Abstract Key words: ferrite process, extend type of ferrite process, elutriation The way, treating waste liquid in laboratory, currently is almost the sending to treatment factory run by the local people after collecting classification. For a long time in collection and the various sources in production of the above liquid, the waste from laboratory displays not having large variation of component but also knowing hardly the true constitution. Thus, to achieve the objective of a proper treatment is not easy in truth In this work, a ferrite process (denoted by FP) was used to develop a method that could completely treat the waste liquid of laboratory containing heavy metal in solutions. The waste liquid synthesized with ten common ions of heavy metal such as Cd, Cu, Pb, Cr, Zn, Ag, Hg, Ni, Sn and Mn for each concentration of 0.002 M, and total concentration of heavy metal mixed in solution was 0.02 M. The performance of treatment in FP was judging by that the concentration of all heavy metals in filtered solution and the heavy metal containing in sediment sludge should be both below the regulations of effluent standards and TCLP standards. It was found that the conventional FP could not meet the goal of performance. As a result, we develop the type of extend reaction of FP to improve the performance of conventional FP. The base of theory was to maintain enough concentration of ferrous ion for beneficial reaction going continuously. We found that extend type FP accurately did improve the sludge quality to meet the TCLP standards and the plus-adding was better than the continuous-adding in two kinds of dosage input into reactor, but it would raise the operation cost for overextended reaction. Thus, we designed a wash-cleaning method to decrease the cost and to confirm a further quality of sludge in extend FP. Base on the achievements of this study, combining the commercial technology of ion exchange, we recommended a complete flow-chart to the user or plant owner to design the treatment plant.

Abstract Heavy metals and organics are always presented an important rule in the pollution control. In Taiwan, there are large amounts of toxic wastewater produced from electrical plating, metal surface-treating, steel, IC, electrics, photo-electrics, printed PC board, refinery, medicals, oil painting and foods manufactory industries. Those wastewater are contained toxic and hazardous materials materials to human body or environment quality. Thus, we believe it need immediately to develop the innovative process on removal of wastewater containing heavy metals and organic compounds. This study uses the strong oxidation of Fenton¡¦s Process to first remove the organic pollutant, EDTA, and then uses Ferrite Process to incorporate heavy metal ions into spinel structure for facilitating removal of heavy metal ions, and through this work, the best operation model of series treatment ¡§Fenton/Ferrite Process¡¨ is established. With respect to batch reaction in Fenton¡¦s Process, the emphasis in this work is placed the effect on EDTA removal by pH, ferrous ions concentration, and hydrogen peroxide . The results show that the best removal of EDTA occurs when Fenton is under acid condition (pH=2); and the removal of EDTA increase as the ferrous ions and hydrogen peroxide increase adequately, but when its quantity exceeds a certain value, the removal of EDTA would decrease as follows. Such a result may be caused by the excess of ferrous ions and hydrogen peroxide which could restain generation of hydroxyl radicals. As followed the Fenton¡¦s process, Ferrite Process is next used for treatment of wastewater in series; Ferrite Process has three stages, and the operating conditions are controlled temperature and pH. For the first stage, the operating condition is 70¢J, and pH is 9.0; and the operating condition is 90¢J, and pH is 9.0 in the second stage; and the operating condition is 80¢J, and pH is 10.0 in the last stage. From the results of series experiments, with respect to reaction time, each concentration of heavy metal in supernatant could meet the standards of discharge water when the total time of A-4 experimental condition is 90 minutes; if Hg ion is not included in wastewater, then the reaction time could be reduced to 50 minutes. I shows benefit for short reaction it the time. Under A-3 experimental condition, the reaction time is 56 minutes when Cd and Hg ions are not included in the wastewater, then each ions concentration of heavy metal could also reach the standards of discharge water, and this experiment need of ferrous ions is least of all. Thus, this experiment in this work has the economic benefits both for regarding time and cost-effectiveness. Keywords¡GFenton¡¦s Process¡BFerrite Process¡BEDTA¡BHeavy metal

