. ABSTRACT......... 1 1.1... 1 1.1.1... 1 1.1.2... 2 1.2... 3 1.2.1... 3 1.2.2... 5 1.2.3... 7 1.3... 8 1.3.1... 8 1.3.2... 10 1.4... 11... 13 2.1... 13 2.1.1... 13 2.1.2... 14 2.2... 15 2.2.1... 15 2.2.2... 16 2.2.3... 16 2.2.4... 16 2.2.5... 17 2.3.6.. 18...18 3.1... 18 3.2... 20 3.2.1 ph... 20 3.2.2... 21 3.2.3... 22 3.3... 23 3.4... 24 3.5... 27 VII
...27 4.1...27 4.1.1...28 4.1.2...28 4.1.3...29 4.2...30 4.2.1...30 4.2.2...31 4.2.3...32 4.3...32 4.4...34 4.4.1.......35 4.4.2... 36 4.5... 37...38 5.1 FTIR...38 5.2 XPS 40 5.2.1 XPS... 41 5.2.2 XPS...41 5.2.3.42 5.3 Ca 2+ Mg 2+...43 5.4...43...44 6.1...44 6.1.1.44 6.1.2 ph 45 6.1.3.46 6.2...47 6.2.1.....47 6.2.2.51 6.2.3...51 6.3...52...53...55 1...59 2...62...65 VIII
biosorption 0-100ppm, 114% ph ph 4.5 25~30 1.58~2.03mm 13h 50mg/L 15.2 mg/g Freundlich Freundlich 30 min 13h - I -
7% X- 1.58-2.03mm ph 4.5 27 Freundlich - II -
ABSTRACT ABSTRACT In company with the fast development of the metal plating, mining, dying, petrochemical and battery industries, a great deal of waste water containing the excessive dangerous heavy metal ions, such as lead and cadmium ions, has been discharged into the environment and would engender the great harm to the environmental ecology and the human health. In this paper, biosorption method was used to remove the cadmium and lead ions from the solution. The biomass materials used in this study were the mycelial pellets of Phanerochaete chrysosporium. These biosorbents could be directly used to adsorb the heavy metals from the solution. Another advantage of these biosorbents is that the subsequent solid-liquid separation procedure filtration- is very easy and simple to be conducted without the need of centrifugation. Firstly, The properties of cadmium adsorption by Phanerochaete chrysosporium in the form of mycelial pellets were investigated. Pretreatment of the biomass by formaldehyde cross-linking and subsequent boiling with alkaline could considerably improve the adsorption capacity compared to other sorts of pretreatments. Bioremoval of cadmium ions using these nonliving microorganisms was affected by several factors, such as temperature, ph, the pellets diameter. The experimental results indicated that the optimum adsorption conditions were the solution ph 4.5, temperature 25-30 0 C, and the pellet diameter in the range of 1.58-2.03 mm. On these conditions, the biosorption uptake capacity was up to 15.2 mg per cell dry weight. The adsorption equilibrium on the optimum adsorption conditions was studied and adsorption isotherm was developed. It was shown that the adsorption - III -
ABSTRACT equilibrium data fitted Freundlich adsorption model. Biosorption kinetic results showed that the biosorption involved two phases. The first phase was very quick and took place in the initial thirty minutes, in which most of cadmium ions finally adsorbed by the biomass were sequestered. The other was a very slow process and the adsorption uptake capacity increased very slowly. After thirty hours, the adsorption equilibrium reached. Secondly, an adsorption particle model was proposed to analyze the biosorption kinetic behavior of the mycelial pellets. In this model, both the intraparticle diffusion and the external mass transfer were considered and a nonlinear partial differential equation was built. Combined with the boundary and initial conditions, this differential equation could be solved by the finite difference numeric method. The fact that the