A highly hydrothermal stable copper-based catalyst for catalytic wet air oxidation of m-cresol in coal chemical wastewater

Catalytic wet air oxidation(CWAO) can degrade some refractory pollutants at a low cost to improve the biodegradability of wastewater. However, in the presence of high temperature and high pressure and strong oxidizing free radicals, the stability of catalysts is often insufficient, which has become a bottleneck in the application of CWAO. In this paper, a copper-based catalyst with excellent hydrothermal stability was designed and prepared. TiO_(2) with excellent stability was used as the carrier to ensure the longterm anchoring of copper and reduce the leaching of the catalyst. The one pot sol–gel method was used to ensure the super dispersion and uniform distribution of copper nanoparticles on the carrier, so as to ensure that more active centers could be retained in a longer period. Experiments show that the catalyst prepared by this method has good stability and catalytic activity, and the catalytic effect is not significantly reduced after 10 cycles of use. The oxidation degradation experiment of m-cresol with the strongest biological toxicity and the most difficult to degrade in coal chemical wastewater was carried out with this catalyst. The results showed that under the conditions of 140℃, 2 MPa and 2 h, m-cresol with a concentration of up to 1000 mg·L^(-1) could be completely degraded, and the COD removal rate could reach 79.15%. The biological toxicity of wastewater was significantly reduced. The development of the catalyst system has greatly improved the feasibility of CWAO in the treatment of refractory wastewater such as coal chemical wastewater.

Life cycle assessment of high concentration organic wastewater treatment by catalytic wet air oxidation

There have been many studies on life cycle assessment in sewage treatment,but there are scarce few studies on the treatment of industrial wastewater in combination with advanced oxidation technology,especially in catalytic wet air oxidation(CWAO).There are no cases of using actual industrialized data onto life cycle assessment.This paper uses Simapro 9.0 software to establish a life cycle assessment model for the treatment of high-concentration organic wastewater by CWAO,and comprehensively explains the impact on the environment from three aspects:the construction phase,the operation phase and the demolition phase.In addition,sensitivity analysis and uncertainty analysis were performed.The results showed that the key factors affecting the environment were marine ecotoxicity,mineral resource consumption and global warming,the operation stage had the greatest impact on the environment,which was related to high power consumption during operation and emissions from the treatment process.Sensitivity analysis showed that electricity consumption has the greatest impact on abiotic depletion and freshwater aquatic ecotoxicity,and it also proved that global warming is mainly caused by pollutant emissions during operation phase.Monte Carlo simulations found slightly higher uncertainty for abiotic depletion and toxicity-related impact categories.

Degradation of H-acid in aqueous solution by microwave assisted wet air oxidation using Ni-loaded GAC as catalyst

A novel process, microwave assisted catalytic wet air oxidation(MW-CWO), was applied for the degradation of H-acid(1-amino-8-naphthol-3, 6-disulfonic acid) in aqueous solution. Ni-loaded granular activated carbon(GAC), prepared by immersion-calcination method, was used as catalyst. The results showed that the MW-CWO process was very effective for the degradation of H-acid in aqueous solution under atmospheric pressure with 87.4% TOC (total organic carbon) reduction in 20 min. Ni on GAC existed in the form of NiO as specified by XRD. Loss of Ni was significant in the initial stage, and then remained almost constant after 20 min reaction. BET surface area results showed that the surface property of GAC after MW-CWO process was superior to that of blank GAC.

