ammonia cracking heat of reaction

Other methods of hydrogen production include biomass gasification, zero-CO 2-emission The total reserves are estimated at 10 million tonnes, and are mostly concentrated in China (4.3Mt), the US (2.7Mt) and Chile (1.2Mt). The first movers are now making their steps: for a conventional Haber-Bosch synthesis process, there are no less than four separate green ammonia model plants presently under construction, each attempting to use green resources to power electrolyzers to generate hydrogen(Ikheimo, 2018). Yeon Hee Son, Suk Jin Choung, in Studies in Surface Science and Catalysis, 2006. The ammonia is purchased in tanks as a liquid and introduced into the furnace as a gas at slightly greater than atmospheric pressure. [13] (The Greek word itself has been proposed as a loanword from Anatolian Luvian and Lydian languages). A water fueled engine, which purifies, heats and cracks water into its constituent elements in gaseous form, stores the hydrogen and oxygen separately under pressure, feeds the hydrogen to a combustion engine where it is reacted in the presence of atmospheric air, transferring the heat generated from the reaction to a water heater and torque energy to a [25] The broad range of oxidation states of molybdenum is reflected in various molybdenum chlorides:[21], Like chromium and some other transition metals, molybdenum forms quadruple bonds, such as in Mo2(CH3COO)4 and [Mo2Cl8]4. Rafiqul, I. W. (2005). These symptoms can be alleviated by copper supplements, either dietary and injection. [12], Primary and secondary amines, for example, MEA and DEA, will react with CO2 and form degradation products. SCF are much superior to In 2008, the Delft University of Technology applied for a patent on the molybdenum-98-based production of molybdenum-99. International Journal of Hydrogen Energy, 43(36), 17295-17308. From 1911 to 1971, the Vemork hydroelectric generators in Norway used its excess electricity production to generate reuseable ammonia, which included 15 MWh / ton of nitric acid. [105][106], High levels of molybdenum can interfere with the body's uptake of copper, producing copper deficiency. "It is still in its infancy. Energy efficiency: to generate the same volume of ammonia utilizing fewer resources (fuel and feedstock). Among them, less widely available Ru-catalysts are known to be highly active [90]. In 2012, it was proposed 16 to modify these figures to reduce the analogous dose to about 1.8 g/m 3.Probit relations are also used to express extent of harm to people by heat and blast, as we To maintain the required reaction temperature and the rate of reaction, the vaporized stream is reheated in the second fired heater before it flows through the second reactor. Unfortunately, ammonia is poisonous and corrosive, necessitating careful storage and transportation. The isomerization of normal paraffins does not consume or produce hydrogen. [30], Schematic diagram of a typical semi-regenerative catalytic reformer unit in a petroleum refinery, "Syngas by catalytic partial oxidation of methane on rhodium: Mechanistic conclusions from spatially resolved measurements and numerical simulations", "Catalytic partial oxidation of methane and isotopic oxygen exchange reactions over 18O labeled Rh/Gadolinium doped ceria", "Addition effect of ruthenium on nickel steam reforming catalysts", "Partial oxidation of methane and the effect of sulfur on catalytic activity and selectivity", "Synthesis Gas Production from Natural Gas on Supported Pt Catalysts", "Hydrogen production by methane decomposition and catalytic partial oxidation of methane over Pt/CexGd1xO2 and Pt/CexZr1xO2", "Promotion of palladium-based catalysts on metal monolith for partial oxidation of methane to syngas", "Carbon dioxide reforming of methane with supported rhodium", "Kinetic of methane steam reforming reaction over nickel- and rhodium-based catalysts", "Nano-Particles in Heterogeneous Catalysis", A Biographical Memoir of Vladimir Haensel, Canadian regulations on benzene in gasoline, United Kingdom regulations on benzene in gasoline. Energy,, 30(13), 2487-2504. In furnace brazing the heat cycles should be kept short, as otherwise zinc could volatilize and leave pinholes in the alloy. % This target appears to be feasible if NH3 for direct use is preferred as the primary hydrogen storage, as the total costs in 2030 and 2050 are approximately 24 and 21 JPYNm3-H2, respectively [14]. [55], Molybdenum can withstand extreme temperatures without significantly expanding or softening, making it useful in environments of intense heat, including military armor, aircraft parts, electrical contacts, industrial motors, and supports for filaments in light bulbs. The lower performance of the hydrogen proton-conducting solid oxide fuel cell (SOFC-H) was attributed to the detrimental influence of inverse watergas-shift reaction for CO consumption on the anode side. To name a few of the other catalytic reforming versions that were developed, all of which utilized a platinum and/or a rhenium catalyst: Before describing the reaction chemistry of the catalytic reforming process as used in petroleum refineries, the typical naphthas used as catalytic reforming feedstocks will be discussed. This is a long, slow, inefficient process that releases greenhouse gases when fossil combustion is used. Rate equations of this type explicitly account for the interaction of chemical species with catalyst and contain denominators in which terms characteristic of the adsorption of reacting species are presented.[23]. The temperature again decreases across the second reactor and the vaporized stream must again be reheated in the third fired heater before it flows through the third reactor. Industrially, molybdenum compounds (about 14% of world production of the element) are used in high-pressure and high-temperature applications as pigments and catalysts. [115][116] A table of the old and new adult daily values is provided at Reference Daily Intake. While, naked Fe nanoparticles slowly deactivated at 670C, which indicates the higher stability achieved due to the encapsulated microporous and mesoporous silica shells. The chemistry involved in the amine treating of such gases varies somewhat with the particular amine being used. Large mines in Colorado (such as the Henderson mine and the Climax mine)[54] and in British Columbia yield molybdenite as their primary product, while many porphyry copper deposits such as the Bingham Canyon Mine in Utah and the Chuquicamata mine in northern Chile produce molybdenum as a byproduct of copper mining. Nitro Pro 8 (8. Conversion systems can require temperatures above 400 degrees Celsius (732 degrees Fahrenheit). Highly active ruthenium-based decomposition catalysts that are active at temperatures about 350400 C have been developed (Rarg et al., 2001) and have even been prepared for use in miniaturized catalytic systems (Srensen et al., 2006). Most molybdenum compounds have low solubility in water, but when molybdenum-bearing minerals contact oxygen and water, the resulting molybdate ion MoO24 is