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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

邮发代号 80-969

2019 Impact Factor: 3.552

Frontiers of Chemical Science and Engineering  2018, Vol. 12 Issue (4): 718-730   https://doi.org/10.1007/s11705-018-1771-2
  本期目录
Extension of pilot tests of cyanide elimination by ozone from blast furnace gas washing water through Aspen Plus® based model
Ismael Matino(), Valentina Colla, Teresa A. Branca
Scuola Superiore Sant’Anna, TeCIP Institute—ICT-COISP, 56124 Pisa, Italy
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Abstract

For improving wastewater quality, one of the dare of steelworks is reducing cyanide in wastewater of gas washing treatment of blast furnaces. Costs of existing treatments, stringent environmental regulations and changeable composition of water from gas treatment, have led to study how available treatments can be modified and to examine new ones. Ozonation is one of cyanide treatments, tested within a European project. A process model was set up with Aspen Plus®, to assess operating conditions and wastewater distinctive characteristics and to demonstrate treatment robustness. Process was modeled by theoretical reactors, taking into account all more affecting reactions. A genetic algorithm was exploited to find kinetic parameters of these reactions. After validation, the model was used to analyse scenarios, by considering also real contexts. Pilot tests were extended, process knowledge was enhanced and suggestions were obtained. To promote cyanide removal with ozone, temperature and pH values were 30°C and 10, respectively. With an ozone (mg/h)/water (L/h) ratio of 100 mg/L, batch mode ensure reaching cyanide regulation limit (0.2 mg/L) after maximum 4.5 h, if initial amount was less than 20 mg/L. Higher removal was obtained than in continuous mode due to constraints related to this last run. Higher wastewater contamination needed further time and more ozone.

