Sulfuric acid processes

Small amounts of acid aerosols are always formed if the gas is cooled or SO3 reacts with water below the dew point of sulfuric acid. This is of course highly undesirable with regard to corrosion and emissions. Therefore, the absorbers in sulfuric acid plants are equipped with demisters, for example, consisting of beds of small-diameter glass. 

To determine this integral, we use the 1 versus X plot, and by graphical integration we obtain the minimal mass of catalyst. 

Modern sulfuric acid plants use the double absorption process to reach a SO2 conversion of 98%, which is needed to meet current environmental standards. The intermediate removal of SO3 by absorption after the third bed enables a conversion of SO2 after the fourth bed of 99%. 

NH3 burner of a nitric acid plant built in 1924 for 0.40t HNO3 per day. Courtesy of Uhde, Germany 

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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. 

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). 

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. 

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%. 

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. 

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. 

The indirect hydration, also called the sulfuric acid process, practiced by the three U.S. domestic producers, was the only process used worldwide until ICI started up the first commercial direct hydration process in 1951. Both processes use propylene and water as raw materials. Early problems of high corrosion, high energy costs, and air pollution using the indirect process led to the development of the direct hydration process in Europe. However, a high purity propylene feedstock is required. In the indirect hydration process, C -feedstock streams from refinery off-gases containing only 40—60 wt % propylene are often used in the United States. 

The bottoms from the stripper (40—60 wt % acid) are sent to an acid reconcentration unit for upgrading to the proper acid strength and recycling to the reactor. Because of the associated high energy requirements, reconcentration of the diluted sulfuric acid is a cosdy operation. However, a propylene gas stripping process, which utilizes only a small amount of added water for hydrolysis, has been described (63). In this modification, the equiUbrium quantity of isopropyl alcohol is stripped so that acid is recycled without reconcentration. Kquilibrium is attained rapidly at 50°C and isopropyl alcohol is removed from the hydrolysis mixture. Similarly, the weak sulfuric acid process minimizes the reconcentration of the acid and its associated corrosion and pollution problems. 

Isopropyl Alcohol. Propylene may be easily hydrolyzed to isopropyl alcohol. Eady commercial processes involved the use of sulfuric acid in an indirect process (100). The disadvantage was the need to reconcentrate the sulfuric acid after hydrolysis. Direct catalytic hydration of propylene to 2-propanol followed commercialization of the sulfuric acid process and eliniinated the need for acid reconcentration, thus reducing corrosion problems, energy use, and air pollution by SO2 and organic sulfur compounds. Gas-phase hydration takes place over supported oxides of tungsten at 540 K and 25... 

The reduction ia tetraethyl lead for gasoline production is expected to iacrease the demand for petroleum alkylate both ia the U.S. and abroad. Alkylate producers have a choice of either a hydrofluoric acid or sulfuric acid process. Both processes are widely used. However, concerns over the safety or potential regulation of hydrofluoric acid seem likely to convince more refiners to use the sulfuric acid process for future alkylate capacity. 

There are two main processes for the synthesis of ethyl alcohol from ethylene. The eadiest to be developed (in 1930 by Union Carbide Corp.) was the indirect hydration process, variously called the strong sulfuric acid—ethylene process, the ethyl sulfate process, the esterification—hydrolysis process, or the sulfation—hydrolysis process. This process is stiU in use in Russia. The other synthesis process, designed to eliminate the use of sulfuric acid and which, since the early 1970s, has completely supplanted the old sulfuric acid process in the United States, is the direct hydration process. This process, the catalytic vapor-phase hydration of ethylene, is now practiced by only three U.S. companies Union Carbide Corp. (UCC), Quantum Chemical Corp., and Eastman Chemical Co. (a Division of Eastman Kodak Co.). UCC imports cmde industrial ethanol, CIE, from SADAF (the joint venture of SABIC and Pecten [Shell]) in Saudi Arabia, and refines it to industrial grade. 

Other synthetic methods have been investigated but have not become commercial. These include, for example, the hydration of ethylene in the presence of dilute acids (weak sulfuric acid process) the conversion of acetylene to acetaldehyde, followed by hydrogenation of the aldehyde to ethyl alcohol and the Fischer-Tropsch hydrocarbon synthesis. Synthetic fuels research has resulted in a whole new look at processes to make lower molecular weight alcohols from synthesis gas. 

Other Methods of Preparation. In addition to the direct hydration process, the sulfuric acid process, and fermentation routes to manufacture ethanol, several other processes have been suggested. These include the hydration of ethylene by dilute acids, the hydrolysis of ethyl esters other than sulfates, the hydrogenation of acetaldehyde, and the use of synthesis gas. None of these methods has been successfilUy implemented on a commercial scale, but the route from synthesis gas has received a great deal of attention since the 1974 oil embargo. 

