40 8 2012 8 JOURNAL OF THE CHINESE CERAMIC SOCIETY 1197 Vol. 40 No. 8 August 2012 ( 230009) ph 3 h (< 16 mg/l) (< 33:1) (> 3 h) (> 16 mg/l) (> 33:1) Al Fe TQ170.9 A 0454 5648(2012)08 1197 07 2012 07 30 13:23:34 http://www.cnki.net/kcms/detail/11.2310.tq.20120730.1323.201208.1197_019.html Removal of Nitrite in Wastewater with Goethite Reduced by Hydrogen CHANG Dongyin CHEN Tianhu LIU Haibo QING Chengsong XIE Qiaoqin ZOU Xuehua LIU Yu (Hefei University of Technology, School of Resources and Environmental Engineering, Hefei 230009, China) Abstract: Reduced iron powders were obtained via the reduction of natural goethite and synthetic goethite by hydrogen. Effects of reaction time, ph value, initial nitrite concentration on the removal rate of nitrite by two kinds of reduced iron powders were investigated. The results show that nitrite removal rate by the reduced iron powder prepared by reduction of synthetic goethite is greater than that reduction of natural goethite when reaction time is < 3 h, initial nitrite concentration is < 16 mg/l and ratio of iron-to-nitrite is < 33:1. However, nitrite removal rate by the reduced iron powder prepared from natural goethite is greater than nitrite removal rate by the reduced iron powder prepared from synthetic goethite when reaction time is > 3 h, initial nitrite concentration is > 16 mg/l and ratio of iron-to-nitrite is > 33:1. The substitution of aluminum in the structure of goethite affects the formation of passivation film on iron powder, increasing the stability of iron powder for the removal of nitrite and the nitrite removal efficiency. Key words: synthetic goethite; natural goethite; reduced iron powder; nitrite removal rate; aluminum substitution [1] 1 mg/l 0.1 mg/l [2] (GB 7549 2006) 1mg/L [1] [3] [4] Wang [5] NO 2 H 2 O 2 NH + 4 NO 2 H 2 O 2 [6] NO 2 2012 01 07 2012 04 02 (20110111112003) (1985 ) (1962 ) Received date: 2012 01 17. Revised date: 2012 04 02. First author: CHANG Dongyin (1985 ), female, Doctorial candidate. E-mail: changdongyin127@163.com Correspondent author: CHEN Tianhu (1962 ), male, Professor. E-mail: chentianhu168@vip.sina.com
1198 2012 Hoorold [7] (5%) (1.25%) Al 2 O 3 (98%) 100 mg/l (ph 6 8) [8] 100 1 h NO 2 NH + 4 NO 2 33 ( ) [1] [1,9] [10] Mike [11] Kuenen [12] Munce [13] Delft SHARON (single reactor for high activity ammonia removal over nitrite) [14] NH 3 NH + 4 NO 2 NO 3 N 2 Yong 1964 [15 16] NO 2 N 2 NH 3 /NH + 4 [17 18] [19] ph 1 1.1 0.154 0.125 mm X (XRF) 74%Fe 2 O 3 16.5%SiO 2 0.8%Al 2 O 3 Cu Zn Mn Ca 7.7% 20 g 150 ml/min 250 350 450 550 650 6 h HGNI NGNI 1.2 D/max-rB X Cu K α 40 kv 100 ma 4( )/min 2θ = 10 70 Quantachrome Nova 3000e BET-N 2 1800 X (XRF) 40 kv 95 ma 250 ml ph 120 r/min 5 h 1 h 1 N (1 ) [18]
