Nowadays, the reforming of natural gas is the most common of hydrogen or syngas generation process. Each reforming process leads to the achievement of specific goals and benefits related to investment costs. The disadvantage of the reforming process is the need to preclean it mostly from the sulfur and nitrogen compounds. The solution to this problem may be liquefied natural gas (LNG). Liquefied natural gas has recently been seen as an energy source and may be a promising replacement for natural gas. The constant development of the pipeline network, safe transport and a lot of advantages of LNG were contributed to the research development related to the usage of LNG in energy generation technologies. The presented review is a literature discussion on the processing of methane used to produce hydrogen with particular emphasis on the processes of oxy-steam reforming of natural or liquefied natural gas (OSR-LNG). In addition, a key consideration in this article includes Ni catalyst systems used in the oxy-steam reforming of methane or LNG reactions. An analysis of the OSR process conditions, the type of catalyst and the OSR of the methane reaction mechanism may contribute to the development of a modern, cheap catalyst system, which is characterized by high activity and stability in the oxy-steam reforming of natural gas or LNG (OSR-LNG).

The production of pure hydrogen is one of the most important problems of the modern chemical industry. While high volume production of hydrogen is well under control, finding a cheap method of hydrogen production for small, mobile, or his receivers, such as fuel cells or hybrid cars, is still a problem. Potentially, a promising method for the generation of hydrogen can be oxy–steam-reforming of methanol process. It is a process that takes place at relatively low temperature and atmospheric pressure, which makes it possible to generate hydrogen directly where it is needed. It is a process that takes place at relatively low temperature and atmospheric pressure, which makes it possible to generate hydrogen directly where it is needed. This paper summarizes the current state of knowledge on the catalysts used for the production of hydrogen in the process of the oxy–steam-reforming of methanol (OSRM). The development of innovative energy generation technologies has intensified research related to the design of new catalysts that can be used in methanol-reforming reactions. This review shows the different pathways of the methanol-reforming reaction. The paper presents a comparison of commonly used copper-based catalysts with other catalytic systems for the production of H₂ via OSRM reaction. The surface mechanism of the oxy–steam-reforming of methanol and the kinetic model of the OSRM process are discussed.

Ni catalysts supported on ZrO₂, 5%CeO₂-ZrO₂, and 5%La₂O₃-ZrO₂ were prepared via the impregnation method and tested in the oxy-steam reforming of methane and liquified natural gas (LNG). All tested catalysts exhibited high catalytic activity in the studied process at 700 and 900 °C. The improvement of the stability of Ni catalysts after the addition of CeO₂ oxide in the studied oxy-steam reforming of LNG process was confirmed. In addition, high activity and selectivity towards hydrogen was proven in the oxy-steam reforming process at 900 °C over a 20%Ni/5%CeO₂-ZrO₂ catalyst. It was also proved that the addition of CeO₂ onto a ZrO₂ carrier leads to a decrease in the NiO and metallic Ni crystallite sizes that were detected by the X-Ray diffraction (XRD) technique. The solid solution formation between NiO and ZrO₂ and/or NiO and CeO₂ was proved. Superior reactivity in the oxy-steam reforming of CH₄ and the LNG process exhibited a 20%Ni/ZrO₂ catalyst, which showed the highest methane conversions at 500 and 600 °C, equal to 63% and 89%, respectively. In addition, also in the case of the LNG reforming reaction, the most active catalyst was the 20%Ni/ZrO₂ system, which demonstrated 46.3% and 76.9% of the methane conversion value at 500 and 600 °C and the total conversion of others hydrocarbons (ethane, propane and butane). In addition, this catalytic system exhibited the highest selectivity towards hydrogen formation in the oxy-steam reforming of the LNG reaction equal to 71.2% and 71.3% at 500 and 600 °C, respectively. The highest activity of this system can be explained by the uniform distributions of Ni species and their highest concentration compared to the rest of the monometallic Ni catalysts. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) results also confirmed a strong interaction of NiO with ZrO₂ in the case of the 20%Ni/ZrO₂ catalysts. The presence of selected NiZrO⁺ ions emitted from the investigated surface of the 20%Ni/ZrO₂ system was detected.

The oxy-steam reforming of liquefied natural gas reaction (OSR-LNG) is promising process for syngas generation. In this paper, the catalytic properties of NiO/La₂O₃ systems prepared by wet impregnation and co-precipitation methods were extensively investigated in OSR-LNG reaction. The physicochemical properties of the studied catalytic materials were determined using various techniques including Temperature programmed reduction (TPR-H₂), Temperature programmed desorption (TPD-NH₃), Brunauer, Emmett and Teller (BET), X-ray diffraction (XRD) and Scanning electron microscopy (SEM) with an energy dispersive X-Ray spectrometer (EDS). Reactivity measurements performed in the OSR-LNG process showed that the catalyst preparation method and the calcination temperature significantly affected the activity of NiO/La₂O₃ catalysts in the OSR-LNG reaction. The catalytic activity tests showed that NiO/La₂O₃ system prepared by a wet impregnation method and calcined at 700 °C showed the total conversion of the LNG component at 900 °C and the highest H₂ yield at 700 and 900 °C. The phase composition studies confirmed the formation of the LaNiO₃ structure in the case of the NiO/La₂O₃ catalyst prepared by wet impregnation, calcined at the temperature of 700 °C. Catalytic activity measurements showed that the reactivity of the catalysts was related to their phase composition and acidity. SEM images of spent catalysts showed that the smallest amount of carbon deposit was detected on the surface of the most active systems.

Biodiesel production from rapeseed oil and methanol via transesterification reaction facilitated by various monometallic catalyst supported on natural zeolite (NZ) was investigated. The physicochemical characteristics of the synthesized catalysts were studied by X-ray diffraction (XRD), Brunauer–Emmett–Teller method (BET), temperature-programmed-reduction in hydrogen (H₂-TPR), temperature-programmed-desorption of ammonia (NH₃-TPD), Scanning Electron Microscope equipped with EDX detector (SEM-EDS), and X-ray photoelectron spectroscopy (XPS) methods. The highest activity and methyl ester yields were obtained for the Pt/NZ catalyst. This catalyst showed the highest triglycerides conversion of 98.9% and fatty acids methyl esters yields of 94.6%. The activity results also confirmed the high activity of the carrier material (NZ) itself in the investigated reaction. Support material exhibited 90.5% of TG conversion and the Fatty Acid Methyl Esters yield (FAME) of 67.2%. Introduction of noble metals improves the TG conversion and FAME yield values. Increasing of the metal loading from 0.5 to 2 wt.% improves the reactivity properties of the investigated catalysts.

This work interrogates for the first time the catalytic properties of various monometallic Ni catalysts in the oxy-steam reforming of LNG. Various research techniques, including X-ray diffraction (XRD), specific surface area and porosity analysis (BET method), scanning electron microscopy with X-ray microanalysis (SEM-EDS), temperature-programmed desorption of ammonia (TPD-NH₃), temperature-programmed reduction (TPR-H₂) and the FTIR method, were used to study their physicochemical properties. The mechanism of the oxy-steam reforming of LNG is also discussed in this paper. The high activity of monometallic catalysts supported on 5% La₂O₃–CeO₂ and 5% ZrO₂–CeO₂ oxides in the studied process have been proven and explained on the basis of their acidity, specific surface area, sorption properties in relation to the reaction products, the crystallite size of the metallic nickel and their phase composition.