Application of Catalytic Wet Air Oxidation to Treatment of Landfill Leachate on Co/Bi Catalyst

Catalytic wet air oxidation(CWAO) was employed to reduce the organic compounds in landfill leachate and the effects of temperature, oxygen pressure, catalyst dosage, and concentration of the organic compounds on the TOC and COD Cr removal rates were studied. The degradation kinetics of landfill leachate was also investigated and an exponential experiential model consisting of four influential factors was established to describe the reduction of the organic compounds in the landfill leachate. Meanwhile, the GC-MS technique was used to detect the components of the organic intermediates for the inference of the decomposition mechanisms of the organic compounds in landfill leachate. The results reveal that the reaction temperature and the catalyst dosage are the most important factors affecting the degradation reaction of the organic compounds and that the principal intermediates confirmed by GC-MS are organic acids at a percentage of more than 88% with no aldehydes or alcohols detected. The decomposition mechanisms of the organic compounds in landfill leachate were inferred based on the GC-MS information as follows: the activated gas phase O 2 captured the hydrogen of the organic pollutants to produce free radicals, which then initiated the catalytic reaction. So most of the organic compounds were oxidized into CO 2 and H 2O ultimately. In general, catalytic wet air oxidation over catalyst Co 3O 4/Bi 2O 3 was a very promising technique for the treatment of landfill leachate.

Catalytic wet air oxidation of phenol over RuO_2/γ-Al_2O_3 catalyst

A kind of CWAO catalyst, RuO_2/γ-Al_2O_3, was prepared by dipping Al_2O_3into the aqueous solution of RuCl_3·3H_2O. XRD, SEM and TEM were used to determine the catalyticstructure. Influences of the calcination temperature, the initial pH of the feed solution anddegradation temperature on the activity of the RuO_2/γ-Al_2O_3 catalyst were investigated and thereaction mechanism was preliminarily studied. Results showed that uniform dispersion of RuO_2crystallites was observed on the surface of the catalyst. The activity of the catalyst was higher atcalcination temperature of 300℃ for 3 h and the particle reunion occurred and some large RuO_2crystallites were abundant at high calcination temperature of 500℃ The activity of the catalyst wasbetter in the acid solution than in the alkaline solution. Increasing degradation temperature andusing the catalyst could shorten the induction periods so that the phenol and COD removal wereincreased. For RuO_2/γ-Al_2O_3 catalyst, the phenol and COD removal were respectively 98% and 80%in a temperature of 150℃, pH of 5.6 and pressure of 3 MPa after a 2 h reaction. This indicated thatRu/γ-Al_2O_3 catalyst had good activity.

Catalytic Wet Air Oxidation of oChlorophenol in Wastewater

Catalytic wet air oxidation (CWAO) was investigated in laboratory-scale experiments for the treatment of o-chlorophenol in wastewater. Experimental results showed that wet air oxidation (WAO) process in the absence of catalyst was also effective for o-chlorophenol in wastewater treatment. Up to 80% of the initial CODCr was removed by wet air oxidation at 270℃ with twice amount of the required stoichiometric oxygen supply. At temperature of 150℃, the removal rate of CODCr was only 30%. Fe2(SO4)3, CuSO4, Cu(NO3)2 and MnSO4 exhibited high catalytic activity. Higher removal rate of CODCr was obtained by CWAO. More than 96% of the initial CODCr was removed at 270℃ and 84.6%-93.6% of the initial CODCr was removed at 150℃. Mixed catalysts had better catalytic activity for the degradation of o-chlorophenol in wastewater.

Structure, characterization, and dynamic performance of a wet air oxidation catalyst Cu–Fe–La/γ-Al_2O_3

A Cu–Fe–La/γ-Al_2O_3(CFLA) catalyst was prepared by the excessive impregnation method and characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results indicate that the catalyst contained mostly Cu^(2+), Fe^(3+), and La^(3+)and a small amount of Cu^+, Fe^(2+), and La. The active components were uniformly distributed in the catalyst, and the particle size of the components was approximately 7.5 nm. The CFLA catalyst was used for the treatment of methyl orange(MO) solution by catalytic wet air oxidation(CWAO), and it exhibited a high catalytic activity. The catalytic reaction involved variable valence states of metals and free-radical reaction mechanism. The CWAO reaction of MO solution was fitted by a segmented first-order dynamic model, and the rapid reaction apparent activation energy was 13.9 k J·mol^(-1).

