Master s Thesis SUBMITTED FOR M.Eng. DEGREE IN CHEMICAL ENGINEERING Wet Oxidation Process of High-Concentration Dyeing Wastewater in a Commercial Dyei

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讪久瓜郑
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1 UDC Professor Po-Lock Yue

2 Master s Thesis SUBMITTED FOR M.Eng. DEGREE IN CHEMICAL ENGINEERING Wet Oxidation Process of High-Concentration Dyeing Wastewater in a Commercial Dyeing Machine Yuelin Hu Supervised by Prof. Qingbiao Li (XMU) Prof. Po-Lock Yue (HKUST) Associate Prof. Guohua Chen (HKUST) Department of Chemical Engineering Institute of Chemistry and Chemical Engineering Xiamen University(Amoy University), P.R.China JUNE 2003

3 CAS-85-4 Sampad-3 WPO CWPO CAS-85-4 WPO 100% ph % 0.5g/L 90min (4 ) CODcr(42.74mg/L) GB CODcr 150 mg/l 2h CODcr 99.9% 90% 2.5g/L KN-R 3h 99.9% CODcr 85% 90min (39 ) GB Sampad-3 CWPO 100% ph 3 60 Fe 2+ / H 2 O t=0min t=30min 100% 0.5g/L CODcr 400 mg/l t=0min 5min CODcr 65.96% 99.71% CODcr I

4 140.32mg/L GB WPO CWPO CWPO WPO CODcr >1000 mg/l CWPO +CWPO+ : II

5 Abstract Abstract The printing and dyeing wastewater is always hard to be treated efficiently because of its complicated nature. The available options for the treatment of such wastewater can be grouped as physical methods, chemical methods and biological methods. But it is rather pitiful to find that those early systems cannot treat the effluent perfectly any more due to more and more pollutants recalcitrant to be biodegraded going into the effluent. Among the new methods developed, more attentions are paid to various Wet Oxidation processes because of their obvious advantages, which include fast oxidation rate, no further pollution and less land area required and so on. The main purpose of this research is to find a way to treat dyeing wastewater online without going to waste treatment department for further operation. In this thesis, Wet Peroxide Oxidation (WPO) and Catalytic Wet Peroxide Oxidation (CWPO) were employed to treat dyeing effluent (simulated dyeing wastewater or true wastewater). Two commercial dyeing machines were used as the reactors for some commercial reasons. The main research results were listed as follows. When CAS-85-4 Air Pad Package dyeing machine was used as the reactor in the WPO process, the preferable reaction conditions were: initial ph 3.0, at 130, the highest power of circulation pump and the total H 2 O 2 calculated injected at zero time. For 0.5g/L of KN-R (Reactive Brilliant Blue) solution, the ultimate color removal efficiency was higher than 99.9% and the CODcr removal efficiency was about 90% after being treated for 120 min. And with 90 min treatment, the CODcr and color of this treated solution had met the requirements in GB For 2.5g/L of KN-R solution, more than 99.9% of the color was removed and about 85% of the CODcr was reduced after being treated for 180 min. In addition, the color was also acceptable after this solution was treated for III

6 Abstract 90 min. When Sampad-3 Package dyeing machine was used as the reactor in the CWPO process, the optimum reaction conditions were: initial ph 3.0, at 60, the highest power of circulation pump, 0.05 of Fe 2+ / H 2 O 2 (molar ratio), the total H 2 O 2 calculated injected for twice at t=0min and t=30min respectively, the total catalyst (FeSO 4 7H 2 O) injected for once at t=0min. But for the low-concentration dyestuff solution (CODcr < 500 mg/l), it seemed better to add the total amount of H 2 O 2 and FeSO 4 7H 2 O required into the reaction system at t=0min. For 0.5g/L of KN-R solution (CODcr 400mg/L), the color removal efficiency and CODcr removal efficiency reached 99.71% and 65.96% respectively with only 5 min treatment, which already made this treated solution meet the requirements in GB It was also found that CWPO (FeSO 4 7H 2 O used as catalyst) process was the better option to treat dyeing wastewater than WPO process. And the reactive dyestuffs (brilliant blue, yellow, red and black) were easier to be oxidized by CWPO (or WPO) than the disperse dyestuffs (red and black). For the high-concentration dyeing effluent, the effective pre-treatment (or post-treatment) was required to be combined with CWPO process. And the flocculation process was testified to be a good alternative. The involvement of dyeing additives was helpful to the oxidation of simulated KN-R solution and simulated disperse dyestuff wastewater when they were treated with CWPO. In addition, the integrated process such as flocculation +CWPO + flocculation, was found better for the treatment of true dyeing effluent, especially for the high-concentration dyeing effluent. Key words: printing & dyeing wastewater, wet peroxide oxidation, dyeing machine IV

7 SCWO WAO CAS Sampad CODcr V

8 2.4.3 ph X n Y n ph WPO CWPO Fe 2+ /H 2 O ph Fe VI

9 4.2.3 CWPO CWPO CWPO I II VII

10 [1,2] BOD COD SS PVA BOD COD BOD 200 mg/l BOD COD SS 3% ~ 5% ph 12 ~ 13 BOD COD SS COD BOD SS COD BOD [3] 1

11 2 [4] [6] BOD mg/l [5] COD 93%~95% BOD 95%~96% 27.5% [7] [8] [6] [9] [4] COD

12 [6] PAC [5] H 2 O 2 /UV O 3 /UV O 3 / H 2 O 2 /UV UV/TiO 2 [10] CO 2 H 2 O [5] 75%~95% COD [11] 50%~70% COD COD [5,12] ACF [13] TOC [14] TOC ACF 15V ph=6.0 60min CODcr 62% ~85% 95%~100% 3

13 4 [15] [5,16] COD 70% ~ 90% 50% [17] BOD 5 80% COD [18] [5] [3] PVA [18,19] PVA 80 % PVA 75%~90% [5] [3] SBR COD 2000mg/L [5] - PVA ph [18,20] PVA

14 IMBRs [21] IMBRs [22] [23] COD MBAS CTAS [23] TOC / + / + COD [5] PVA COD [5] COD 70% 50% [5] 5

15 (Wet oxidation WO) (398 K~593 K) (0.5 MPa~20MPa) CO 2 H 2 O [24,25] (Catalytic Wet Oxidation CWO) Wet Air Oxidation WAO Wet Peroxide Oxidation WPO Strehlenert [26] 453K Hanglin Stauf [27] WAO 403K 0.2 MPa 1954 Stora KopParbergs BA [28] Sterling Drug Inc. [29,30] 1958 Borregaard WAO [24] 1958 Zimmermann [31] WAO 423K ~ 623K 5 Mpa ~20 MPa COD 90 % 1960 WAO WAO Zimpro WAO 1970 WAO [32] 6

16 [33] 1992 Zimpro CWAO [32] [24] WAO [34] 50% WAO 20 [35] [36] [37] [38] Phull [39] 90%~99% CODcr 20,000 mg/l WAO CODcr WAO [40] [24,32] BOD 5 CODcr BOD 5 CODcr [41] [24,41] N 2 CO 2 7

17 Degree papers are in the Xiamen University Electronic Theses and Dissertations Database. Full texts are available in the following ways: 1. If your library is a CALIS member libraries, please log on and submit requests online, or consult the interlibrary loan department in your library. 2. For users of non-calis member libraries, please mail to [email protected] for delivery details.

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