Hydrodenitrogenation (HDN) is an industrial process for the removal of nitrogen from petroleum. Organonitrogen compounds, even though they occur at low levels, are undesirable because they cause poisoning of downstream catalysts. Furthermore, upon combustion, organonitrogen compounds generate NOx, a pollutant. HDN is effected as general hydroprocessing, which traditionally focuses on hydrodesulfurization (HDS) because sulfur compounds are even more problematic. To some extent, hydrodeoxygenation (HDO) is also effected. [1]
Typical organonitrogen compounds in petroleum include quinolines and porphyrins and their derivatives. The total nitrogen content is typically less than 1% and the targeted levels are in the ppm range. As described in organic geochemistry, organonitrogen compounds are derivatives or degradation products of the compounds in the living matter that comprised the precursor to fossil fuels. In HDN, the organonitrogen compounds are treated at high temperatures with hydrogen in the presence of a catalyst, the net transformation being: [2]
The catalysts generally consist of cobalt and nickel as well as molybdenum disulfide or less often tungsten disulfide supported on alumina. The precise composition of the catalyst, i.e. Co/Ni and Mo/W ratios, are tuned for particular feedstocks. A wide variety of catalyst compositions have been considered, including metal phosphides. [3]
Catalysis is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst. Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quickly, very small amounts of catalyst often suffice; mixing, surface area, and temperature are important factors in reaction rate. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process regenerating the catalyst.
The Haber process, also called the Haber–Bosch process, is an artificial nitrogen fixation process and is the main industrial procedure for the production of ammonia today. It is named after its inventors, the German chemists Fritz Haber and Carl Bosch, who developed it in the first decade of the 20th century. The process converts atmospheric nitrogen (N2) to ammonia (NH3) by a reaction with hydrogen (H2) using a metal catalyst under high temperatures and pressures:
Molybdenum is a chemical element with the symbol Mo and atomic number 42 which is located in period 5 and group 6. The name is from Neo-Latin molybdaenum, which is based on Ancient Greek Μόλυβδος molybdos, meaning lead, since its ores were confused with lead ores. Molybdenum minerals have been known throughout history, but the element was discovered in 1778 by Carl Wilhelm Scheele. The metal was first isolated in 1781 by Peter Jacob Hjelm.
Rhodium is a chemical element with the symbol Rh and atomic number 45. It is a very rare, silvery-white, hard, corrosion-resistant transition metal. It is a noble metal and a member of the platinum group. It has only one naturally occurring isotope: 103Rh. Naturally occurring rhodium is usually found as a free metal or as an alloy with similar metals and rarely as a chemical compound in minerals such as bowieite and rhodplumsite. It is one of the rarest and most valuable precious metals.
A Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, is a catalyst used in the synthesis of polymers of 1-alkenes (alpha-olefins). Two broad classes of Ziegler–Natta catalysts are employed, distinguished by their solubility:
Ferrocene is an organometallic compound with the formula Fe(C5H5)2. The molecule is a complex consisting of two cyclopentadienyl rings bound to a central iron atom. It is an orange solid with a camphor-like odor, that sublimes above room temperature, and is soluble in most organic solvents. It is remarkable for its stability: it is unaffected by air, water, strong bases, and can be heated to 400 °C without decomposition. In oxidizing conditions it can reversibly react with strong acids to form the ferrocenium cation Fe(C5H5)+2.
A substance is pyrophoric if it ignites spontaneously in air at or below 54 °C (129 °F) or within 5 minutes after coming into contact with air. Examples are organolithium compounds and triethylborane. Pyrophoric materials are often water-reactive as well and will ignite when they contact water or humid air. They can be handled safely in atmospheres of argon or nitrogen. Class D fire extinguishers are designated for use in fires involving pyrophoric materials.
Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to reduce or saturate organic compounds. Hydrogenation typically constitutes the addition of pairs of hydrogen atoms to a molecule, often an alkene. Catalysts are required for the reaction to be usable; non-catalytic hydrogenation takes place only at very high temperatures. Hydrogenation reduces double and triple bonds in hydrocarbons.
Hydrogenolysis is a chemical reaction whereby a carbon–carbon or carbon–heteroatom single bond is cleaved or undergoes lysis (breakdown) by hydrogen. The heteroatom may vary, but it usually is oxygen, nitrogen, or sulfur. A related reaction is hydrogenation, where hydrogen is added to the molecule, without cleaving bonds. Usually hydrogenolysis is conducted catalytically using hydrogen gas.
Organosulfur compounds are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur derivatives, e.g., saccharin. Nature abounds with organosulfur compounds—sulfur is essential for life. Of the 20 common amino acids, two are organosulfur compounds, and the antibiotics penicillin and sulfa drugs both contain sulfur. While sulfur-containing antibiotics save many lives, sulfur mustard is a deadly chemical warfare agent. Fossil fuels, coal, petroleum, and natural gas, which are derived from ancient organisms, necessarily contain organosulfur compounds, the removal of which is a major focus of oil refineries.