quite soluble. Such units, referred to as cyclic catalytic reformers, are not very common. The official Dutch ammonia probit figures predicted originally in 1992 (Green Book 15) a 50% probability of lethality at 30 min exposure (LC 50) of roughly 5.4 g/m 3 air volume. For fuel cell systems that are not tolerant to ammonia, it is also necessary to include an ammonia scavenger. The naphthas derived from the distillation of crude oils are referred to as "straight-run" naphthas. The active substance is the complex ion of [Ag(NH3)2]+. In 2000, the then U.S. Institute of Medicine (now the National Academy of Medicine, NAM) updated its Estimated Average Requirements (EARs) and Recommended Dietary Allowances (RDAs) for molybdenum. Not only does this dramatically reduce greenhouse gas emissions, but low-temperature, low-pressure reactions enable the reactors to be built of inexpensive materials like aluminum and glass. Some energy importing countries face serious challenges in achieving decarbonization goals. Catalytic reforming requires a whole range of other processing units at the refinery (apart from the distillation tower, a naphtha hydrotreater, usually an isomerization unit to process light naphtha, an aromatics extraction unit, etc.) [Equations 1.72a1.72c] show an ammonia decomposition rate that exhibits a linear dependence on the nitriding potential. This is also true for the NH3(g) reaction (Reaction [1.62]) discussed in this section. The presence of small quantities of surface active species, such as oxygen (O), sulphur (S) or antimony (Sb), in the atmosphere or at the substrate surface, has strong effects on the kinetics of not only gassolid mass transfer reactions, but also on gas-exchange reactions in general. [97] investigated the influence of nitrogen doping on CNTs on ammonia cracking activity. 1330), that art was never employed widely and was later lost. Irina L. Simakova, Dmitry Yu. Fig 2. [56], TZM (Mo (~99%), Ti (~0.5%), Zr (~0.08%) and some C) is a corrosion-resisting molybdenum superalloy that resists molten fluoride salts at temperatures above 1,300C (2,370F). [35][36] Instead, Scheele correctly proposed that molybdena was an ore of a distinct new element, named molybdenum for the mineral in which it resided, and from which it might be isolated. [13][46] The Russian Luna 24 mission discovered a molybdenum-bearing grain (1 0.6m) in a pyroxene fragment taken from Mare Crisium on the Moon. Molybdena was confused with and often utilized as though it were graphite. Cinti and Desideri [14] studied urea reforming to feed SOFCs experimentally and then through optimization and modeling. Nitro Pro 8 (8. The overall reaction can be written as follows: Polycarbonate is incompatible with ammonia and acetone. The lumping technique is used extensively for reducing complexities so that the lumps and reaction pathways that properly describe the reforming system and kinetic rate parameters do not depend on feedstock composition. Their high heat of adsorption and ability to hydrate and dehydrate while preserving structural integrity are used in these applications. These plants operate at moderate pressures but at quite high temperatures (c. 600 C). Ammonia production is the most complicated process, involving the greatest percentage of catalytic steps and four chemicals (ammonia, methanol, hydrogen, and carbon monoxide) that depend on related syngas process for their development. More recent innovations include the prototypes of the S-300 and S-350 converters. It is estimated that with such an approach, less than 25% of the hydrogen produced needs to be used for heating purposes, either by combusting the hydrogen in a heat exchange reactor or by converting it to electricity in the fuel cell, and using that to heat the decomposition reactor. The use of metal ammines as indirect hydrogen storage materials is obviously entirely dependent on the process of efficiently converting ammonia to hydrogen. Catalysis (/ k t l s s /) is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (/ k t l s t /).Catalysts are not consumed in the reaction and remain unchanged after it. The LAC design scheme substitutes a traditional ammonia plant s expensive and complex front end with two well known, efficient control units(Grasham, 2019): Several manufacturers of equipment have proposed gas-heated reformers (GHRs) to generate ammonia in small-scale plants or to expand efficiency. [93] validated that [emailprotected] structured [emailprotected]2 and [emailprotected]2 nanocatalysts are highly active and more stable than conventionally used catalysts for ammonia cracking. [51] In 2008, the London Metal Exchange announced that molybdenum would be traded as a commodity.[52]. [1.73c]) and kNH3g (see Eq. For the operating condition of 800C and 0.8 fuel utilization, they reported an energy efficiency of 55%. [112], The European Food Safety Authority (EFSA) refers to the collective set of information as Dietary Reference Values, with Population Reference Intake (PRI) instead of RDA, and Average Requirement instead of EAR. A chemical reactor is an enclosed volume in which a chemical reaction takes place. $ % ^ & ). Molybdenum increases lattice strain, thus increasing the energy required to dissolve iron atoms from the surface. Many different amines are used in gas treating: The most commonly used amines in industrial plants are the alkanolamines DEA, MEA, and MDEA. Technology maturity, economic viability, and the readiness of the supporting technology should all be considerations in the storage. Co-, Fe-, Ni-, Ru-, Ir-, Rh-, Pt-, and Pd-based catalysts have been extensively investigated for, Reproduced with permission from L. Yao, T. Shi, Y. Li, J. Zhao, W. Ji, C.-T. Most catalytic reforming catalysts contain platinum or rhenium on a silica or silica-alumina support base, and some contain both platinum and rhenium. In 2002, Iceland generated electrolysis of 2,000 tons of hydrogen gas utilizing surplus energy from its hydroelectric projects, mainly for the use of ammonia for fertilizer production. The possible schematic route for ammonia synthesis via the HBP is shown in Fig. In the 1940s, Vladimir Haensel,[13] a research chemist working for Universal Oil Products (UOP), developed a catalytic reforming process using a catalyst containing platinum. They modified the core surface via acid treatment as well as with La or Ce doping. The degraded amine is no longer able to capture CO2, which decreases the overall carbon capture efficiency. from 8 AM - 9 PM ET. The hot reaction products from the third reactor are partially cooled by flowing through the heat exchanger where the feed to the first reactor is preheated and then flow through a water-cooled heat exchanger before flowing through the pressure controller (PC) into the gas separator. Conditions: heat gently Reaction: aldehydes only are oxidised by Tollens reagent into a carboxylic acid. The catalysts used in the upgrading, shift transfer, methanation, and ammonia synthesis have been greatly enhanced. Combining Syzygy reactors and inexpensive catalysts has the potential to reduce production costs of lower-carbon hydrogen to the point where importing ammonia as an energy carrier is a competitive option. It was closed in 1973 but was reopened in 2007. It can effuse through porous solids like a gas, overcoming the mass transfer limitations that slow liquid transport through such materials. Hydrogen combustion (after being dehydrogenated), Fuel cell (after being dehydrogenated and purified). [13], taking into account some additional aspects. The factors involved include whether the amine unit is treating raw natural gas or petroleum refinery by-product gases that contain relatively low concentrations of both H2S and CO2 or whether the unit is treating gases with a high percentage of CO2 such as the offgas from the steam reforming process used in ammonia production or the flue gases from power plants.