On the utilization of modified red mud in dimethyl disulfide and methyl mercaptan emission abatement

In this paper, a novel application of industrial waste, namely red mud (RM), in the abatement of two malodorous and harmful sulfur compounds, dimethyl disulfide (DMDS) and methyl mercaptan (MM), is presented. The effects of calcination and activations with hydrochloric acid or a mixture of hydrochloric and orthophosphoric acid on the properties and performance of RM are compared using laboratory-scale experiments. The RM-based materials were characterized by XRF, XRD, FE-SEM, N2 -physisorption, TGA/DTA, and FTIR analyses. RM exhibits very promising catalytic properties in the abatement of both DMDS and MM. The hydrochloric acid-activated RM was the most active in both cases, which was explained by its rather high specific surface area (144 m2 g −1 ), higher contents of Fe2O3 and TiO2, as well as lower content of phosphorus. For both DMDS and MM, the main oxidation products were sulfur dioxide, carbon monoxide, and carbon dioxide. DMDS was observed as a reaction intermediate in MM oxidation. While the final conversions of DMDS and MM were high, the oxidation was not complete, indicated by the formation of carbon monoxide. Nevertheless, the modified RM appears as a very interesting alternative to the existing DMDS and MM abatement catalysts.Web of Science121art. no.

Catalytic oxidation of chlorinated volatile organic compounds, dichloromethane and perchloroethylene:new knowledge for the industrial CVOC emission abatement

