Acid recovery

Commercial production of acetic acid has been revolutionized in the decade 1978—1988. Butane—naphtha Hquid-phase catalytic oxidation has declined precipitously as methanol [67-56-1] or methyl acetate [79-20-9] carbonylation has become the technology of choice in the world market. By-product acetic acid recovery in other hydrocarbon oxidations, eg, in xylene oxidation to terephthaUc acid and propylene conversion to acryflc acid, has also grown. Production from synthesis gas is increasing and the development of alternative raw materials is under serious consideration following widespread dislocations in the cost of raw material (see Chemurgy). 

Although acetic acid and water are not beheved to form an azeotrope, acetic acid is hard to separate from aqueous mixtures. Because a number of common hydrocarbons such as heptane or isooctane form azeotropes with formic acid, one of these hydrocarbons can be added to the reactor oxidate permitting separation of formic acid. Water is decanted in a separator from the condensate. Much greater quantities of formic acid are produced from naphtha than from butane, hence formic acid recovery is more extensive in such plants. Through judicious recycling of the less desirable oxygenates, nearly all major impurities can be oxidized to acetic acid. Final acetic acid purification follows much the same treatments as are used in acetaldehyde oxidation. Acid quahty equivalent to the best analytical grade can be produced in tank car quantities without difficulties. 

Acrylic Acid Recovery. The process flow sheet (Fig. 3) shows equipment and conditions for the separations step. The acryUc acid is extracted from the absorber effluent with a solvent, such as butyl acetate, xylene, diisobutyl ketone, or mixtures, chosen for high selectivity for acryUc acid and low solubihty for water and by-products. The extraction is performed using 5—10 theoretical stages in a tower or centrifiigal extractor (46,61—65). 

The bottoms from the solvent recovery (or a2eotropic dehydration column) are fed to the foremns column where acetic acid, some acryflc acid, and final traces of water are removed overhead. The overhead mixture is sent to an acetic acid purification column where a technical grade of acetic acid suitable for ester manufacture is recovered as a by-product. The bottoms from the acetic acid recovery column are recycled to the reflux to the foremns column. The bottoms from the foremns column are fed to the product column where the glacial acryflc acid of commerce is taken overhead. Bottoms from the product column are stripped to recover acryflc acid values and the high boilers are burned. The principal losses of acryflc acid in this process are to the aqueous raffinate and to the aqueous layer from the dehydration column and to dimeri2ation of acryflc acid to 3-acryloxypropionic acid. If necessary, the product column bottoms stripper may include provision for a short-contact-time cracker to crack this dimer back to acryflc acid (60). 

N). This area of the process has received considerable attention in recent years as companies strive to improve efficiency and reduce waste. Patents have appeared describing addition of SO2 to improve ion-exchange recovery of vanadium (111), improved separation of glutaric and succinic acids by dehydration and distillation of anhydrides (112), formation of imides (113), improved nitric acid removal prior to dibasic acid recovery (114), and other claims (115). 

Liquid Effluents. Recycling of acid, soda, and zinc have long been necessary economically, and the acid—soda reaction product, sodium sulfate, is extracted and sold into other sectors of the chemical industry. Acid recovery usually involves the degassing, filtering, and evaporative concentration of the spent acid leaving the spinning machines. Excess sodium sulfate is removed by crystallization and then dehydrated before sale. Traces of zinc that escape recovery are removable from the main Hquid effluent stream to the extent that practically all the zinc can now be retained in the process. 

The typical SEA process uses a manganese catalyst with a potassium promoter (for solubilization) in a batch reactor. A manganese catalyst increases the relative rate of attack on carbonyl intermediates. Low conversions are followed by recovery and recycle of complex intermediate streams. Acid recovery and purification involve extraction with caustic and heat treatment to further decrease small amounts of impurities (particularly carbonyls). The fatty acids are recovered by freeing with sulfuric acid and, hence, sodium sulfate is a by-product. 

E. O. Jones and K. L. Kensington, Spent acid recovery using WFDdprocess system, ACS meeting, Chicago, HI., Aug. 19, 1993. 

The only valuable components in low temperature tar are the phenols and an oil fraction distilled over the range of 180—310°C, which is collected for tar-acid recovery is taken. A typical primary distillation is given in Table 3. 