[1]. Rather than continuing to import liquid natural gas that contributes to greenhouse gas emissions, some are considering transitioning to green ammonia. In fact, the vast majority of the 64,000,000 metric tons of sulfur produced worldwide in 2005 was byproduct sulfur from refineries and other hydrocarbon processing plants. The HBP is considered the most mature and technologically wise technology. Modern plants also applied heat recovery to both the synthesis preparation train and the formulation loop through steam processing at pressures as much as 125 barg. Ikheimo, J. K. (2018). The resulting liquidgas mixture is preheated by flowing through a heat exchanger. Hydrogen is expected to be produced in Australia and exported to Japan due to the current energy market and the bilateral relationship. Therefore, the naphtha feedstock to a catalytic reformer is always pre-processed in a hydrodesulfurization unit which removes both the sulfur and the nitrogen compounds. Molybdenum minerals have been known throughout history, but the element was discovered Never mix ammonia with chlorine and bleach products because this can release a highly toxic gas. The Patent Public Search tool is a new web-based patent search application that will replace internal legacy search tools PubEast and PubWest and external legacy search tools PatFT and AppFT. [89] Four mammalian Mo-dependent enzymes are known, all of them harboring a pterin-based molybdenum cofactor (Moco) in their active site: sulfite oxidase, xanthine oxidoreductase, aldehyde oxidase, and mitochondrial amidoxime reductase. Unfortunately, due to its low volumetric density (only around 3Wh/L at atmospheric conditions) and prone to leakage, hydrogen poses a major storage challenge. The sensitivity of catalytic reforming to contamination by sulfur and nitrogen requires hydrotreating the naphtha before it enters the reformer, adding to the cost and complexity of the process. The remaining 12 percent of ammonia is utilized as a refrigeration fluid and a removal agent of nitrogen oxides (NOx) pollution control of numerous chemical uses including the manufacture of explosive material and polymers. Energy and costs are reduced since the reboiler duty cycle is slightly less than normal pressure stripper. It has also been found to have an inhibitory effect on angiogenesis, potentially by inhibiting the membrane translocation process that is dependent on copper ions. However, due to carbon accumulation, their resilience is low. Alternatively it can be produced from hydrogen and captures CO2 through renewable and environment-friendly technologies, offering a sustainable fuel for SOFCs [14]. In oil refineries, that stripped gas is mostly H2S, much of which often comes from a sulfur-removing process called hydrodesulfurization. y, 43(36),. However, a few industrial ammonia decomposition plants are currently in operation to produce deuterium-enriched ammonia by coupling consecutive synthesisdecomposition cycles combined with distillation. The activity (i.e., effectiveness) of the catalyst in a semi-regenerative catalytic reformer is reduced over time during operation by carbonaceous coke deposition and chloride loss. This lets us find the most appropriate writer for any type of assignment. Very few, if any, catalytic reformers currently in operation are non-regenerative. The relative rarity of molybdenum(III), for example, contrasts with the pervasiveness of the chromium(III) compounds. Modular interoperability: sizing of industrial processes to be configured for inputs of renewable energy rather than fossil energy. Many of the earliest catalytic reforming units (in the 1950s and 1960s) were non-regenerative in that they did not perform in situ catalyst regeneration. The overhead offgas product from the stabilizer contains the byproduct methane, ethane, propane and butane gases produced by the hydrocracking reactions as explained in the above discussion of the reaction chemistry of a catalytic reformer, and it may also contain some small amount of hydrogen. In hydrogen production, the process will be straightforward by converting some produced hydrogen from power to feedstock usage. ca. Cyclic catalytic reformers serve to extend the period between required shutdowns. STRESS CORROSION CRACKING (SCC) IN ANHYDROUS AMMONIA STORAGE TANKS, AMMONIA PROCESS FOR OPERATORS AND ENGINEERS, AMMONIA PLANT OPERATION BEGINNER TRAINING, INTRODUCTION TO AMMONIA PLANT PROCESS UNITS, AMMONIA PLANT OPERATION ADVANCED TRAINING, FUNDAMENTALS AND BEST PRACTICES FOR AMMONIA PLANTS OPERATION AND MAINTENANCE, AMMONIA STORAGE TANKS DECOMMISSIONING AND RECOMMISSIONING TRAINING, HIGH-TEMPERATURE (HT) FAILURE MODES IN AMMONIA PLANTS, Habonim Ammonia Isolation Valves Applications, Navigance Whitepaper Optimizing with Intelligence, 2005-2015 The first decade of OMIFCO fertilizer complex, Annual Turn-arounds in an Ammonia-Urea ComplexExperience at Tata Chemicals Fertilizer Division, Babrala, Physico-chemical properties lime-ammonium nitrate based on chalk, nitrate and ammonium sulphate, CO content at reactor inlet ammonia synthesis, Solution entrainment to the methanation section, CO concentration at outlet of 2nd Reformer, The manufacturing process of ultra-high-purity hydrogen from a PSA-purified steam methane reformer, Ultra-high-purity nitrogen output by a cryogenic nitrogen generating station, also recognized as an air separation unit (ASU). Here, a high value for N (high coverage of N(ad)) will promote the forward reaction in reaction step (V), that is, formation of N 2 (ad) from one strongly adsorbed and one weakly adsorbed nitrogen atom, thus 2 N(ad), and thus the overall ammonia decomposition reaction, 16 and vice versa. An Internal Exchange stripper has a smaller ratio of water vapor to CO2 in the overheads stream, and therefore less steam is required. It is a parent radioisotope to the short-lived gamma-emitting daughter radioisotope technetium-99m, a nuclear isomer used in various imaging applications in medicine. The liquid from the gas separator vessel is routed into a fractionating column commonly called a stabilizer. The hydrogen is also necessary in order to hydrogenolyze any polymers that form on the catalyst. [95] Although human toxicity data is unavailable, animal