Tuning adsorption properties of GaxIn2−xO3 catalysts for enhancement of methanol synthesis activity from CO2 hydrogenation at high reaction temperature

Light olefins can be produced from CO2 hydrogenation in a single reactor using a combination of a methanol synthesis catalyst and a methanol-to-olefin (MTO) catalyst. However, commercial methanol synthesis catalysts are active at low temperatures (200–260 °C), while MTO reaction is feasible at higher temperatures (>300 °C). Herein, we report the CO2 hydrogenation to methanol at high temperatures (320–400 °C) over GaxIn2−xO3 catalysts. By tuning the Ga/In ratios, phase, crystallinity, pore structure, morphology, electronic properties as well as adsorptive properties of GaxIn2−xO3 catalysts can be modified. At the lowest temperature (320 °C), the pure In2O3 shows the highest methanol yield. However, the maximum methanol yield declines significantly with increasing reaction temperatures. Incorporation of Ga into the In2O3 crystal lattices at x = 0.4 (Ga0.4In1.6O3) maximizes the methanol yield at higher reaction temperatures of 340–360 °C. This enhancement can be attributed to an increased binding energy of adsorptive molecules with the catalyst surface to promote the hydrogenation of CO2 to methanol. Further increasing Ga content (x > 0.4) leads to greatly strengthen the binding for adsorptive molecules, resulting in a lower methanol yield and the formation of methane. The surface chemisorbed oxygen is found to be a key factor determining the CO yield

Nitrogen-phosphorous co-doped palladium electrocatalyst for glycerol electro-oxidation reaction (GEOR): An efficient system for mesoxalic acid and dihydroxyacetone production

Electro-oxidation reaction of glycerol (GEOR) is a promising and eco-friendly technique for producing commercially valuable organic acids. In contrast to conventional non-metallic doping into single or multiwalled carbon nanotubes, our work reported the incorporation of N, and P into the Pd/CNTs framework for selective oxidation of glycerol to 1, 3-dihydroxyacetone and mesoxalic acid. Electrochemical and physicochemical characterization showed that the NP doped/PdCNTs has superior electrocatalytic performance for GEOR in alkaline media compared to counter catalysts. NP doped/PdCNTs exhibits better resistivity (If/Ib = 1.71) and requires only 0.09 V electrocatalysis voltage to achieve 76.67 mA cm−2 current density, demonstrating an energy-efficient and cost-competitive method to produce mesoxalic acid and dihydroxyacetone. At 0.09 V vs Ag/AgCl in 0.5 M Gly/0.5 M KOH, the Pd mass activity of NP doped/PdCNTs was 307.30 mAmg-1 Pd, representing 2.45, 1.06, and 1.051 times higher than Pd/CNTs, N doped/PdCNTs, and P doped/PdCNTs, respectively. The yield of 1, 3-dihydroxyacetone was 29.76 times higher than Pd/CNTs, 24.06 times higher than N doped/PdCNTs, and 1.06 times higher than P doped/PdCNTs

Effect of reaction conditions on the lifetime of SAPO-34 catalysts in methanol to olefins process – A review

There is a rising demand for light olefins production to meet the increase in human population, burgeoning transportation network and rapid pace of industrialization. Methanol-to-olefins (MTO) conversion process is the most preferentially-selected route to synthesize olefins even though obtaining the high selectivity remains a challenge to this day. Methanol is industrially-produced via two-steps catalytic routes, viz. gasification of coal to syngas followed by syngas conversion. Due to the abundance of methanol, conversion of methanol to light olefins (ethylene and propylene) or polyolefins (polypropylene and high-density polyethylene) is most desired. Although, natural gas or syngas routes are well established and implemented at industrial level but still direct or indirect transformation of methanol to petrochemicals gained core interest. Significantly, the use of molecular sieves as a catalyst support or directly as a catalyst has been an area of active commercial developments for the past two decades. The engineered molecular sieves possess specialized topographical structure that can efficiently reduce the rate of coke deposition, enhance mass transport and improve the catalytic performance, viz. lifetime and olefins selectivity for methanol to olefins reaction. In this regard, the SAPOs molecular sieves are highly selective for the synthesis of ethylene and propylene. Among them, SAPO-34 molecular sieves exhibit the best performance for the MTO process. The current review highlights the importance of SAPO-34 supported catalysts in terms of lower chain hydrocarbon (C2–C4) selectivity, lower paraffinic and aromatic by-products ratio, catalyst stability, and renderability. In addition, the conditions causing the SAPO-34 catalysts deactivation such as coking, crystal size, water content, pressure metal incorporation, acid site strength, and influence of process conditions on triglyceride-based feeds are also thoroughly reviewed

