United States Patent (19) 11 Patent Number: 5,907,059 Cami Et Al
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USOO5907059A United States Patent (19) 11 Patent Number: 5,907,059 Cami et al. (45) Date of Patent: May 25, 1999 54 PROCESS FOR THE PREPARATION OF 3,655,746 4/1972 Shiraishi et al. ........................ 260/527 MONOSODIUM GLUTAMATE 4.956,471 9/1990 Ito et al. ................................. 548/344 (75) Inventors: Pierre Cami, Nesle, Switzerland; FOREIGN PATENT DOCUMENTS Aharon Eyal, Jerusalem, Israel 939573 10/1963 United Kingdom. 2 095 232 9/1982 United Kingdom. 73) Assignees: Amylum Belgium N.V., Aalst, 2095232 9/1982 United Kingdom. Belgium; A.E. Staley Manufacturing 2 103 221 2/1983 United Kingdom. Company, Decatur, Ill. 2103221 2/1983 United Kingdom. 96/31.459 10/1996 WIPO. Appl. No.: 08/930,629 Primary Examiner Samuel Barts PCT Fed: Apr. 4, 1996 Assistant Examiner Rosalynd Keys Attorney, Agent, or Firm-Jacobson, Price, Holman & PCT No.: PCT/IB96/00286 Stern, PLLC S371 Date: Feb. 10, 1998 57 ABSTRACT S 102(e) Date: Feb. 10, 1998 The invention provides a process for the preparation of 87) PCT Pub. No.: WO96/31459 monosodium glutamate from a fermentatively prepared Solution containing monoammonium glutamate, the process PCT Pub. Date: Oct. 10, 1996 comprising: a) contacting the Solution containing monoam 30 Foreign Application Priority Data monium glutamate Salt with a basic anion exchange resin of at least medium Strength to Split the Salt, whereby glutamate Apr. 7, 1995 IIL Israel ........................................ 113299 anions attach to the anion eXchanger and ammonia is Int. Cl. ................................................. C07C 229/00 released in the Solution; b) Subjecting the ammonia 51 containing Solution to distillation, to recover volatile ammo 52) U.S. Cl. .............................................................. 562/573 nia therefrom; c) contacting the glutamate-containing anion 58 Field of Search ............................................... 562/573 eXchange resin with a Sodium base Solution to regenerate the basic anion exchanger and to directly form monosodium 56) References Cited glutamate Salt in Solution; and d) crystallizing monosodium U.S. PATENT DOCUMENTS glutamate Salt directly from the monosodium glutamate containing Solution, wherein the crystallized Salt has a purity 2,306,646 12/1942 Shildneck ................................ 260/534 2.584,731 2/1952 Ogawa et al. ... of at least 98%. 2,905,711 9/1959 Novak et al. ........................... 260/533 3,360,555 12/1967 Frump et al. ........................... 260/534 17 Claims, No Drawings 5,907,059 1 2 PROCESS FOR THE PREPARATION OF "Heretofore a number of processes have been proposed MONOSODIUM GLUTAMATE for the preparation of MSG from a glutamic acid fermentation broth, but those processes invariably The present invention relates to a proceSS for the prepa involve the Steps of allowing glutamic acid ration of monosodium glutamate (hereinafter referred to as hydrochloride, calcium glutamate, Zinc glutamate, MSG) from a glutamic acid fermentation broth. More particularly, the present invention relates to a ammonium glutamate or glutamic acid to crystallize process for the preparation of MSG from a fermentatively from the broth, then recovering those crystals and prepared Solution containing monoammonium glutamate. Subsequently neutralizing them with, for instance, MSG is a well-known food additive which has been used Sodium hydroxide or Sodium carbonate to obtain for decades and which is used today mainly in the Far East, 1O MSG. with a consumption of about 800,000 tons annually. Because “Those processes not only require complicated Steps, but of the great demand for MSG, many processes have been developed and/or proposed for the preparation thereof. also result in unsatisfactory yields. Aside from those Thus, e.g., U.S. Pat. Nos. 2,877,160 and 2,978,384 teach processes, a proceSS is known in which an organic Various fermentation processes for the production of 15 Solvent is used to directly allow MSG to crystallize glutamic acid; U.S. Pat. Nos. 2,773,001 and 2,947,666 teach from the broth, but the resulting crystals are so low in Such processes in conjunction with the use of Strong cation purity that they must require aftertreatment.” eXchange resins to absorb glutamic acid, which is then “While the conventional purification processes employing eluted with normal hydrochloric acid or with dilute ammo cation exchange resin involve the adsorption and des nium hydroxide, respectively. orption of glutamic acid itself on and from resins, the In 1967, U.S. Pat. No. 3,325,539 was published, in which resin in the present invention is employed for the there was described and claimed a method for Separating adsorption of impurities, which makes it possible to glutamic acid and Salts thereof from a fermentation broth purify by far a greater quantity of broth per unit volume containing the same and Solid materials, which