Superior Pillared Clay Catalysts for Selective Catalytic Reduction of Nitrogen Oxides for Power Plant Emission Control

ABSTRACT

Fe³+-, Cr³+-, Cu²+-, Mn²+-, Co²+-, and Ni²+-exchanged Al₂O₃-pillared interlayer clay (PILC) or TiO₂-PILC catalysts are investigated for the selective catalytic reduction (SCR) of nitric oxide by ammonia in the presence of excess oxygen. Fe³+-exchanged pillared clay is found to be the most active. The catalytic activity of Fe-TiO₂-PILC could be further improved by the addition of a small amount of cerium ions or cerium oxide. H₂O and SO₂ increase both the activity and the product selectivity to N₂. The maximum activity on the Ce-Fe-TiO₂-PILC is more than 3 times as active as that on a vanadium catalyst. Moreover, compared to the V₂O₅-WO₃/TiO₂ catalyst, the Fe-TiO₂-PILC catalysts show higher N₂/N₂O product selectivities and substantially lower activities (by ~85%) for SO₂ oxidation to SO₃ under the same reaction conditions. A 100-hr run in the presence of H₂O and SO₂ for the CeO₂/Fe-TiO₂-PILC catalyst showed no decrease in activity.     

The effects of manganese precursors on Mn-based/TiO2 catalysts for catalytic reduction of NO with NH3

Manganese acetate (MnAc) and manganese nitrate (MnN) were employed as precursors for the preparation of MnAc)/TiO2, Mn (N)/TiO2, Mn(Ac)-Ce/TiO2, and Mn(N)-Ce/TiO2 by impregnation. These complexes were used as catalysts in the low-temperature selective catalytic reduction of NO with NH3. The influence of manganese precursors on catalyst characteristics, the reduction activity, and the stability of the catalysts to poisoning by H2O and SO2 were studied. Experiments showed that Mn(N) produced MnO2 with large grain sizes in Mn(N)/TiO2 catalyst. On the contrary, Mn(Ac) led to highly dispersed and amorphous Mn2O3 in Mn (Ac)/TiO2 catalyst, which had better catalytic activity and stability to SO2 at low temperatures. The doping of cerium reduced the differences in catalytic performance between the catalysts derived from different Mn precursors.     

Fe2O3-Cr2O3/TiO2系列催化剂的结构和脱硝性能

研究以纳米TiO2为载体,浸渍负载过渡金属氧化物,以CO为还原剂的脱硝催化剂的脱硝性能。实验中以计算量的Ni（NO3）2和Fe（NO3）3混合溶液浸渍纳米TiO2粉末,室温下搅拌30 min至混合均匀,放入旋转蒸发器中,70℃下至水分蒸干为止;所得粉末在550℃下、空气气氛中焙烧4 h即得所需催化剂。用以上方法分别制备2%Fe2O3-10%Cr2O3/TiO2、4%Fe2O3-8%Cr2O3/TiO2、6%Fe2O3-6%Cr2O3/TiO2、8%Fe2O3-4%Cr2O3/TiO2与10%Fe2O3-2%Cr2O3/TiO2等5种催化剂样品。实验结果表明,制备的催化剂具有较好的结构,分散较为均匀。对于CO＋NO反应,Fe2O3-Cr2O3/TiO2系列催化剂具有较好的催化活性,NO的转化率都达到了100%。其中,10%Fe2O3-2%Cr2O3/TiO2样品具有最好的低温活性,H2-TPR结果表明,这是由于10%Fe2O3-2%Cr2O3/TiO2催化剂更易于被CO预还原。     

TiO2纳米管催化活性再生处理技术

采用H2O2、Fe2（SO4）3和Fenton溶液对失活的TiO2纳米管进行再生处理，重点考察了3种溶液的浓度和处理时间等对再生效果的影响，初步分析了经处理后TiO2纳米管催化活性得到再生或增强的机理。结果表明，经H2O2溶液处理后TiO2催化活性能得到有效再生，经Fe2（SO4）3，和Fenton溶液处理后其催化活性不仅得到再生，还能显著增强，这与H2O2和Fenton的强氧化作用，及进入TiO2纳米管的Fe3＋的阻止电子．空穴对再复合作用有关。     

Effects of NO2 and SO2 on selective catalytic reduction of nitrogen oxides by ammonia

The selective catalytic reduction (SCR) characteristics of NO and NO(2) over V(2)O(5)-WO(3)-MnO(2)/TiO(2) catalyst using ammonia as a reducing agent have been determined in a fixed-bed reactor at 200-400 degrees C. The presence of NO(2) enhances the SCR activity at lower temperatures and the optimum ratio of NO(2)/NO(x) is found to be 0.5. During the SCR reactions, there are some side reactions occurred such as ammonia oxidation and N(2)O formation. At higher temperatures, the selective catalytic oxidation of ammonia and the nitrous oxide formation compete with the SCR reactions. The denitrification (DeNO(x)) conversion decreases at lower temperatures but it increases at higher temperatures with increasing SO(2) concentration. The presence of SO(2) in the feeds inhibits N(2)O formation.     