Abstract The releases of chlorinated volatile organic compounds (CVOCs) are controlled by strict regulations setting high demands for the abatement systems. Low temperature catalytic oxidation is a viable technology to economically destroy these often refractory emissions. Catalysts applied in the oxidation of CVOCs should be highly active and selective but also maintain a high resistance towards deactivation. In this study, a total of 33 different γ-Al2O3 containing metallic monoliths were studied in dichloromethane (DCM) and 25 of them in perchloroethylene (PCE) oxidation. The active compounds used were Pt, Pd, Rh or V2O5 alone or as mixtures. The catalysts were divided into three different testing sets: industrial, CVOC and research catalysts. ICP-OES, physisorption, chemisorption, XRD, UV-vis DRS, isotopic oxygen exchange, IC, NH3-TPD, H2-TPR and FESEM-EDS were used to characterise the catalysts. Screening of the industrial catalysts revealed that the addition of V2O5 improved the performance of the catalyst. DCM abatement was easily affected by the addition of VOC or water, but the effect on the PCE oxidation was only minor. Based on these screening tests, a set of CVOC catalysts were developed and installed into an industrial incinerator. The comparison between the laboratory and industrial scale studies showed that DCM oxidation in an industrial incinerator could be predicted relatively well. Instead, PCE was always seen to be oxidised far better in an industrial unit indicating that the transient oxidation conditions are beneficial for the PCE oxidation. Before starting the experiments with research catalysts, the water feed was optimised to 1.5 wt.%. Besides enhancing the HCl yields, water improved the DCM and PCE conversions. In the absence of oxygen, i.e. during destructive adsorption, the presence of water was seen to have an even more pronounced effect on the HCl formation and on the catalysts’ stability. In the DCM oxidation, the addition of the active compound on the catalyst support improved the selectivity, while the enhancing effect on the DCM conversion was only small. The high acidity together with the increased reducibility was seen to lead to an active catalyst. Among the research catalysts Pt/Al2O3 was the most active in the DCM oxidation. With PCE the addition of the active compound proved to be very beneficial also for the PCE conversion. Now Pt and Pd supported on Al2O3-CeO2 were the most active. The enhanced reducibility was seen to be the key feature of the catalyst in PCE oxidation.Tiivistelmä Klooratuille orgaanisille hiilivedyille (CVOC) on asetettu tiukat päästörajoitukset niiden haitallisten vaikutusten takia. Tästä johtuen myös puhdistusmenetelmien tulee olla tehokkaita. Katalyyttinen puhdistus on teknologia, jolla nämä usein vaikeasti käsiteltävät yhdisteet voidaan taloudellisesti tuhota. Käytettävien katalyyttien tulee olla aktiivisia ja selektiivisiä sekä hyvin kestäviä. Tässä työssä tutkittiin yhteensä 33 erilaista γ-Al2O3-pohjaista hapetuskatalyyttiä metyleenikloridin (DCM) käsittelyssä, niistä 25 testattiin myös perkloorietyleenin (PCE) hapetuksessa. Aktiivisina metalleina katalyyteissä käytettiin platinaa, palladiumia, rhodiumia ja vanadiinia yksin tai seoksina. Katalyytit jaettiin kolmeen ryhmään: teolliset-, CVOC- ja tutkimuskatalyytit. Aktiivisuuskokeiden lisäksi katalyyttejä karakterisoitiin ICP-OES-, fysiorptio-, kemisorptio-, XRD-, UV-vis DRS-, isotooppivaihto-, IC-, NH3-TPD-, H2-TPR- ja FESEM-EDS-pintatutkimusmenetelmillä. Koetulokset osoittivat, että vanadiini paransi teollisuuskatalyyttien aktiivisuutta ja selektiivisyyttä. VOC-yhdisteen tai veden lisäys paransi DCM:n hapettumista, mutta PCE:n hapettumiseen niillä ei ollut vaikutusta. Testien perusteella kehitettiin CVOC-katalyytit, jotka asennettiin teolliseen polttolaitokseen. Laboratoriossa ja teollisuudessa tehdyissä testeissä havaittiin, että DCM:n hapettuminen oli laboratoriokokeiden perusteella ennustettavissa. Sen sijaan PCE hapettui teollisuudessa aina paljon paremmin kuin laboratorio-olosuhteissa. Tämä osoittaa, että muuttuvat hapettumisolosuhteet vaikuttivat positiivisesti PCE:n hapettumiseen. Veden määrä syöttövirrassa optimoitiin 1,5 %:iin ennen tutkimuskatalyyttien testausta. Selektiivisyyden lisäksi vesi paransi DCM:n ja PCE:n konversiota. Hapettomissa olosuhteissa, ts. tuhoavien adsorptiokokeiden aikana, vesi paransi reaktion selektiivisyyttä HCl:ksi ja CO2:ksi vielä entisestään. Tämän lisäksi vesi lisäsi katalyytin stabiilisuutta. DCM:n hapetuksessa aktiivisen metallin lisäys paransi selektiivisyyttä, mutta sen sijaan vaikutus DCM:n konversioon oli hyvin pieni. Tulokset osoittivat, että aktiivisella DCM:n hapetuskatalyytillä tulee olla korkea happamuus ja hyvä pelkistyvyys. Pt/Al2O3 oli testatuista tutkimuskatalyyteistä aktiivisin. PCE:n hapetuksessa aktiivisen metallin lisäys paransi selektiivisyyden lisäksi huomattavasti myös konversiota. Katalyytin lisääntyneen pelkistymiskyvyn todettiin olevan keskeisin ominaisuus PCE:n hapettumisessa. Pt/Al2O3-CeO2 ja Pd/Al2O3-CeO2 olivat tutkimuskatalyyteistä aktiivisimpia

Oxidation of Dichloromethane over Au, Pt, and Pt-Au Containing Catalysts Supported on γ-Al2O3 and CeO2-Al2O3

Au, Pt, and Pt-Au catalysts supported on Al2O3 and CeO2-Al2O3 were studied in the oxidation of dichloromethane (DCM, CH2Cl2). High DCM oxidation activities and HCl selectivities were seen with all the catalysts. With the addition of Au, remarkably lower light-off temperatures were observed as they were reduced by 70 and 85 degrees with the Al2O3-supported and by 35 and 40 degrees with the CeO2-Al2O3-supported catalysts. Excellent HCl selectivities close to 100% were achieved with the Au/Al2O3 and Pt-Au/Al2O3 catalysts. The addition of ceria on alumina decreased the total acidity of these catalysts, resulting in lower performance. The 100-h stability test showed that the Pt-Au/Al2O3 catalyst was active and durable, but the selectivity towards the total oxidation products needs improvement. The results suggest that, with the Au-containing Al2O3-supported catalysts, DCM decomposition mainly occurs via direct DCM hydrolysis into formaldehyde and HCl followed by the oxidation of formaldehyde into CO and CO2

On the Utilization of Modified Red Mud in Dimethyl Disulfide and Methyl Mercaptan Emission Abatement

