Nickel, hydrocarbons

The sensitivity is very good for nickel and vanadium but for these metals for which distribution data would be of great value, the chromatographic process is the lirniting factor, heavy molecules are not eluted from the column with the exception of some porphyrins. This detector can be used to supply H/C and S/C profiles for hydrocarbon cuts with the chromatograph operating in the simulated distillation mode. 

Solids materials that are insoluble in hydrocarbon or water can be entrained in the crude. These are called bottom sediments and comprise fine particles of sand, drilling mud, rock such as feldspar and gypsum, metals in the form of minerals or in their free state such as iron, copper, lead, nickel, and vanadium. The latter can come from pipeline erosion, storage tanks, valves and piping systems, etc. whatever comes in contact with the crude oil. 

Appreciable quantities are also obtained as a by-product in the manufacture of hydrogen from naphtha-gaseous hydrocarbons. In this process the gaseous hydrocarbon and superheated steam under a pressure of about 10 atmospheres and at a temperature of 1000 K are passed over a nickel-chromium catalyst. Carbon monoxide and hydrogen are produced ... 

The selective addition of the second HCN to provide ADN requires the concurrent isomerisation of 3PN to 4-pentenenitrile [592-51 -8] 4PN (eq. 5), and HCN addition to 4PN (eq. 6). A Lewis acid promoter is added to control selectivity and increase rate in these latter steps. Temperatures in the second addition are significandy lower and practical rates may be achieved above 20°C at atmospheric pressure. A key to the success of this homogeneous catalytic process is the abiUty to recover the nickel catalyst from product mixture by extraction with a hydrocarbon solvent. 2-Methylglutaronitrile [4553-62-2] MGN, ethylsuccinonitfile [17611-82-4] ESN, and 2-pentenenitrile [25899-50-7] 2PN, are by-products of this process and are separated from adiponitrile by distillation. 

Fischer-Tropsch Process. The Hterature on the hydrogenation of carbon monoxide dates back to 1902 when the synthesis of methane from synthesis gas over a nickel catalyst was reported (17). In 1923, F. Fischer and H. Tropsch reported the formation of a mixture of organic compounds they called synthol by reaction of synthesis gas over alkalized iron turnings at 10—15 MPa (99—150 atm) and 400—450°C (18). This mixture contained mostly oxygenated compounds, but also contained a small amount of alkanes and alkenes. Further study of the reaction at 0.7 MPa (6.9 atm) revealed that low pressure favored olefinic and paraffinic hydrocarbons and minimized oxygenates, but at this pressure the reaction rate was very low. Because of their pioneering work on catalytic hydrocarbon synthesis, this class of reactions became known as the Fischer-Tropsch (FT) synthesis. 

Fluorocarbons are made commercially also by the electrolysis of hydrocarbons in anhydrous hydrogen fluoride (Simons process) (14). Nickel anodes and nickel or steel cathodes are used. Special porous anodes improve the yields. This method is limited to starting materials that are appreciably soluble in hydrogen fluoride, and is most useflil for manufacturing perfluoroalkyl carboxyflc and sulfonic acids, and tertiary amines. For volatile materials with tittle solubility in hydrofluoric acid, a complementary method that uses porous carbon anodes and HF 2KF electrolyte (Phillips process) is useflil (14). 

Oxidative Fluorination of Aromatic Hydrocarbons. The economically attractive oxidative fluorination of side chains in aromatic hydrocarbons with lead dioxide or nickel dioxide in Hquid HF stops at the ben2al fluoride stage (67% yield) (124). 

Direct hydrohquefaction of biomass or wastes can be achieved by direct hydrogenation of wood chips on treatment at 10,132 kPa and 340 to 350°C with water and Raney nickel catalyst (45). The wood is completely converted to an oily Hquid, methane, and other hydrocarbon gases. Batch reaction times of 4 hours give oil yields of about 35 wt % of the feed the oil contains about 12 wt % oxygen and has a heating value of about 37.2 MJ /kg (16,000 Btu/lb). Distillation yields a significant fraction that boils in the same range as diesel fuel and is completely miscible with it. 

The second reaction is called the Fischer-Tropsch synthesis of hydrocarbons. Depending on the conditions and catalysts, a wide range of hydrocarbons from very light materials up to heavy waxes can be produced. Catalysts for the Fischer-Tropsch reaction iaclude iron, cobalt, nickel, and mthenium. Reaction temperatures range from about 150 to 350°C reaction pressures range from 0.1 to tens of MPa (1 to several hundred atm) (77). The Fischer-Tropsch process was developed iadustriaHy under the designation of the Synthol process by the M. W. Kellogg Co. from 1940 to 1960 (83). 