SO2-4/TiO2光催化降解苯酚

以工业硫酸氧钛为原料水解制得SO42-/TiO2光催化剂,并以苯酚为目标降解物,考察了SO24-/TiO2的光催化性能。结果表明:随着SO42-/TiO2制备过程中焙烧温度的升高,其光催化活性逐渐增加,650℃焙烧获得的SO24-/TiO2的光催化活性最好,此后再升高温度会因催化剂中硫的挥发而下降;在确定苯酚原液初始浓度为50 mg/L条件下,SO42-/TiO2的光催化降解苯酚的最佳工艺条件为反应时间2 h、苯酚pH为7、催化剂用量1 g/L。XRD、SEM和FTIR的分析结果显示实验温度下制得的SO42-/TiO2均为锐钛型TiO2;其间掺杂的SO24-在TiO2表面分散性较好,没有聚集成大的颗粒;红外分析的结果初步判定低温(<550℃)焙烧制得的催化剂SO42-在TiO2表面是螯合双配位吸附,高温焙烧时(>550℃)SO42-在TiO2表面是桥式配位吸附。     

Effect of the carbon coating in Fe-C-TiO(2) photocatalyst on phenol decomposition under UV irradiation via photo-Fenton process

Fe-C-TiO(2) photocatalysts which contained the residue carbon (0.2-3.3 mass%) were prepared from a mixture of TiO(2) and FeC(2)O(4) through the heating at 673-1173 K in Ar. These photocatalysts did not show a high adsorption of phenol, but they were active in photo-Fenton reactions during decomposition of phenol under UV irradiation with addition of H(2)O(2). It was proved that Fe(2+) governed the photoactivity of Fe-C-TiO(2) photocatalysts, it decreased with heat-treatment temperature above 773 K. For comparison, Fe-TiO(2) photocatalyst was prepared by heating TiO(2) and FeC(2)O(4) at 823 K in air for 3h. Phenol decomposition was going much slower on Fe-TiO(2) photocatalyst in comparison with Fe-C-TiO(2), of which mechanism was different, on the former phenol was decomposed by the radical reaction, on the latter through a complex reaction with iron and intermediates of phenol decomposition. Therefore carbon-coating TiO(2) was found to be advantageous for mounting iron and its application for the phenol decomposition via photo-Fenton process.     

CuCoOx／TiO2催化氧化NO性能研究

采用浸渍法制备了CuCoOx／TiO2催化剂，考察了焙烧温度、反应温度、氧含量、NO浓度和空间速度对催化剂催化氧化NO性能的影响，并考察了催化剂的抗硫抗水性能。XRD、TPR和BET分析表明，350℃焙烧的催化剂具有CuCo2O4尖晶石结构，比表面积大，对NO的氧化效果好。在空速为5000h^-1，NO进口浓度500mg／m^3，含氧量10％的条件下，反应温度300℃时NO转化率可达79．5％，250℃时NO转化率接近50％。该催化剂具有良好的单独抗SO2、抗H2O毒化性能，H2O和SO2同时存在时很快失活。该催化剂可用于不同时含H2O和SO2的含NO气体催化氧化后再吸收处理。     

Supported transition-metal oxide catalysts for reduction of sulfur dioxide with hydrogen to elemental sulfur

This work is for the purpose to find a high performance catalyst for the catalytic reduction of SO2 with H2 as a reducing agent. NiO/gamma-Al2O3 catalyst was found to be the most active catalyst among the seven gamma-Al2O3-supported metal-oxide catalysts tested. With NiO as the active species, of the supports tested, gamma-Al2O3 was the most suitable one and the optimal Ni content was 16 wt%. Using this NiO/gamma-Al2O3 catalyst, we found that the optimal feed ratio of H2/SO2 is 2:1 and the catalyst presulfided with H2 + H2S exhibits a higher performance than that pretreated with H2 or He. XRD patterns reveal that the nickel oxide experienced a transformation to Ni3S2 and NiS, and then to NiS2, the most active nickel sulfide, during the reaction process. The reason for the highest catalyst activity of 16 wt% Ni was attributed to the largest amount of NiS2. Water vapor in the feed gas reactant caused inhibition of catalyst activity, whereas H2S promoted the reduction of SO2. These phenomena were rationalized with the aid of Claus reaction.     

