Costs of acid

Economics. In contrast to NSP, the high nutrient content of TSP makes shipment of the finished product preferable to shipping of the raw materials. Plants, therefore, are located at or near the rock source. The phosphoric acid used, and the sulfuric acid required for its manufacture, usually are produced at the site of the TSP plant. As in the case of NSP, the cost of raw materials accounts for more than 90% of the total cost. Most of this is the cost of acid. 

In most ores, sufficient Fe is already present. For some ores, it is necessary to add metallic iron. In practice, the oxidation potential of the solution can be monitored and controlled using the Fe /Fe ratio. Very high leaching efficiencies with H2SO ate common, eg, 95—98% dissolution yield of uranium (39). If acid consumption exceeds 68 kg/1 of ore treated, alkaline leaching is preferred. The comparative costs of acid, sodium hydroxide, and sodium carbonate differ widely in different areas and are the determining factor. 

Smelter Acid. If acid is produced involuntarily, as in a smelter operation, it is possible to estimate the cost of acid production in the same manner as that for an elemental sulfur acid plant. To the smelter, however, acid output is simply a mandated concomitant of the process required to produce the metal. Depending on the location of the smelter, the sources of demand, the size of the market, and competition from other producers, the acid sale price may or may not be sufficiently high even to yield a positive net-back, much less a desired rate of return on investment for the acid portion of the operation. This situation does not necessarily lead to closure. Positive or negative, the effect should be registered only in the overall profitability of the entire smelter operation. 

The cost of acid gas removal depends strongly on its concentration and the need for downstream compression. In the case of very sour gas the combination of a bulk removal step ahead of the final sweetening unit can reduce the overall add gas removal cost. If the acid gas is re-injeded the bulk removal process should offer... 

Second, an attempt may be made to arrive at the actual costs of acid rain. Since acid-rain is a form of atmospheric corrosion, the total costs of corrosion for metals of approximately of the GNP would certainly be a high upper limit for the costs of acid rain on metals. Even the inclusion of irreplaceable artistic and architectural items in the cost of acid rain would appear to leave the total costs well short of the total corrosion costs. 

The selective hydrogenation of butadiene from the C4 stream is essential for its conversion to normal butenes to avoid the increased consumption and regeneration cost of acid in alkylation units. RD technology offered by CR L for the C4 stream selectively hydrogenates butadiene in the same column that is used for MTBE. The existing MTBE columns can be conveniently modified to suit this purpose. The butadiene content can be brought down to less than 100 ppm [57, 64). 

Concentrated acid High glucose yield Ambient temperatures High cost of acid needs to be recovered Reactor corrosion problems Formation of inhibitors... 

The main operating cost in acid leaching of nickel laterites is the cost of acid for leaching. The proof of concept economics therefore starts with consideration of the relative cost of acid and the value of the nickel and cobalt produced in a mixed hydroxide. This is intended to determine indicative economics. 

If the capital cost were doubled to 217.4 Million, the simple payback would be 2.8 years. This would still be an attractive proposition. Of course these numbers will vary according to the local cost of acid, the prevailing value of nickel and cobalt in mixed hydroxide, etc. 

Levin TR, Kunz K, Henke CJ, Selby JV (1997) Costs of acid-related disorders to a helth maintenance organization. Am JMed 103 520-528... 

Segal R, Russel WL, Ben-Joseph R, Mansheim B (1996) Cost of acid peptic disorders in a managed-care organization. Clin Ther 18(2) 319-333... 

The advantages of vacuum distillation for producing lubricants from topped crude oils are obvious, because the asphalt in such stocks makes the cost of acid treatment almost prohibitive. In the case of paraffin-base oils the advantages are not so obvious. The advantage with such oils lies in the larger recovery of the valuable heavy stocks, which in the case of residual steam operation are partly decomposed into lower-boiling, less viscous oils. 

The second consequence is the potential deterioration of strip surface quality caused by scale [17]. Incorrect thickness and type of scale on the strip surface during hot rolling can reduce the service life of work rolls, which in turn can cause strip defects. If the scale is too thick, it increases the cost of acid pickling and affects pickling speed, particularly when the scale develops a thick hematite layer on the surface [18-20]. 

The cost of this preparation (particularly for large classes) can be appreciably reduced by using a solution of 20 g. of sodium hydroxide in 25 ml. of water, in place of the potassium hydroxide solution. In this case, however, the product on standing overnight forms a very hard mass, which should be dissolved in tcarm water. The yields of alcohol and acid are unchanged. 

Owing to the comparatively negligible difference in the cost of bromine and the equivalent quantity of constat boiling point hydrobromio acid, there is little to be gained—apart from the instructional value—in preparing the hydrobromio acid from bromine in the preparation of alkyl bromides. 

Acetylation with acetic anhydride is comparatively expensive because of the cost of the reagent. The use of the inexpensive glacial acetic acid depends upon the displacement of the reversible equilibrium ... 

Carboxylate exchangers contain —COOH groups which have weak acidic properties and will only function as cation exchangers when the pH is sufficiently high (pH > 6) to permit complete dissociation of the —COOH site. Outside this range the ion exchanger can be used only at the cost of reduced capacity. 