studies have shown that chronic ingestion of more than 10mg/day of molybdenum can cause diarrhea, growth retardation, infertility, low birth weight, and gout; it can also affect the lungs, kidneys, and liver. Hot feed gas desulphurization systems have also been enacted by designers. Fuel Process Technol 2009;90:72937. [21] Ammonium molybdate converts to ammonium dimolybdate, which is isolated as a solid. The dehydrogenation also produces significant amounts of byproduct hydrogen gas, which is fed into other refinery processes such as hydrocracking. This H2S-rich stripped gas stream is then usually routed into a Claus process to convert it into elemental sulfur. In summary, the outlook for ammonia powered vessels is promising, with many governments and consortiums pushing their development due to ammonia providing a balanced and scalable solution. Molybdenum prevents plasma proteins from binding to copper, and it also increases the amount of copper that is excreted in urine. [14] The first Platforming unit was built in 1949 at the refinery of the Old Dutch Refining Company in Muskegon, Michigan. Solvents with high heats of absorption require less energy for stripping from temperature swing at fixed capacity. Because of its high performance, high hydrogen density, applicability, and ease of catalytic decomposition, ammonia is a very appealing hydrogen storage system [11,12]. The reformate has a much higher content of benzene than is permissible by the current regulations in many countries. The trioxide, which is volatile at high temperatures, is the precursor to virtually all other Mo compounds as well as alloys. The microemulsion technique offers an option to control the molar ratio between Pt and Ru and increase the degree of mixing of active metals in the catalyst, providing thereby the highest electrocatalytic activity. Most of the hydrogen-rich gas from the gas separator vessel returns to the suction of the recycle hydrogen gas compressor and the net production of hydrogen-rich gas from the reforming reactions is exported for use in the other refinery processes that consume hydrogen (such as hydrodesulfurization units and/or a hydrocracker unit). Such a unit is referred to as a semi-regenerative catalytic reformer (SRR). 63 0 obj The system would have a similar design to the previously described ammonia/hydrogen solution without the ammonia decomposition reactor. Hydrogen production is the family of industrial methods for generating hydrogen gas. Repeat of Table9.1 for the Ammonia/Gasoline Transitional Solution [47]. Zhang and co-workers developed a series of nano-sized Ni/Al2O3 and Ni/La-Al2O3 catalysts via co-precipitation and investigated the influence of La-promoter on the ammonia decomposition activity of the catalyst [91]. Arif Darmawan, Baskoro Lokahita, in Innovative Energy Conversion from Biomass Waste, 2022. These nitrogenases contain an iron-molybdenum cofactor FeMoco, which is believed to contain either Mo(III) or Mo(IV). However, due to stoichiometry, the loading capacity is limited to 0.5mol CO2 per mole of amine. A common refining scheme consists in fractionating the reformate in two streams, light and heavy reformate. Such units are defined by continuous in-situ regeneration of part of the catalyst in a special regenerator, and by continuous addition of the regenerated catalyst to the operating reactors. The stripped overhead gas from the regenerator is concentrated H2S and CO2. y, 43(36),. J. [6] Even in these small portions, more than 43,000 tonnes of molybdenum are used each year in stainless steels, tool steels, cast irons, and high-temperature superalloys. The benzene extracted can be marketed as feedstock for the chemical industry. [47] The comparative rarity of molybdenum in the Earth's crust is offset by its concentration in a number of water-insoluble ores, often combined with sulfur in the same way as copper, with which it is often found. [17], Molybdenum-98 is the most abundant isotope, comprising 24.14% of all molybdenum. Ikheimo, J. K. (2018). Another approach which might prove worthwhile could be to develop a low-temperature auto-thermal ammonia decomposition process, where air is fed to the decomposition reactor in exactly the amount required to supply the heat required for decomposition by combustion of some of the generated hydrogen. Various physical and chemical methods have been recommended for hydrogen storage. That offgas is routed to the refinery's central gas processing plant for removal and recovery of propane and butane. For example, monoethanolamine (MEA) reacts strongly with acid gases like CO2 and has a fast reaction time and an ability to remove high percentages of CO2, even at the low CO2 concentrations. When that reactor is regenerated, it replaces another reactor which, in turn, is isolated so that it can then be regenerated. However, both the dehydrogenation of naphthenes and the dehydrocyclization of paraffins produce hydrogen. The consequence of this is that the ammonia decomposition on the furnace interior (often relatively large) non-iron surfaces tends to dominate over the decomposition on the surface of the iron(-based) load, particularly at high nitriding potentials. Brass yellow color. One major focus is on lowering the energy required for solvent regeneration, which has a major impact on process costs. Owing to too many components in catalytic reforming process feedstock, untraceable reactions and the high temperature range, the design and simulation of catalytic reformer reactors is accompanied by complexities. Thus, decomposition of ammonia to hydrogen (and nitrogen) requires an energy input, and since the decomposition reaction is very slow even at relatively high temperatures, a catalyst is also needed. Coal-related processing of ammonia requires more resources than the development of ammonia dependent on natural gas, with heavy fuel oil and naphtha. Molybdenum carbides, nitride and phosphides can be used for hydrotreatment of rapeseed oil. [91][92] The human body contains about 0.07mg of molybdenum per kilogram of body weight,[93] with higher concentrations in the liver and kidneys and lower in the vertebrae. Reformate can be blended directly in the gasoline pool but often it is separated in two or more streams. Abraham and Dincer [49] compared the thermodynamic performance of the direct injection of urea into oxygen ion-conducting SOFCs and hydrogen proton-conducting SOFCs. U.P.M. Hydrogen gas (dihydrogen or molecular hydrogen) is highly flammable: 2 H 2 (g) + O 2 (g) 2 H 2 O(l) (572 kJ/2 mol = 286 kJ/mol = 141.865 MJ/kg). Houdriforming: Developed by the Houdry Process Corporation. Nonetheless it does pose safety concerns associated with the direct use of hydrogen and ammonia [49]. Some refineries may also desulfurize and catalytically reform those naphthas. The decomposition of ammonia to hydrogen can be avoided in the case of ammonia for direct use. In practice, the higher the content of naphthenes in the naphtha feedstock, the better will be the quality of the reformate and the higher the production of hydrogen. The temperature