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

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.     

Surface properties and catalytic performance of La(1-x)Sr(x)FeO(3) perovskite-type oxides for methane combustion

La(1-x)Sr(x)FeO(3) (x=0.0-1.0) perovskites were prepared and tested for the combustion of methane. X-ray diffraction (XRD) patterns revealed the presence of a single perovskite structure for substitutions 0x0.3, however Fe(2)O(3), SrCO(3) and SrFeO(3) phases were observed for substitutions x>0.3. The results of activity test indicate that with La(1-x)Sr(x)FeO(3) as the catalyst, the combustion of methane can take place at low temperatures around 400 degrees C. Partial substitution of La with Sr increases the activity and an optimal substitution fraction (x=0.5) exists in the La(1-x)Sr(x)FeO(3) catalysts. Catalyst activity can be well correlated to the product of the specific surface area and atomic ratio of Fe to La+Sr on the catalyst surface. Experimental results of O(2)-TPD and CH(4)-TPD in the range of 350-500 degrees C indicate that the amount of oxygen desorbed from the La(1-x)Sr(x)FeO(3) catalysts is far larger than that of methane. Therefore, it can be proposed that the catalytic oxidation of CH(4) over these catalysts proceeds with the surface reaction between CH(4) in the gas phase and the adsorbed O(2). Addition of water vapor or CO(2) to the feed inhibited catalyst activity, but the inhibition was reversible and became negligible at high reaction temperature.     

Effect of CO on NO oxidation over platinum based catalysts for hybrid fast SCR process

The oxidation characteristics of NO over Pt/TiO2 (anatase, rutile) catalysts have been determined in a fixed bed reactor as a function of O2, CO and SO2 concentrations in the presence of 8% water. The conversion of NO to NO2 increases with increasing O2 concentration up to 12% and it levels off. This saturation effect is more pronounced over rutile-Pt/TiO2 (r-Pt/TiO2) than that of anatase-Pt/TiO2 (a-Pt/TiO2). The presence of CO increases NO oxidation significantly and this enhanced effect is more pronounced on a-Pt/TiO2 than that on r-Pt/TiO2 with increasing CO concentration at lower temperatures. The same effect is also observed on the catalysts with different Pt and tungsten oxide (WO3) loadings. With increasing Pt and WO3 loadings on TiO2 support (Pt-WO3/TiO2), formation of NO2 is high even at lower temperatures. The presence of SO2 significantly suppresses the oxidation of NO over both r-Pt/TiO2 and a-Pt/TiO2 catalysts but it is less pronounced due to low stability of sulfate on a-Pt/TiO2.     

H2O和SO2对V2O5-WO3/TiO2催化剂催化氧化NO的影响

研究了在120℃的反应温度下,H2O和SO2对V2O5-WO3/TiO2催化剂选择性催化氧化（SCO）NO的影响。结果表明,在H2O和SO2存在的情况下催化剂失活很快,停止通入H2O和SO2后活性不能恢复,但在加热到250℃后催化活性基本恢复。FT-IR分析表明,催化剂表面形成了金属硝酸盐和Ti的硫酸盐,对催化活性有一定影响,但不影响催化剂在250℃下催化活性的恢复。SO2、H2O和NO的竞争吸附与SO2和NO2的铅室反应是影响催化剂活性的主要原因。     

Catalytic reduction of N2O over Ag-Pd/Al2O3 bimetallic catalysts

A study of the catalytic conversion of N2O to N2 over a bimetallic Ag-Pd catalyst is described in this article. Several Ag-Pd catalytic systems were prepared supported on Al2O3 with different ratios and their catalytic activity for the direct decomposition of N2O and their reduction with CO was measured. Based on the experimental results, it was observed that Ag-Pd bimetallic catalyst (5-0.5%) was the most active for both nitrous oxide reduction and direct decomposition. This high activity seems to be connected with a synergistic effect between Ag and Pd.     

