Preparation of sludge derived carbon with Fenton and NaClO activated and the application on the odor abatement Lou Ziyang Dr. Associate Prof. 2015-07-02
Content Background SBC preparation Characterization of SBC The adsorption capacity of MB The odorous removal capacity of SBC Conclusions 2
1. Background -sludge Sludge=35 M ton Waste water=46.5 B m 3 Bailonggang WWTP: 200 Million Ton/d 3
Waste activited sludge (WAS) Organic contents Pathogens Heavy metals Stabilization and Resource Pyrolysis of sludge and activated carbon 4
Activation additives ell membrane Cytoplasm Sludge Activation Carbonization SBC Cell wall nucleus Porous Activated methods: Physical method water stream, CO 2 Chemical method ZnCl 2, H 2 PO 4, KOH Physico-Chemical methods..
Macro-MW Organic matter Volatile Organic matter Porous Sludge Activation process Carbonization Process I:Fenton II: NaClO Sludge activated SBC 4NaClO + 2H 2 O 4NaOH + 2Cl 2 + O 2. 6NaOH + C 2Na+2Na 2 CO 3 + 3H 2
ph TS (mg/l) Characteristics of waste sludge VS (mg/l) TCOD (mg/l) SCOD (mg/l) STN (mg/l) STP (mg/l) 6.64~6.80 29.3~42.4 19.1~22.5 29.2~32.1 96.2~435.3 45.4~120.7 15.2~38.9 Raw Sludge Sludge Activation Sludge Precursor Carbon Wash Fig. the preparation of SBC Carbonization
2. SBC preparation 2.1 NaClO control 43m 2 /g Variations of BET of carbon and the activations (m 2 /g)
Characterization of SBC Sample BET (m 2 /g) V total (cm 3 /g) V micro (cm 3 /g) V micro / V total (%) Control sample 43 0.097 0.035 36 0.1KOH 56 0.158 0.046 29 0.3KOH 68 0.264 0.053 20 0.5KOH 263 0.456 0.158 35 0.7KOH 107 0.198 0.075 38 1.0KOH 93 0.165 0.057 35 0.1KCl 73 0.152 0.054 36 0.3KCl 63 0.158 0.048 30 0.5KCl 129 0.202 0.086 43 0.7KCl 211 0.404 0.133 33 1.0KCl 80 0.199 0.062 31 0.1NaClO 95 0.302 0.069 23 0.3NaClO 248 0.440 0.148 34 0.5NaClO 423 0.513 0.238 46 0.7NaClO 312 0.442 0.181 41 1.0NaClO 264 0.493 0.159 32
Variations of C, H, O distribution ratio a) control, b) KCl, c) KOH, d) NaClO
2.2 Fenton H 2 O 2 5% 347mg/g Effect of H 2 O 2 dosage on the iodine value Effect of H 2 O 2 dosage on the rate of change of VS and TS
Activation process H 2 O 2 /Fe 2+ ph 5:1 Low ph: 3 Fe 2+ +HO-OH { Fe 2+ -O-OH+H + } Fe 3+ -OH+HO Fe 3+ ----O----OH Fe(Ⅳ)= O+H 2 O Reaction T H H+ Fe 3+ +H 2 O Solid content 2h 1.0% High ph Fe 2 Fe 3+ +OH - Fe(OH) 3 Effect of activation conditions on the iodine value
Carbonization process T t 600 2h Heating rate 10 /min Effect of carbonization conditions on the iodine value
Chemical properties of sludge-based carbon Control activation Yield(%) 32.3 35.7 Ash content(w%) 52.8 60.9 C(w%) 35.6 32.3 N(w%) 1.75 1.57 S(w%) 0.44 0.56 H(w%) 0.99 0.83 O(w%) 14.5 17.3 Ash analysis(weight% in the ash) Fe 18.9 49.7 Si 32.1 25.6 Al 17.6 14.1 Cu 0.25 1.18 Ca 0.41 0.68 Mg 0.43 0.64 Zn 0.09 0.01 Cr 0.02 0.04 Na 0.19 0.31
Control Activation TGA 6Fe 2 O 3 +C 4Fe 3 O 4 +CO 2 TG-DTG curves of sewage sludge with and without activation Fe 3 O 4 +2C 3Fe 0 +2CO 2 0~120, water evaporation 0~120, water evaporation 200~450, Aliphatic Organic 250~400, low MW material compounds 400~520, Carbohydrate etc. 450~650, protein 600~800
