effect of salt
 Ion effect
 Effect of temperature
 Effect of beads composition
Solid to liquid ratio
Inaccesable beads surface effect
Effect of pH
Effect of salt
Ion effect
Effect of temperature
Effect of beads composition
Conclusion

Can be an effective adsorbent to remove Cr(VI) while;

 Solid to liquid ratio : 0.05 g/ml
 pH : 8.9
 no salt added
 no ion added (especially big ions)
 temperature is 25-35 C
 increasing sodium alginate, gelatin or gluteraldehyde conc.
 no high conc. of gelatin!
Disadvantages of other techniques
 Ion exchange resins are derived from petroleum
 Chemical precipitation makes sludge
 Reverse osmosis and filtration removes Ca,Na,Mg,K (no selectivity)
 Evaporation is required more energy
 Reusable biomaterials have to be investigated
Adsorbant materials Adsorbated ion Amount (mg/g) Time
chitosan Cr(VI) 27.5 mg/g 2h
Lentinus Sajor Caju
Cr(CI) 25 mg/g 4h
(fungus)
Sorel’s cement
(Magnesium Cr(VI) 21.41 mg/g 15 min
oxychloride)
wool Cr(VI) 5 - 13.1 mg/g 2h
Activated Carbon Cr(VI) 3.46 mg/g 3h
beads Cr(VI) 0.8 mg/g 2h

beads Cr(VI) 0.8 mg/g 2h

beads Ni(II) 3.15 mg/g 2h

Graphical representation for Ni & Cr adsorption

In Turkey leather tanning regions
 İstanbul,Tuzla
 İzmir,Menemen
 Niğde,Bor
 Bolu,Gerede
 Çorlu,Isparta,Uşak

In Turkey 600 tons of leather processed in a day. After processing of 1

kg leather 30-40 kg waste water occurs.
In outflow waste water at leather tanning containing about 3000-
6000 mg/L.
Chromium recovery made in Germany,France,Italy,South America and
Pakistan.
According to the economic aspects, the investment cost of the waste
water treatment plant can be recovered in about 3 years.
Granulated Activated Carbon used in adsorption and Alüm is used for coagulation
Thanks for your care &
listening!
References
1. Selective adsorption of chromium(VI) in industrial wastewater using low-cost
abundantly available adsorbents, “Advances in Environmental Research 6 (2002)
533-540”
2. Removal of Cr(VI) from aqueous solution by adsorption onto activated carbon,
“Bioresource Technology 80 (2001) 87-89”
3. Binary Biopolymeric Beads of Alginate and Gelatin as Potential Adsorbent for
Removal of Toxic Ni2+ Ions: A Dynamic and Equilibrium Study, “Published online in
Wiley InterScience (www.interscience.wiley.com)”
4. Deri Atıksularının Arıtımında Kimyasal Arıtma ve Adsorpsiyon Yöntemlerinin
Uygulanması,” Fırat Univ. Journal of Science 21 (2), 95-101, 2009”
5. Recent developments in polysaccharide-based materials used as adsorbents in
wastewater treatment,” Prog. Polym. Sci. 30 (2005) 38–70”
6. Removal of chromium(VI) from wastewater using Sorel’s cement, “Journal of
Radioanalytical and Nuclear Chemistry, Vol. 269, No.1 (2006) 135–140”
7. Cr(VI) biosorption from aqueous solutions using free and immobilized biomass of
Lentinus sajor-caju: preparation and kinetic characterization, “Colloids and
Surfaces A: Physicochem. Eng. Aspects 253 (2005) 203–211”
8. DERİ SANAYİNDE KROMUN GERİ KAZANILMASI VE ÜRETİMDE TEKRAR
KULLANILMASI, [email protected]
9. Electrocoagulation removal of Cr(VI) from simulated wastewater using response
surface methodology, “Journal of Hazardous Materials 172 (2009) 839–846”
10. Continuous electrodeionization for removal and recovery of Cr(VI) from
wastewater, “Separation and Purification Technology 67 (2009) 123–126”
11. Alginate Gel Based Adsorbents for Heavy Metal Removal,”United States Patent,
Patent no: US 6,989,102 B1; Jan 24,2006”
Gelatin Properties:
 is a translucent, colorless, brittle, nearly tasteless
solid substance
 forms a solution of high viscosity in water derived
from the collagen inside animal‘s skin and bones
 can be dispersed in a relatively concentrated acid
Gelatin uses:
 marshmallows, jams, yoghurt, cream cheese, margarine
 Gelatin is one of the few foods that cause a net loss of
protein if eaten exclusively. In the 1960s, several people died
of malnutrition while on popular liquid protein diets.
 shells of capsules
 it is used to hold silver halide crystals in an emulsion in
virtually all photographic films and photographic papers
Gelatin structure:
 gelatin is 98-99% protein by dry weight
 The approximate amino acid composition of gelatin is: glycine
21%, proline 12%, hydroxyproline 12%, glutamic acid 10%,
alanine 9%, arginine 8%, aspartic acid 6%, lysine 4%, serine
4%, leucine 3%, valine 2%, phenylalanine 2%, threonine 2%,
isoleucine 1%, hydroxylysine 1%, methionine and histidine
<1% and tyrosine <0.5%
Alginate structure:

Molecular formula (C6H8O6)n

Molar mass 10,000 - 600,000
Appearance white to yellow, fibrous
powder
Density 1.601 g/cm3
Acidity (pKa) 1.5-3.5
Alginate Properties:
 is an anionic polysaccharide distributed widely in the cell
walls of brown algae
 forms a viscous gum with water
 In extracted form it absorbs water quickly; it is capable of
absorbing 200-300 times its own weight in water
Alginate uses:
 is useful as an additive in the manufacture of paper and
textiles.
 is also used for waterproofing and fireproofing fabrics, as a
gelling agent.
 for thickening drinks, soups and jellies
 as a detoxifier that can absorb poisonous metals from the
blood