The ester is washed thoroughly in iron-free water to remove acid and any desirable salts these wash Hquids are sent for acid recovery. The final wash may contain some sodium, calcium, or magnesium ions to stabilize traces of sulfate esters remaining on the cellulose acetate. 

The largest single use area for UPVC is for pipes and fittings. One particular area here is in chemical plant. It is of course necessary to check that all of the components of the PVC compound will be resistant to any of the chemicals with which the plant is liable to come into contact (at the appropriate temperatures) and also that additives will not be leached out by these chemicals. Particular uses are in acid recovery plant and in plant for handling hydrocarbons. 

The checkers dissolved the crude acid in the minimum amount of 2N sodium hydroxide (about 3 ml./g.) and reprecipitated it in 5 portions with IN hydrochloric acid recovery 75-85%. Alternatively, they added the acid to boiling ethyl acetate (9 ml./g.), added decolorizing carbon to the solution, boiled the mixture for 5 minutes, separated the carbon by filtration, and cooled the hot filtrate recovery 45-55%. The checkers found no difference in the infrared spectra of material purified in the two ways, but recrystallized material was reduced more quickly by hydrogen. 

Acid Manufacture. Relatively small mostly leakage plus drainings from air pollution abatement scrubbers. Also included are a) acid waters, neutralized with lime or soda ash b) sometimes azeotroping agents such as n-propyl acetate c) sometimes heavy metals from equipment corrosion and d) nitrobodies from acid recovery... 

Acid waste streams are sent through a nitric acid recovery process, and then to a secondary plutonium recovery anion exchange process. The acid waste streams are then sent to waste treatment. 

Acid waste streams are processed through nitric acid recovery and then sent to a secondary plutonium recovery process which uses anion exchange. Acid, basic, and laundry waste streams are sent to waste treatment. A discussion of the process steps shown on Figure 1 follows. 

U.S. Department of Energy, Office of Industrial Technologies, Hydrochloric Acid Recovery Systems for Galvanizers and Steel Manufacturers (NICE3 fact sheet), DOE/CH10093-233, 1993. 

Wastewater is generated in the primary zinc and primary cadmium recovery subcategories by acid plant blowdown, which results from sulfuric acid recovery, air pollution control, leaching, anode/ cathode washing, and contact cooling. The streams may contain significant concentrations of lead, arsenic, cadmium, and zinc. Tables 3.26 and 3.27 present classical and toxic pollutant data for the primary zinc and primary cadmium subcategories. 

Acid recovery systems are used to recover the free acid in the WPL. They are not employed in larger facilities because they recover only 2-4% free HC1 from the spent acid, but leave the FeCl2 in the solution that must be processed or disposed of separately. These acid recovery systems are generally closed-loop processes that do not emit HC1. In their survey, U.S. EPA compiled data from different types of pickling operations and their estimated emissions.5 This information is reproduced in Table 28.11. 

J. Douda and V.A. Basiuk, Pyrolysis of ammino acids, recovery of starting materials and yields of condensation products, J. Anal. Appl. Pyrol., 56, 113 121 (2000). 

Dehairs et al. [78] describe a method for the routine determination ofbarium in seawater using graphite furnace atomic absorption spectrometry. Barium is separated from major cations by collection on a cation exchange column. The barium is removed from this resin with nitric acid. Recoveries are greater than 99%. 

SAR [Sulfuric Acid Recovery] A process for purifying and concentrating used sulfuric acid for re-use. The acid is heated with oxygen at 1,040°C to convert the acid to sulfur dioxide. This is then oxidized over a vanadium-containing catalyst to sulfur trioxide, which is dissolved in fresh sulfuric acid to give 98 percent acid. Developed by L Air Liquide and ICI. First demonstrated in 1991 at a methyl methacrylate plant in Taiwan. 

SARP [Sulphuric acid recovery process] A method for recovering sulfuric acid which has been used for alkylation, for re-use. The acid is reacted with propylene, yielding dipropyl sulfate, which is extracted from the acid tar with isobutane. It is not necessary to hydrolyze the sulfate to sulfuric acid because the sulfate itself is an active alkylation catalyst. 

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