Citric acid Salts

Ammonium salts of citric acid are made by adding either aqueous or anhydrous ammonia to citric acid dissolved in water. They are usually used in the hquid form rather than isolated as a dry product. Citric acid salts are Hsted in Table 5. SolubiUty data is as follows (1). 

Salts Compounds formed by the union of acids and bases, by the action of alkalies upon metals, or by the direct union of elements. The term is often incorporated in the common name of salts used as pharmaceuticals bitter salts, epsom salt, or Seidlitz salt (magnesium sulfate), preparing salt (sodium stannate), Preston s salts (ammonium chloride), Rochelle salt or Seignette s salt (potassium and ammonium tartrate), salt of Mars (ferrous sulfate), salt of Saturn (lead acetate), salt of tartar (potassium carbonate), salt of tin (stannous chloride), salt of wisdom (mercury bichloride and ammonium chloride), sore-throat salt (fused potassium nitrate), vinegar salts (calcium acetate), and vomiting salt (zinc sulfate). The term is also applied to some acids, such as salt of lemon or sour salt (citric acid), salt of sorrel (oxalic acid), and spirit of salt (muriatic acid). ... 

Nitrilotriacetlc acid was supplied by the Hampshire Chemical Co., Division of W. R. Grace Co., Nashua, New Hampshire. For feeding studies It was neutralized with 1 M sodium hydroxide to provide a 1% NTA solution. Ethyl nltrllotrlacetate was obtained as a clear colorless viscous oil by refluxing 30g of nltrllotrl-acetlc acid In 1 liter of absolute alcohol In the presence of 3g of toluenesulphonlc acid for forty-eight hours. The alcohol was removed by distillation from a water bath in vacuo, the residue mixed with 100 ml of 0.5 percent sodium bicarbonate solution and extracted with one liter of benzene. The benzene solution was extracted twice more with bicarbonate solution, washed with water and concentrated from a water bath In vacuo. The clear colorless residual oil was dissolved by shaking with an aqueous solution of 1.5 M citric acid and the volume adjusted by addition of distilled water to provide a final solution of 1% NTA ethyl ester as citric acid salt. 

Yarrowia lipolytica Lipids, citric acid. Salt tolerant, utilization of crude [6, 9,10]... 

Citric Acid - 105 41 - E E E mixed fermentation tank effluent, some citric acid salt. 5 to 65% solids. 0.08 to 1.2% chloride, pH 5... 

Bryan JM (1950) The corrosion of aluminium and aluminium alloys by citric acid and citric acid-salt solutions. J Sci EoodAgric 1 84-87... 

The first step is a washing procedure with - fatty alcohol ethoxylates or, especially for wet blue (semitanned chromium leather), with fatty alcohol ether phosphates, wdiich are able to dissolve chromium soaps. The second step is neutralization with sodium acetate or - citric acid salts that contribute complexing effects. The third step is retanning, mostly with vegetable tannins. 

Crystallizes from water in large colourless prisms containing 2H2O. It is poisonous, causing paralysis of the nervous system m.p. 101 C (hydrate), 189°C (anhydrous), sublimes 157°C. It occurs as the free acid in beet leaves, and as potassium hydrogen oxalate in wood sorrel and rhubarb. Commercially, oxalic acid is made from sodium methanoate. This is obtained from anhydrous NaOH with CO at 150-200°C and 7-10 atm. At lower pressure sodium oxalate formed from the sodium salt the acid is readily liberated by sulphuric acid. Oxalic acid is also obtained as a by-product in the manufacture of citric acid and by the oxidation of carbohydrates with nitric acid in presence of V2O5. 

A) AMMONIUM SALTS. R COONH4. Ammonium salts of formicy acetic oxalic, succinic, tartaric, citric acid benzoic, salicylic (and other substituted benzoic acids) phthalic and cinnamic acids. 

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. 

Certain factors and product precursors are occasionally added to various fermentation media to iacrease product formation rates, the amount of product formed, or the type of product formed. Examples iaclude the addition of cobalt salts ia the vitamin fermentation, and phenylacetic acid and phenoxyacetic acid for the penicillin G (hen ylpenicillin) and penicillin V (phenoxymethylpenicillin) fermentations, respectively. Biotin is often added to the citric acid fermentation to enhance productivity and the addition of P-ionone vastly iacreases beta-carotene fermentation yields. Also, iaducers play an important role ia some enzyme production fermentations, and specific metaboHc inhibitors often block certain enzymatic steps that result in product accumulation. 

