Acid process

Product removal during reaction. Separation of the product before completion of the reaction can force a higher conversion, as discussed in Chap. 2. Figure 2.4 showed how this is done in sulfuric acid processes. Sometimes the product (or one of the products) can be removed continuously from the reactor as the reaction progresses, e.g., by allowing it to vaporize from a liquid phase reactor. 

Diethyl ether may be prepared from ethyl alcohol by the sulphuric acid process. A mixture of alcohol and sulphuric acid in equimolecular proportions is heated to about 140° and alcohol is run in at the rate at which the ether produced distils from the reaction mixture. Ethyl hydrogen sulphate (or ethyl sulphuric acid) is first formed and this yields ether either by reacting directly with a molecule of alcohol or by the formation and alcoholysis of diethyl sulphate (I) ... 

Fatty acid nitriles Fatty acid-oil process Fatty acid process... 

Adiponitrile is made commercially by several different processes utilizing different feedstocks. The original process, utilizing adipic acid (qv) as a feedstock, was first commercialized by DuPont in the late 1930s and was the basis for a number of adiponitrile plants. However, the adipic acid process was abandoned by DuPont in favor of two processes based on butadiene (qv). During the 1960s, Monsanto and Asahi developed routes to adiponitrile by the electrodimerization of acrylonitrile (qv). 

Conversion of acetaldehyde is typically more than 90% and the selectivity to acetic acid is higher than 95%. Stainless steel must be used in constmcting the plant. This is an estabHshed process and most of the engineering is weU-understood. The problems that exist are related to more extensively automating control of the system, notably at start-up and shutdown, although even these matters have been largely solved. This route is the most rehable of acetic acid processes. 

The Acetic Acid Process. Prior to the energy crisis of the 1970s, acetic anhydride was manufactured by thermal decomposition of acetic acid at pressures of 15—20 kPa (2.2—2.9 psi) (22), beginning with the first step ... 

The amide group is readily hydrolyzed to acrylic acid, and this reaction is kinetically faster in base than in acid solutions (5,32,33). However, hydrolysis of N-alkyl derivatives proceeds at slower rates. The presence of an electron-with-drawing group on nitrogen not only facilitates hydrolysis but also affects the polymerization behavior of these derivatives (34,35). With concentrated sulfuric acid, acrylamide forms acrylamide sulfate salt, the intermediate of the former sulfuric acid process for producing acrylamide commercially. Further reaction of the salt with alcohols produces acrylate esters (5). In strongly alkaline anhydrous solutions a potassium salt can be formed by reaction with potassium / /-butoxide in tert-huty alcohol at room temperature (36). 

The ratio of reactants had to be controlled very closely to suppress these impurities. Recovery of the acrylamide product from the acid process was the most expensive and difficult part of the process. Large scale production depended on two different methods. If soHd crystalline monomer was desired, the acrylamide sulfate was neutralized with ammonia to yield ammonium sulfate. The acrylamide crystallized on cooling, leaving ammonium sulfate, which had to be disposed of in some way. The second method of purification involved ion exclusion (68), which utilized a sulfonic acid ion-exchange resin and produced a dilute solution of acrylamide in water. A dilute sulfuric acid waste stream was again produced, and, in either case, the waste stream represented a... 

Citric Acid Separation. Citric acid [77-92-9] and other organic acids can be recovered from fermentation broths usiag the UOP Sorbex technology (90—92). The conventional means of recovering citric acid is by a lime and sulfuric acid process ia which the citric acid is first precipitated as a calcium salt and then reacidulated with sulfuric acid. However, this process generates significant by-products and thus can become iaefficient. 

Acetic Acid and Anhydride. Synthesis of acetic acid by carbonylation of methanol is another important homogeneous catalytic reaction. The Monsanto acetic acid process developed in the late 1960s is the best known variant of the process. 

Processes for Triacetate. There are both batch and continuous process for triacetate. Many of the considerations and support faciUties for producing acetate apply to triacetate however, no acetyl hydrolysis is required. In the batch triacetate sulfuric acid process, however, a sulfate hydrolysis step (or desulfonation) is necessary. This is carried out by slow addition of a dilute aqueous acetic acid solution containing sodium or magnesium acetate (44,45) or triethanolamine (46) to neutrali2e the Hberated sulfuric acid. The cellulose triacetate product has a combined acetic acid content of 61.5%. 