Naphtha desulfurization is conducted in the vapor phase as described for natural gas. Raw naphtha is preheated and vaporized in a separate furnace. If the sulfur content of the naphtha is very high, after Co—Mo hydrotreating, the naphtha is condensed, H2S is stripped out, and the residual H2S is adsorbed on ZnO. The primary reformer operates at conditions similar to those used with natural gas feed. The nickel catalyst, however, requires a promoter such as potassium in order to avoid carbon deposition at the practical levels of steam-to-carbon ratios of 3.5—5.0. Deposition of carbon from hydrocarbons cracking on the particles of the catalyst reduces the activity of the catalyst for the reforming and results in local uneven heating of the reformer tubes because the firing heat is not removed by the reforming reaction. 

Selectivity is primarily a function of temperature. The amount of by-products tends to increase as the operating temperature is raised to compensate for declining catalyst activity. By-product formation is also influenced by catalyst impurities, whether left behind during manufacture or otherwise introduced into the process. Alkaline impurities cataly2e higher alcohol production whereas acidic impurities, as well as trace iron and nickel, promote heavier hydrocarbon formation. 

Black nickel oxide is used as an oxygen donor in three-way catalysts containing rhodium, platinum, and palladium (143). Three-way catalysts, used in automobiles, oxidize hydrocarbons and CO, and reduce NO The donor quaUty, ie, the abiUty to provide oxygen for the oxidation, results from the capabihty of nickel oxide to chemisorb oxygen (see Exhaust control, automotive). 

In the catalytic steam reforming of natural gas (see Fig. 2), the hydrocarbon stream, principally methane, is desulfurized and, through the use of superheated steam (qv), contacts a nickel catalyst in the primary reformer at ca 3.04 MPa (30 atm) pressure and 800°C to convert methane to H2. 

Tubular Fixed-Bed Reactors. Bundles of downflow reactor tubes filled with catalyst and surrounded by heat-transfer media are tubular fixed-bed reactors. Such reactors are used most notably in steam reforming and phthaUc anhydride manufacture. Steam reforming is the reaction of light hydrocarbons, preferably natural gas or naphthas, with steam over a nickel-supported catalyst to form synthesis gas, which is primarily and CO with some CO2 and CH. Additional conversion to the primary products can be obtained by iron oxide-catalyzed water gas shift reactions, but these are carried out ia large-diameter, fixed-bed reactors rather than ia small-diameter tubes (65). The physical arrangement of a multitubular steam reformer ia a box-shaped furnace has been described (1). 

Steam Reforming Processes. In the steam reforming process, light hydrocarbon feedstocks (qv), such as natural gas, Hquefied petroleum gas, and naphtha, or in some cases heavier distillate oils are purified of sulfur compounds (see Sulfurremoval and recovery). These then react with steam in the presence of a nickel-containing catalyst to produce a mixture of hydrogen, methane, and carbon oxides. Essentially total decomposition of compounds containing more than one carbon atom per molecule is obtained (see Ammonia Hydrogen Petroleum). 

Materials of Construction. GeneraHy, carbon steel is satisfactory as a material of construction when handling propylene, chlorine, HCl, and chlorinated hydrocarbons at low temperatures (below 100°C) in the absence of water. Nickel-based aHoys are chiefly used in the reaction area where resistance to chlorine and HCl at elevated temperatures is required (39). Elastomer-lined equipment, usuaHy PTFE or Kynar, is typicaHy used when water and HCl or chlorine are present together, such as adsorption of HCl in water, since corrosion of most metals is excessive. Stainless steels are to be avoided in locations exposed to inorganic chlorides, as stainless steels can be subject to chloride stress-corrosion cracking. Contact with aluminum should be avoided under aH circumstances because of potential undesirable reactivity problems. 

The first demonstration of catalytic conversion of synthesis gas to hydrocarbons was accompHshed ia 1902 usiag a nickel catalyst (42). The fundamental research and process development on the catalytic reduction of carbon monoxide was carried out by Fischer, Tropsch, and Pichler (43). Whereas the chemistry of the Fischer-Tropsch synthesis is complex, generalized stoichiometric relationships are often used to represent the fundamental aspects ... 

With substances that give up an electron more readily than aromatic hydrocarbons, such as potassium, nickel carbonyl, cyanide ion, or iodide ion, complete transfer of an electron occurs and the TCNE anion radical is formed (11). Potassium iodide is a particulady usefiil reagent for this purpose, and merely dissolving potassium iodide in an acetonitrile solution of TCNE causes the potassium salt of the anion radical to precipitate as bronze-colored crystals. 

Fischer-Tropsch Synthesis The best-known technology for producing hydrocarbons from synthesis gas is the Fischer-Tropsch synthesis. This technology was first demonstrated in Germany in 1902 by Sabatier and Senderens when they hydrogenated carbon monoxide (CO) to methane, using a nickel catalyst. In 1926 Fischer and Tropsch were awarded a patent for the discovery of a catalytic technique to convert synthesis gas to liquid hydrocarbons similar to petroleum. 

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