Kinetics study on catalytic wet air oxidation of phenol by several metal oxide catalysts

Four metal oxide catalysts composed of copper(Cu), stannum(Sn), copper-stannum(Cu-Sn) and copper-cerium(Cu-Ce) respectively were prepared by the co-impregnation method, and γ-alumina(γ-Al 2O 3) is selected as support. A first-order kinetics model was established to study the catalytic wet air oxidation of phenol at different temperature when these catalysts were used. The model simulations are good agreement with present experimental data. Results showed that the reaction rate constants can be significantly increased when catalysts were used, and the catalyst of 6% Cu—10%Ce/γ-Al 2O 3 showed the best catalytic activity. This is consistent with the result of catalytic wet air oxidation of phenol and the COD removal can be arrived at 98.2% at temperature 210℃, oxygen partial pressure 3 MPa and reaction time 30 min. The activation energies of each reaction with different catalysts are nearly equal, which is found to be about 42 kJ/mol and the reaction in this study is proved to be kinetics control.

Pretreatment of apramycin wastewater by catalytic wet air oxidation

The pretreatment technology of wet air oxidation(WAO) and coagulation and acidic hydrolysis for apramycin wastewater was investigated in this paper. The COD, apramycin, NH^+_4 concentration, and the ratio of BOD_5/COD were analyzed, and the color and odor of the effluent were observed. WAO of apramycin wastewater, without catalyst and with RuO_2/Al_2O_3 and RuO_2-CeO_2/Al_2O_3 catalysts, was carried out at degradation temperature of 200℃ and the total pressure of 4 MPa in a 1 L batch reactor. The result showed that the apramycin removals were respectively 50 2% and 55 0%, COD removals were 40 0% and 46 0%, and the ratio of BOD_5/COD was increased to 0 49 and 0 54 with RuO_2/Al_2O_3 and RuO_2-CeO_2/Al_2O_3 catalysts in catylytic wet air oxidation(CWAO) after the reaction of 150 min. With the pretreatment of coagulation and acidic hydrolysis, COD and apramycin removals were slight decreased, and the ratio of BOD_5/COD was increased to 0 45, and the effluents was not suitable to biological treatment. The color and odor of the wastewater were effectively controlled and the reaction time was obviously shortened with WAO. HO_2· may promote organic compounds oxidized in WAO of the apramycin wastewater. The addition of CeO_2 could promote the activity and stability of RuO_2/Al_2O_3 in WAO of apramycin wastewater.

Role of Bismuth Oxide in Bi-MCo_2O_4(M=Co,Ni,Cu,Zn) Catalysts for Wet Air Oxidation of Acetic Acid

Two series of cobalt(Ⅲ)\|containing spinel catalysts were prepared by the decomposition of the corresponding nitrates. The catalysts doped with bismuth oxide exhibit a higher activity in the wet air oxidation of acetic acid than those without dopant bismuth oxide. The catalysts were investigated by XRD,TEM,ESR,UV\|DRS and XPS,and the interaction between Co and Bi was studied as well. It has been found that nano\|sized bismuth oxide is paved on the surface of cobalt spinel crystal and the structures of cobalt(Ⅲ)\|containing spinel are still maintained. The shift of the binding energy of Bi\-\{\%4f\%\-\{7/2\}\} is related to the catalytic activity of these catalysts doped with bismuth oxide.

Wet air oxidation treatment of H-acid wastewater

This paper presents the effect of reaction factors on wet air oxidation(WAO) of H acid wastewater. Higher COD Cr removal were observed at low initial pH, high reaction temperature and no addition of Na 2SO 4. Initial oxygen pressure P O 2 should be consistent with the initial H acid concentration. The changes of some indexes were also studied. A significant initial (about 10 min) rapid reduction in COD Cr was observed at 200℃ and 250℃. The decline of pH and the increase of SO 2- 4 concentration were found in all the experiments. Some formic acid and large amount of acetic acid were detected in the treated solution in this study. The analysis of off gas indicated undetectable amount of SO 2 and nitrogen oxides. The biodegradability of H acid solution was greatly improved after WAO treatment. The ratio of BOD 5/COD Cr increased from initial 3 4% to 33 3% after one hour reaction at 160℃ and 3 MPa initial oxygen pressure(initial H acid concentration:10 g/L, mixing speed:300 r/min). The result of WAO of H acid production wastewater was similar to that of WAO of H acid pure compound in distilled water.

