Corrosion-resistant reactors

At high concentrations, corrosion-resistant reactors and an effective acid recovery process are needed, raising the cost of the intermediate glucose. Dilute acid treatments minimize these problems, but a number of kinetic models indicate that the maximum conversion of cellulose to glucose under these conditions is 65 to 70 percent because subsequent degradation reactions of the glucose to HMF and lev-ulinic acid take place. The modem biorefinery is learning to exploit this reaction manifold, because these decomposition products can be manufactured as the primary product of polysaccharide hydrolysis (see below). 

The lowest cost process for preparing all-arcmatic liquid crystalline polyesters involves the reaction of aromatic carboxylic acids with acetates of aromatic hydroxy ocnpounds a recent history (2) describes the development of these ICP s. Because aoetic acid is evolved in the process and reaction temperatures are above 300°C, expensive corrosion-resistant reactors must be installed for ccranercial production. In cur latest paper (2) of this ICP series, we described a number of aliphatic-aromatic ICP s which can be produced in conventional polyester reactors and injection molded to give plastics with very high mechanical properties, heat-deflection temperatures (HDT s), and solvent resistance. These ICP s (la) were prepared by the reaction of the dimethyl ester of... 

Alkyl chloroformates are generally prepared by reaction of anhydrous alcohols with a stoicheiometric excess of dry phosgene in a corrosion-resistant reactor. For the lower... 

Pretreatment is one of the most expensive and least technologically mature steps in the proeess for converting biomass to fermentable sugars [4]. Costs are due to the use of steam and chemical products and the need for expensive corrosion resistant reactors however, pretreatment also has great potential for efficiency improvement and lowering of costs through research and development [5-8],... 

Several complications in the Enichem process constrain the scale of the reactor volume [12]. The reaction is so exothermic that the reactor needs to be cooled to maintain the optimal 130 °C temperature. Vaporization of the reaction mixture removes only a fraction of the water by-product, and concentration of the water in the reactor hampers the selectivity and rate of the reaction. Therefore, the methanol conversion per run is limited to 20%. The presence of HCl necessitates the use of corrosion-resistant reactors, and either glass linings or high-nickel alloys are used. 

As shown in the step 3, the ethanol is used to react with fermented lactic acid via an esterification reaction to form ethyl lactate (generally known as lactate ester). The reason lactate ester is preferable over lactic acid for conversion into lactic acid prepolymer is because lactic acid has a corrosive nature. Therefore, synthesizing PLA from lactic ester can help to reduce costs by avoiding the need to invest in corrosive-resistant reactors and equipment. This represents significant cost reduction in the long term. 

In this process, wastes are mixed with compressed air. The waste-air mixture then is preheated in a heat exchanger before entering a corrosion-resistant reactor where exothermic reactions increase the temperature to the desired level. The exit stream from the reactor is used at the place where the spent process vapors (i.e., noncondensable gases consisting primarily of air and carbon dioxide) are separated from the oxygenated liquid phase. 

Because the element not only has a good absorption cross section for thermal neutrons (almost 600 times that of zirconium), but also excellent mechanical properties and is extremely corrosion-resistant, hafnium is used for reactor control rods. Such rods are used in nuclear submarines. 

Aqueous formaldehyde is corrosive to carbon steel, but formaldehyde in the vapor phase is not. AH parts of the manufacturing equipment exposed to hot formaldehyde solutions must be a corrosion-resistant alloy such as type-316 stainless steel. Theoretically, the reactor and upstream equipment can be carbon steel, but in practice alloys are required in this part of the plant to protect the sensitive silver catalyst from metal contamination. 

Niobium is also important in nonferrous metallurgy. Addition of niobium to tirconium reduces the corrosion resistance somewhat but increases the mechanical strength. Because niobium has a low thermal-neutron cross section, it can be alloyed with tirconium for use in the cladding of nuclear fuel rods. A Zr—l%Nb [11107-78-1] alloy has been used as primary cladding in the countries of the former USSR and in Canada. A Zr—2.5 wt % Nb alloy has been used to replace Zircaloy-2 as the cladding in Candu-PHW (pressurized hot water) reactors and has resulted in a 20% reduction in wall thickness of cladding (63) (see Nuclear reactors). 

The excellent corrosion resistance means that tantalum is often the metal of choice for processes carried out in oxidising environments or when freedom from reactor contamination of the product or side reactions are necessary, as in food and pharmaceutical processing. Frequently, the initial investment is relatively high, but this is offset by low replacement costs owing to the durabiUty of the metal. 