Hydrodesulfurization (HDS) is a catalytic chemical process widely used to remove sulfur (S) from natural gas and from refined petroleum products, such as gasoline or petrol, jet fuel, kerosene, diesel fuel, and fuel oils. The purpose of removing the sulfur, and creating products such as ultra-low-sulfur diesel, is to reduce the sulfur dioxide emissions that result from using those fuels in automotive vehicles, aircraft, railroad locomotives, ships, gas or oil burning power plants, residential and industrial furnaces, and other forms of fuel combustion.
Catalyst poisoning refers to the partial or total deactivation of a catalyst by a chemical compound. Poisoning refers specifically to chemical deactivation, rather than other mechanisms of catalyst degradation such as thermal decomposition or physical damage. Although usually undesirable, poisoning may be helpful when it results in improved catalyst selectivity. An important historic example was the poisoning of catalytic converters by leaded fuel.
A migratory insertion is a type of reaction in organometallic chemistry wherein two ligands on a metal complex combine. It is a subset of reactions that very closely resembles the insertion reactions, and both are differentiated by the mechanism that leads to the resulting stereochemistry of the products. However, often the two are used interchangeably because the mechanism is sometimes unknown. Therefore, migratory insertion reactions or insertion reactions, for short, are defined not by the mechanism but by the overall regiochemistry wherein one chemical entity interposes itself into an existing bond of typically a second chemical entity e.g.:
Organoiron chemistry is the chemistry of iron compounds containing a carbon-to-iron chemical bond. Organoiron compounds are relevant in organic synthesis as reagents such as iron pentacarbonyl, diiron nonacarbonyl and disodium tetracarbonylferrate. While iron adopts oxidation states from Fe(−II) through to Fe(VII), Fe(IV) is the highest established oxidation state for organoiron species. Although iron is generally less active in many catalytic applications, it is less expensive and "greener" than other metals. Organoiron compounds feature a wide range of ligands that support the Fe-C bond; as with other organometals, these supporting ligands prominently include phosphines, carbon monoxide, and cyclopentadienyl, but hard ligands such as amines are employed as well.
Jacobsen's catalyst is the common name for N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) chloride, a coordination compound of manganese and a salen-type ligand. It is used as an asymmetric catalyst in the Jacobsen epoxidation, which is renowned for its ability to enantioselectively transform prochiral alkenes into epoxides. Before its development, catalysts for the asymmetric epoxidation of alkenes required the substrate to have a directing functional group, such as an alcohol as seen in the Sharpless epoxidation. This compound has two enantiomers, which give the appropriate epoxide product from the alkene starting material.
Organorhodium chemistry is the chemistry of organometallic compounds containing a rhodium-carbon chemical bond, and the study of rhodium and rhodium compounds as catalysts in organic reactions.
2-Mercaptopyridine is an organosulfur compound with the formula HSC5H4N. This yellow crystalline solid is a derivative of pyridine. The compound and its derivatives serve primarily as acylating agents. A few of 2-mercaptopyridine’s other uses include serving as a protecting group for amines and imides as well as forming a selective reducing agent. 2-Mercaptopyridine oxidizes to 2,2’-dipyridyl disulfide.
Cu-Y zeolites are derivatives of the faujasite mineral group which in turn is a member of the zeolite family. Cu-Y zeolites are synthesized through aqueous or gaseous ionic exchange unlike the naturally occurring faujasites: faujasite-Ca, faujasite-Mg, and faujasite-Na. The exchanged copper atom can vary in oxidation states, but the most studied Cu-Y zeolite variants include Cu(I) or Cu(II) cations. Due to their high catalytic potential, they are utilized as desulfurization agents and in the production of nitrogen gas from nitrogen monoxide.
Renewable hydrocarbon fuels via decarboxylation/decarbonylation. With an increasing demand for renewable fuels, extensive research is under way on the utilization of biomass as feedstock for the production of liquid transportation fuels. Using biomass is an attractive alternative, since biomass removes carbon dioxide from the atmosphere as it grows through photosynthesis, thus closing the carbon cycle and making biofuels carbon neutral when certain conditions are met. First generation biofuels such as biodiesel have important drawbacks, as they are normally derived from edible feedstock and are not fully compatible with standard diesel engines. Given that the majority of the problems associated with these fuels stem from their high oxygen content, methods to deoxygenate biomass-derived oils are currently being pursued. The ultimate goal is to convert inedible biomass feeds into hydrocarbon biofuels fully compatible with existing infrastructure. These so-called second generation biofuels can be used as drop-in substitutes for traditional petroleum-derived hydrocarbon fuels.
The main player in oil refining processes such as fluid catalytic cracking (FCC), hydroprocessing, hydrocracking is the catalyst or zeolitic material, that breaks down complex and long-chain hydrocarbons into simple, useful hydrocarbons.