method of the resin.” comprises passing fermentation broth containing glutamic 25 acid, Salts thereof, and Solid materials upflow through a bed With this background in mind, U.S. Pat. No. 3,655,746 of Strongly acidic cation exchange resin on the hydrogen teaches and claims a proceSS for producing MSG which cycle at a rate sufficient to expand the bed between 1.05 and comprises contacting a glutamic acid fermentation broth at 1.6 times its original depth, thereby adsorbing glutamic acid a pH between about 5 and about 9 with an amount of 1 liter on Said resin; discontinuing the flow of fermentation broth by wet Volume of a strongly basic anion eXchange resin over Said resin; and eluting Said adsorbed glutamic acid from relative to about 0.2 to 0.6 molecular equivalent at the said resin with a 0.5-2 N sodium hydroxide solution. anionic impurities contained in Said broth; adding to the MSG production via adsorbing glutamic acid on an effluent from the resin a Stoichiometric amount of Sodium acidic cation exchanger, as suggested in U.S. Pat. No. hydroxide relative to the glutamic acid contained therein; 3,325,539, suffers from several disadvantages: (1) a high and recovering the crystals of MSG thus obtained. consumption of reagents, entailing production of large 35 AS described in Said patent, the resin is employed in an amounts of by-product Salts; (2) using an acidic cation amount enough to Substantially adsorb the Soluble impuri eXchanger frequently results in crystallization of glutamic ties in the broth, but not in Such an exceSS as to adsorb acid on the resin material (column 3, lines 18–20); (3) the glutamic acid itself. cation exchanger adsorbs the glutamic acid as well as the U.S. Pat. No. 3,655,746 uses strongly basic anion cation bound to it, and the cations present as impurities in the 40 eXchangers to remove Soluble anionic impurities and color fermentation liquor, mostly resulting from the carbohydrate ing matter from the fermentation liquor. However, cationic feed. As a result, large Volumes of the resin are required. In and neutral impurities, particularly non-fermentables, are many cases, only about one-third of the total available cation left with the glutamic acid and interfere in the crystallization eXchange capacity is available for glutamic acid adsorption. of pure MSG. As a result, “it is particularly suitable for the The reactions involved with the process using acidic 45 treatment of broth which is low in the concentration of cation exchangers to adsorb glutamic acid (HG) from an impurities other than organic acids.” (column 4, lines acidic Solution and regeneration by a base are as follows: 28–33). Today, more than twenty years later, the major commer cial processes for producing MSG from a fermentation broth (1) Neutralization in 50 involve acidulation with a mineral acid to a pH of about 3.2 fermentation (2) to form the mineral acid salt, followed by crystallization of (3) glutamic acid. Said glutamic acid is then Separated, purified (4) through recrystallization, and then reacted with Sodium hydroxide to produce MSG. (5) 55 However, even the commercial processes used today Suffer from many disadvantages and problems. Thus, referring, e.g., to a known commercial proceSS in Such a process doubles the consumption of extra base which Sulfuric acid is the mineral acid used, the reactions and acid values, and produces two equivalents of by-product involved in the formation of MSG (NaHG) can be repre Salt per mole of the product. In fact, reagent consumption 60 sented as follows: and by-product formation are even higher, as shown in U.S. Pat. No. 3,325,539. The MSG obtained in reaction (3) above is acidulated to pH=3.2 to crystallize the glutamic acid, (1) NH + H.G + NHHG Neutralization in which is then neutralized. fermentation (6) NHHGA + 1/2 HSO + HG + Acidulation Five years later, in 1972, U.S. Pat. No. 3,655,746 was 65 % (NH)2SO published, which describes the attempts to find a Satisfactory (7) H.G + NaOH + NaHGA Reacting the acid with process for producing MSG, as follows: 5,907,059 3 4 -continued NaOH The Strongly acidic cation eXchanger is regenerated by a (8) H.G + NaOH + NH + 2 HSO + NaHG + 2 (NHA)SO Strong acid, e.g., HCl: RNH'+HCl-R H+NHCl (12) Producing a mole of MSG consumes, in addition to the base required, one mole of ammonia and an equivalent of The over-all proceSS is: Sulfuric acid, and forms an equivalent amount of the by-product ammonium Sulfate. HG+NH+NaOH+HC->NaHG+NHCI (13) Thus, the proceSS uses up reagents and is therefore either 1O This process consumes, per mole of MSG, a mole of wasteful or expensive, Since ammonium Sulfate is not a high ammonia and a mole of HCl; it produces a mole of NHCl, value fertilizer or desired Side product, and crystallization of a by-product of low or even negative value. Another disad ammonium Sulfate is expensive. Vantage is the large Volume to be processed, due to the low Secondly, the purity of the glutamic acid precipitating in Solubility of glutamic acid.