Kinetics of catalytic oxidation of benzene, n-hexane, and emission gas from a refinery oil/water separator over a chromium oxide catalyst

With the advances made in the past decade, catalytic incineration of volatile organic compounds (VOCs) has become the technology of choice in a wide range of pollution abatement strategies. In this study, a test was undertaken for the catalytic incineration, over a chromium oxide (Cr2O3) catalyst, of n-hexane, benzene, and an emission air/vapor mixture collected from an oil/water separator of a refinery. Reactions were carried out by controlling the feed stream to constant VOC concentrations and temperatures, in the ranges of 1300-14,700 mg/m3 and 240-400 degrees C, respectively. The destruction efficiency for each of the three VOCs as a function of influent gas temperature and empty bed gas residence time was obtained. Results indicate that n-hexane and the oil vapor with a composition of straight- and branch-chain aliphatic hydrocarbons exhibited similar catalytic incineration effects, while benzene required a higher incineration temperature or longer gas retention time to achieve comparable results. In the range of the VOC concentrations studied, at a given gas residence time, increasing the operating temperature of the catalyst bed increased the destruction efficiency. However, the much higher temperatures required for a destruction efficiency of over 99% may be not cost-effective and are not suggested. A first-order kinetics with respect to VOC concentration and an Arrhenius temperature dependence of the kinetic constant appeared to be an adequate representation for the catalytic oxidation of these volatile organics. Activation energy and kinetic constants were estimated for each of the VOCs. Low-temperature destruction of the target volatile organics could be achieved by using the Cr2O3 catalyst.     

催化强化臭氧氧化处理化工园区生化尾水

以陶粒为载体,以TiO2,Fe2O3,MnO2为活性组分,考察不同活性组分的陶粒作为催化剂对化工园区生化尾水臭氧氧化能力的强化情况。结果表明,3种负载型催化剂均能有效强化臭氧氧化过程,显著降低生化尾水Abs、UV254以及COD等指标,其中以Fe2O3/陶粒的催化强化效果最为显著,能显著降低生化尾水在200~250 nm处的吸波强度,尾水UV254从0.580降至0.320,COD从240 mg/L降至194 mg/L。     

Kinetics of Catalytic Oxidation of Benzene,n-Hexane,and Emission Gas from a Refinery Oil/Water Separator over a Chromium Oxide Catalyst

ABSTRACT

With the advances made in the past decade, catalytic incineration of volatile organic compounds (VOCs) has become the technology of choice in a wide range of pollution abatement strategies. In this study, a test was undertaken for the catalytic incineration, over a chromium oxide (Cr₂O₃) catalyst, of n-hexane, benzene, and an emission air/vapor mixture collected from an oil/water separator of a refinery. Reactions were carried out by controlling the feed stream to constant VOC concentrations and temperatures, in the ranges of 1300–14,700 mg/m³ and 240–400 ° C, respectively. The destruction efficiency for each of the three VOCs as a function of influent gas temperature and empty bed gas residence time was obtained.

Results indicate that n-hexane and the oil vapor with a composition of straight- and branch-chain aliphatic hydrocarbons exhibited similar catalytic incineration effects, while benzene required a higher incineration temperature or longer gas retention time to achieve comparable results.

In the range of the VOC concentrations studied, at a given gas residence time, increasing the operating temperature of the catalyst bed increased the destruction efficiency. However, the much higher temperatures required for a destruction efficiency of over 99% may be not cost-effective and are not suggested. A first-order kinetics with respect to VOC concentration and an Arrhenius temperature dependence of the kinetic constant appeared to be an adequate representation for the catalytic oxidation of these volatile organics. Activation energy and kinetic constants were estimated for each of the VOCs. Low-temperature destruction of the target volatile organics could be achieved by using the Cr₂O₃ catalyst.     