In this paper, a novel application of industrial waste, namely red mud (RM), in the abatement of two malodorous and harmful sulfur compounds, dimethyl disulfide (DMDS) and methyl mercaptan (MM), is presented. The effects of calcination and activations with hydrochloric acid or a mixture of hydrochloric and orthophosphoric acid on the properties and performance of RM are compared using laboratory-scale experiments. The RM-based materials were characterized by XRF, XRD, FE-SEM, N2-physisorption, TGA/DTA, and FTIR analyses. RM exhibits very promising catalytic properties in the abatement of both DMDS and MM. The hydrochloric acid-activated RM was the most active in both cases, which was explained by its rather high specific surface area (144 m2 g−1), higher contents of Fe2O3 and TiO2, as well as lower content of phosphorus. For both DMDS and MM, the main oxidation products were sulfur dioxide, carbon monoxide, and carbon dioxide. DMDS was observed as a reaction intermediate in MM oxidation. While the final conversions of DMDS and MM were high, the oxidation was not complete, indicated by the formation of carbon monoxide. Nevertheless, the modified RM appears as a very interesting alternative to the existing DMDS and MM abatement catalysts

Catalytic Oxidation of Dimethyl Disulfide over Bimetallic Cu–Au and Pt–Au Catalysts Supported on γ-Al2O3, CeO2, and CeO2–Al2O3

Dimethyl disulfide (DMDS, CH3SSCH3) is an odorous and harmful air pollutant (volatile organic compound (VOC)) causing nuisance in urban areas. The abatement of DMDS emissions from industrial sources can be realized through catalytic oxidation. However, the development of active and selective catalysts having good resistance toward sulfur poisoning is required. This paper describes an investigation related to improving the performance of Pt and Cu catalysts through the addition of Au to monometallic “parent” catalysts via surface redox reactions. The catalysts were characterized using ICP-OES, N2 physisorption, XRD, XPS, HR-TEM, H2-TPR, NH3-TPD, CO2-TPD, and temperature-programmed 18O2 isotopic exchange. The performance of the catalysts was evaluated in DMDS total oxidation. In addition, the stability of a Pt–Au/Ce–Al catalyst was investigated through 40 h time onstream. Cu–Au catalysts were observed to be more active than corresponding Pt–Au catalysts based on DMDS light-off experiments. However, the reaction led to a higher amount of oxygen-containing byproduct formation, and thus the Pt–Au catalysts were more selective. H2-TPR showed that the higher redox capacity of the Cu-containing catalysts may have been the reason for better DMDS conversion and lower selectivity. The lower amount of reactive oxygen on the surface of Pt-containing catalysts was beneficial for total oxidation. The improved selectivity of ceria-containing catalysts after the Au addition may have resulted from the lowered amount of reactive oxygen as well. The Au addition improved the activity of Al2O3-supported Cu and Pt. The Au addition also had a positive effect on SO2 production in a higher temperature region. A stability test of 40 h showed that the Pt–Au/Ce–Al catalyst, while otherwise promising, was not stable enough, and further development is still needed

Effect of nanoparticle size in Pt/SiO2 catalyzed nitrate reduction in liquid phase

Effect of platinum nanoparticle size on catalytic reduction of nitrate in liquid phase was examined under ambient conditions by using hydrogen as a reducing agent. For the size effect study, Pt nanoparticles with sizes of 2, 4 and 8 nm were loaded silica support. TEM images of Pt nanoparticles showed that homogeneous morphologies as well as narrow size distributions were achieved during the preparation. All three catalysts showed high activity and were able to reduce nitrate below the recommended limit of 50 mg/L in drinking water. The highest catalytic activity was seen with 8 nm platinum; however, the product selectivity for N-2 was highest with 4 nm platinum. In addition, the possibility of PVP capping agent acting as a promoter in the reaction is highlighted.Web of Science111art. no. 19

Oxidation of dichloromethane over Au, Pt, and Pt-Au containing catalysts supported on γ-Al₂O₃ and CeO₂-Al₂O₃