Corrosion. Copper-base alloys are seriously corroded by sodium thiosulfate (22) and ammonium thiosulfate [7783-18-8] (23). Corrosion rates exceed 10 kg/(m yr) at 100°C. High siUcon cast iron has reasonable corrosion resistance to thiosulfates, with a corrosion rate <4.4 kg/(m yr)) at 100°C. The preferred material of constmction for pumps, piping, reactors, and storage tanks is austenitic stainless steels such as 304, 316, or Alloy 20. The corrosion rate for stainless steels is <440 g/(m yr) at 100°C (see also Corrosion and corrosion control). 

Properties. Most of the alloys developed to date were intended for service as fuel cladding and other stmctural components in hquid-metal-cooled fast-breeder reactors. AHoy selection was based primarily on the following criteria corrosion resistance in Hquid metals, including lithium, sodium, and NaK, and a mixture of sodium and potassium strength ductihty, including fabricabihty and neutron considerations, including low absorption of fast neutrons as well as irradiation embrittlement and dimensional-variation effects. Alloys of greatest interest include V 80, Cr 15, Ti 5... 

Zirconium is used as a containment material for the uranium oxide fuel pellets in nuclear power reactors (see Nuclearreactors). Zirconium is particularly usehil for this appHcation because of its ready availabiUty, good ductiUty, resistance to radiation damage, low thermal-neutron absorption cross section 18 x 10 ° ra (0.18 bams), and excellent corrosion resistance in pressurized hot water up to 350°C. Zirconium is used as an alloy strengthening agent in aluminum and magnesium, and as the burning component in flash bulbs. It is employed as a corrosion-resistant metal in the chemical process industry, and as pressure-vessel material of constmction in the ASME Boiler and Pressure Vessel Codes. 

Hydrogenations can be carried out in batch reactors, in continuous slurry reactors, or in fixed-bed reactors. The material of constmetion is usually 316 L stainless steel because of its better corrosion resistance to fatty acids. The hydrogenation reaction is exothermic and provisions must be made for the effective removal or control of the heat a reduction of one IV per g of C g fatty acid releases 7.1 J (1.7 cal), which raises the temperature 1.58°C. This heat of hydrogenation is used to raise the temperature of the fatty acid to the desired reaction temperature and is maintained with cooling water to control the reaction. 

Corrosiveness. The catalyst solutions are corrosive, and the reactors, separation devices, etc that come in contact with them must be made of expensive corrosion-resistant materials. 

Oxychlorination of Ethylene or Dichloroethane. Ethylene or dichloroethane can be chlorinated to a mixture of tetrachoroethylene and trichloroethylene in the presence of oxygen and catalysts. The reaction is carried out in a fluidized-bed reactor at 425°C and 138—207 kPa (20—30 psi). The most common catalysts ate mixtures of potassium and cupric chlorides. Conversion to chlotocatbons ranges from 85—90%, with 10—15% lost as carbon monoxide and carbon dioxide (24). Temperature control is critical. Below 425°C, tetrachloroethane becomes the dominant product, 57.3 wt % of cmde product at 330°C (30). Above 480°C, excessive burning and decomposition reactions occur. Product ratios can be controlled but less readily than in the chlorination process. Reaction vessels must be constmcted of corrosion-resistant alloys. 

Nonferrous alloys account for only about 2 wt % of the total chromium used ia the United States. Nonetheless, some of these appHcations are unique and constitute a vital role for chromium. Eor example, ia high temperature materials, chromium ia amounts of 15—30 wt % confers corrosion and oxidation resistance on the nickel-base and cobalt-base superaHoys used ia jet engines the familiar electrical resistance heating elements are made of Ni-Cr alloy and a variety of Ee-Ni and Ni-based alloys used ia a diverse array of appHcations, especially for nuclear reactors, depend on chromium for oxidation and corrosion resistance. Evaporated, amorphous, thin-film resistors based on Ni-Cr with A1 additions have the advantageous property of a near-2ero temperature coefficient of resistance (58). 

Special quality steels - A vast range of special quality steels is made in electric arc furnaces by adding other metals to form steel alloys. The most commonly known of these is stainless steel, which has chromium and nickel added to form a corrosion-resistant steel. There are very many others however the very hard steels used to make machine tools, the steels specially formulated to make them suitable for engineering, steels developed to survive for decades the hostile environment of nuclear reactors, light but strong steels used in aerospace, extra tough steels for armor plating - to name but a few. 

---