Key wordsblast furnace    cyanide removal    gas washing water    modeling and simulation    ozonation
收稿日期: 2018-04-06      出版日期: 2019-01-03
Corresponding Author(s): Ismael Matino   
 引用本文:   
. [J]. Frontiers of Chemical Science and Engineering, 2018, 12(4): 718-730.
Ismael Matino, Valentina Colla, Teresa A. Branca. Extension of pilot tests of cyanide elimination by ozone from blast furnace gas washing water through Aspen Plus® based model. Front. Chem. Sci. Eng., 2018, 12(4): 718-730.
 链接本文:  
https://academic.hep.com.cn/fcse/CN/10.1007/s11705-018-1771-2
https://academic.hep.com.cn/fcse/CN/Y2018/V12/I4/718
Fig.1  
Type Stoichiometry A B C D E
Equilibrium CaOH+←→ Ca2+ + OH
Equilibrium HPO42–←→ H+ + PO43– –3.94518 –5114 0 –0.037555 0
Equilibrium HCN ←→ CN + H+ 22.9025 –9945.53 0 –0.049579 0
Equilibrium H2PO4←→ H+ + HPO42– 8.59044 –4601.7 0 –0.046162 0
Equilibrium H3PO4←→ H+ + H2PO4 19.9374 –3734.8 0 –0.053841 0
Equilibrium HNO3←→ H+ + NO3
Equilibrium HCl ←→ Cl + H+
Equilibrium HSO4←→ H+ + SO42–
Equilibrium H2SO4←→ H+ + HSO4
Equilibrium NH3 + HCO3←→ H2O+ NH2COO –4.58344 2900 0 0 0
Equilibrium NH3 + H2O ←→ OH + NH4+ –1.25656 –3335.7 1.4971 –0.037057 0
Equilibrium HCO3←→ CO32– + H+ 216.05 –12431.7 –35.4819 0 0
Equilibrium H2O+ CO2←→ HCO3 + H+ 231.465 –12092.1 –36.7816 0 0
Equilibrium H2O ←→ OH + H+ 132.899 –13445.9 –22.4773 0 0
Salt CaHPO4(S) ←→ Ca2+ + HPO42–
Salt Ca(OH)2←→ CaOH+ + OH
Salt ZnSO4(S) ←→ SO42– + Zn2+
Salt ZnCl2(S) ←→ Zn2+ + 2 Cl –414.356 10694.1 74.8057 –0.127556 0
Salt NaNO3(S) ←→ NO3 + Na+ –125.441 2290.56 21.6864 –0.036756 0
Salt NaHCO3←→ HCO3 + Na+ –63.4345 –1296.96 11.9061 –0.029058 0
Salt NaH2PO4(S) ←→ Na+ + H2PO4 –262.828 8190.72 42.8442 –0.0489 0
Salt Na2CO3←→ CO32– + 2 Na+ –30.468 6566.26 0 0 0
Salt Na2HPO4 (S) ←→ HPO42– + 2 Na+ –2.29115 –3402.43 2.95392 –0.052975 0
Salt NaCN(S) ←→ CN+ Na+
Salt (NH4)2HPO4(S) ←→ HPO42– + 2 NH4+ 47.3093 –1545.23 –9.00873 –0.020729 0
Salt (NH4)2SO4←→ SO42– + 2 NH4+ –216.555 4262.38 37.5177 –0.079869 0
Salt NH4NO3(S) ←→ NO3 + NH4+ 421.947 –17793.8 –68.0478 0.066833 0
Salt NH4HCO3←→ HCO3 + NH4+ 554.818 –22442.5 –89.0064 0.064732 0
Salt NH4Cl(S) ←→ Cl + NH4+ –141.676 –880.103 27.7806 –0.06317 0
Salt CaSO4(S) ←→ Ca2+ + SO42–
Salt MgSO4(S) ←→ Mg2+ + SO42–
Salt Mg(NO3)2(S) ←→ Mg2+ + 2 NO3
Salt MgCl2(S) ←→ Mg2+ + 2 Cl
Salt MgCO3(S) ←→ CO32– + Mg2+
Salt K2SO4(S) ←→ SO42– + 2 K+
Salt KNO3(S) ←→ K+ + NO3 60.8334 –6040.28 –8.04887 –0.00998 0
Salt KNO2(S) ←→ K+ + NO2 –46.5107 439.725 8.3329 –0.022522 0
Salt K2HPO4(S) ←→ HPO42– + 2 K+
Salt KHSO4(S) ←→ K+ + HSO4 –49.5431 533.602 7.11446 0 0
Salt KH2PO4(S) ←→ K+ + H2PO4 624.859 –19644.6 –108.15 0.161639 0
Salt KCl(S) ←→ Cl + K+ –226.338 2268.98 42.2051 –0.092909 0
Salt KCN(S) ←→ CN + K+
Salt FeCl3(S) ←→ Fe3+ + 3 Cl
Salt KOH(S) ←→ OH + K+
Salt NaOH(S) ←→ OH + Na+ 433.324 –21656.7 –63.2311 0 0
Salt KHCO3(S) ←→ HCO3 + K+ –38.1042 –2142.08 6.84536 0 0
Salt K2CO3(S) ←→ CO32– + 2 K+ –175.998 17765.2 21.6865 0 0
Salt Na2SO4(S) ←→ SO42– + 2 Na+ –446.514 11171.8 77.4897 –0.151582 0
Salt NaCl(S) ←→ Cl + Na+ –203.587 4381.18 35.8752 –0.067216 0
Salt Ca(NO3)2←→ Ca2+ + 2 NO3 –195.31 3344.97 36.4549 –0.092639 0
Dissociation Zn(CN)2→ Zn2+ + 2 CN
Dissociation NaCN → CN + Na+
Dissociation KCN → CN + K+
Dissociation FeCl3→ Fe3+ + 3 Cl
Dissociation CaSO4→ Ca2+ + SO42–
Dissociation CaCl2→ Ca2+ + 2 Cl
Dissociation CaCO3→ CO32– + Ca2+
Dissociation KOH → OH + K+
Tab.1  
Reaction number a (cyanide, nitrite, ammonia) b (ozone) K0 or K GA error
Cyanide 2 5.4 × 10?1 1.3 × 10?3 K0 = 1.5 × 10?8 0.3%
Nitrite 4 5.6 × 10?1 3.6 × 10?5 K0 = 9.9 × 10?6 0.5%
Ammonia 5 0 1.5 × 10?2 K = 5.1?× 10?8 12.3%
Tab.2  
Fig.2  
Fig.3  
Compound Average values /(mg?L–1) Min limit /(mg?L–1) Max limit /(mg?L–1)
WAD cyanide 5 5 20
NH4+ 100 50 200
CaO 50 50 150
MgO 100 100 300
Tab.3  
Fig.4  
pH at the beginning Temperature /°C O3GWW/(mg·L–1) Other conditions Mode
9 10 50 Without unreacted O3 recycling Batch
10 Ambient temperature 100 With unreacted O3 recycling Continuous
12 30 200
50
80
Tab.4  
Fig.5  
Fig.6  
Fig.7  
Energy Investment depreciation Maintenance Manpower Fresh water cost Operating hours/year
0.0842 €/kWh a) 5 years and 5% 5% of the investment 28.1 €/h b) 0.54 €/m3 7680
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