2.3 Summary Surface Characteristics of porous structure of SBC BET (m 2 g -1 ) V total (cm 3 g -1 ) V micro (cm 3 g -1 ) V micro / V total (%) Control 38.7 0.066 0.004 6 SBC-Fenton 253 0.184 0.078 42 SBC-NaClO 423 0.513 0.238 46.39 The element distribution in SBC SBC-Control SBC-NaClO SBC-Fenton Yield(%) 32.3 31.2 35.7 Ash content(w%) 52.8 50.4 60.9 C(w%) 35.6 37.51 32.3 N(w%) 1.75 1.65 1.57 S(w%) 0.44 0.72 0.56 H(w%) 0.99 3.30 0.83 O(w%) 14.5 15.77 17.3 Fe(w% in the ash) 18.9 20.1 49.7
a b c d SEM image of SBC, a) SBC-control and b) SBC-NaClO; c) SBC-control and d) SBC-Fenton
(a) Dried sludge and SBC-control, (b)sbc-naclo (c)sbc-fenton FTIR spectra scan of SBC with and without activation
2.4 Adsorption process-naclo The removal efficiency of SBC by MB Saturated extend of adsorption MB: 68-109 mg/g The removal of MB by SBC
Optimum process-sbc-fenton Adsorption equilibrium of MB(A) and MO(B) of different SBC-Fenton ([ 亚甲基蓝 ]=[ 甲基橙 ]=100mg/L;[ 活性炭 ]=1g/L; 温度 =25 ;ph=7) Saturated extend of adsorption MB: C-44.9mg/g, A-67.3mg/g Saturated extend of adsorption MO: C-20.1mg/g, A-46.1mg/g
Adsorption capacity Initial ph T Effect of different adsorption conditions of MB
Parameters of adsorption models of dye on SBC-Fenton Isotherms Parameters Methyl blue Methyl orange q m (mg/g) 71.5 57.7 Langmuir K l (L/mg) 0.0148 0.0844 R 2 0.995 0.965 Freundlich Kf(mg/g) 56.6 24.9 1/n 0.0534 0.216 Effective absorption Fit for Langmuir equation R 2 0.661 0.826 The change of R L as a function of C 0 on the dye adsorption by carbon
2.5 Adsorption process-naclo For NH 3 removal- SBC NaClO Sample b (K/min) T p (K) E d (KJ/mol) A (10 13 min -1 ) NaClO KCl Kinetic parameters of activated carbon adsorption of ammonia 5 365 10 383 15 385 5 366 10 386 15 401 The isothermal equation of NH 3 adsorbent using SBC-NaClO 93 0.54 95 0.55
For H 2 S removal influence dosage of SBC- Fenton on H 2 S removal rate (H 2 S:N 2 (v/v)=5:5, T=25, vibration rate=100rmp) 5ds, 10g SBC-Fenton, removal rate of 44.2%
Injection volume of H 2 S The influence of H 2 S concentration on H 2 S removal rate (AR:SBC=7:3, T=25,vibration rate=100rmp) H 2 S:N 2 =2:8 and 1:9, total H 2 S removal rate reach to 100%
4. Conclusions Higher quality SBC was prepared with the activators of Fenton and NaClO. Both of them contributed to the increase of BET and V micro / V total, which were 6.7 and 11 times higher than SBC-control Activation process was necessary to applied to improve the SBC quality by destroying of cell wall barrier and decompose of the complex macro compounds. The intermediate products of Fe and NaOH contributed to SBC-activated structure The saturation adsorption capacity could be around 71.5, 67.8 and 33.1 mg g -1 in SBC-Fenton, SBC-NaClO and SBC-control using MB
Thank You!
Postdoctoral/Ph.D Position Shanghai JiaoTong Univ., China Lou Ziyang: louworld12@sjtu.edu.cn; +8613564381973 Research field Solid waste treatment and resource GHG accounting (LCA) and reduction methods Advanced treatment of industry waste and leachate Upconversion photocatalysts synthesis and its application