Reactor nickel

Nickel sulfate also is made by the reaction of black nickel oxide and hot dilute sulfuric acid, or of dilute sulfuric acid and nickel carbonate. The reaction of nickel oxide and sulfuric acid has been studied and a reaction induction temperature of 49°C deterrnined (39). High purity nickel sulfate is made from the reaction of nickel carbonyl, sulfur dioxide, and oxygen in the gas phase at 100°C (40). Another method for the continuous manufacture of nickel sulfate is the gas-phase reaction of nickel carbonyl and nitric acid, recovering the soHd product in sulfuric acid, and continuously removing the soHd nickel sulfate from the acid mixture (41). In this last method, nickel carbonyl and sulfuric acid are fed into a closed-loop reactor. Nickel sulfate and carbon monoxide are produced the CO is thus recycled to form nickel carbonyl. 

Figs. 25 to 28 show that the metal deposition in CoMo/A1203 hydrotreating catalysts is a function of the radial position within the catalyst and the axial location of the catalyst sample within the fixed-bed reactor. Nickel and vanadium both exhibit radial profiles with internal maxima, termed M-shaped profiles, at the reactor entrance. These maxima shift to the pellets edge at the reactor outlet, generating the classic U-shaped profile. 

Catalyst/metal recovery e g., catalysts from fluidized catalytic reactors, nickel, platinum, pharmaceutical products, silicon several hundred plants are currently operating worldwide for such purposes. 

Alternately, a static bomb reactor [nickel or Monel (an NiCuCFe alloy), prefluorin-ated] and a total pressure of the Fj-HF mixture of 5 atm can be used. The HF is introduced first ( 1 atm), and then the pressure is slowly raised to 5 atm by adding Fj. The reaction is complete in 15 min Caution The bomb may become hot owing to the exothermic reaction producing (C4F, ) . Therefore, the use of thick-walled bombs is recommended. ... 

The isomer mixture is hydrolysed in a long tubular reactor (nickel-steel alloy) under pressure of 280 to 300 bar, at 390 °C, yielding o-, m- and p-cresol in the ratio 1 2 1, respectively. The higher proportion of m-cresol can be explained by an aryne mechanism. 

For high-temperature operations, materials, and fuels are key technologies. There is a century of large-scale experience in the use of fluoride molten salts. Aluminum is made by electrolysis of a mixture of bauxite and sodium aluminum fluoride salts at 1000 C in large graphite baths. Fluoride salts are compatible with graphite fuels. A smaller nuclear experience base exists with molten fluoride salts in molten salt reactors. Nickel alloys such as modified Hastelloy-N have been qualified for service to 750 C. A number of metals and carbon-carbon composites have been identified for use at much higher temperatures however, these materials have not yet been fully developed or tested for such applications. 

The reaction is initiated with nickel carbonyl. The feeds are adjusted to give the bulk of the carbonyl from carbon monoxide. The reaction takes place continuously in an agitated reactor with a Hquid recirculation loop. The reaction is mn at about atmospheric pressure and at about 40°C with an acetylene carbon monoxide mole ratio of 1.1 1 in the presence of 20% excess alcohol. The reactor effluent is washed with nickel chloride brine to remove excess alcohol and nickel salts and the brine—alcohol mixture is stripped to recover alcohol for recycle. The stripped brine is again used as extractant, but with a bleed stream returned to the nickel carbonyl conversion unit. The neutralized cmde monomer is purified by a series of continuous, low pressure distillations. 

Reppe s work also resulted in the high pressure route which was estabUshed by BASF at Ludwigshafen in 1956. In this process, acetylene, carbon monoxide, water, and a nickel catalyst react at about 200°C and 13.9 MPa (2016 psi) to give acryUc acid. Safety problems caused by handling of acetylene are alleviated by the use of tetrahydrofuran as an inert solvent. In this process, the catalyst is a mixture of nickel bromide with a cupric bromide promotor. The hquid reactor effluent is degassed and extracted. The acryUc acid is obtained by distillation of the extract and subsequendy esterified to the desked acryhc ester. The BASF process gives acryhc acid, whereas the Rohm and Haas process provides the esters dkecdy. 

Chlorine Trifluoride. Chlorine trifluoride is produced commercially by the continuous gas-phase reaction of fluorine and chlorine ia a nickel reactor at ca 290°C. The ratio of fluorine to chlorine is maintained slightly in excess of 3 1 to promote conversion of the chlorine monofluoride to chlorine trifluoride. Sufficient time ia the reactor must be provided to maintain high conversions to chlorine trifluoride. Temperature control is also critical because the equiHbrium shift of chlorine trifluoride to chlorine monofluoride and fluorine is significant at elevated temperatures. 

In this pyrolysis, sub atmospheric partial pressures are achieved by employing a diluent such as steam. Because of the corrosive nature of the acids (HE and HCl) formed, the reactor design should include a platinum-lined tubular reactor made of nickel to allow atmospheric pressure reactions to be mn in the presence of a diluent. Because the pyrolysate contains numerous by-products that adversely affect polymerization, the TFE must be purified. Refinement of TFE is an extremely complex process, which contributes to the high cost of the monomer. Inhibitors are added to the purified monomer to avoid polymerization during storage terpenes such as t7-limonene and terpene B are effective (10). 