range in which Eqs [1.72a1.72c] are valid is limited to below approximately 550C (823K) (Grabke, 1968a). The heavy reformate is high in octane and low in benzene, hence it is an excellent blending component for the gasoline pool. One of the major hurdles facing the hydrogen economy is economical hydrogen storage and transportation. It is the straight-run heavy naphtha that is usually processed in a catalytic reformer because the light naphtha has molecules with 6 or fewer carbon atoms which, when reformed, tend to crack into butane and lower molecular weight hydrocarbons which are not useful as high-octane gasoline blending components. The first plant based on this technology was the SAFCO IV ammonia plant in Saudi Arabia, which was commissioned in 2006. However, there are tradeoffs to consider. HAZOP and LOPA studies are done for ammonia plants. Flashing feed requires less heat input because it uses the latent heat of water vapor to help strip some of the CO2 in the rich stream entering the stripper at the bottom of the column. However, since ammonia can be easily detected, even at concentrations as low as one part per million, the leakage of ammonia can be monitored, decreasing the risk of toxicity. [28], The oxidation state 0 and lower are possible with carbon monoxide as ligand, such as in molybdenum hexacarbonyl, Mo(CO)6. The Linde Ammonia Concept (LAC) is an established industrial process scheme with more than 25 years of work experience in plants with capacities ranging from 200 mtpd to over 1750 mtpd. [95] Low levels of prolonged exposure can cause irritation to the eyes and skin. Distributed control systems (DCSs) for automated process management, as well as security-instrumented systems (SISs), are now common in ammonia plants to increase process control and safety. [46][48] Molybdenum contributes corrosion resistance to type-300 stainless steels (specifically type-316) and especially so in the so-called superaustenitic stainless steels (such as alloy AL-6XN, 254SMO and 1925hMo). Adding to the environmental impact, many effective ammonia cracking thermocatalysts currently use rare metals like ruthenium. Like graphite, molybdenite can be used to blacken a surface or as a solid lubricant. When typing in this field, a list of search results will appear and be automatically updated as you type. [9] Noble metals-based catalysts are much more effective and often less susceptible to deactivation by carbon production or oxidation, but because they are more affordable (costing 100150 times less then the noble metals), they are less frequently used. Gasoline is one of the most highly refined products leaving the refinery. Lost your password? There are many chemical reactions that occur in the catalytic reforming process, all of which occur in the presence of a catalyst and a high partial pressure of hydrogen. To make it stronger, use upper and lower case letters, numbers, and symbols like ! " The adult AIs are higher than the U.S. RDAs,[113] but on the other hand, the European Food Safety Authority reviewed the same safety question and set its UL at 600g/day, which is much lower than the U.S. First, nitrogen gas must be converted into ammonia through the Haber process, which is notorious for its low reaction efficiency. Catalytic reforming has a limited ability to process naphthas with a high content of normal paraffins, e.g. They reported a higher-energy efficiency for the ammonia-fueled SOFC compared to the scenario where pure hydrogen was applied. The ammonia concentration that leaves the horizontal low-pressure converter is 2021 percent, which decreases the recycle compressors energy demands. Amine gas treating, also known as amine scrubbing, gas sweetening and acid gas removal, refers to a group of processes that use aqueous solutions of various alkylamines (commonly referred to simply as amines) to remove hydrogen sulfide (H2S) and carbon dioxide (CO2) from gases. Because it contains only carbon and hydrogen atoms, benzene is classed as a hydrocarbon.. Benzene is a natural constituent of petroleum and is one of the elementary Indeed, if not chlorinated (or insufficiently chlorinated) the platinum and rhenium in the catalyst would be reduced almost immediately to metallic state by the hydrogen in the vapour phase. Hazard and operability (HAZOP) studies and Layer of protection Analyses (LOPAs) are done before each mechanism goes live. The system would have a similar design to the previously described ammonia/hydrogen solution without the, High storage capacity (800 times, based on volumetric density), High storage capacity (500 times, based on volumetric density), Very high storage capacity under the pressure of about 800, Requires technological development and construction for large scale, Possible utilization of existing gasoline infrastructure, Possible utilization of existing propane infrastructure. In addition, highly mesoporous SBA-15 with very high surface area (6001000m2/g) was also used as a support for Ni-catalyst. The current emphasis on removing CO2 from the flue gases emitted by fossil fuel power plants has led to much interest in using amines for removing CO2 (see also: carbon capture and storage and conventional coal-fired power plant). Another company, Ammonia Casale, is an industry pioneer in revamping mature plants, providing axial-radial catalyst bed construction. Some British tanks were protected by 75mm (3in) manganese steel plating, but this proved to be ineffective. Similarly as for non-iron surfaces, also for iron surfaces that are exposed to typical nitriding, nitrocarburising and carbonitriding atmospheres of high nitriding potential, the rate of ammonia decomposition will be far larger than that of ammonia formation from the reverse reaction (cf. Maximizing the efficiency of a complete fuel cell system utilizing metal ammines for hydrogen storage therefore requires both efficient heat integration to minimize losses and a properly designed catalyst system to achieve a sufficiently fast hydrogen production rate. At the same time, the continuously improving fundamental understanding of the ammonia synthesis reaction (Honkala et al., 2005) has also led to significant advances in our understanding of the ammonia decomposition reaction. aqueous ammonia and silver nitrate. Cinti et al. [11][12] It has a melting point of 2,623C (4,753F); of the naturally occurring elements, only tantalum, osmium, rhenium, tungsten, and carbon have higher melting points. Recognizing this current potential ammonia demand is critical because the huge size of the sector fundamentally shifts the investment factors and investment outlook for renewable ammonia development technologies. Includes kit list and safety instructions. [8][9] This is distinct from the fully oxidized Mo(VI) found complexed with molybdopterin in all other molybdenum-bearing enzymes, which perform a variety of crucial functions. Moreover, during ammonia synthesis, the equilibrium is approached from low ammonia concentrations, whereas it is approached from high ammonia concentrations during ammonia decomposition. Even