Long-term evaluation of palm oil mill effluent (POME) steam reforming over lanthanum-based perovskite oxides

To replace the obsolete ponding system, palm oil mill effluent (POME) steam reforming (SR) over net-acidic LaNiO3 and net-basic LaCoO3 were proposed as the POME primary treatments, with promising H2-rich syngas production. Herein, the long-term evaluation of POME SR was scrutinized with both catalysts under the optimal conditions (600 °C, 0.09 mL POME/min, 0.3 g catalyst, & 74–105 μm catalyst particle size) to examine the catalyst microstructure changes, transient process stability, and final effluent evaluation. Extensive characterization proved the (i) adsorption of POME vapour on catalysts before SR, (ii) deposition of carbon and minerals on spent SR catalysts, and (iii) dominance of coking deactivation over sintering deactivation at 600 °C. Despite its longer run, spent LaCoO3 (50.54 wt%) had similar carbon deposition with spent LaNiO3 (50.44 wt%), concurring with its excellent coke resistance. Spent LaCoO3 (6.12 wt%; large protruding crystals) suffered a harsher mineral deposition than spent LaNiO3 (3.71 wt%; thin film coating), confirming that lower reactivity increased residence time of reactants. Transient syngas evolution of both SR catalysts was relatively steady up to 4 h but perturbed by coking deactivation thereafter. La2O2CO3 acted as an intermediate species that hastened the coke removal via reverse Boudouard reaction upon its decarbonation. La2O2CO3 decarbonation occurred continuously in LaCoO3 system but intermittently in LaNiO3 system. LaNiO3 system only lasted for 13 h as its compact ash blocked the gas flow. LaCoO3 system lasted longer (17 h) with its porous ash, but it eventually failed because KCl crystallites blocked its active sites. Relatively, LaCoO3 system offered greater net H2 production (72.78%) and POME treatment volume (30.77%) than LaNiO3 system. SR could attain appreciable POME degradation (>97% COD, BOD5, TSS, & colour intensity). Withal, SR-treated POME should be polished to further reduce its incompliant COD and BOD5

A review on advances in green treatment of glycerol waste with a focus on electro-oxidation pathway

Over the past decades, research efforts are being devoted into utilizing the biomass waste as a major source of green energy to maintain the economic, environmental, and social sustainability. Specifically, there is an emerging consensus on the significance of glycerol (an underutilised waste from biodiesel industry) as a cheap, non-toxic, and renewable source for valuable chemicals synthesis. There are numerous methods enacted to convert this glycerol waste to tartronic acid, mesoxalic acid, glyceraldehyde, dihydroxyacetone, oxalic acid and so on. Among these, the green electro-oxidation technique is one of the techniques that possesses potential for industrial application due to advantages such as non-toxicity process, fast response, and lower energy consumption. The current review covers the general understanding on commonly used techniques for alcohol (C1 & C2) conversion, with a specific insight on glycerol (C3) electro-oxidation (GOR). Since catalysts are the backbone of chemical reaction, they are responsible for the overall economy prospect of any processes. To this end, a comprehensive review on catalysts, which include noble metals, non-noble metals, and non-metals anchored over various supports are incorporated in this review. Moreover, a fundamental insight into the development of future electrocatalysts for glycerol oxidation along with products analysis is also presented

Tuning interactions of surface‐adsorbed species over Fe−Co/K−Al2O3 catalyst by different K contents: selective CO2 hydrogenation to light olefins

Selective CO2 hydrogenation to light olefins over Fe−Co/K−Al2O3 catalysts was enhanced by tuning bonding strengths of adsorbed species by varying the content of the K promotor. Increasing the K/Fe atomic ratio from 0 to 0.5 increased the olefins/paraffins (O/P) ratio by 25.4 times, but then slightly raised upon ascending K/Fe to 2.5. The positive effect of K addition is attributed to the strong interaction of H adsorbed with the catalyst surface caused by the electron donor from K to Fe species. Although the Fe−Co/K−Al2O3 catalyst with K/Fe=2.5 reached the highest O/P ratio of 7.6, the maximum yield of light olefins of 16.4 % was achieved by the catalyst promoted with K/Fe of 0.5. This is explained by the considerable reduction of amount of H2 adsorbed on the catalyst surface with K/Fe=2.5