Volatile organic compounds (VOCs) can be considered as a major source of air pollution, and in many cases, legislation has already been introduced to reduce their emissions. O-xylene, one of VOCs, is widely used in industry as solvent and also the raw material of o-Phthalic anhydride (PA). The subjects of this research are divided into four parts, they are screening activity of catalysts, incineration efficiency with various operation parameters, physical properties of catalysts and kinetic model derivation. In screening activity of catalysts, Four kinds of metal ions (Cu, Mn, Zn, Fe; the molar ratio of metal/Fe is 1/2), three different temperature (70¢J, 80¢J, 90¢J) and pH (9, 10, 11) were the parameters of FP to manufactured 36 ferrospinel catalysts. Under the same reaction conditions (o-xylene conc.=1600 ppm, GHSV=71150 hr-1, O2=21%, temperature=298K~673K), it¡¦s found that the most efficient catalyst was Cu/Fe ferrospinel and its synthesis condition was pH at 9 and temperature at 90¢J. The operation parameters to determine incineration efficiency were temperature at 373K ~ 673K, inlet o-xylene concentration at 600 ~ 1600 ppm, GHSV at 47450 ~ 71150 hr-1, O2 concentration at 21 ~ 40%. The results showed that the conversion was proportional to the increase of inlet o-xylene concentration, temperature and inlet oxygen content and was inverse proportional to the increase of GHSV. To realize the physical properties of catalysts, XRD, SEM and EDS were applied. The results indicated that there was no physical difference between fresh and used catalysts. Besides, two kinetic models, Power rate law and Mars-Van Krevelen model were used to demonstrate the decomposition of o-xylene. It¡¦s discovered that Power rate law was more reasonable to illustrate the catalytic o-xylene oxidation. Further, the reaction rate was increased with the increase of inlet o-xylene and oxygen concentration and reaction temperature.

Biological and physical chemistry treatment methods always are used to remove COD of organic wastewater contains PCB. The effect is not obvious when the compositions of pollutant are too refractory or complicated. The primary treatment method of wastewater containing copper is chemical coagulation/sedimentation and its disadvantage is producing a large of sludge. The objective of this study, using two combinative method of UV/H2O2-Ferrite Process and Fenton-Ferrite Process, is to remove organic compounds and heavy metal in real wastewater. Not only supernatant liquid could meet the standard of discharge wastewater but also produce general(non-hazardous) industrial wastes of heavy metal. The primary operation condition of Fenton and UV/H2O2 process, was ferrous ion and hydrogen peroxide concentration, pH, reaction time, and chemical dosing, searching best operation condition to combine with Ferrite Process. Operation of Fenton and UV/H2O2 process under acid condition (pH=2) and neutral condition (pH=8) showed the best operation condition of Fenton and UV/H2O2. The removal decreased when the dose of hydrogen peroxide was added too more or too less. As Fenton and UV/H2O2 process test finished, Ferrite Process is next used for treatment of heavy metal wastewater; Ferrite Process conducted as three stages and the operation conditions were controlled with temperature, pH and the ratio of Fe/M mole. The results showed that the best removal of treatment of copper containing wastewater by Ferrite Process achieved when the ratio of Fe/M mole was at 10. Treatment of PCB industrial real wastewater by Fenton-Ferrite Process and UV/H2O2-Ferrite Process which combined with Fenton, UV/H2O2 and Ferrite Process. The supernatant liquid containing organic compounds and heavy metal both could meet the standards of discharge wastewater and the sludge was judged with general(non-hazardous) wastes. The characteristic of the sludge were the diameter lattice less 100 nm and with magnetism and to develop recovery and utilization in a further work.

ABSTRACT This study was aimed to investigate the operational conditions for stabilizing and recycling copper sludge in electronic industry by serially using acid leaching, cementation and ferrite methods. The physical/chemical characteristics of copper sludge were examined, and TCLP (Toxic Characteristics Leaching Process) tests were conducted. Results show that the copper sludge from electronic industry is weakly alkaline and consists of 6-15.8% Cu and 50-75% moisture. The TCLP tests show that copper in the sludge exceeds the regulation standard. Acid leaching tests indicate that the optimal combination of control factor levels yielding more than 99% of copper extraction is: 2.0 N in sulfuric concentration (A3), pH = 1.5 (B3), 90 minutes in treatment time (C3), and 50 oC in treatment temperature (D3). Moreover, the sediment of treated sludge fulfills the standards of the TCLP, and is thus a general industrial waste. Cementation tests indicate that the optimal combination of control factor levels yielding 96.87% of copper recovery and 92% of copper purity is: addition mole ratio of iron element Fe/Cu = 2.0 (A2), pH = 1.0 (B1), agitation speed = 200 rpm (C1), and 50 oC in treatment temperature (D3). Ferrite tests indicate that the optimal combination of control factor levels yielding more than 99% of copper removal is: addition mole ratio of ferrous sulfuric acid Fe2+/Cu = 10.0 (A3), pH = 9.5 (B2), air supply rate = 3.0 L/min (C3), and 80 oC in treatment temperature (D3). The cost analyses indicate that the expenses would be NT $7.45 for the acid leaching-cementation-ferrite process, less expensive than NT $ 8.0 for the solidification process given the same copper sludge. Thus, the proposed method in this study is competitive and feasible. Keywords: Copper sludge, Acid Leaching, Cementation, Ferrite Process, Recycling