Isopropyl Ether. Isopropyl ether is manufactured by the dehydration of isopropyl alcohol with sulfuric acid. It is obtained in large quantities as a by-product in the manufacture of isopropyl alcohol from propylene by the sulfuric acid process, very similar to the production of ethyl ether from ethylene. Isopropyl ether is of moderate importance as an industrial solvent, since its boiling point Hes between that of ethyl ether and acetone. Isopropyl ether very readily forms hazardous peroxides and hydroperoxides, much more so than other ethers. However, this tendency can be controlled with commercial antioxidant additives. Therefore, it is also being promoted as another possible ether to be used in gasoline (33). 

Hydrochloric acid-water Maximum-hoiling azeotrope Sulfuric acid, calcium chloride for salt process Sulfuric acid process relies heavily on boundary curvature... 

In the sulfuric acid process, the sulfuric acid removed must be regenerated in a sulfuric acid plant which is generally not a part of the alkylation unit and may be located off-site. Spent sulfuric acid generation is substantial typically in the range of 13 to 30 pounds per barrel of alkylate. Air emissions from the alkylation process may arise from process vents and fugitive emissions. 

Another improvement (less by-products) has been made over the fuming sulfuric acid process operated commercially for the hydrolysis of 2-perfluoroal-kylethyl iodides. It entails the use of sulfur trioxide in liquid sulfur dioxide [52, 5J (equation 52). 

A block diagram for tlie double-absorption sulfuric acid process is gi en in Fig. 8.6.1. Atomized molten sulfur is burned in a horizontal, brick-... 

Figure 8.6.1. Conceptual diagram of typical double-absorption sulfuric acid process.

Contact Sulfuric Acid Process Monsanto, Parsons, Davy Powergas, others Can accept elemental sulfur, or H2S and S02-bearlng streams down to about 5Z sulfur content A double contact/double absorption plant can recover up to 99.8Z of the sulfur fed to it. All sulfur compounds handled... 

Traditionally, citric acid is recovered from fermentation broth via a Ume and sulfuric acid process. In this process, filtered fermentation broth is treated with lime to precipitate calcium citrate. This precipitate is washed and acidified with sulfuric acid to convert the calcium citrate to solid calcium sulfate (gypsum) and... 

Wet Process Phosphoric Acid. A production process flow diagram is shown in Figure 8. Insoluble phosphate rock is changed to water-soluble phosphoric acid by solubilizing the phosphate rock with an acid, generally sulfuric or nitric. The phosphoric acid produced from the nitric acid process is blended with other ingredients to produce a fertilizer, whereas the phosphoric acid produced from the sulfuric acid process must be concentrated before further use. Minor quantities of fluorine, iron, aluminum, sUica, and uranium are usually the most serious waste effluent problems. 

Sulfuric acid was used extensively several decades ago to reduce fuel mercaptans, olefins, and to some extent, aromatics. Today, sulfuric acid processing has been almost entirely replaced by more effective and safer processes. Mercaptan removal was accomplished by converting mercaptans to disulfides through the following reaction ... 

S. K. Brubaker, Materials of Construction for Sulfuric Acid, Process Industries Corrosion, National Association of Corrosion Engineers meeting,... 

The more significant commercial catalytic polymerization processes have proved to be phosphoric acid processes and sulfuric acid processes. 

Commercial alkylation may be divided into three distinct types depending on whether the catalyst used is sulfuric acid, hydrofluoric acid, or aluminum chloride. These types of alkylation are similar in many respects but have some outstanding differences. In 1946 there were 32 plants in the United States employing the sulfuric acid process, 27 using the hydrofluoric process, and one using aluminum chloride (I, 9). Since sulfuric acid alkylation is the most widely practiced of the three, it will be discussed first. 

As in sulfuric acid alkylation, the hydrocarbon-acid emulsion passes from the contactor into an acid settler for separation of acid and hydrocarbon phases and the acid layer recirculates to the reactor. Unlike sulfuric acid, however, hydrofluoric acid is appreciably soluble in hydrocarbons, and as much as 1% by weight may be retained in the hydrocarbon layer. The necessity of recovering this acid from the hydrocarbon phase results, in another difference between hydrofluoric and sulfuric acid processing in that a hydrofluoric acid stripper is required. This stripper is ordinarily packed with aluminum rings which serve not only as tower packing but also as a catalyst for the decomposition of organic fluorides into hydrocarbons and free hydrofluoric acid. 

In contrast to the sulfuric acid process, regeneration of the catalyst in hydrofluoric acid alkylation is continuous. During processing, both hydrofluoric acid and sulfuric acid... 

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