Tropsch Method Research Articles

A bifunctional cobalt catalyst for the synthesis of waxy diesel fuel by the Fischer–Tropsch method – from the development to implementation. Part 3. The experience of industrial implementation of the preparation technology

The work summarizes the results of testing the technology for preparing a bifunctional cobalt catalyst for the synthesis of hydrocarbons from CO and H2, obtained by extruding a mixture of Co-Al2O3 /SiO2 catalyst powders and HZSM-5 zeolite with a binder – boehmite in industrial conditions (2 batches of 50 kg each were prepared). The catalyst technology was implemented on the equipment of Ishimbay Specialized Chemical Catalyst Plant LLC. The obtained industrial samples of the catalyst were characterized by XRF, TPR H2, DTG, and tested in the synthesis of hydrocarbons from CO and H2 at a temperature of 250 °C, a pressure of 2.0 MPa, GHSV 1000 h–1. It has been shown that the implementation of the technology of a bifunctional cobalt catalyst for the production of low pour point diesel fuel in industrial conditions makes it possible to reproduce the characteristics of the catalyst obtained in laboratory conditions. The technology for producing the catalyst can be recommended for the production of industrial batches. It was determined that changes in the heat treatment conditions of the catalyst, as well as the presence/absence of a peptizer and pore former do not lead to a significant decrease in the productivity of C5+ hydrocarbons. The contentof the diesel fraction in C5+ products obtained from industrial samples of the catalyst remains at the level of the value obtained from the laboratory sample of the catalyst. At the same time, the low-temperature properties of diesel fuel obtained using all catalyst samples have similar values. Using an industrial sample synthesized without the use of a peptizing agent and a pore-forming component, the best lowtemperature properties of diesel fuel were achieved – the cloud point and fluid loss point were minus 16 and minus 24, respectively.

Fischer–Tropsch Synthesis Catalysts for Selective Production of Diesel Fraction

The Fischer–Tropsch process is considered one of the most promising eco-friendly routes for obtaining synthetic motor fuels. Fischer–Tropsch synthesis is a heterogeneous catalytic process in which a synthesis gas (CO/H2) transforms into a mixture of aliphatic hydrocarbons, mainly linear alkanes. Recently, an important direction has been to increase the selectivity of the process for the diesel fraction. Diesel fuel synthesized via the Fischer–Tropsch method has a number of advantages over conventional fuel, including the high cetane number, the low content of aromatic, and the practically absent sulfur and nitrogen impurities. One of the possible ways to obtain a high yield of diesel fuel via the Fischer–Tropsch process is the development of selective catalysts. In this review, the latest achievements in the field of production of diesel via Fischer–Tropsch synthesis using catalysts are reviewed for the first time. Catalytic systems based on Al2O3 and mesoporous silicates, such as MCM-41, SBA-15, and micro- and mesoporous zeolites, are observed. Together with catalytic systems, the main factors that influence diesel fuel selectivity such as temperature, pressure, CO:H2 ratio, active metal particle size, and carrier pore size are highlighted. The motivation behind this work is due to the increasing need for alternative processes in diesel fuel production with a low sulfur content and better exploitation characteristics.

Bifunctional cobalt catalyst for the synthesis of waxy diesel fuel by the Fischer–Tropsch method – from development to introduction. Part 2. Optimization of the catalyst component composition

The effect exerted by the content of metallic (Co-Al2O3/SiO2 catalyst) and acidic (ZSM-5 zeolite in the H-form) components on the properties of bifunctional catalyst for the integrated synthesis of waxy diesel fuel by the Fischer–Tropsch method was studied. Catalysts represented by a composite mixture with a boehmite binder were characterized by XRD, BET and TPR methods. The testing was performed in a flow reactor with a fixed catalyst bed at a pressure of 2.0 MPa, temperature 240 °С and gas hourly space velocity 1000 h–1. Activity and selectivity of the catalysts as well as the fractional and hydrocarbon composition of the products were investigated in dependence on the ratio of components. It was found that productivity of the synthesis for С5+ hydrocarbons and selectivity for the С11–С18 diesel fraction products with a high content of isomeric products correlated with the ratio of metallic and acidic components in the catalysts. The composition of the catalyst recommended for the diesel fuel production has the 1.17 ratio of metallic and acidic components.