Abstract Au, Pt, and Pt-Au catalysts supported on Al₂O₃ and CeO₂-Al₂O₃ were studied in the oxidation of dichloromethane (DCM, CH₂Cl₂). High DCM oxidation activities and HCl selectivities were seen with all the catalysts. With the addition of Au, remarkably lower light-off temperatures were observed as they were reduced by 70 and 85 degrees with the Al₂O₃-supported and by 35 and 40 degrees with the CeO₂-Al₂O₃-supported catalysts. Excellent HCl selectivities close to 100% were achieved with the Au/Al₂O₃ and Pt-Au/Al₂O₃ catalysts. The addition of ceria on alumina decreased the total acidity of these catalysts, resulting in lower performance. The 100-h stability test showed that the Pt-Au/Al₂O₃ catalyst was active and durable, but the selectivity towards the total oxidation products needs improvement. The results suggest that, with the Au-containing Al₂O₃-supported catalysts, DCM decomposition mainly occurs via direct DCM hydrolysis into formaldehyde and HCl followed by the oxidation of formaldehyde into CO and CO₂

Oxidation of Methanol and Dichloromethane on TiO₂-CeO₂-CuO, TiO₂-CeO₂ and TiO₂-CuO@VUKOPOR^®A Ceramic Foams

The application-attractive form of TiO2, CeO2 and CuO-based open-cell foam supported catalysts was designed to investigate their catalytic performance in oxidation of two model volatile organic compounds—methanol and dichloromethane. TiO2-CeO2, TiO2-CuO and TiO2-CeO2-CuO catalysts as thin films were deposited on VUKOPOR®A ceramic foam using a reverse micelles-controlled sol-gel method, dip-coating and calcination. Three prepared catalytic foams were investigated via light-off tests in methanol and dichloromethane oxidation in the temperature range of 45–400 °C and 100–500 °C, respectively, at GHSV of 11, 600 h−1, which fits to semi-pilot/industrial conditions. TiO2-CuO@VUKOPOR®A foam showed the best catalytic activity and CO2 yield in methanol oxidation due to its low weak Lewis acidity, high weak basicity and easily reducible CuO species and proved good catalytic stability within 20 h test. TiO2-CeO2-CuO@VUKOPOR®A foam was the best in dichloromethane oxidation. Despite of its lower catalytic activity compared to TiO2-CeO2@VUKOPOR®A foam, its highly-reducible -O-Cu-Ce-O- active surface sites led to the highest CO2 yield and the highest weak Lewis acidity contributed to the highest HCl yield. This foam also showed the lowest amount of chlorine deposits

Catalytic oxidation of dimethyl disulfide over bimetallic Cu–Au and Pt–Au catalysts supported on γ-Al₂O₃, CeO₂, and CeO₂–Al₂O₃

Abstract Dimethyl disulfide (DMDS, CH3SSCH3) is an odorous and harmful air pollutant (volatile organic compound (VOC)) causing nuisance in urban areas. The abatement of DMDS emissions from industrial sources can be realized through catalytic oxidation. However, the development of active and selective catalysts having good resistance toward sulfur poisoning is required. This paper describes an investigation related to improving the performance of Pt and Cu catalysts through the addition of Au to monometallic “parent” catalysts via surface redox reactions. The catalysts were characterized using ICP-OES, N2 physisorption, XRD, XPS, HR-TEM, H2-TPR, NH3-TPD, CO2-TPD, and temperature-programmed 18O2 isotopic exchange. The performance of the catalysts was evaluated in DMDS total oxidation. In addition, the stability of a Pt–Au/Ce–Al catalyst was investigated through 40 h time onstream. Cu–Au catalysts were observed to be more active than corresponding Pt–Au catalysts based on DMDS light-off experiments. However, the reaction led to a higher amount of oxygen-containing byproduct formation, and thus the Pt–Au catalysts were more selective. H2-TPR showed that the higher redox capacity of the Cu-containing catalysts may have been the reason for better DMDS conversion and lower selectivity. The lower amount of reactive oxygen on the surface of Pt-containing catalysts was beneficial for total oxidation. The improved selectivity of ceria-containing catalysts after the Au addition may have resulted from the lowered amount of reactive oxygen as well. The Au addition improved the activity of Al2O3-supported Cu and Pt. The Au addition also had a positive effect on SO2 production in a higher temperature region. A stability test of 40 h showed that the Pt–Au/Ce–Al catalyst, while otherwise promising, was not stable enough, and further development is still needed