Catalytic wet air oxidation for the treatment of emulsifying wastewater

The wet air oxidation(WAO) and catalytic WAO(CWAO) of the high strength emulsifying wastewater containing nonionic surfactants have been investigated in terms of COD and TOC removal. The WAO and homogeneous CWAO processes were carried out at the temperature from 433 K to 513 K, with initial oxygen pressure 1 2 MPa. It was found that homogeneous catalyst copper(Cu(NO_3)_2) had an fairly good catalytic activity for the WAO process, and the oxidation was catalyzed when the temperature was higher than 473 K. Moreover, several heterogeneous catalysts were proved to be effective for the WAO process. At the temperature 473 K, after 2 h reaction, WAO process could achieve about 75% COD removal and 66% TOC removal, while catalysts Cu/Al_2O_3 and Mn-Ce/Al_2O_3 elevated the COD removal up to 86%—89% and that of TOC up to 82%. However, complete elimination of COD and TOC was proved to be difficult even the best non-noble catalyst was used. Therefore, the effluent from WAO or CWAO process need to be further disposed. The bioassay proved that the effluent from WAO process was amenable to the biochemical method.

Wet Air Oxidation of Wastewater from Tricylazole Production

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Wet Air Oxidation of Organic Wastewater Catalyzed by Doped Ceria

The catalytic wet air oxidation (CWAO) of H acid and phenol was investigated in the presence of Cu or Fe doped CeOsolid solutions, which were obtained by sol-gel method. The experiment results showed that the incorporation of Cu or Fe into the fluorite lattice of CeOstrongly enhanced the oxidation activity of the catalyst. At 90 ℃ and 0.1 MPa, H acid conversion was 70% for the Ce0.9Fe0.1O2-δ and 60% for the Ce0.9Cu0.1O2-δ catalyst. For phenol removal, the conversion was 70% for the Ce0.9Cu0.1O2-δ catalyst, while for the Ce0.9Fe0.1O2-δ the conversion was 30%. The results indicated that Ce0.9Cu0.1O2-δ was suitable for the treatment of organic wastewaters while Ce0.9Fe0.1O2-δ was suitable for the removal of H acid. The 70% phenol removal rate with Ce0.9Cu0.1O2-δ catalyst was markedly increased to 90% with Ce0.8Cu0.2O2-δ catalyst. However, the phenol removal reduced from 30% to 15% with Fe content increasing from 10% to 20%. For the H acid, the increase of the content of Cu or Fe tended to obviously increase the original reaction rate while the COD removal changed little.

Treatment of desizing wastewater from the textile industry by wet air oxidation

This paper describes the application of wet air oxidation to the treatment of desizing wastewater from two textile companies. A two\|liter high temperature, high pressure autoclave reactor was used in the study. The range of operating temperatures examined was between 150 and 290℃, and the partial pressure of oxygen ranged from 0.375 to 2.25 MPa. Variations in pH, COD Cr and TOD content were monitored during each experiment and used to assess the extent of conversion of the process. The effects of temperature, pressure and reaction time were explored extensively. More than 90% COD Cr reduction and 80% TOC removal have been obtained. The results have also been demonstrated that WAO is a suitable pre\|treatment methods due to improvement of the BOD\-5/COD\-\{Cr\} ratio of desizing wastewater. The reaction kinetics of wet air oxidation of desizing wastewater has been proved to be two steps, a fast reaction followed by a slow reaction stage.