Phosphorus and nitrogen doped CoNi nanocrystals supported on carbon based materials for electro- reduction of CO2 to syngas with controllable CO/H2

The products of electrocatalytic CO2 reduction reaction (CO2RR) and hydrogen evolution reaction (HER) are the raw materials CO and H2 of synthesis gas respectively. The synthesis gas can generate usable fuel by Fischer Tropsch method to realize the carbon cycle. At present, it is still challenging to control the synthesis gas generation in the low potential and wide potential range. In order to solve this problem, we used a simple template method to embed different proportions of Ni and Co elements in the three-dimensional network structure of carbon carrier, between − 0.55 to − 1.15 V vs RHE, to generate synthetic gas with an adjustable CO/H2 ratio of 0.3–3. When Ni/Co ratio is 2:1(CoNi2 @NCP), the ratio of CO/H2 is kept at 1–3. At the potential of − 1.05 V vs RHE, the Faraday efficiency of CoNi2 @NCP catalyst to produce CO reaches 57 %, and that of H2 reaches 25 %. When the ratio of Ni-Co is 1:1 and 2:1, it can be used to produce methanol, ethanol and other alcohol products. Catalysts with different proportions can generate different synthesis gases at different potentials, which can be better used to generate downstream thermochemical synthesis of methane, ethylene, and alcohols. The sources of CO2RR and HER can be determined as Ni−Nx and Co−Nx sites by electrochemical analysis.

Selective Synthesis of Olefins on a Co-Al2O3/SiO2 Catalyst by the Fisher–Tropsch Method

Selective Synthesis of Olefins on a Co-Al2O3/SiO2 Catalyst by the Fisher–Tropsch Method

Supported and polyfunctional hybrid cobalt catalysts for selective Fischer – Tropsch synthesis (A review)

The review considers modern approaches to the development of a technology for producing cobalt catalysts that are applied in the majority of known processes aimed to synthesize hydrocarbons from СО and Н2 by the Fischer – Tropsch method. The development of efficient catalysts makes it possible to replace the fuel produced from fossil oil by an alternative ultrapure fuel, thus reducing the detrimental effect on the environment. The results of R&D studies, particularly those obtained recently by the authors, were analyzed to reveal topical trends in the development of high-performance catalysts for the synthesis of hydrocarbons by the Fischer – Tropsch method within the classical and integrated GTL technology, including the creation of polyfunctional systems of new types. The review provides information mainly on the catalytic characteristics of the supported cobalt catalysts synthesized by impregnation and the related polyfunctional hybrid catalysts for the selective synthesis of fuel fraction hydrocarbons. The control of selectivity and productivity as well as changes in activity and physicochemical properties of the catalysts during a long-term operation are considered.

Bifunctional Cobalt Catalyst for the Synthesis of Waxy Diesel Fuel by the Fischer–Tropsch Method: From Development to Commercialization. Part 1: Selection of the Industrial Sample of the Zeolite Component HZSM-5

Bifunctional Cobalt Catalyst for the Synthesis of Waxy Diesel Fuel by the Fischer–Tropsch Method: From Development to Commercialization. Part 1: Selection of the Industrial Sample of the Zeolite Component HZSM-5

Hybrid Catalyst for the Selective Synthesis of Fuel Range Hydrocarbons by the Fischer–Tropsch Method

Hybrid Catalyst for the Selective Synthesis of Fuel Range Hydrocarbons by the Fischer–Tropsch Method

Методичний аспект вибору інноваційних технологій з виробництва альтернативних видів моторного палива

The article is aimed at developing a methodological approach to a consistent and rational choice of promising for the development in Ukraine types of alternative motor fuel and innovative technologies for its production, substantiation of the system of technical and economic indicators of the complex for the production of synthetic motor fuel from the low-grade raw materials. One of the key problems of Ukraine’s energy provision today is its high dependence on the import of finished motor fuel, which can be reduced by the development in the country of alternative types of motor fuel based on the latest technologies. The article, based on the provisions of economic theory, discloses the essence of the developed methodological approach to the consistent choice of promising types of alternative motor fuel for their development in Ukraine and innovative technologies of its production. The developed methodological approach for rational choice of promising for the production in Ukraine and use of motor fuel types includes an evaluation of the following: compliance of consumer properties of certain types of motor fuel with the requirements of the existing motor fleet (target); efficiency of motor fuel production technologies (capabilities); sufficiency of resource provision for the production of motor fuel (restrictions). The methodical approach is brought to the level of the methodology, the use of which allows to identify promising types of alternative motor fuel for use in the country and innovative technologies of their production. Along with the developed methodical approach, the expediency of development in Ukraine of the synthetic motor fuel industry is proved on the basis of using the method of indirect coal liquefaction (according to the Fisher–Tropsch method). The result of the work is a system of technical and economic indicators of the complex for the production of synthetic motor fuel from the low-grade raw materials.