Catalytic oxidation of organic compounds in incineration flue gas by a commercial palladium catalyst

The object of this study is to investigate the effect of different operation conditions on the catalytic oxidation of trace organic compounds [i.e., benzene, toluene, ethylbenzene, and xylene (BTEX); and polyaromatic hydrocarbons (PAHs)] in incineration flue gas. A commercial Pd-based honeycomb catalyst, which is applied to treat flue gas with low organic concentrations and high gas velocity, is employed in this study. The investigated parameters include (1) effect of different space velocities, (2) effect of heavy metals, (3) effect of acid gas, and (4) effect of water vapor and ash particles. In this work, an effective catalyst oxidation system is constructed and expected to purify the incineration flue gas. Catalyst oxidation is a potential purification system that will meet the stricter regulations on the emissions of incineration systems. Experimental results showed that the destruction efficiency of PAHs and BTEX in Pd catalyst was generally greater than 80%. Decreasing the space velocity increased the decomposition efficiency of organic compounds. When the feedstock contained the heavy metals Pb and Cr, the oxidation of organic compounds was not inhibited. But the presence of Cd significantly decreased the oxidation efficiency. The acid gases SO2 and HCl in the flue gas could have influenced the crystal structure of PdO and subsequently deactivated/poisoned the Pd catalyst. The effect of water vapor on the catalytic destruction of PAHs and BTEX was not obvious.     

Al2O3-supported transition-metal oxide catalysts for catalytic incineration of toluene

The catalytic incineration of toluene over gamma-Al2O3-supported transition-metal oxide catalysts in the temperature range of 200-380 degrees C was investigated employing a fixed bed flow reactor. CuO/gamma-Al2O3 was found to be the most active of seven catalysts tested. Using this catalyst with different wt% Cu in the incineration of toluene, we found that the optimal Cu content was 5 wt%. X-ray diffraction, BET surface area and hydrogen-temperature-programmed reduction showed that it was mainly the formation of large CuO crystals that caused declines in catalyst activity at Cu content above 5 wt%. Addition of water vapor or CO2 inhibited catalyst activity, but this effect was reversible. Although coexistence of toluene and n-hexane resulted in a reduction in n-hexane conversion, the impact on toluene oxidation was only negligible. Temperature-programmed desorption revealed that this differential effect was due to more competitive adsorption of toluene onto active sites of the catalyst.     

基于催化陶瓷纤维滤管的一体化烟气净化工艺处理危废焚烧烟气的中试示范工程

实现烟气多污染物一体化净化成为危废焚烧烟气治理领域的新趋势。提出了基于催化陶瓷纤维滤管的危废焚烧烟气一体化处理工艺,并依托江苏某危险废物焚烧厂建设了中试示范工程,以考察该工艺的处理效果。结果表明：该工程可实现对危废焚烧烟气进行除尘、脱酸、脱硝及降解二恶英等处理的集约、高效运行;其关键技术为催化陶瓷纤维管的应用;运行成本较传统工艺降低了约30%,且具有处理效率更高、占地面积更小、投资和运行费用更低等优点。本示范工程可为现役危废焚烧烟气净化工程的改造及新建项目实现深度净化提供参考。     

The promoter effect and a rate expression of the catalytic incineration of (CH3)2S2 over an improved CuO-MoO3/gamma-Al2O3 catalyst

The CuO-MoO3/gamma-Al2O3 catalyst, confirmed previously as having good activity in the catalytic incineration of (CH3)2S2, was employed as the principal catalyst in this study. With the aim of improving catalyst activity and resistance to deactivation by sulfur compounds, a promoter was added either before adding the precursors of Cu and Mo or together with Cu and Mo onto the gamma-Al2O3. Promoters included transition metals and elements from groups IA-VIIA in the chemical periodic table. Experimental results reveal Cr2O3 as the most effective promoter, with an optimal composition of 5 wt.% Cu, 6 wt.% Mo and 4 wt.% Cr (designated as Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3). Knowing that higher acidity can improve activity, we further investigated the effect of acid treatment on the performance of the Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3 catalyst. Experimental results indicate the H2SO4-treated catalyst (Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3) has a better activity and durability. A study for finding an appropriate rate expression for the catalytic incineration of (CH3)2S2 by Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3 was carried out in a differential reactor. The results show that the Mars-Van Krevelen model is applicable to this destructive oxidation reaction. Results additionally reveal that competitive adsorption of CH4 reduces conversion of (CH3)2S2.     

Incinerating volatile organic compounds with ferrospinel catalyst MnFe2O4: an example with isopropyl alcohol

This paper concerns the incineration of isopropyl alcohol (IPA) using the ferrospinel catalyst MnFe2O4. It covers the preparation of the ferrospinel catalyst, the screening of catalytic activity, catalytic incineration testing, and 72-hr decay testing of the catalyst. The experimental results of catalyst screening reveal that the Mn/Fe catalyst is the best of five prepared catalysts (chromium/iron [Cr/Fe], manganese/iron [Mn/Fe], zinc/iron [Zn/Fe], nickel/iron [Ni/Fe], and pure magnetite [Fe3O4]). In tests of the catalytic incineration system used to convert IPA, 98% conversion was obtained at a space velocity of 24,000 hr(-1), an oxygen (O2) content of 21%, 1700 ppm of IPA, and a reaction temperature of 200 degrees C.     