Table 2 Hsts examples of compounds with taste and their associated sensory quaUties. Sour taste is primarily produced by the presence of hydrogen ion slightly modified by the types of anions present in the solution, eg, acetic acid is more sour than citric acid at the same pH or molar concentration (43). Saltiness is due to the salts of alkaU metals, the most common of which is sodium chloride. However, salts such as cesium chloride and potassium iodide are bitter potassium bromide has a mixed taste, ie, salty and bitter (44). Thus saltiness, like sourness, is modified by the presence of different anions but is a direct result of a small number of cations.

In appHcations as hard surface cleaners of stainless steel boilers and process equipment, glycoHc acid and formic acid mixtures are particularly advantageous because of effective removal of operational and preoperational deposits, absence of chlorides, low corrosion, freedom from organic Hon precipitations, economy, and volatile decomposition products. Ammoniated glycoHc acid Hi mixture with citric acid shows exceUent dissolution of the oxides and salts and the corrosion rates are low. 

The lanthanides form many compounds with organic ligands. Some of these compounds ate water-soluble, others oil-soluble. Water-soluble compounds have been used extensively for rare-earth separation by ion exchange (qv), for example, complexes form with citric acid, ethylenediaminetetraacetic acid (EDTA), and hydroxyethylethylenediaminetriacetic acid (HEEDTA) (see Chelating agents). The complex formation is pH-dependent. Oil-soluble compounds ate used extensively in the industrial separation of rate earths by tiquid—tiquid extraction. The preferred extractants ate catboxyhc acids, otganophosphoms acids and esters, and tetraaLkylammonium salts. 

Two types of magnesia, caustic-calcined and periclase (a refractory material), are derived from dolomitic lime. Lime is required in refining food-grade salt, citric acid, propjiene and ethylene oxides, and ethylene glycol, precipitated calcium carbonate, and organic salts, such as calcium stearate, lactate, caseinate. 

Evaporated milk is a Hquid product obtained by the partial removal of water only from milk. It has a minimum milk-fat content of 7.5 mol % and a minimum milk-solids content of 25.0 mol %. Evaporated skimmed milk is a Hquid product obtained by the partial removal of water only from skimmed milk. It has a minimum milk-solids content of 20.0 mol %. Sweetened condensed milk is a product obtained by the partial removal of water only from milk with the addition of sugars. It has a minimum milk-fat content of 8.0 mol % and a minimum milk-solids content of 28.0 mol %. Skimmed sweetened condensed milk is a product obtained by the partial removal of water only from skimmed milk with the addition of sugars. It has a minimum milk-solids content of 24.0 mol %. AH may contain food additives (qv) as stabilizers, in maximum amounts, including sodium, potassium, and calcium salts of hydrochloric acid at 2000 mg/kg singly citric acid, carbonic acid, orthophosphoric acid, and polyphosphoric acid at 3000 mg/kg in combination, expressed as anhydrous substances and in the evaporated milk carrageenin may be added at 150 mg/kg. 

Complexing agents, which act as buffers to help control the pH and maintain control over the free metal—salt ions available to the solution and hence the ion concentration, include citric acid, sodium citrate, and sodium acetate potassium tartrate ammonium chloride. Stabilizers, which act as catalytic inhibitors that retard the spontaneous decomposition of the bath, include fluoride compounds thiourea, sodium cyanide, and urea. Stabilizers are typically not present in amounts exceeding 10 ppm. The pH of the bath is adjusted. 

Because of its functionaUty and environmental acceptabiUty, citric acid and its salts (primarily sodium and potassium) are used in many industrial appbcations for cbelation, buffering, pH adjustment, and derivatization. These uses include laundry detergents, shampoos, cosmetics, enhanced oil recovery, and chemical cleaning. 

Salt Formation. Citric acid forms mono-, di-, and tribasic salts with many cations such as alkahes, ammonia, and amines. Salts may be prepared by direct neutralization of a solution of citric acid in water using the appropriate base, or by double decomposition using a citrate salt and a soluble metal salt. 

Trisodium citrate is more widely used than any of the other salts of citric acid. It is generally made by neutralization of a water solution of citric acid using sodium hydroxide. The neutralization reaction is highly exothermic giving off 1109 J/g of citric acid. To conserve energy, the heat evolved can be used in the sodium citrate concentration and crystallization steps. 