simulation curve and the experimental data points were in a good agreement with acceptable errors which were lower than 5% demonstrated that this model could describe this biosorption process. Thirdly, The mechanism of cadmium adsorption by the pretreated biomass of Phanerochaete chrysosporium was studied by using experimental techniques such as Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and chemical modification experiments. Experimental evidences indicated that the nitrogen-containing groups and the oxygen-containing groups are involved in the compellation with cadmium in the adsorption process. In addition, the increase of the quantities of calcium and magnesium ions showed that the ion exchange mechanism also contributes to the biosorption of cadmium by this biomass. Finally, Biosorption of lead and simultaneous biosorption of cadmium and lead ions by Phanerochaete chrysosporium from the binary mixtures was described. Experimental results indicated that the optimum lead adsorption conditions by - IV -
ABSTRACT Phanerochaete chrysosporium were the solution ph 4.5, temperature 27 0 C. Also, Freundlich adsorption equilibrium model was developed. In addition, Effects of the presence of one metal ion on the biosorption of the other metal were investigated in terms of equilibrium isotherms and adsorption rate. The uptake capacity and adsorption rate of one metal ion was reduced by the presence of the other metal ion. Furthermore, biosorption of lead ion by the biomass of Phanerochaete chrysosporium is preferential to the cadmium ion. Keywords: biosorption, cadmium, lead, simultaneous, particle model, mechanism, Phanerochaete chrysosporium, kinetics. - V -
C 0,C A0 mg/l(ppm) C A mg/l(ppm) C AL mg/l(ppm) C AS mg/l(ppm) Ce mg/l(ppm) q mg/g R m g/l d r P mm F k,n Freudlich q max Langmuir b Langmuir De cm 2 /s K m t min h T K ε p Np ρ s g/l y,x,τ V ml - VI -
1.1 1.1.1, 3~9 1947 [1] 10~20min 30mg ( - 1 -
) [2-3] 22-33 g/l, 5mg/L 500-700mg/L 1000mg/L mg/l mg/l 1.1.2 ( ) ( ) [2-3] Ruchhoft [4] ( ) Pu 239 [5] Kratochril [6] - 2 -
( ) ( ) [7] [8] [9] [10] [11] [6] 1 100mg/L [6] 1.2 1.2.1 [12] [13] [14] [15] [16] [17] Holan [8] Tsezo [17] X - 3 -
- Ashkenazy [18] [19] [20] (1) (2) (3) ( ) [21] ( ) Matin [22] - 4 -
1.2.2 1.2.2.1 Langmuir Freundlich [23-25] Langmuir Freundlich ph Schiewer [26] - - Langmuir ph Crist [27] Langmuir Langmuir King [28] ph Ting [29] + 1-1 - 5 -
1-1 Langmuir [23-25] q/qmax=kc/(1+kc) qmax,k Freundlich [23-25] q=kx 1/n K,n Schiewer [26] - q=0.5ctkcm[m] 0.5 /{(1+KCH[H]+KCM[M] 0.5 )+ KCH,KCM,KSH,KSM 0.5StKSM[M] 0.5 /(1+KSH[H]+KSM[M] 0.5 )} Crist [27] KEX={[Ca 2+ ][MX2]}/{[M 2+ ][CaX2]} [Ca 2+ ] [MX2] [M 2+ ],[CaX2] King [28], Ting [29] + M=KC1 dx[c2]/dt=xr1{(ct-c2) (X+R2(K+X))}/(K+X) K,R1,R2 C,S X M R1 CH SH R2 CM CM0.5,SM0.5 C1 t C2 1.2.2.2 [30], Sag [20] Langmuir 0.996 Kong [31] Langmuir, Langmuir Ki Ki Langmuir Langmuir Langmuir Kong [32] Langmuir - 6 -
Kong [31] Decarvalho [33] Kong [32] 1-2 1-2 Langmuir [30-31] q(mi)=(qmax/ki)cf[mi]/{(1+(1/k1)cf[m1]+ (1/K2)Cf[M2]} K1,K2,qmax q(mi)=(qmax/ki)cf[mi]{1+(k1/k)cf[m2]}/{(ki [31] +Cf[M1]+(K1/K2)Cf[M2]+2(K1/K)Cf[M1]Cf[M2]} K1,K2,K,qmax K3 q(mi)=(qmax/ki)cf[mi]/{(1+(1/k1)cf[m1] + [31] K4 (1/K2)Cf[M2] } K1,K2,K3,K4,qmax q(mi)=(qmax/ki)cf[mi]/{(1+(1/k1)cf[m1]+ [32] Langmuir (1/K2)Cf[M2]+(1/K3)Cf[M3]} K1,K2,K3,K4,qmax King [27] M Cf q qmax Ki 1.2.3 ph [34-35] [20,36-37] - 7 -
1.3 1.3.1, 1.3.1.1, 1-1 - 8 -
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