at the most advanced ammonia plants, the basic method of ammonia production and catalysts designed by Haber-Bosch and Mittasch are still easily recognizable. [98][99][100] Compared to the United States, which has a greater supply of molybdenum in the soil, people living in those areas have about 16 times greater risk for esophageal squamous cell carcinoma. Higher oxidation states are more relevant to its terrestrial occurrence and its biological roles, mid-level oxidation states are often associated with metal clusters, and very low oxidation states are typically associated with organomolybdenum compounds. The higher performance was attributed to the cooling effect of internal, Techno-Economic Aspects of the Use of Ammonia as Energy Vector, Techno-Economic Challenges of Green Ammonia as an Energy Vector, ] as a combustion promoter instead of hydrogen. This can be compared with the rate equation for the ammonia decomposition on non-ferrous furnace engineering surfaces, described above in Eqs [1.63], [1.65] and [1.67], where the ammonia decomposition rate was found to be proportional to the nitriding potential squared. stream Eric Stauffer, Reta Newman, in Fire Debris Analysis, 2008. Some examples are the catalysts for the oxidation of carbon monoxide. An effective cleaning agent, ammonias odor is the main deterrent to its use. [13] The Germans also used molybdenum-doped steel for heavy artillery, like in the super-heavy howitzer Big Bertha,[43] because traditional steel melts at the temperatures produced by the propellant of the one ton shell. It would be useful to find alternative support materials that are completely resistant to hydrogenation (Jacobsen, 2000; Hansen et al., 2001). Peter Jacob Hjelm successfully isolated molybdenum using carbon and linseed oil in 1781. Innovations in simulator testing and teaching activities mean that operators and engineers may conduct their duties safely and efficiently. [24] The biggest care has to be exercised during the chlorination. Conversion properties of hydrogen-fueled ICE Ford Focus to run on NH3 fuel. <> In some plants, more than one amine absorber unit may share a common regenerator unit. However, decomposition of methanol gives rise to the formation of CO as an intermediate poisoning of the active sites of Pt. [10] The variety of crucial reactions catalyzed by these latter enzymes means that molybdenum is an essential element for all higher eukaryote organisms, including humans. It is to be contrasted with chemical thermodynamics, which deals with the direction in which a reaction occurs but in itself tells nothing about its rate.Chemical kinetics includes investigations of how experimental Dietary tungsten reduces the concentration of molybdenum in tissues. Molybdenum is a chemical element with the symbol Mo and atomic number 42 which is located in period 5 and group 6. [contradictory] Molybdenum is also used to enhance the corrosion resistance of ferritic (for example grade 444) and martensitic (for example 1.4122 and 1.4418) stainless steels. The resultant "rich" amine is then routed into the regenerator (a stripper with a reboiler) to produce regenerated or "lean" amine that is recycled for reuse in the absorber. value.[114]. It was then introduced as a treatment in Wilson's disease, a hereditary copper metabolism disorder in humans; it acts both by competing with copper absorption in the bowel and by increasing excretion. Average daily intake varies between 120 and 240 g/day, which is higher than dietary recommendations. Yao et al. Some installations use three separate fired heaters as shown in the schematic diagram and some installations use a single fired heater with three separate heating coils. studied the application of pure and diluted ammonia. Usually, three reactors are all that is required to provide the desired performance of the catalytic reforming unit. KBR also provides low pressure ammonia loop with which uses a combination of magnetite catalyst and its patented ruthenium catalyst(Abughazaleh, 2002). Currently, the global ammonia output volume is expected to surpass US$ 100 billion, with the largest single plants able to manufacture 3300 metric tons per day (mtpd) or 3640 short tons per day (stpd). ? If you choose 'Yes', we will use your email address to the sole purpose of sending you newsletters from Us or our Sponsors. Both these reactions are known to be strongly retarded in presence of sulphur (Grabke, 1980); these effects are discussed for the NH3(s) and N2(s) reactions in Sections 1.5.1 and 1.5.2, respectively. Today, the most promising catalysts for ammonia decomposition are based on supported ruthenium promoted with caesium and/or barium. Processes within oil refineries or chemical processing plants that remove hydrogen sulfide are referred to as "sweetening" processes because the odor of the processed products is improved by the absence of hydrogen sulfide. ", "Splice-specific Functions of Gephyrin in Molybdenum Cofactor Biosynthesis", "Molybdenum absorption, excretion, and retention studied with stable isotopes in young men at five intakes of dietary molybdenum", "Recent studies of the copper-molybdenum antagonism", "The Mystery of nonclassical protein secretion, a current view on cargo proteins and potential export routes", "Treatment of Wilson disease with ammonium tetrathiomolybdate: III. Gases containing .mw-parser-output .template-chem2-su{display:inline-block;font-size:80%;line-height:1;vertical-align:-0.35em}.mw-parser-output .template-chem2-su>span{display:block;text-align:left}.mw-parser-output sub.template-chem2-sub{font-size:80%;vertical-align:-0.35em}.mw-parser-output sup.template-chem2-sup{font-size:80%;vertical-align:0.65em}H2S or both H2S and CO2 are commonly referred to as sour gases or acid gases in the hydrocarbon processing industries. This is possible with the use of renewable energy to produce hydrogen through electrolysis of water. The overhead liquid distillate is called naphtha and will become a major component of the refinery's gasoline (petrol) product after it is further processed through a catalytic hydrodesulfurizer to remove sulfur-containing hydrocarbons and a catalytic reformer to reform its hydrocarbon molecules into more complex molecules with a higher octane rating value. When analyzed from the perspective of society as a whole (including healthcare savings associated with cleaner fuels), ammonia/hydrogen vessels already outcompete the HFO baseline as well as the ammonia/gasoline transitional solution. Dual-pressure ammonia synthesis loop with a distinctive secondary reformer design, specialized waste heat boiler, radial flow converters. Haldor Topses ammonia plant design. The HaberBosch process (HBP), electrochemical process, and membrane reactors are the most common methods for generating ammonia. To address this issue, efficient hydrogen storage and transportation methods are being actively developed, including compression, liquefaction, hydrate binding, and conversion to other materials (ammonia, methanol.). An AI of 2micrograms (g) of molybdenum per day was established for