Ti-Ce-Zr-Ox复合脱硝催化剂的制备及其性能研究

采用共混法制备了Ti-Ce-Zr-Ox复合脱硝催化剂TiCe0.1Zr0.1O2.4,运用X射线衍射、氮气物理吸附、扫描电镜等表征手段,分别对该催化剂的晶型、表面积、孔分布及结构形貌进行了分析,同时考察了反应温度、空速、水蒸气和SO2对该催化剂NH3选择性催化还原NO的影响.结果表明,TiCe0.1Zr0.1O2.4催...     

Catalytic degradation of Orange II by UV-Fenton with hydroxyl-Fe-pillared bentonite in water

Although homogeneous photo-Fenton system is a very efficient method for organic wastewater treatment, it suffers from costly pH adjustment as well as difficult separation of catalysts from aqueous in practical application. Through cation exchange reaction, hydroxyl-Fe-pillared bentonite (H-Fe-P-B) was successfully prepared as a solid catalyst for UV-Fenton to degrade non-biodegradable azo-dye Orange II. Compared with raw bentonite, the content of iron, interlamellar distance and external surface area of H-Fe-P-B increased remarkably. H-Fe-P-B had good photosensitivity and catalyst reactivity. And the catalytic activity of H-Fe-P-B for H(2)O(2) came from hydroxyl-Fe between sheets rather than Fe(3+) or Fe(2+) in tetrahedral or octahedral sheets of bentonite. In UVA-H(2)O(2) system, H(2)O(2) could destroy the azo bond of excited Orange II molecules but could not effectively mineralize it. After 120 min treatment, 83% discoloration was obtained while only 2% of TOC was removed. When H-Fe-P-B was used as catalyst, a significant degradation of Orange II was observed at the same condition as UVA-H(2)O(2) system. Almost 100% discoloration and more than 60% TOC removal of Orange II could be achieved after 120 min treatment. Because of the strong surface acidity and the electronegativity of H-Fe-P-B, the pH range of this catalyst in the Orange II discoloration could be extended up to 9.5. And this catalyst showed good stability during Orange II degradation in water in wide range of pH (3.0-9.5). These results indicated that the H-Fe-P-B was a promising catalyst for UV-Fenton system.     

铁氧化物复合氧化铝催化臭氧化过程中溴酸盐的生成控制

以市售活性炭、硅藻土和氧化铝小球为载体，考察了负载铁基活性组分对催化臭氧化过程中溴酸盐的控制情况，其中，铁基复合氧化铝小球体现出更好的溴酸盐还原特性和催化剂稳定性，证实催化剂中铁氧化物是溴酸盐得到有效控制的主要活性组分。进一步考察了铁基复合氧化铝小球催化臭氧化处理实际原水过程中对溴酸盐的生成控制，以及反应过程中溶解性有机碳（DOC）的去除情况。结果表明，与单独臭氧化相比，该催化剂既能有效去除水中的溶解性有机物，又能明显抑制溴酸盐的生成，反应50h，其活性并没有明显下降。催化剂失活主要归因于吸附位点数量的下降，可以通过负载铁氧化物来实现催化剂的再生。     

Performance of the supported copper oxide catalysts for the catalytic incineration of aromatic hydrocarbons

A fixed bed reactor was used to assess the catalytic incineration of toluene by various transition-metal oxide species supported on gamma-Al(2)O(3). CuO/gamma-Al(2)O(3) was found to be the most active of seven catalysts investigated. The CuO species, with a Cu content of 5% (wt), was hence used with four different supports (CeO(2), gamma-Al(2)O(3), TiO(2) and V(2)O(5)) in order to define the optimal combination. Results of the catalytic incineration of toluene, X-ray diffraction (XRD) analysis, oxygen-temperature programmed desorption (O(2)-TPD), toluene-temperature programmed desorption (toluene-TPD) and hydrogen-temperature programmed reduction (H(2)-TPR) showed that CuO/CeO(2) was the most active catalyst, followed by CuO/gamma-Al(2)O(3). The activity of CuO/CeO(2) with respect to the VOC molecule was observed to follow this sequence: toluen>p-xylene>benzene. The addition of water vapor or CO(2) significantly inhibited the activity of the CuO/CeO(2) and CuO/gamma-Al(2)O(3) catalysts. The inhibiting effect of both was reversible for CuO/gamma-Al(2)O(3). For CuO/CeO(2), the inhibiting effect of CO(2) was reversible and even insignificant at a higher temperature (220 degrees C), but the effect of H(2)O vapor was somewhat irreversible at lower incineration temperatures (220 degrees C). For complete oxidation of toluene, the required reaction temperature increased with gas hourly space velocity (GHSV) and toluene inlet concentration.     

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.