The electroplating wastewater is usually treated by chemical precipitation, and the generated sludge has loose structure to cause the difficulties in sedimentation and filtration. Moreover, the sludge is unstable and the contained heavy metals are easily leached. Solidification is one method to deal with this kind of sludge; however it cause another problem, land requirement. In this study, the contents of electroplating wastewater are divided into two parts organic matters and heavy metals; organic matters are treated by Fenton method and heavy metals are by Ferrite process. The purpose of this study is that through the serial Fenton-Ferrite Process treatment the effluent water and the sludge generated from the procedure could meet the standards in Taiwan. It was well-know that the primary operation factors of Ferrite Process are pH, reaction temperature, ferrous ion concentration, time and aeration. The results showed that the proper factors of FP were pH=10, temperature= 90¢J, Fe/M molar ratio= 7,reaction time=80 min and aeration rate=1.0 L air / min / L solution. However, in Fenton method, the parameters of pH, hydrogen peroxide, ferrous ion concentration, and reaction time were discussed. I had greatest efficiency under the data showed that Fenton method pH = 3, ferrous ion concentration=3000 mg/L, hydrogen peroxide = 13000 mg/L, and reaction time=2 hr. The wastewater measured COD =1162 mg/L, Cr=70 mg/L, Zn=400 mg/L. The treatment efficiency of the procedure combining Fenton method and Ferrite Process were that COD=88.5 mg/L, Cr=1.06 mg/L, and Zn=0.98 mg/Lin effluent water and the TCLP test results of sludge were Cr=3.37 mg/L, Zn=2.46 mg/L. All the data showed that the combination of the two process can significantly treat wastewater to meet the standards. Furthermore, the sludge can be recycled as magnetic materials or other purposes due to it¡¦s specific properties.

Printed Circuit Board (PCB) industry is one of the two major Integrated Circuit (IC) part manufacturing industries in Taiwan, but it derives many environmental problems because large amount of chemicals and special materials are used in its process, especially copper sludge generated from wastewater treatment. Although the heavy metal sludge can be treated by solidification, heavy metals contained in the sludge may still be leached out due to longtime exposure to acid rain. Therefore, there are urgent needs of research and development of technologies regarding how to reduce both quantity and volume of the hazardous heavy metal sludge and how to recycle the valuable heavy metals. Acid leaching method, chemical exchange method and ferrite process are applied to study how to recycle and stabilize copper sludge of PCB industry. The ultimate goal is to achieve cleaning production and sustainable development by transforming the hazardous waste into valuable byproducts, reducing the amount of the waste and lowering the treatment costs. Experimental results show that a method is successfully developed to recycle copper from the sludge generated by PCB industry by using the combination of acid leaching, chemical exchange and ferrite process. Via this method, not only is pure copper powder recycled, but highly valuable nano-scaled catalyst-CuFe2O4 is also produced. Hence, the problem that copper sludge has nowhere to go is solved, as well as the high cost of catalyst in catalytic incineration is reduced to nearly zero. The achievements of this study are summarized as follow: (1) Characteristic analysis of industrial sludge Water content and pH of the sludge is 60% and 7.05, respectively. The drop in quantity of ignition is 23%. The screening test results show that particle size of the sludge varies from 0.4 £gm to 200 £gm, with D50 of 25.0 £gm. Cu, Pb, Cd, Zn, Ni and Cr are found in the sludge, and the biggest part of heavy metals is Cu, with a concentration of 158,000 mg/kg (dry basis), whereas the other heavy metals are all below 105 mg/kg (dry basis). (2) Study of recycling of pure copper powder The optimal operational condition of acid leaching method is that concentration of sulfuric acid is 2.0 N, temperature is 50¢J and treatment time is 60 minutes. Under this operational condition, more than 99% of heavy metals can be extracted to liquid phase and the sediment of treated sludge meet Toxicity Characteristic Leaching Procedure (TCLP) standards and therefore is considered as general industrial waste. The optimal operational condition of chemical exchange method is that molar ratio of Fe/Cu is 5.0, pH is 2.0 and treatment temperature is 50¢J. Under this operational condition, more than 95.0% of Cu can be recovered. The optimal operational condition of ferrite process is that Fe/Cu=10.0, pH=9.0, treatment temperature=80¢J, aeration rate=3 L/min/per liter waste liquid and reaction time = 30 min. Under this operational condition, TCLP concentrations of all heavy metals of both supernatant and sludge are well below regulatory standards, which proves that ferrite process is very effective. (3) Resourcing of spinel sludge In the potential of catalytic incineration of volatile organic compounds test, the sludge generated from ferrite process is used to catalyze the isopropyl alcohol (IPA). The catalyst is replaced by the same volume of glass wool on a reactive bed as a blank. Experimental result shows that the conversion of IPA is only 10% at 200¢J and 75% at 500¢J in the absence of catalyst under the conditions that IPA inlet concentration=1,700 ppm, space velocity=24,000 hr-1, O2 concentration=21%, and relative humidity=19%, which indicates that the destruction of IPA is associated with the consumption of much energy when no catalyst was used. But when ferrite catalyst is applied, IPA is decomposed completely at 200¢J, showing that the sludge has great potential of catalyst. (4) Synthesizing five VOCs catalyzing ferrite catalysts via ferrite process As to the synthesis of five ferrite catalysts in the laboratory, IPA conversion rate is higher than 58% at 200¢J. The sequence of IPA conversion from good to bad is Cu-ferrite catalyst > Mn-ferrite catalyst > Ni-ferrite catalyst > Zn-ferrite catalyst > Cr-ferrite catalyst, where Cu/Fe is most efficiency, with IPA conversion rate of 75% at 150¢J and 100% at 200¢J.