Effect of pore size and surface chemistry of porous silica on CO2 adsorption

In the present study, porous silica synthesized using sodium silicate as a low-cost raw material was selected as a CO2sorbent. The effects of pore size and amount of silanol content on CO2 adsorption capacity were investigated. The physicalproperties and surface chemistry (silanol content) of the porous silica products were characterized by means of N2-physisorption, Fourier transform infrared spectroscopy and thermogravimetric analysis technique. The pore size of the poroussilica materials did not affect the equilibrium CO2 capacity; however the porous silica with large pore size could enhance thediffusion of CO2. The amount of silanol content was found to be a key factor for the CO2 adsorption capacity. A greater CO2adsorption capacity would be obtained with an increase of the silanol concentration on the surface of the porous silicamaterials

Treatment technologies of palm oil mill effluent (POME)and olive mill wastewater (OMW): A brief review

Attributable to the enormous population growth, tonnes of effluents are unavoidably generated throughout the agricultural activities. The inadequate effluents disposal induces perpetual contamination to the sea and river water sources, which has subsequently raised the public environmental concern. For that reason, the handling protocol of agricultural effluents was flagged up as an interest area for research. Despite the environmental hazards, agricultural effluents have the potential to be transformed from wastes into wealth via biological, physicochemical, thermochemical or a combination of processes thereof. The identical characteristics of palm oil mill effluent (POME)and olive mill wastewater (OMW)render the possibility of treating these wastes using the similar treatment method. Generally, biological treatment requires a longer process time compared to physicochemical and thermochemical technologies despite its easy and low-cost operation. Comparatively, physicochemical and thermochemical methods extend their potentiality in converting the agricultural effluents into higher value products more efficiently. This paper reviews the source and characteristics of both POME and OMW. Subsequently, a comparison of the current and alternative treatments for both effluents was done before the future perspectives of both effluents’ treatment are paved based on the well-being of the human, environment, and economic

Ethylene production from ethanol dehydration over mesoporous SBA-15 catalyst derived from palm oil clinker waste

The silica-rich palm oil clinker (POC) from oil palm agroindustry is often dumped in landfill. This work investigated the valorisation of POC into Santa Barbara Amorphous-15 (SBA-15) catalyst, the modulation of its surface acidity, and its application in dehydration of ethanol to ethylene. With commercial SBA-15 [SBA-15(Comm.)] as reference, the successful fabrication of POC-derived SBA-15 [POC-SBA-15(pH = 3, 5, and 7)] were validated by spectroscopic and microscopic characterisation. From the results of temperature-programmed desorption of ammonia, the SBA-15(Comm.) have high strong acidity while POC-SBA-15 exhibit enriched weak-moderate acidity. For ethanol dehydration over SBA-15 at 200–400 °C, the ethanol conversion (XC2H5OH) and ethylene selectivity (SC2H4) rise with temperature. The catalytic activity was ranked as SBA-15(Comm.) 16 mL/g•h, the saturation of finite active sites with adsorbates renders the drastic declination of XC2H5OH and SC2H4. For ethanol dehydration over POC-SBA-15(5), the optimal conditions are temperature of 400 °C, initial ethanol concentration of 50 wt%, and LHSV of 16 mL/g•h. Fresh POC-SBA-15(5) steadily catalyses the optimal process (73.33% XC2H5OH and 84.70% SC2H4) up to 105 h. Meanwhile, regenerated POC-SBA-15(5) achieves a lower catalytic activity (71.95% XC2H5OH and 81.96% SC2H4)

Dehydrogenation of Propane to Propylene Using Promoter-Free Hierarchical Pt/Silicalite-<i>1</i> Nanosheets

Propane dehydrogenation (PDH) is the extensive pathway to produce propylene, which is as a very important chemical building block for the chemical industry. Various catalysts have been developed to increase the propylene yield over recent decades; however, an active site of monometallic Pt nanoparticles prevents them from achieving this, due to the interferences of side-reactions. In this context, we describe the use of promoter-free hierarchical Pt/silicalite-1 nanosheets in the PDH application. The Pt dispersion on weakly acidic supports can be improved due to an increase in the metal-support interaction of ultra-small metal nanoparticles and silanol defect sites of hierarchical structures. This behavior leads to highly selective propylene production, with more than 95% of propylene selectivity, due to the complete suppression of the side catalytic cracking. Moreover, the oligomerization as a side reaction is prevented in the presence of hierarchical structures due to the shortening of the diffusion path length