In both the sulfuric and nitric acid processes, the dorn metal must be in shot form prior to treatment to secure a reasonably rapid reaction. A number of steps also may be required in processing the dorne metal to remove miscellaneous impurities, particularly in treating material from copper-anode slime (31). 

Decomposition of Metal Chlorides by Acids. Two commercial processes employing the acidic decomposition of metal chlorides are the salt—sulfuric acid process and the Hargreaves process. Although these processes are declining in importance, they are used mainly because of the industrial demand for salt cake [7757-82-6] by the paper (qv) and glass (qv) industries. In the United States, however, Httle HCl is produced this way. 

The SaltSulfuric Acid Process. The reaction between NaCl and sulfuric acid occurs in two stages, both endothermic. 

Recovery from Ores and Clays. The preferred method of extraction of lithium from spodumene ore is the sulfuric acid process (18), used on ore concentrates of 5—6% Li O, representing 62—74% pure spodumene. Methods suitable for extraction from spodumene also can be used for petaUte, because the latter mineral converts to P-spodumene—Si02 soHd solution on heating to a high temperature. 

Because of restrictions in equipment si2e, magnesium nitrate processes were initially limited to small plants. Improvements in the materials of constmction have led to increased capacities and a lower capital cost. Sulfuric acid processes are usually preferred when reconcentration of the sulfuric acid is not requited, ie, when the dilute sulfuric can be used to make another product. 

Weak Acid. Stainless steels (SS) have exceUent corrosion resistance to weak nitric acid and are the primary materials of constmction for a weak acid process. Low carbon stainless steels are preferred because of their resistance to corrosion at weld points. However, higher grade materials of constmction are required for certain sections of the weak acid process. These are limited to high temperature areas around the gau2e (ca 900°G) and to places in which contact with hot Hquid nitric acid is likely to be experienced (the cooler condenser and tail gas preheater). 

Latest Nitric Acid Process Design," Nitrogen (165) (fan.—Feb. 1987). 

Environmental aspects, as well as the requirement of efficient mixing in the mixed acid process, have led to the development of single-phase nitrations. These can be divided into Hquid- and vapor-phase nitrations. One Hquid-phase technique involves the use of > 98% by weight nitric acid, with temperatures of 20—60°C and atmospheric pressure (21). The molar ratios of nitric acid benzene are 2 1 to 4 1. After the reaction is complete, excess nitric acid is vacuum distilled and recycled. An analogous process is used to simultaneously produce a nitrobenzene and dinitrotoluene mixture (22). A conversion of 100% is obtained without the formation of nitrophenols or nitrocresols. The nitrobenzene and dinitrotoluene are separated by distillation. 

Dimersol is a commercial process for the dimeri2ation of propylene, butylenes, or a mixture of both, to and Cg olefins this process produces a more linear olefin than the phosphoric acid process. The reaction is conducted at ambient temperature, using a water-soluble catalyst complex (16). 

Toluene—Benzoic Acid Process. The toluene—benzoic acid process was first introduced by Dow-Canada, Ltd. in 1961 (13). It accounts for 4% of the total synthetic phenol capacity in the world. 

The three chemical reactions in the toluene—benzoic acid process are oxidation of toluene to form benzoic acid, oxidation of benzoic acid to form phenyl benzoate, and hydrolysis of phenyl benzoate to form phenol. A typical process consists of two continuous steps (13,14). In the first step, the oxidation of toluene to benzoic acid is achieved with air and cobalt salt catalyst at a temperature between 121 and 177°C. The reactor is operated at 206 kPa gauge (2.1 kg/cm g uge) and the catalyst concentration is between 0.1 and 0.3%. The reactor effluent is distilled and the purified benzoic acid is collected. The overall yield of this process is beheved to be about 68 mol % of toluene. 

The second processing step, in which benzoic acid is oxidized and hydrolyzed to phenol, is carried out in two reactors in series. In the first reactor, the benzoic acid is oxidized to phenyl benzoate in the presence of air and a catalyst mixture of copper and magnesium salts. The reactor is operated at 234°C and 147 kPa gauge (1.5 kg/cm g uge). The phenyl benzoate is then hydrolyzed with steam in the second reactor to yield phenol and carbon dioxide. This occurs at 200°C and atmospheric pressure. The overall yield of phenol from benzoic acid is around 88 mol %. Figure 2 shows a simplified diagram for the toluene—benzoic acid process. 

Fig. 2. Toluene—benzoic acid process for phenol production.

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