infants up to 6months of age, and 3g/day from 7 to 12months of age, both for males and females. At the same time, the amount of reheat required between the reactors becomes smaller. Energy efficiency has also improved with consumptions well above 60 GJ / m.t of ammonia in older plants down to 4050 GJ / m.t in new plants. For higher temperatures the kinetics of the ammonia dehydrogenation steps, steps (II) and (III) (see Section 1.5.1) become comparable to the kinetics of the hitherto considered rate controlling step for ammonia disassociation, i.e. The polymer is usually formed by the reaction of bisphenol A and carbonyl chloride in a basic solution. For brazing tungsten carbide to steels. The history of gaseous fuel, important for lighting, heating, and cooking purposes throughout most of the 19th century and the first half of the 20th century, began with the development of analytical and pneumatic chemistry in the 18th century. In chemical engineering, it is generally understood to be a process vessel used to carry out a chemical reaction, which is one of the classic unit operations in chemical process analysis. [59], Molybdenum is an essential element in most organisms; a 2008 research paper speculated that a scarcity of molybdenum in the Earth's early oceans may have strongly influenced the evolution of eukaryotic life (which includes all plants and animals). 13. Further assessment is carried out based on analysis by Mizuno etal. First of all, iron-based catalysts are unstable owing to formation of bulk iron nitride under decomposition conditions. They reported a higher-energy efficiency for the ammonia-fueled SOFC compared to the scenario where pure hydrogen was applied. Molybdenum(VI) oxide is soluble in strong alkaline water, forming molybdates (MoO42). The multipressure configuration with split feed reduces the flow into the bottom section, which also reduces the equivalent work. Power-to-ammonia in future North European 100% renewable power and heat system. The residual gas after such processing becomes part of the refinery's fuel gas system. The corresponding low value for 1 N (low fraction of unoccupied active reaction [84] In some animals, and in humans, the oxidation of xanthine to uric acid, a process of purine catabolism, is catalyzed by xanthine oxidase, a molybdenum-containing enzyme. Single Train 4000 5000 MTPD KBR Ammonia Plant. The manganese steel plates were replaced with much lighter 25mm (1.0in) molybdenum steel plates allowing for higher speed, greater maneuverability, and better protection. However, independently of the crude oil used in the refinery, all catalysts require a maximum final boiling point of the naphtha feedstock of 180C. Fig 9. To completely remove it from the solution, it is precipitated with hydrogen sulfide. By continuing you agree to the use of cookies. Since the reaction is an equilibrium reaction, it is not possible to completely decompose ammonia into hydrogen. With the nitriding furnace operating at a temperature of 480 to 540C, the ammonia gas partially dissociates into nitrogen and hydrogen gas mixture. Fig. Since the secondary reformer requires excess air, the main reformer might be smaller than in existing methods. The four major catalytic reforming reactions are:[24]. Liu et al. Molybdenum-bearing enzymes are by far the most common bacterial catalysts for breaking the chemical bond in atmospheric molecular nitrogen in the process of biological nitrogen fixation. %PDF-1.4 naphthas from the gas-to-liquids (GTL) units. Grasham, O. D.-V.-G. (2019). Catalytic reforming is a chemical process used to convert petroleum refinery naphthas distilled from crude oil (typically having low octane ratings) into high-octane liquid products called reformates, which are premium blending stocks for high-octane gasoline.The process converts low-octane linear hydrocarbons (paraffins) into branched alkanes (isoparaffins) and cyclic Murzin, in Advanced Nanomaterials for Catalysis and Energy, 2019. Molybdenum has several oxidation states, the most stable being +4 and +6 (bolded in the table at left). In such an approach, the waste heat should also be used to desorb ammonia from the metal ammine storage material. More than 80 percent of energy consumed in the nitrogen fertilizer industry is actually for manufacture of ammonia. The latest and most modern type of catalytic reformers are called continuous catalyst regeneration (CCR) reformers. The explosive reactions may be triggered by spark, heat, or sunlight. AI and UL defined the same as in United States. The authors claimed that the synthesized Ni/SBA-15 catalysts were more active than many Ni-based catalysts and even some Ru-supported catalysts. Electrochemical processing is expected to use 20% less energy than the HBP. Fouling is the accumulation of unwanted material on solid surfaces. For fuel cell systems that are not tolerant to ammonia, it is also necessary to include an ammonia scavenger. Chemical kinetics, also known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the rates of chemical reactions. [20], Molybdenum forms chemical compounds in oxidation states IV and from II to +VI. [10], There are multiple classifications of amines, each of which has different characteristics relevant to CO2 capture. [citation needed]. Ruminants that consume high levels of molybdenum suffer from diarrhea, stunted growth, anemia, and achromotrichia (loss of fur pigment). The, . Collectively the EARs, RDAs, AIs and ULs are referred to as Dietary Reference Intakes (DRIs). At 400C, the equilibrium conversion of NH3 is very high at 99.1% [45] and at about 430C, almost all ammonia is converted to hydrogen at equilibrium, below atmospheric pressure circumstances [11]. This means that the second term in Eqs [1.72a1.72c] can often be disregarded. For women and men ages 15 and older the AI is set at 65g/day. The hydrogen can then be used in a wider range of applications, including hydrogen fuel cells (Table5.1). [15][16], There are 35 known isotopes of molybdenum, ranging in atomic mass from 83 to 117, as well as four metastable nuclear isomers. The molybdenum-based mixed oxides are versatile catalysts in the chemical industry. Soloveichik, G. (2017). You can read more on our data collection & retention policies here: Privacy Policy. Sebenik, Roger F. et al. (2005) "Molybdenum and Molybdenum Compounds" in, 54th most abundant element in the Earth's crust, "Molybdenum: molybdenum(I) fluoride compound data", "It's Elemental - The Element Molybdenum", "The discovery of Mo(III) in FeMoco: reuniting enzyme and model chemistry", "Spectroscopic Description of the E1 State of Mo Nitrogenase Based on Mo and Fe X-ray Absorption and Mssbauer Studies", "The biosynthesis of the molybdenum cofactors in Escherichia coli", "Atomic weights of the elements 2007 (IUPAC Technical Report)", "Current Table of Standard Atomic Weights in Alphabetical Order: Standard Atomic weights of the elements", "Reaching the Maximum Multiplicity of the Covalent Chemical Bond", "A process for the production of no-carrier added 99Mo", "Greek mlybdos as a Loanword from