高表面氧MnOx/类水滑石催化剂常温催化低浓度甲醛的性能

常温催化氧化技术是去除室内低浓度甲醛(HCHO)的一种有效方法,其中过渡金属氧化物锰基催化剂在催化降解方面性能优异,相较于贵金属催化剂,具有成本低、活性高、稳定性良好、应用前景广等优点。采用共沉淀法制备了类水滑石载体和锰基/类水滑石催化剂,将类水滑石与锰基氧化物相结合用于常温催化氧化,克服了锰基氧化物常温条件下因大量吸附水蒸气而导致稳定性降低的缺点,同时研究考察了载体组成、煅烧温度、氧化锰负载量等对催化剂常温催化氧化性能的影响,并通过XRD、SEM、BET、EPR、XPS等技术对催化剂进行了微观表征。结果表明,当类水滑石中n(Mg)∶n(Al)=4∶1,氧化锰负载量 (质量分数) 为40%,煅烧温度为200 ℃时,所述MnO_x/Mg₄Al₁催化剂性能最佳,其48 h甲醛去除率高达98.5%,甲醛质量浓度由1.000 mg·m^-3降至0.015 mg·m⁻³。类水滑石载体表面存有大量羟基基团,有利于吸附低浓度甲醛及中间产物进而利于催化剂催化氧化性能提升。通过XPS分析可知,相较于MnO_x催化剂,MnO_x/Mg₄Al₁催化剂中O_β/(O_α+O_β)相对含量比例由35.7%提升至88.0%,表面氧含量(O_β)大幅提升,其在甲醛常温催化氧化过程中发挥着极其重要作用。本研究结果可为常温催化氧化甲醛提供参考。     

CuxFe1-x@γ-Al2O3催化剂湿式氧化陶瓷印花废水的性能及表征

采用常温浸渍法制备催化剂CuxFe1-x@γ-Al2O3,并用于陶瓷印花废水的催化湿式氧化处理,考察组分构成对催化剂CuxFe1-x@γ-Al2O3活性和稳定性的影响。结果表明：在4种样品Cu0.5Fe0.5@γ-Al2O3,Cu@γ-Al2O3,Fe@γ-Al2O3和γ-Al2O3中,Cu0.5Fe0.5@γ-Al2O3的催化活性和稳定性最高。催化剂Cu0.5Fe0.5@γ-Al2O3中的Fe促进Cu进入γ-Al2O3载体内部并形成稳定的固溶体Al2CuO4,故此催化剂的硬度和稳定性最高;此催化剂应用前后的SEM图无明显的形貌变化,XRD谱图无明显的物相变化,证实了其稳定性的存在。在优化的操作条件下,催化剂Cu0.5Fe0.5@γ-Al2O3催化湿式氧化陶瓷印花废水的COD及色度分别为280 mg·L-1、20倍,达到《污水综合排放标准》（GB 8978-1996）中染料类废水的三级排放标准。     

负载型钌铈催化剂的甲苯催化氧化性能

以ZSM-5分子筛为载体,采用浸渍法制备了RuCe/ZSM-5催化剂,研究了催化剂在不同Ru负载量、空速、反应温度、甲苯浓度下对甲苯的催化氧化性能,并探讨了催化剂的CO₂选择性及稳定性。结果表明：Ru的负载可提升CeO₂(20)/ZSM-5催化剂催化甲苯使其降解成高浓度CO₂的能力;Ru(1.0)/CZ催化剂表现出优异的低温催化性能、CO₂选择性及稳定性,在210 ℃条件时即可转化90%的甲苯,且CO₂选择性达到90%以上。本研究制备的催化剂在较大空速及甲苯浓度范围内对甲苯具有优越的低温催化性能,未来可应用于VOC的工业化处理应用中。     

Catalytic NOx reduction with simultaneous dioxin and furan oxidation

The engineering, construction, performance and running costs of a catalytic flue gas cleaning component in the low dust area of a municipal waste incinerator is discussed. For this purpose, the case study of a Flemish incineration plant is presented, covering the history, the design procedure of the catalyst, relevant process data and the financial aspects. A reliable PCDD/F-destruction by means of oxidation by the catalyst to typical values of 0.001 ng TEQ/Nm3 has been demonstrated. At the same time, NOx- and CO-emissions are reduced by 90% and 20% to about 50 mg/Nm3 and below 10 mg/Nm3, respectively.     