1199 2 2.1 XRD 1 6 h XRD 1 ( XRF 16.5%) 250 6 h 450 250 450 550 Fe 0 Fe 0 Fe 3+ Fe 0 Fe 2+ XRD Fe 3+ 250 Fe 2+ Fe 2+ Fe 0 550 [20 21] 1 XRD Fig 1 XRD patterns of natural goethite reduced at different temperatures 6 h XRD 2 2 2 250 6 h 350 450 Fe 0 Fe 3+ 450 Fe 0 650 Fe 0 450 550 XRF [22 23] 2 XRD Fig 2 XRD patterns of synthetic goethite reduced at different temperatures Al Fe [24] XRD 550 6 h 2.2 SEM 3a SEM EDS Al Al Fe XRD ( 1) Al Al Fe [24 28] 3c 550 6 h SEM 3c XRD 20 nm 4a SEM 40 nm 4c 550 6 h SEM 4c BET 550 6 h 14.5 m 2 /g 4.9 m 2 /g Fe 0 Al
1200 2012 3 SEM Fig. 3 SEM images of natural goethite and reduced iron powder Al 2.3 20 mg/l 80:1 ( 5) 4 SEM Fig. 4 SEM images of synthesis goethite and reduced iron powder 5 HGNI NGNI 6 h 74.9% 90.2% 1 h 33.8% 54.6% 4 h HGNI NGNI 5 h HGNI 5 3 h HGNI
1201 6 HGNI NGNI 5 h 75.3% 89% 15 mg/l HGNI 20 mg/l NGNI 16 mg/l HGNI NGNI 16 mg/l NGNI HGNI NGNI 5 Fig. 5 Comparison experiment of reaction time on nitrite removal rate ph =7; Initial concentration of nitrite c 0 was 20 mg/l; Mass ratio of iron powder to nitrite was 80:1; NGNI Natural goethite nano iron; HGNI Hydrothermal goethite nano iron. NGNI 3 h HGNI NGNI HGNI NGNI Al Fe NGNI HGNI [29] Al Fe Al Al [19 20,24 25] Al Al Al HGNI NGNI NGNI HGNI 2.4 (ph = 7) 80:1 5 h (5 10 15 20 25 30 mg/l) 6 Fig. 6 Effects of initial concentration of nitrite on nitrite removal rate ph = 7; Mass ratio of iron powder to nitrite was 80:1; Reacted for 5 h. 2.5 ph 20 mg/l 80:1 5 h ph (1 2 4 6 8) ( 7) 7 ph (95% ) ph HGNI NGNI 72% 84% ph ph ph H + ( ) ph ph 2
1202 2012 7 ph Fig. 7 Comparison of effect of various ph values on nitrite removal rate Initial concentration of nitrite c 0 was 20 mg/l;mass ratio of iron powder to nitrite was 80:1; Reacted for 5 h. Al ph ph Al ph 4 NGNI HGNI NGNI ph XRF EDS Al NGNI 2.6 20 mg/l 5 h (5:1 10:1 20:1 40:1 80:1 100:1) 8 100:1 HGNI NGNI 75.3% 89% HGNI 30:1 75% NGNI 40:1 90% 8 Fig. 8 Effects of iron-to-nitrite ratio on nitrite removal rate ph = 7; Initial concentration of nitrite c 0 was 20 mg/l; Reacted for 5 h. 33:1 NGNI HGNI (> 33:1) NGNI 3 XRD XRF SEM EDS Al Al Al 3 h 15 mg/l ph 2.3 8 30 85% [1],,,. [J]. ( ), 2002, 23(4): 102 106. YANG Jiashu, WANG Liucheng, LI Guoshun, et al. J Zhengzhou Univ: Eng Sci, 2002, 23(4): 102 106. [2]. [J]. ( ), 2001, 14(3): 16 20. HE Xuehua. J Ningbo Univ: NSEE, 2001, 14(3): 16 20. [3],,,. [R]. :, 2001. SONG Chengying, ZHANG Liying, YANG Jiashu, et al. Zhengzhou City Groundwater of Treating Nitrite (in Chinese). Zhengzhou: Science and Technology Committee of Henan Province, 2001. [4],,. UV-H 2 O 2
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