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

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

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

A novel method for automated SCR catalyst uniformity measurement

Abstract Exhaust after treatment systems are becoming more complicated with the ever-stricter emission regulations. To meet the regulation limits, a tightly packed high-performance system is required. In selective catalytic reduction (SCR) systems, ammonia (NH³) uniformity is a key performance indicator. In this work, a low flow intrusion automated device was designed to measure NOₜ reduction from the SCR catalyst outlet. A topological surface was reconstructed from the measurement data to obtain the shape of the distribution. Before the actual measurements, the method was theoretically tested with distribution extracted from computational fluid dynamics (CFD) simulations. The results show that in stable engine load conditions, uncertainty of the measurement was low, approximately 1.1% from the measured value. In the case of high uniformity, a satisfactory result can be obtained with 10 to 20 measurement positions, whereas in the case of low uniformity, the number of positions should be increased. The distribution shape between the measurements was consistent throughout the measurements

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

Abstract 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 N₂ was highest with 4 nm platinum. In addition, the possibility of PVP capping agent acting as a promoter in the reaction is highlighted

Substitution potential of rare earth catalysts in ethanol steam reforming

Abstract This study suggests the possibility of substituting rare earths containing catalysts in ethanol steam reforming by means of sustainability assessment. Four Ni-catalysts are assessed; two of the Ni-catalysts are rare earths containing catalysts Ni/Al₂O₃-CeO₂and Ni/La₂O₃ while the other two are non-rare earths containing catalysts Ni/Al₂O₃ and Ni/ZnO. The sustainability assessment tool used covers environmental, health and safety and economic indicators in conjunction with a linear scale transformation (Max) normalization technique and an analytical hierarchy method to evaluate the sustainability performance of the catalysts. The sustainability assessment results obtained demonstrated that Ni/Al₂O₃ is the best performing catalysts in terms of the overall sustainability of the ethanol steam reforming reaction. The rare earths containing catalyst supports, i.e. cerium and lanthanum oxides can be successfully substituted with aluminum oxide catalyst support whilst still maintaining the overall sustainability performance of the reaction

Sustainability assessment of products:case study of wind turbine generator types

Abstract This study proposes a product sustainability assessment tool (PSAT) that addresses the environmental, health and safety, social, and economic sustainability aspects from a life cycle perspective. The proposed PSAT uses the principles of Green Chemistry, Industrial Ecology, and Green Engineering as guidelines in the development of its assessment criteria. The developed assessment criteria are expressed as easy-to-answer questions covering the environmental, social, health and safety and economic aspects of sustainability. PSAT also incorporates life cycle assessment impact categories and the Circular Economy approach. PSAT comprises an Excel checklist of a questionnaire with a drop-down list of answers to select from describing the sustainability impact of the assessed product. PSAT serves to highlight the sustainability hotspots in a product’s life cycle. The questionnaire consists of qualitative and quantitative assessment criteria and contains a total of 97 questions, out of which there are 11 design questions, 22 materials selection questions, 31 manufacturing questions, 24 use questions, and 9 end-of-life questions. The PSAT scoring system enables users to compare the sustainability performance of their products. PSAT aims to aid users in making informed decisions before purchasing a product based on the information on how the product is designed and what materials it contains, how it was manufactured, how it will perform during its use, and what will happen at the end of its useful life. It also aims to aid product manufacturers and designers in incorporating sustainability into all stages of the product life cycle. The PSAT methodology promotes a holistic view of a product life cycle, including the design, materials selection, manufacturing, use, and end-of-life stage. As a case study, PSAT was used to perform a comparative sustainability assessment of two types of 3 MW rated power wind turbines: a direct-drive permanent magnet synchronous generator (PMSG) and a doubly-fed induction generator with a gearbox (DFIG). The results from the sustainability assessment reveal that the DFIG wind turbine had a better sustainability impact than the direct-drive PMSG in the materials selection, manufacturing, and end-of-life life cycle stages. On the other hand, the direct-drive PMSG had a better sustainability impact than DFIG in the life cycle stages design and use. Overall, DFIG demonstrated a better sustainability impact than the direct-drive PMSG

Modified geopolymers as promising catalyst supports for abatement of dichloromethane

Abstract Geopolymers have not been extensively employed as catalytic materials despite of their zeolite-resembling Si–Al structure. Geopolymerization offers a novel way for preparation of catalysts and possibility to use waste or industrial side-stream derived raw material as a resource for catalyst manufacturing. This work concentrates on metakaolin-based geopolymer materials that were prepared, characterized and tested as alternative environmentally benign catalyst supports for the oxidation of dichloromethane. The geopolymers with the Si/Al ratio of 1.5 were modified with HCl to increase their specific surface area, which is important in catalytic applications. Significant increase in specific surface areas was achieved via leaching of Na and Al from the geopolymer structure. Highest specific surface areas achieved for calcined geopolymers were over 500 m²g⁻¹. Use of acid concentrations higher than 1 M led to the dehydroxylation of the geopolymer. Dehydroxylation decreased the total acidity of geopolymer through the loss of the Brønsted acid sites, which are responsible for the adsorption of dichloromethane in the beginning of the catalytic reaction. Absence of Brønsted acid sites was observed by the formation of CH₂O as the only reaction intermediate. The best result in the dichloromethane oxidation was found with the geopolymer treated with 1 M HCl. Without using any additional active sites, the maximum dichloromethane conversion of 90% was reached at 525 °C with the maximum HCl yield of 83%. This result indicates the good potential of modified geopolymers to be used as catalyst supports in environmental applications

Oxidation of methanol and dichloromethane on TiO₂-CeO₂-CuO, TiO₂-CeO₂ and TiO₂-CuO@VUKOPOR®A ceramic foams

Abstract 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 CO₂2 yield and the highest weak Lewis acidity contributed to the highest HCl yield. This foam also showed the lowest amount of chlorine deposits

Recycling and substitution of light rare earth elements, cerium, lanthanum, neodymium, and praseodymium from end-of-life applications:a review

Abstract The light rare earth elements (LREEs) lanthanum, cerium, neodymium and praseodymium are increasingly used in renewable energy technology and are applicable in portable electronic devices, such as phosphors in lightning applications and in catalysis. The extraction of REEs from virgin ores causes environmental degradation. LREEs are considered as critical metals. To overcome the environmental and criticality challenges of LREEs, recycling presents means by which they can be obtained from secondary sources. Presently, the recycling rate of LREEs is still very low. Substitutes of LREEs in most cases are either inferior or still undiscovered. This study investigates the criticality challenges and environmental impacts of producing LREEs from virgin ores. It focuses on LREEs obtainable in selected end-of-life products considered to have significant recycling potential; these include NdFeB magnets, Ni-MH batteries, phosphors in lighting and catalysts. Current recycling technologies, including representative methods and current recycling challenges are also reviewed. Although current recycling technologies have recorded growth, there is still a need for further improvements. The article highlights current LREEs substitution advances and the faced challenges in finding suitable LREEs substitutes. Furthermore, future ways to promote sustainability of LREEs recycling, to improve substitution, and to tackle the criticality challenges of LREEs are proposed