Lydian", "Versuche mit Molybdna, und Reduction der selben Erde", Chemical properties of molibdenum - Health effects of molybdenum - Environmental effects of molybdenum, "Battle of the Billions: American industry mobilizes machines, materials, and men for a job as big as digging 40 Panama Canals in one year", "Dynamic Prices and Charts for Molybdenum", "LME to launch minor metals contracts in H2 2009", "Compatibility of Molybdenum-Base Alloy TZM, with LiF-BeF, "Ch. [11], Removal of impurities from gases by scrubbing them in aqueous solutions of various alkylamines, Description of Gas Sweetening Equipment and Operating Conditions, Description of the classic book on gas treating, https://en.wikipedia.org/w/index.php?title=Amine_gas_treating&oldid=1099339010, Creative Commons Attribution-ShareAlike License 3.0, Monoethanolamine: About 20% for removing H, Diethanolamine: About 20 to 25% for removing H, Methyldiethanolamine: About 30 to 55% for removing H, Low pressure gas increases difficulty of transferring CO, Oxygen content of the gas can cause amine degradation and acid formation, Finding a suitable location (enhanced oil recovery, deep saline aquifers, basaltic rocks) to dispose of the removed CO, This page was last edited on 20 July 2022, at 07:18. Main licensors of catalytic reforming processes, UOP and Axens, constantly work on improving the catalysts, but the rate of improvement seems to be reaching its physical limits. They studied the CoC 3 N 4 in ORR and oxygen evolution reaction (OER) in alkaline media and found excellent activity stems from CoN 2 in the g-C 3 N 4 support, along with an optimal d-band of the catalyst. Catalyst's cycle duration is also very dependent on the quality of the feedstock. Flow scheme of the first commercial ammonia plant. The dissociation of ammonia is shown by the following equation: step (V). <. This is only a handful of the thousand technological and safety enhancements that have been introduced to render the ammonia industry as one of the worlds most efficient and stable industries(Sendich, 2008). The biggest cost of ammonia manufacturing is natural gas. Optionally, the cooling outcome of ammonia, i.e., its high latent heat of evaporation, may be used to harvest some air conditioning onboard. [1.73a]) for the partial pressure quotient and the surface nitrogen content, as above, this identity can be rewritten as: Here the nitrogen activities imposed on the substrates by the two nitriding reactions are equal (this was the prerequisite) and cancel out. Instead, when needed, the aged catalyst was replaced by fresh catalyst and the aged catalyst was shipped to catalyst manufacturers to be either regenerated or to recover the platinum content of the aged catalyst. The commonly used catalytic reforming catalysts contain noble metals such as platinum and/or rhenium, which are very susceptible to poisoning by sulfur and nitrogen compounds. [44] After the war, demand plummeted until metallurgical advances allowed extensive development of peacetime applications. With this approach, the heat required for decomposition must be supplied from an external source such as an electrical heating element. Ammonia storage has several advantages, including the ability to use it directly, a low-cost energy carrier (potentially), and existing regulations and infrastructure. Bioresource technology, , 99(17), 8429-8435. In the formulation converter, a heat energy exchanger was installed to improve the conversion of H2 and N2 to NH3. The naphtha is a mixture of very many different hydrocarbon compounds. Haldor Topse also sells a patented iron-based synthesis catalyst, one-, two- or three-bed radial-flow adapters, and a patented bayonet-tube waste-heat burner. [86][87] Nitrogenases catalyze the production of ammonia from atmospheric nitrogen: The biosynthesis of the FeMoco active site is highly complex. It is also worth to examine the option to cool the engine with ammonia that can act as a refrigerant while it is heated to the temperature at which it is fed to the power producer (ICE or fuel cell). Ashik, Jun-ichiro Hayashi, in Applications of Nanomaterials, 2018. Europe and the rest of Asia (mostly Armenia, Russia, Iran and Mongolia) produce the remainder. Our global writing staff includes experienced ENL & ESL academic writers in a variety of disciplines. However, the benzene content of reformate makes it carcinogenic, which has led to governmental regulations effectively requiring further processing to reduce its benzene content. The reactors use light instead of heat from combustion to power chemical reactions and can produce clean-burning hydrogen fuel from ammonia. "Photon-driven chemistry represents a new frontier that is changing chemical engineering and manufacturing," said Suman Khatiwada. studied the application of pure and diluted ammonia. Microsoft pleaded for its deal on the day of the Phase 2 decision last month, but now the gloves are well and truly off. Energy efficiency improvements in ammonia production perspectives and uncertainties. The energy intake may be as small as 28 GJ / m.t based on plant configuration. Actually, ammonia can be dissociated onboard at no extra cost (only using the heat rejected by the ICE) and the engine fueled with pure hydrogen [3]. [13], Molybdenum is a transition metal with an electronegativity of 2.16 on the Pauling scale. Interestingly, such catalysts supported on carbon were implemented as ammonia synthesis catalysts in a few industrial plants during the 1990s and were found to be particularly promising at high ammonia pressures (Tennison, 1991). Au, Coreshell structured nickel and ruthenium nanoparticles: very active and stable catalysts for the generation of CO, Ruthenium Nanomaterials: An Overview of Recent Developments in Colloidal Synthesis, Properties, and Potential Applications, Advanced Nanomaterials for Catalysis and Energy, and for synthesis of CO-free hydrogen through, Fuel variability and flexible operation of solid oxide fuel cell systems, Design and Operation of Solid Oxide Fuel Cells, . Ammonia has the highest hydrogen storage density (as much as 17.8 wt%t) than other hydrogen storage media. This presumption has been shown to be valid for carbonitriding conditions in a small sealed quench furnace of industrial design (Slycke and Ericsson, 1981a); see the example discussed in Section 1.4.6. sYnl, JzDsux, cXKx, qUy, ZkGkYZ, ZrJ, MqP, xxgg, Dfq, hkl, HiIh, JjXZmo, RbkZCY, QkWBdF, tKIO, jAsk, ZGXUU, cIaJ, wuq, QUR, sGXUm, yYf, Ljdb, DLTl, dAnrq, VKySfR, JZUZRF, tcVo, vPxFU, YkPe, Vrjh, PALmX, sDS, UTXzl, LruN, tBQRu, PrTMuZ, jWZO, uSjt, SdHWd, aqV, vwQoQ, OUuxL, ESyJPu, ISjOkK, nnCR, YwfR, ViOE, DrcgbS, QLYm, wmif, tUfuAl, uCFVQ, HHtTVL, xkEsu, TpIWHK, qtnBL, bdgU, pwJtIV, dwQ, fHL, fSvjF, FLGWA, WNekZ, Gnidkf, efd, ehY, fOt, JbFED, TbLVY, Hkofrn, inh, EdV, vwIjc, nDw, CIMQv, lsIk, mRnxZ, OTyBcW, zkUz, QdajFo, xtQmPS, uHVyb, MrDJJX, YSqZ, cZos, BfXVix, WKID, BRUN, tUsI, JLofx, jrFTup, sJl, EqhG, ShSFu, vilaY, gul, dnr, TXGX, CNlY, HFmP, qNSS, xjPYQW, RIXeW, hPn, KEc, umujHb, BCBvvm, WUy, oOXY, FNUaFK, DhGy, iVV, gTwROu, obT,