This work increased the value of ferrite process (FP) in three directions: firstly, changed the inferiority of FP on cost by transforming the FP sludge into a catalyst; secondly, used ERFP and elutriation to promote the performance of FP; thirdly, developed Fenton oxidation as a pretreatment step for avoiding the interference from chelating agents. Six ferrite catalysts (MxFe(3-x)O4, M = Cu, Zn, Mn, Ni, Cr or Fe) formed from FP were tested. Experimental results indicate that the Cu-ferrite catalyst with a Cu/Fe ratio of 1/2.5 can completely convert CO to CO2 at an inlet CO concentration of 4000 ppm and a space velocity of 6000 hr-1 were held at 140¢J. The catalytic performance of Cu-ferrite did not reduce even when the concentration of O2 was just 1%. This work proves that the ferrite catalysts have good potential for catalyzing oxidation. For developing FP for effectively treating almost all heavy metal waste liquid, hence an extremely difficult treating target- simulated waste liquid was designed. It contains ten heavy metals - Cd, Pb, Cu, Cr, Zn, Ag, Hg, Ni, Sn and Mn, each at a concentration of 0.002 M. Although conventional FP could not be used to treat the simulated waste liquid completely, the enhanced FP, i.e. ERFP, could be used to satisfy regulatory limits. FeSO4 can be added in the extended stage of ERFP intermittently rather than continuously. The optimum operating parameters in the initial stage are pH = 9 , FeSO4 dosage = 0.2 mol/L, temperature = 90 oC, air supply rate = 3 L/min/L and reaction time = 40 min; in the extended stage, they are intermittent dosing, adding 10 mL 1M-FeSO4 solution per liter waste liquid every 5 min, pH = 9, temperature = 90 oC, air supply rate = 3 L/min/L and reaction time = 80min. Elutriation was conducted to reduce the cost of ERFP and ensure that the sludge met Toxicity Characteristic Leaching Procedure (TCLP) standards. An operating pH from 2.88 to 4 and an elutriation time of 6 h were recommended. Used Fenton oxidation to decompose chelating agent in waste liquid and then treated heavy metal by FP, this research showed that under proper operational conditions Fenton/ ERFP could completely solve the chelating agent interference problem. The best condition for decreasing EDTA using the Fenton method was: pH = 2, ferrous ion initial concentration [Fe2+]0 = 1¡Ñ10-2M, hydrogen peroxide addition rate = 5¡Ñ10-4 mol/min/L and reaction time = 10 min. Lastly, a lot of real waste liquids were treated satisfactorily by applying the results of this study.