Production of copper-based rare earth composite metal materials by coprecipitation and applications for gaseous ammonia removal

This study addresses the oxidation of ammonia (NH3) at temperatures between 423 and 673 K by selective catalytic oxidation (SCO) over a copper-based, rare earth composite metal material that was prepared by coprecipitating copper nitrate, lanthanum nitrate, and cerium nitrate at various molar ratios. The catalysts were characterized using Brunner, Emmett, and Teller spectroscopy, Fourier-transform infrared spectroscopy, Xray diffraction, ultraviolet-visible spectroscopy, cyclic voltammetric spectroscopy, and scanning electron microscopy. At a temperature of 673 K and an oxygen content of 4%, approximately 99.5% of the NH3 was reduced by catalytic oxidation over the 6:1:3 copper-lanthanum-cerium (molar ratio) catalyst. Nitrogen (N2) was the main product of this NH3-SCO process. Results from the activity and selectivity tests revealed that the optimal catalyst for catalytic performance had the highest possible cerium content and specific surface area (43 m2/g).     

Incinerating Volatile Organic Compounds with Ferrospinel Catalyst MnFe2O4: An Example with Isopropyl Alcohol

Abstract

This paper concerns the incineration of isopropyl alcohol (IPA) using the ferrospinel catalyst MnFe₂O₄. It covers the preparation of the ferrospinel catalyst, the screening of catalytic activity, catalytic incineration testing, and 72-hr decay testing of the catalyst. The experimental results of catalyst screening reveal that the Mn/Fe catalyst is the best of five prepared catalysts (chromium/iron [Cr/Fe], manganese/iron [Mn/Fe], zinc/iron [Zn/Fe], nickel/iron [Ni/Fe], and pure magnetite [Fe₃O₄]). In tests of the catalytic incineration system used to convert IPA, 98% conversion was obtained at a space velocity of 24,000 hr^?1, an oxygen (O₂) content of 21%, 1700 ppm of IPA, and a reaction temperature of 200 °C.     

Catalytic NO(chi) reduction with simultaneous dioxin and furan oxidation

The engineering, construction, performance and running costs of a catalytic flue gas cleaning component in the low dust area of a municipal waste incinerator is discussed. For this purpose, the case study of a Flemish incineration plant is presented, covering the history, the design procedure of the catalyst, relevant process data and the financial aspects. A reliable PCDD/F-destruction by means of oxidation by the catalyst to typical values of 0.001 ng TEQ/Nm3 has been demonstrated. At the same time, NO(chi)- and CO-emissions are reduced by 90% and 20% to about 50 mg/N m3 andbelow 10 mg/N m3, respectively.     

贵金属催化剂活性组分分布对催化湿式氧化处理非达霉素提炼废水的影响

采用均匀型和蛋白型Ru/TiO₂催化剂为湿式氧化催化剂,应用于催化湿式氧化非达霉素提炼废水,以出水COD和TOC去除率作为指标来评价2种催化剂的催化活性差异;采用实验室连续评价装置对柱状颗粒催化剂在不同pH、不同废水流量和不同温度下处理非达霉素提炼废水进行了优化评价。结果表明：在265 ℃、pH=4.1、废水流量为10 mL·h⁻¹时,催化剂的催化活性最高,故确定此条件为该废水处理的最优条件;同时对比均匀型和蛋白型2种催化剂,蛋白型催化剂具有更高的催化效率;结合SEM及N₂-物理吸附结果,推断蛋白型催化剂活性组分集中分布在催化剂颗粒的较浅层,有利于降低反应过程中的扩散阻力,提高贵金属活性组分的利用率,进而提高催化剂的催化活性。以上结果对开发高效湿式氧化催化剂,充分利用贵金属活性组分降低催化剂成本具有十分重要的意义。     