Catalytic methanation processes include (/) fixed or fluidized catalyst-bed reactors where temperature rise is controlled by heat exchange or by direct cooling using product gas recycle (2) through wall-cooled reactor where temperature is controlled by heat removal through the walls of catalyst-filled tubes (J) tube-wall reactors where a nickel—aluminum alloy is flame-sprayed and treated to form a Raney-nickel catalyst bonded to the reactor tube heat-exchange surface and (4) slurry or Hquid-phase (oil) methanation. 

Hafnium is obtained as a by-product of the production of hafnium-free nuclear-grade 2irconium (see Nuclear reactors Zirconiumand zirconium compounds). Hafnium s primary use is as a minor strengthening agent in high temperature nickel-base superakoys. Additionally, hafnium is used as a neutron-absorber material, primarily in the form of control rods in nuclear reactors. 

Many instances of intergranular stress corrosion cracking (IGSCC) of stainless steel and nickel-based alloys have occurred in the reactor water systems of BWRs. IGSCC, first observed in the recirculation piping systems (21) and later in reactor vessel internal components, has been observed primarily in the weld heat-affected zone of Type 304 stainless steel. 

Water as coolant in a nuclear reactor is rendered radioactive by neutron irradiation of corrosion products of materials used in reactor constmction. Key nucHdes and the half-Hves in addition to cobalt-60 are nickel-63 [13981 -37-8] (100 yr), niobium-94 [14681-63-1] (2.4 x 10 yr), and nickel-59 [14336-70-0] (7.6 x lO" yr). Occasionally small leaks in fuel rods allow fission products to enter the cooling water. Cleanup of the water results in LLW. Another source of waste is the residue from appHcations of radionucHdes in medical diagnosis, treatment, research, and industry. Many of these radionucHdes are produced in nuclear reactors, especially in Canada. 

The solvent is 28 CC-olefins recycled from the fractionation section. Effluent from the reactors includes product a-olefins, unreacted ethylene, aluminum alkyls of the same carbon number distribution as the product olefins, and polymer. The effluent is flashed to remove ethylene, filtered to remove polyethylene, and treated to reduce the aluminum alkyls in the stream. In the original plant operation, these aluminum alkyls were not removed, resulting in the formation of paraffins (- 1.4%) when the reactor effluent was treated with caustic to kill the catalyst. In the new plant, however, it is likely that these aluminum alkyls are transalkylated with ethylene by adding a catalyst such as 60 ppm of a nickel compound, eg, nickel octanoate (6). The new plant contains a caustic wash section and the product olefins still contain some paraffins ( 0.5%). After treatment with caustic, cmde olefins are sent to a water wash to remove sodium and aluminum salts. 

Shell Higher Olefins Process (SHOP). In the Shell ethylene oligomerization process (7), a nickel ligand catalyst is dissolved in a solvent such as 1,4-butanediol (Eig. 4). Ethylene is oligomerized on the catalyst to form a-olefins. Because a-olefins have low solubiUty in the solvent, they form a second Hquid phase. Once formed, olefins can have Htfle further reaction because most of them are no longer in contact with the catalyst. Three continuously stirred reactors operate at ca 120°C and ca 14 MPa (140 atm). Reactor conditions and catalyst addition rates allow Shell to vary the carbon distribution. 

The reactor outlet is flashed to remove ethylene which is then compressed and recycled a-olefins are separated from the solvent that contains the catalyst, treated to remove catalyst, and then distilled into commercial fractions. Most of the catalyst in the solvent is recycled but a portion is purged. The catalyst in the purge stream is recovered by reducing the oxidized nickel with boron hydride. 

The predominant process for manufacture of aniline is the catalytic reduction of nitroben2ene [98-95-3] ixh. hydrogen. The reduction is carried out in the vapor phase (50—55) or Hquid phase (56—60). A fixed-bed reactor is commonly used for the vapor-phase process and the reactor is operated under pressure. A number of catalysts have been cited and include copper, copper on siHca, copper oxide, sulfides of nickel, molybdenum, tungsten, and palladium—vanadium on alumina or Htbium—aluminum spinels. Catalysts cited for the Hquid-phase processes include nickel, copper or cobalt supported on a suitable inert carrier, and palladium or platinum or their mixtures supported on carbon. 

A process based on a nickel catalyst, either supported or Raney type, is described ia Olin Mathieson patents (26,27). The reduction is carried out ia a continuous stirred tank reactor with a concentric filter element built iato the reactor so that the catalyst remains ia the reaction 2one. Methanol is used as a solvent. Reaction conditions are 2.4—3.5 MPa (350—500 psi), 120—140°C. Keeping the catalyst iaside the reactor iacreases catalyst lifetime by maintaining a hydrogen atmosphere on its surface at all times and minimises handling losses. Periodic cleaning of the filter element is required. 

Another nickel cataly2ed process is described ia a Tolochimie patent (28). Reaction conditions claimed are 1—2.4 MPa (150—350 psi) at 100°C minimum. The combination continuous stirred reactor and gravity decanter uses density-driven circulation between the two vessels to recirculate the catalyst to the reaction 2one without the use of filters or pumps. Yield and catalyst usage can be controlled by varying the feed rates. 

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). 

Because of its low neutron absorption, zirconium is an attractive stmctural material and fuel cladding for nuclear power reactors, but it has low strength and highly variable corrosion behavior. However, ZircaHoy-2, with a nominal composition of 1.5 wt % tin, 0.12 wt % iron, 0.05 wt % nickel, 0.10 wt % chromium, and the remainder zirconium, can be used ia all nuclear power reactors that employ pressurized water as coolant and moderator (see... 

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