The mono- and disodium citrate salts are made by limiting the amount of sodium available by using only one mole of base for each mole of citric acid for the monosodium citrate and two moles for the disodium citrate. The result is primarily the mono or disalt with small amounts of the other forms and citric acid being present. Other salts that have been offered commercially are shown in Table 5. 

Citric acid occurs widely in the plant and animal kingdoms (12). It is found most abundantiy in the fmits of the citms species, but is also present as the free acid or as a salt in the fmit, seeds, or juices of a wide variety of flowers and plants. The citrate ion occurs in all animal tissues and fluids (12). The total ckculating citric acid in the semm of humans is approximately 1 mg/kg body weight. Normal daily excretion in human urine is 0.2—1.0 g. This natural occurrence of citric acid is described in Table 7. 

Fermentation. The microbial production of citric acid on a commercial scale was begun in 1923 utilizing certain strains yispergillus nigerio produce citric acid on the surface of a sucrose and salt solution. This tray fermentation technique is still used today, although it is being replaced by a submerged process known as deep tank fermentation (14—22). 

Lime-Sulfuric. Recovery of citric acid by calcium salt precipitation is shown in Figure 3. Although the chemistry is straightforward, the engineering principles, separation techniques, and unit operations employed result in a complex commercial process. The fermentation broth, which has been separated from the insoluble biomass, is treated with a calcium hydroxide (lime) slurry to precipitate calcium citrate. After sufficient reaction time, the calcium citrate slurry is filtered and the filter cake washed free of soluble impurities. The clean calcium citrate cake is reslurried and acidified with sulfuric acid, converting the calcium citrate to soluble citric acid and insoluble calcium sulfate. Both the calcium citrate and calcium sulfate reactions are generally performed in agitated reaction vessels made of 316 stainless steel and filtered on commercially available filtration equipment. 

Although not as corrosive as the acid, the sodium and potassium salts of citric acid should be handled in the same type of equipment as the acid to avoid corrosion problems. 

It was estimated that 1990 U.S. citric acid and citrate salt consumption was 152,000 t. Citric acid represents approximately 90% of this volume. This citric acid/citrate use and its historical distribution in various markets is described in Table 9. From Table 9 it can be seen that although citric acid usage in the United States has shown steady growth at an average aimual rate of 4.4% from 1986—1990, the end use patterns have been quite stable. 

An enzymatic method (45), which is specific for the citrate moiety, can be used as a combined assay and identification test for citric acid and its common salts down to 20 ppm. 

Citric acid and its salts are used in dry beverage mixes, convenience teas, and cocktail mixes for pH control and flavor, and are used in wine coolers at 0.10—0.55%, combining well with fmity and light flavors. 

Medical Uses. Citric acid and citrate salts are used to buffer a wide range of pharmaceuticals at their optimum pH for stabiUty and effectiveness (65—74). Effervescent formulations use citric acid and bicarbonate to provide rapid dissolution of active ingredients and improve palatabiUty. Citrates are used to chelate trace metal ions, preventing degradation of ingredients. Citrates are used to prevent the coagulation of both human and animal blood in plasma and blood fractionation. Calcium and ferric ammonium citrates are used in mineral supplements. 

Agricultural Use. Citric acid and its ammonium salts are used to form soluble chelates of iron, copper, magnesium, manganese, and zinc micronutrients in Hquid fertilizers (97—103). Citric acid and citrate salts are used in animal feeds to form soluble, easily digestible chelates of essential metal nutrients, enhance feed flavor to increase food uptake, control gastric pH and improve feed efficiency. 

Electrodeposition of Metals. Citric acid and its salts are used as sequestrants to control deposition rates in both electroplating and electroless plating of metals (153—171). The addition of citric acid to an electroless nickel plating bath results in a smooth, hard, nonporous metal finish. 

Concrete, Mortar, and Plaster. Citric acid and citrate salts are used as admixtures in concrete, mortar, and plaster formulations to retard setting times and reduce the amount of water requited to make a workable mixture (172—180). The citrate ion slows the hydration of Portland cement and acts as a dispersant, reducing the viscosity of the system (181). At levels below 0.1%, citrates accelerate the setting rate while at 0.2—0.4% the set rate is retarded. High early strength and improved frost resistance have been reported when adding citrate to concrete, mortar, and plaster. 

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