Conversion of Waste Plastic to Oils for Tribological Applications

Plastics are widely used owing to their light weight, easy production, and low cost. Even though plastics find application in different fields of industries and households, they do not degrade easily. If plastics are not disposed of appropriately, it has been shown that they cause widespread environmental pollution, which poses risks to human health. Recycling waste plastics has been an alternative to mitigating plastic pollution, which usually requires high labour costs and produces contaminated water during processing. If plastic recycling will contribute to the development of tribological products like lubricating oils, it is a safer alternative to disposing of plastics in the environment. In order to understand the tribological use of plastics by recycling, the present study reviews different techniques that can be employed to transform waste plastics into petroleum-based oils. The viscosity, density, and friction of pyrolyzed waste plastic oils are investigated and compared with commercial lubricants to assess their potential lubrication applications. The segregation processes, catalytic isomerization dewaxing, and Fischer–Tropsch method to recycle waste plastics are also reviewed to provide an insight into the methods to transform pyrolyzed waste plastic into lubricants.

КАТАЛИТИЧЕСКАЯ ТРАНСФОРМАЦИЯ МЕТАНОЛА / ДИМЕТИЛОВОГО ЭФИРА В УГЛЕВОДОРОДЫ С ИСПОЛЬЗОВАНИЕМ ZN-МОДИФИЦИРОВАННОГО ЦЕОЛИТА H-ZSM-5

The universally depleting reserves of traditional hydrocarbons require the development of a technology for producing synthetic hydrocarbons from renewable sources or human waste. Currently, among the possible methods for producing synthetic hydrocarbons, it is necessary to note the Fischer–Tropsch method and the method of methanol / dimethyl ether catalytic transformation. Moreover, the production of synthetic hydrocarbons from synthesis gas — the Fischer–Tropsch method, is suitable for the production of linear hydrocarbons. The hydrocarbons synthesis using methanol / dimethyl ether is suitable for the production of olefins, branched paraffins, aromatic and polyaromatic hydrocarbons. Depending on the synthesis conditions, it is possible to preferentially obtain a certain type of hydrocarbon, which significantly increases the value of this process. In this article modification of zeolite type H-ZSM-5 with zinc is studied in order to increase the yield of liquid hydrocarbons. Zeolite in acid form was treated with zinс acetate solutions of different concentrations, followed by calcination of the samples. The efficiency of the catalysts was studied in a flow tube reactor set-up, and the surface acidity of the samples was also determined. An increase in the zinc content in zeolite contributed to a decrease in the acidity of the samples and modification of their active centers. However, at high zinc content, a separate oxide phase forms, which contributes to a slight increase in acidity. Modification of zeolite with zinc leads to a decrease in the rate of transformation of dimethyl ether and the rate of liquid hydrocarbons formation. However, a general decrease in acidity and modification of zeolite with zinc contributes to a significant decrease in the amount of heavy aromatic compounds formed, with an increase in the amount of gaseous and liquid hydrocarbons being formed.

Price Risk For Coal Liquefaction in Moderate Scale Development

According to Talla et al,2017 the Linde Hampson Method can be used to process solid changes into liquid. In this study aims to calculate the Linde Hampson method in the temperature range of the Fischer Tropsch method (LTFT /Low temperature fischer tropsch). The temperatures used for comparison include low temperatures of 200 to 250degC. Parameters compared from the four type of coal namely lignite, antrachitre, bituminous and subbituminous are tested with projects on a moderate scale of 100 – 1000 tons.
 Analysis of Price risk is carried out to see the trend of change (increase/decrease) in the price of selling syngas. Price can change because of supply and demand. The main factor that can change price is quantity and quality of heat (HHV) and composition. Development of subbituminous can have higher risk than the antrachite type. Based on the calculation of the standard deviation of the risk values obtained from the four types is 25,3$.