Kinetics of Wet Air Oxidation of Wastewater from Natural Fiber Web Desizing

This work described the application of wet air oxidation (WAO) to the treatment of desizing wastewater from natural fiber processing. A two-liter autoclave batch reactor was used for the experiments. The range of operating temperature examined was between 150 and 290℃, and partial pressure of oxygen ranged from 0.375 to 2.25 MPa standardized at 25℃. Variations in Chemical Oxygen Demand(COD) and Total Organic Carbon(TOC) were monitored during each experiment and used to assess the performance of the process. Experimental results showed that WAO can be an efficient method for the treatment of desizing wastewater. Furthermore, Catalytic Wet Air Oxidation (CWAO) was applied to reduce the reaction temperature and pressure in WAO process. A higher COD removal ratio was achieved under more mild reaction condition with the aid of CWAO. A mathematical model was also proposed to simulate the WAO process of desizing wastewater, in which three distinct kinetics steps were considered to describe the degradation of starch. The model simulations were in well agreement with the experimental data.

Catalytic wet oxidation of aniline over Ru catalysts supported on a modified TiO_2

The catalytic wet air oxidation of aniline over Ru catalysts supported on modified Ti 2 （Ti 2, Ti0.9Ce0.1O2, Ti0.9Zr0.1O2） is investigated. A series of characterization techniques are conducted to determine the relationship between the physico-chemical properties and the catalytic performance. As a result of the good metal dispersion and large number of surface oxygen species, the Ru/Ti0.9 Zr0.1O2 catalyst presents the best catalytic activity among the tested samples. The effects of the operating conditions on the reaction are investigated and the optimal reaction conditions are determined. Based on the relationship between the by-products concentration and the reaction time, the reaction path for the catalytic oxidation of aniline is established. Carbonaceous deposits on the surface of the support are known to be the main reason for catalyst deactivation. The catalysts maintain a constant activity even after three consecutive cycles.

Fe salts as catalyst for the wet oxidation of o-chlorophenol

Catalytic wet air oxidation (CWAO) of o-chlorophenol in wastewater was studied in a stainless steel autoclave using four different Fe catalysts in the temperature range of 100?200 °C. Experimental results showed that high rate of o-chlorophenol and CODCr (Chemical Oxygen Demand, mg/L) removal by CWAO was obtained at relatively low temperature and pressure. The catalysts Fe2(SO4)3, FeSO4, Fe2O3 and FeCl3 all exhibited high catalytic activity. More than 93.7% of the initial CODCr and nearly 100% of o-chlorophenol were removed at 150 °C after 150 min with FeSO4 as catalyst. The CWAO of o-chlorophenol was found to be pseudo-first order reaction with respect to o-chlorophenol, with activation energy of 75.56 kJ/mol in the temperature range of 100-175 °C.

Selective oxidation of methylamine over zirconia supported Pt-Ru, Pt and Ru catalysts

Pt-Ru, Pt and Ru catalysts supported on zirconia were prepared by impregnation method and were tested in selective oxidation of methylamine （MA） in aqueous media. Among three catalysts, Ru/ZrO2 was more active than Pt/ZrO2 while Pt-Ru/ZrO2 demonstrated the best catalytic activity due to the fact that Pt addition efficiently promoted the dispersion of active species in bimetallic catalyst. Therefore, the - 100% TOC conversion and N2 selectivity were achieved over Pt-Ru/ZrO2, Pt/ZrO2 and Ru/ZrO2 catalysts at 190, 220 and 250 ℃, respectively.

WAO和CWAO工艺预处理制药废水的实验研究

采用湿式氧化(WAO)和催化湿式氧化(CWAO)工艺对制药废水进行预处理,考察温度,反应时间,初始氧分压,pH对COD去除率的影响。在反应温度260℃、初始氧分压2 MPa、反应时间2 h的条件下,采用WAO工艺的废水COD去除率达到74.1%,B/C由0.22提高到0.45,生化性显著改善。CWAO工艺通过添加5 g催化剂,COD去除率为91.3%,有效提高了湿式氧化法的处理效果。