• Journal of Korean Society of Environmental Engineers
• /
• v.30 no.5
• /
• pp.524-533
• /
• 2008

Industrial wastewater generated in the electroplating and metal finishing industries typically contain toxic free and complex metal cyanide with various heavy metals. Alkaline chlorination, the normal treatment method destroys only free cyanide, not complex metal cyanide. A novel treatment method has been developed which destroys both free and complex metal cyanide as compared with Practical Plant(I). Prior to the removal of complex metal cyanide by Fe/Zn coprecipitation and removal of others(Cu, Ni), Chromium is reduced from the hexavalent to the trivalent form by Sodium bisulfite(NaHSO$_3$), followed by alkaline-chlorination for the cyanide destruction. The maximum removal efficiency of chromium by reduction was found to be 99.92% under pH 2.0, ORP 250 mV for 0.5 hours. The removal efficiency of complex metal cyanide was max. 98.24%(residual CN: 4.50 mg/L) in pH 9.5, 240 rpm with 3.0 $\times$ 10$^{-4}$ mol of FeSO$_4$/ZnCl$_2$ for 0.5 hours. The removal efficiency of Cu, Ni using both hydroxide and sulfide precipitation was found to be max. 99.9% as Cu in 3.0 mol of Na$_2$S and 93.86% as Ni in 4.0 mol of Na$_2$S under pH 9.0$\sim$10.0, 240 rpm for 0.5 hours. The concentration of residual CN by alkaline-chlorination was 0.21 mg/L(removal efficiencies: 95.33%) under the following conditions; 1st Oxidation : pH 10.0, ORP 350 mV, reaction time 0.5 hours, 2nd Oxidation : pH 8.0, ORP 650 mV, reaction time 0.5 hours. It is important to note that the removal of free and complex metal cyanide from the electroplating wastewater should be employed by chromium reduction, Fe/Zn coprecipitation and, sulfide precipitation, followed by alkaline-chlorination for the Korean permissible limit of wastewater discharge, where the better results could be found as compared to the preceding paper as indicated in practical treatment(I).

• Clean Technology
• /
• v.27 no.2
• /
• pp.168-173
• /
• 2021

The treatment of plated wastewater is subject to various and complex processes depending on the pH, heavy metal, and cyanide content of the wastewater. Alkali chlorine treatment using NaOCl is commonly used for cyanide treatment. However, if ammonia and cyanide are present simultaneously, NaOCl is consumed excessively to treat ammonia. To solve this problem, this study investigated 1) the consumption of NaOCl according to ammonia concentration in the alkaline chlorine method and 2) whether ferrate (VI) could selectively treat the cyanide. Experiments using simulated wastewater showed that the higher the ammonia concentration, the lower the cyanide removal rate, and the linear increase in NaOCl consumption according to the ammonia concentration. Removal of cyanide using ferrate (VI) confirmed the removal of cyanide regardless of ammonia concentration. Moreover, the removal rate of ammonia was low, so it was confirmed that the ferrate (VI) selectively eliminated the cyanide. The cyanide removal efficiency of ferrate (VI) was higher with lower pH and showed more than 99% regardless of the ferrate (VI) injection amount. The actual application to plated wastewater showed a high removal ratio of over 99% when the input mole ratio of ferrate (VI) and cyanide was 1:1, consistent with the molarity of the stoichiometry reaction method, which selectively removes cyanide from actual wastewater containing ammonia and other pollutants like the result of simulated wastewater.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.5
• /
• pp.1675-1680
• /
• 2012

Three new cyanide-bridged $Cr^{III}Mn^{II}$ binuclear complexes, $[Mn(phen)_2Cl][Cr(bpmb)(CN)_2]{\cdot}H_2O$ ($\mathbf{1}$) (phen = 1,10-phenanthroline, $bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate), $[Mn(phen)_2Cl][Cr(bpmb)-(CN)_2]{\cdot}H_2O$ ($\mathbf{2}$) ($bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate), and $[Mn(phen)_2Cl]-[Cr(bpClb)(CN)_2]{\cdot}CH_3OH{\cdot}H_2O$ ($\mathbf{3}$) ($bpClb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate) were obtained based on $Mn(phen)_2Cl_2$ and a series of dicyanidechromate(III) building blocks. Single crystal X-ray diffraction analysis shows the structures of the three complexes are dimeric type with two different metal centers linked by a cyanide group from corresponding dicyanidechromate(III) building block. Magnetic investigations indicate the existence of relatively weak antiferromagnetic coupling between Cr(III) and Mn(II) ions with best-fit constants $J_{CrMn}=-2.78(5)cm^{-1}$ for $\mathbf{1}$, $J_{CrMn}=-3.02(2)cm^{-1}$ for $\mathbf{2}$ and $J_{CrMn}=-2.27(3)cm^{-1}$ for $\mathbf{3}$ based on the spin exchange Hamiltonian = $-2J_{CrMn}\hat{S}_{Cr}\hat{S}_{Mn}$. The magneto-structural correlation of cyanide-bridged $Cr^{III}Mn^{II}$ complexes has been discussed at last.