The Microstructure of Cobalt Silica Gel Catalyst in the Presence of Al2O3 Additive

The physico-chemical characteristics and microstructure of cobalt silica gel catalysts with an Al2O3 additive (up to 10%) for the synthesis of hydrocarbons by the Fischer–Tropsch method are studied using a set of methods including X-ray diffraction, BET, IR spectroscopy, and temperature-programmed reduction of H2, as well as scanning and transmission electron microscopy. Phases with a spinel structure, Со3О4, CoAl2O4, and solid solutions on their basis are identified in the samples. The addition of Al2O3 changes the degree of heterogeneity and the orientation of the cobalt crystallites in the oxide and reduced forms of the catalysts. Addition of 1% Al2O3 stabilizes Со3О4 in the spinel form with a structure close to the normal one and promotes the formation of cobalt with a unimodal distribution of particles with an average size of 8 nm. The catalyst is characterized by maximum activity and selectivity with respect to C5+ carbons.

Influence of selected WMA additives on viscoelastic behaviour of asphalt mixes and pavements

Warm mix asphalt additives are effective in decreasing production, laying and compaction temperatures of asphalt mixes. However, there are still questions concerning influence of warm mix additives on properties of asphalt mixes and pavement performance. This paper presents results of the comprehensive research of viscoelastic behaviour of asphalt mixes and pavement structures with layers made with warm mix asphalt additives at high temperatures. Two additives of significantly different effects on mixes at higher temperatures were selected for analysis, namely aliphatic synthetic wax produced with the use of Fisher–Tropsch method and formulation of surfactant- based molecules (ionic and non-ionic). Viscoelastic properties of mixes with these two additives and, as a reference mix, with neat unmodified asphalt binder were determined in uniaxial compression with sinusoidal loading using Asphalt Mixture Performance Test. The viscoelastic analysis of pavement structures was performed with use of the VEROAD software and data from laboratory testing. Two different pavement structures were analysed, for light and heavy traffic. The temperature distribution in pavement structure during the hottest summer day in northern Poland in 2012 was taken into account. The model of pavement was loaded with moving wheel at different speeds. The analysis has shown that two tested warm mix additives had different effect on viscoelastic transient response at high temperatures. One of them (Fischer–Tropsch wax) evidently caused an increase in resistance of asphalt mix and pavement structure to loading at high temperature. The second additive (formulation of surfactant-based molecules) slightly reduced resistance of asphalt mix and pavement to loading at high temperatures as compared with the reference mix.

Radiation-initiated conversion of paraffins to engine fuel: Direct and indirect initiation

Formation of gasoline and diesel fuel has been investigated using three various radiation-induced ways: (1) cracking of wax, (2) synthesis from methane, (3) high-temperature conversion of wax dilute solution in methane. The wax, synthesized by Fischer–Tropsch method, initially contained a mixture of C17–C120 linear paraffins. The yield of wax conversion to liquid mixture (C4–C27 alkenes and 61.5% alkanes) via mode (1) was 0.83±0.09μmole/J, whereas yield of gas conversion to liquid mixture (C5–C13 alkanes) via mode (2) was 0.95±0.02μmole/J. In the dilute solution wax underwent indirect action of radiation. In comparison with (1) the mode (3) produces similar amount of lighter fuel containing 80% of alkanes (C5–C15). At the same time degree of methane fixation is almost three times higher.

Technologies for the synthesis of ethylene and propylene from natural gas

Different technologies for the synthesis of ethylene and propylene from natural gas are considered. The simplest ethylene synthesis method is the oxidative condensation (or dimerization) of methane (OCM process), but the implementation of this method is discouraged by a low ethylene yield. Among the relatively simple methods for the synthesis of ethylene (together with acetylene) immediately from methane are thermooxidative pyrolysis (TOP process) and pyrolysis in the presence of chlorine (Benson process), whose disadvantages are a high temperature and a great number of by-products. A wide range of processes for the synthesis of ethylene and propylene with a small amount of butylenes are based on the intermediate synthesis of syngas from methane and its further use for the direct synthesis of lower olefins or products for subsequent catalytic pyrolysis to lower olefins, such as methanol (methanol-to-olefins (MTO) and methanol-to-propylene (MTP) processes), dimethyl ether, and liquid fuel (Fischer–Tropsch method). The methyl chloride-to-olefins (MCTO) process consisting of the synthesis of methyl chloride via the oxidative chlorination of methane and the catalytic pyrolysis of methyl chloride differ from these three-stage processes in the absence of the syngas production stage. The direct oxidation of methane to methanol and the homologyzation of methanol to ethanol with further dehydration of ethanol to ethylene are also considered.