The scale of operations, accuracy, precision, sensitivity, time, and cost of methods involving redox titrations are similar to those described earlier in the chapter for acid-base and complexometric titrimetric methods. As with acid-base titrations, redox titrations can be extended to the analysis of mixtures if there is a significant difference in the ease with which the analytes can be oxidized or reduced. Figure 9.40 shows an example of the titration curve for a mixture of Fe + and Sn +, using Ce + as the titrant. The titration of a mixture of analytes whose standard-state potentials or formal potentials differ by at least 200 mV will result in a separate equivalence point for each analyte. 

Figure 3 shows the production of acetaldehyde in the years 1969 through 1987 as well as an estimate of 1989—1995 production. The year 1969 was a peak year for acetaldehyde with a reported production of 748,000 t. Acetaldehyde production is linked with the demand for acetic acid, acetic anhydride, cellulose acetate, vinyl acetate resins, acetate esters, pentaerythritol, synthetic pyridine derivatives, terephthaHc acid, and peracetic acid. In 1976 acetic acid production represented 60% of the acetaldehyde demand. That demand has diminished as a result of the rising cost of ethylene as feedstock and methanol carbonylation as the preferred route to acetic acid (qv). 

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). 

Butane-Naphtha Catalytic Liquid-Phase Oxidation. Direct Hquid-phase oxidation ofbutane and/or naphtha [8030-30-6] was once the most favored worldwide route to acetic acid because of the low cost of these hydrocarbons. Butane [106-97-8] in the presence of metallic ions, eg, cobalt, chromium, or manganese, undergoes simple air oxidation in acetic acid solvent (48). The peroxidic intermediates are decomposed by high temperature, by mechanical agitation, and by action of the metallic catalysts, to form acetic acid and a comparatively small suite of other compounds (49). Ethyl acetate and butanone are produced, and the process can be altered to provide larger quantities of these valuable materials. Ethanol is thought to be an important intermediate (50) acetone forms through a minor pathway from isobutane present in the hydrocarbon feed. Formic acid, propionic acid, and minor quantities of butyric acid are also formed. 

Prospective Processes. There has been much effort invested in examining routes to acetic acid by olefin oxidation or from ethylene, butenes, or j -butyl acetate. No product from these sources is known to have reached the world market the cost of the raw materials is generally prohibitive. 

About half of the wodd production comes from methanol carbonylation and about one-third from acetaldehyde oxidation. Another tenth of the wodd capacity can be attributed to butane—naphtha Hquid-phase oxidation. Appreciable quantities of acetic acid are recovered from reactions involving peracetic acid. Precise statistics on acetic acid production are compHcated by recycling of acid from cellulose acetate and poly(vinyl alcohol) production. Acetic acid that is by-product from peracetic acid [79-21-0] is normally designated as virgin acid, yet acid from hydrolysis of cellulose acetate or poly(vinyl acetate) is designated recycle acid. Indeterrninate quantities of acetic acid are coproduced with acetic anhydride from coal-based carbon monoxide and unknown amounts are bartered or exchanged between corporations as a device to lessen transport costs. 

Acetone cracks to ketene, and may then be converted to anhydride by reaction with acetic acid. This process consumes somewhat less energy and is a popular subject for chemical engineering problems (24,25). The cost of acetone works against widespread appHcation of this process, however. 

Other acetyl chloride preparations include the reaction of acetic acid and chlorinated ethylenes in the presence of ferric chloride [7705-08-0] (29) a combination of ben2yl chloride [100-44-7] and acetic acid at 85% yield (30) conversion of ethyUdene dichloride, in 91% yield (31) and decomposition of ethyl acetate [141-78-6] by the action of phosgene [75-44-5] producing also ethyl chloride [75-00-3] (32). The expense of raw material and capital cost of plant probably make this last route prohibitive. Chlorination of acetic acid to monochloroacetic acid [79-11-8] also generates acetyl chloride as a by-product (33). Because acetyl chloride is cosdy to recover, it is usually recycled to be converted into monochloroacetic acid. A salvage method in which the mixture of HCl and acetyl chloride is scmbbed with H2SO4 to form acetyl sulfate has been patented (33). 

Propylene Oxidation. The propylene oxidation process is attractive because of the availabihty of highly active and selective catalysts and the relatively low cost of propylene. The process proceeds in two stages giving first acrolein and then acryUc acid (39) (see Acrolein and derivatives). 

It is possible to dispense with the extraction step if the oxidation section is operated at high propylene concentrations and low steam levels to give a concentrated absorber effluent. In this case, the solvent recovery column operates at total organic reflux to effect a2eotropic dehydration of the concentrated aqueous acryflc acid. This results in a reduction of aqueous waste at the cost of somewhat higher energy usage. 

The procedure is technically feasible, but high recovery of unconverted raw materials is required for the route to be practical. Its development depends on the improvement of catalysts and separation methods and on the avaHabiUty of low cost acetic acid and formaldehyde. Both raw materials are dependent on ample supply of low cost methanol. 

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