• Journal of the Korean Chemical Society
• /
• v.28 no.2
• /
• pp.121-129
• /
• 1984

The adsorption characteristics of heavy metal ions $(Ni^{2+}$, $Zn^{2+}$) on domestic activated carbon which manufactured from the wood, waste rubber and coal has been studied. The following conclusions were obtained by investigating the effect of pH, halides, cyanide and temperature on the absorption of heavy metal ions and by determining absorption rate and absorption isotherms. When heavy metal ions were adsorbed on activated carbon in the pH range from 6 to 7, treated heavy metal ions were almost come to the equilibrium and recovered in the form of complex anions such as $MX_4^{2- }$and $M(CN)_4^{2-}$ in an hour. The absorption isotherms of heavy matel ions were well fitted in Freundlich's equation. Heavy metal complex anions on activated carbon were easily eluted by using 0.1N HCl solution. These results suggest that the complex anions have unexpectedly strong affinity for the surface of activated carbon.

• Journal of the Korean Chemical Society
• /
• v.68 no.3
• /
• pp.139-145
• /
• 2024

This study aims to elucidate the mechanism involved in the hydrolysis of the hexacyanoferrate(III) complex ion (Fe(CN)₆^3-) and the mechanism leading to the formation of Prussian blue (Fe^III₄[Fe_II(CN)₆]₃·xH₂O, PB) in acidic aqueous solutions at moderately elevated temperatures. Hydrolysis constitutes a crucial step in generating PB through the widely used single-source or precursor method. Recent PB syntheses predominantly rely on the single-source method, where hexacyanoferrate(II/III) is the exclusive reactant, as opposed to the co-precipitation method employing bare metal ions and hexacyanometalate ions. Despite the widespread adoption of the single-source method, mechanistic exploration remains largely unexplored and speculative. Utilizing UV-vis spectrophotometry, negative-ion mode liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS), and a devised reaction, this study identifies crucial intermediates, including aqueous Fe^2+/3+ ions and hydrocyanic acid (HCN) in the solution. These two intermediates eventually combine to form thermodynamically stable PB. The findings presented in this research significantly contribute to understanding the fundamental mechanism underlying the acid-catalyzed hydrolysis of the hexacyanoferrate(III) complex ion and the subsequent formation of PB, as proposed in the sequential mechanism introduced herein. This finding might contribute to the cost-effective synthesis of PB by incorporating diverse metal ions and potassium cyanide.

• Journal of Environmental Science International
• /
• v.3 no.4
• /
• pp.439-443
• /
• 1994

In aqueous acid solution ${[Cr(CN)_6]}^{3-}$ aquates via a series of stepwise stereospecific reactions to give ${[Cr{(H_2O)}_6]}^{3+}$as the final product.Some of the intermediate cyanoaquo complexes in the sequence have been isolated.These complexes aquate by both acid independent and acid denpendent pathways, the latter involving protonation of the cyano ligands followed by aquation of the singly protonated species. The kinetic data for the aquation of {[CrCN{(H_2O)}_5]}^{2+}$ are consistent with the transition state structure ${[{(H_2O)}_4Cr(CN)-OH-Cr{(H_2O)}_5]}^{3+}$. Addition of $Cr^{2+}$ to solutions of cyanocobalt(III) complexes produces the metastable intermediate${[CrNC{(H_2O)}_5]}^{2+}$ This isomerizes to in a $Cr^{2+}$-catalyzed reaction which occurs by a ligand-bridged electron-change mechnism. From acid catalysis on these aquation reactions, it product HCN. Especially, $HSO_3$-ions do the role of catalyst in the formation of HCN from $CrCN^{3-}$

• Membrane Journal
• /
• v.28 no.4
• /
• pp.252-259
• /
• 2018

An acidic, real metal-plating wastewater was treated by a fluidized bed membrane reactor introduced with granular activated carbon (GAC) as fluidized media. With GAC fluidization, there was no increase in suction pressure with time at each flux set-point applied. At neutral solution pH, much less fouling rate was observed than acidic pH under GAC fluidization. Higher solution pH resulted in the increase in particle size in metal-finishing wastewater, thus producing a less dense cake structure on membrane. More than 95% of chemical oxygen demand was observed from the fluidized bed membrane reactor under GAC fluidization. Total suspended solid concentration in membrane permeate was near zero. At the raw wastewater pH, no removal of copper and chromium by the fluidized bed membrane reactor was observed. As the pH was increased to 7.0, removal efficiency of copper and chromium was increased considerably to 99 and 94%, respectively. Regardless of solution pH tested, more than 95% of cyanide was removed possibly due to the strong adsorption of organic-cyanide complex on GAC in fluidized bed membrane reactor.