Effect of the dilution of synthesis gas with nitrogen on the Fischer–Tropsch process for the production of hydrocarbons

The process of the production of hydrocarbons from synthesis gas diluted with nitrogen according to the Fischer–Tropsch method was investigated. It was experimentally established that inert-ballasted synthesis gas facilitated an increase in selectivity for C5+ and C35+ hydrocarbons and a decrease in selectivity for C1–C4 hydrocarbons. The dilution of synthesis gas improved heat exchange conditions in the reaction zone and decreased the synthesis temperature and a temperature gradient across the catalyst bed. A loss of process efficiency upon the dilution of synthesis gas can be compensated due to an increase in the gas space velocity. The applicability of diluted synthesis gas to the production of the high-molecular-weight C35+ hydrocarbons was demonstrated.

Ultradispersed Hydrocarbon Synthesis Catalyst from CO and H2 Based on Electroexplosion of Iron Powder

The structure and properties of disperse particles of electroexplosive iron-based powder are studied with a laser diffraction method, transmission electron microscopy analysis and X-ray photography. The catalytic activity of ultradispersed iron powders in the synthesis of hydrocarbons from CO and H2 by Fischer – Tropsch method is measured by concentration of the paramagnetic particles with electron paramagnetic resonance. In the laboratory of catalytic plant, hydrocarbons are synthesized at various feed mixture. Composition of liquid and gas products of synthesis are studied. Under explosion conditions, the electric wires of iron powders can be prepared with the specified properties (phase composition, particle size and structure). Powder of Fe (CO) can be used as a catalyst of the Fischer – Tropsch synthesis without reduction since during electrical explosion in an atmosphere of carbon monoxide generated phase structure needed to activate hydrocarbon synthesis reaction of a mixture of CO and H2.

Synthesis of hydrocarbon gases from four different carbon sources and hydrogen gas using a gold-tube system by Fischer–Tropsch method

Several series of Fischer–Tropsch synthesis (FTS) experiments were conducted in a gold tube system with montmorillonite K-10 loaded with Fe3+ and Ni3+ as catalysts. Four different carbon sources: graphite, Na2CO3 solution (20%) and two types of CO2 gases with distinctive isotopic compositions were reduced in pure hydrogen gas at 400°C and 50MPa for 2–60h. The experimental results showed that the FTS reaction between liquid carbon and H2 could hardly occur. However, the reaction between gaseous phase carbon (CO2) and H2 gas was easier than that between solid phase carbon (graphite) and H2 gas; and the 13C depleted CO2 is more reactive than the 13C enriched CO2. Our results also show that the production of synthetic hydrocarbon gases from different carbon sources with H2 depends largely on the phases, and structural and thermal stability of carbon sources. In a relatively short reaction time at 400°C, the carbon isotope values of the synthesized alkane gases showed a full reversal trend with their molecular carbon numbers (δ13C1>δ13C2>δ13C3>δ13C4). However, with increasing reaction time, such a reversed isotopic distribution pattern disappeared. Our interpretation is that the final products were gradually replaced by cracking of the hydrocarbon products formed at the earlier stage of the synthesis process. Thus the 13C depleted gas from the thermal cracking was mixed with the 13C enriched residual gas, leading to the occurrence of a partial reversal or a normal isotopic distribution among C1–C4 alkane series (δ13C1<δ13C2<δ13C3<δ13C4), similar to the thermogenic alkane gases in nature. Under longer reaction time or/and higher reaction temperature (700°C), hydrocarbon gases would crack and generate monatomic carbon.The observed great discrepancy between the natural abiogenic gas and synthetic gas is likely due to the big difference in temperatures between geological settings and the laboratory experiment process. FTS experiments conducted under laboratory experimental condition are usually from low to high temperature and differ significantly from the abiogenic synthesis process for hydrocarbons in real geological settings, which is perceived as a cooling process from high to low temperature either under aqueous hydrothermal or volcanic intrusion conditions. Under certain (stable) geological temperature/pressure conditions, hydrocarbon gases generated might never suffer further decomposition, and thus might preserve a fixed “inverse” molecular isotopic fingerprinting as we observed in the laboratory. This has also been proven by a cooling FTS experiment.