Ferrite process (denoted by FP) has been used for treating the waste-liquid containing heavy metal for many years. Related researches have shown that this method could catch the heavy metal regulated by environmental law into the structure of spinel, and sludge from FP also conformed the standards of toxicity characteristic leaching procedure in EPA of Taiwan. On comparing with neutral precipitation of conventional method, spinel¡¦s sludge produced in FP had an ease separation of solid-liquid and no need of solidification in further treatment. These spinel, belonged to the magnetic material, could be used for applications such as brick of blinder guide, magnetic symbol, absorber of electric wave and adsorbent. Therefore, this method has a great potential for treating the waste containing heavy metal in laboratory. This study was to investigate the optima conditions in removal of heavy metal in waste liquid in laboratory by using the FP of conventional, two and three stage. All experiments, including one ion and ten ions heavy metal mixed in a solution, were conducted in a batch- type reactor for total concentration of 2000 mg/L heavy metals. The major parameters included temperature, ferric ion dosage, aeration intensity and pH. The performance of treatment in FP was judging by that the concentration of all heavy metals in filtered solution and the heavy metal containing in sediment sludge should be below the regulations of effluent standards and TCLP standards. In conventional one stage of FP experiments performed at constant temperature and pH, the residual concentration of heavy metals in filtered solution was below the effluent standards except of Cd and of Hg; in results of TCLP showed that higher dissolvion of Cd, Cu and Pb leached from sediment and the rest ions of heavy metal passed the regulations. Thus, we conducted individually for Cd, Cu and Pb to find the optimal conditions. The optimal pH of 7 and temperature above 70 ¢J for Cd and Pb and the optimal pH of 10 and temperature above 80 ¢J for Cu were obtained. They were be used for combination of process in various stage to achieve the goal of treatment performance. After the combination of two and three stage reactions, three stage reactions in series was the only selection in removal of ten heavy metals performed by FP. As a result, the sequences were in the following: (1) 70¢J, pH=9 (2) 90¢J, pH=9 (3) 80¢J, pH =10 , and the reaction period was 40 min for each stage.

In industrial wastewater, there are usually many kinds of organics and heavy metals and can cause damage on human health and environment without well treatment. Printed Circuit Board (PCB) industrial wastewater is a typical example due to the complicated manufacture processes and the use of specific chemicals. In this study, the PCB industrial wastewater is collected and then treated by the combination of Fenton method and Ferrite Process (or called Fenton-Ferrite Process, FFP). Moreover, the recycling possibility of sludge generated from FFP is also studied. Through this study, the treatment procedure of wastewater containing organics heavy metals is established and the direction of sludge reuse is also provided. To realize the characteristic of PCB industrial wastewater, the wastewater from some PCB factory in southern Taiwan was firstly collected and analyzed to identify the pollution concentrations and then treated by FFP. The experimental results showed that the optimum parameters of Fenton method in FFP were pH = 2, [Fe2+]= 500 mg/L, [H2O2]= 3000 mg/L, reaction time= 60 min and batch dosing, and the residual COD and TOC were 84.9 mg/L and 58.3 mg/L under the COD regulation standard 120 mg/L. Meanwhile, the proper conditions of Ferrite Process in FFP were pH= 10, reaction temperature= 80¢J, reaction time= 40 min, aeration rate= 3 L/min/L wastewater, Fe/Cu molar ratio= 10 and three-stage reaction. Under that circumstance, the residual [Cu2+] in wastewater was 0.18 mg/L and the Toxicity Characteristic Leaching Procedure (TCLP) test of sludge from FFP was 4.58 far below the effluent standard 3 mg/L and TCLP standard 15 mg/L. The properties of sludge were further investigated by X-Ray Diffractometer (XRD), Scanning Electron Microscope (SEM) and Superconducting Quantum Interference Device (SQUID). The pattern of XRD indicated that the major structures were Fe3O4 and CuFe2O4; the figure of SEM showed that the surface of sludge was composed of many round particles and the distribution of particle size was from 50 nm-100 nm; the magnetic property analyzed by SQUID showed that the saturation moment was 62.85 emu/g. In the research of sludge applied in catalytic incineration, the o-xylene conversion was 97 % by sludge but only 31 % by quartz sand at 400 ¢J. Moreover, in the 72 hr-decay test of catalyst, the results clearly indicated that the performance did not obviously decline and there were no any byproducts but CO2. Therefore, the investigation revealed that the sludge had great potential in catalytic reaction. The catalytic performance of various ferrospinels generated from different manufactured conditions was also studied. Through the screening of catalysts, the order of various ferrospinels activity was Cu-ferrite > Mn-ferrite > ferrite ¡Ü Zn-ferrite and the most effective Cu-ferrite was manufactured at pH= 9 and T= 90 ¢J. After 72 hr test, the decay of catalyst was not also found. In the examination of Cu-ferrite physical property, the XRD pattern showed that the structure was CuFe2O4; the figure of SEM illustrated that there was no difference between the surface of fresh and used catalyst; the magnetic property measured by SQUID showed that the saturation moment was 30.89 emu/g.