铈锆比率及过渡金属掺杂对Pd/CexZr1-xO2催化剂性能的影响

采用均相共沉淀法制备了不同铈锆比率的复合氧化物,并用等体积浸渍法制备了其负载的Pd/CexZr1-xO2催化剂。考察了铈锆比率对复合氧化物性质及其负载单Pd催化剂催化氧化柴油机尾气性能的影响。在此基础上,掺杂Mn、Ni和Cu对催化剂进行改性并考察反应活性。利用XRD、BET、H2-TPR和TEM等技术对样品进行表征。结果表明,Ce/Zr为1/1时Pd/CZ催化剂抗烧结性能最佳;过渡金属和铈锆协同作用一定程度上提高了柴油机氧化催化剂(DOC)的催化活性;Cu和Mn的掺杂能有效降低CO、碳氢化合物(HC)和NO的起燃温度,提高柴油机尾气催化氧化性能;Ni对催化性能的改善不明显。     

2种制备方法对Pt/Co-Ce催化氧化甲苯性能的影响

针对高效催化氧化甲苯催化剂的开发,采用2种不同制备方法制备Pt纳米颗粒并负载在Co-Ce载体上,以实现甲苯的高效脱除;并通过ICP-OES、XRD、HRTEM、H₂-TPR、XPS等研究了制备方法对Pt/Co-Ce催化氧化甲苯性能的影响。结果表明,铂纳米胶体浸渍法制备的Pt纳米颗粒尺寸均匀分布在2~4 nm,高活性零价Pt比例高达93.37%。Pt纳米颗粒与Co-Ce载体之间存在相互作用,提升了催化剂的表面氧浓度,使得Co³⁺的还原温度降低了158 ℃,强化了催化剂的氧化还原性能。因此,0.5Pt/CoCeO_x-N催化剂具有优异的甲苯催化氧化性能,与氯铂酸浸渍法制备的0.5Pt/CoCeO_x-I催化剂相比,T₅₀下降了68 ℃。本研究结果可为高性能的VOCs催化氧化催化剂的设计提供参考。     

SO2对La0.65X0.35FeO3钙钛矿催化剂协同催化氧化NO和甲苯的影响

采用KIT-6硬模板辅助溶胶凝胶法制备了不同过渡金属元素A位掺杂改性的La_0.65X_0.35FeO₃(X=Cu、Ce、Mn、Co)钙钛矿催化剂,并利用XRD、BET、SEM、H₂-TPR、热重(TGA)、SO₂-TPD及XPS表征了SO₂对La_0.65X_0.35FeO₃钙钛矿催化剂协同催化氧化NO和甲苯的活性影响机制。结果表明,过渡金属的引入可提高催化剂催化性能,La_0.65X_0.35FeO₃钙钛矿催化剂在温度为100~400 ℃时表现出比LaFeO₃催化剂更高的活性。其中,La_0.65Co_0.35FeO₃催化剂活性最佳,在300 ℃时其NO转化率为60%,甲苯的T₉₀为330 ℃。另外,SO₂对La_0.65X_0.35FeO₃钙钛矿催化剂协同催化氧化NO和甲苯的活性均表现为抑制作用。这是由于SO₂容易和催化剂的金属位点发生反应生成表面硫酸盐沉积物,导致活性位点失效并堵塞孔道结构,从而会抑制NO和甲苯的氧化反应。然而,过渡金属的A位掺杂可增大表面积、增强氧化还原性,以引起结构畸变而产生更多的氧空位,提供更多活性位点,从而减弱SO₂的抑制作用。本研究可为开发高效协同催化氧化氮氧化物(NO_x)和挥发性有机化合物(VOCs)的抗硫催化剂提供参考。     

Ni/Fe-supported over hydrotalcites precursors as catalysts for clean and selective oxidation of Basic Yellow 11: Reaction intermediates determination

In this work, Basic Yellow 11 (BY 11) was employed as model compound to study catalytic wet air oxidation as a pre-treatment step to the conventional biological oxidation. Ni and Fe catalysts supported over hydrotalcite (HT) were prepared by incipient wetness and excess impregnation to obtain catalysts with different metal loadings (from 1 to 10 wt.%). HTs were synthesized by co-precipitation and characterized with XRD, X-ray fluorescence (XRF), BET, thermogravimetric analysis and SEM. Results showed that dye conversion increased with Ni and Fe content up to 7 wt.% and that the most effective catalyst were prepared by incipient wetness impregnation. The influence of metal loading in the catalyst, and the preparation method as well as the reaction conditions was investigated. A mechanism and reaction pathways for BY 11 during catalytic liquid phase oxidation have also been proposed.