A survey i s presented of the various oxidation techniques investigated for the industrial production of gluconic acid from glucose. Attention is paid to homogeneous procedures, mainly oxidation by means of halogen compounds and biochemical and heterogeneous processing by use of noble metal catalysts.
alkaline solution can be described as a bimolecular secondorder reaction between the monosaccharide and the hypobromite ion. From t h e influence of t h e p H on t h e reaction rate, it is concluded t h a t t h e hypobromite ion is the actual oxidizing agent. Analogous conclusions have been reported by Ingles and Israel (35, 36) for hypoiodite. More recently, PerlmutterHayman and Persky (57) concluded from t h e dependence of the reaction rate on the bromide ion concentration t h a t molecular bromine is the oxidizing agent. The dependence of t h e reaction rate on p H can be explained b y the assumption t h a t the anionic form of glucose is more reactive than t h e glucose molecule. .iceording to Isbell and Pigman (39), t h e primary oxidation product from the reaction of glucose with bromine in the presence of barium carbonate is t h e 1-5,gluconolactone. The course of the reaction is strongly influenced by t h e steric configuration of the starting material. p-Aldoses react much faster than the corresponding anomers. I n fact, t h e oxidation rate can be determined mainly by the rate of transformation to t h e p-form (6,7 , 37, 40, 62). Xri extensive kinetic study on t h e oxidation of glucose in acidic chlorine solutions has been reported by Lichtin and Saxe (45),Grillo (26),and Urquiza (73).Wetted glucose polymers like starch can be oxidized to gluconic acid by means of chlorine gas (34). Processes have been patented in which glucose is oxidized by bromine-bromate (51) and by bromic acid together with sodium chlorate (53).The latter patent claims a nonquantificational catalytic effect by some metal salts. Biniecki and Moll (10)reported the oxidation by potassium chlorate. The main disadvantage of the above processes consists of the difficulty of separating the gluconate from t h e great quantity of salts and t h e regeneration of the latter. This disadvantage is partly overcome by indirect electrolytic oxidation in which bromine or iodine is formed electrolytically from a small quantity of t h e halic acid. The free halogen is reduced again by Oxidizing t h e monosaccharide (3, 5 , 10, 20,38, 42, 6 3 , 6 4 6 9 ) . T h e direct electrooxidation of glucose to gluconic acid on Pt electrodes has been studied by R a o and Drake (61) in neutral solution. Besides the oxidation with halogens, a number of other homogeneous methods have been published (66). hshida e t al. ( 2 ) reported the conversion of glucose to gluconic acid via. the Cannizarro mechanism, if a hydride ion acceptor was added. Certain ketones and olefins, or oxygen in the presence of Raney nickel are suitable hydride ion acceptors. Overall kinetic studies on the Oxidation of a number of pentoses and hexoses by means of potassium chromabe are given by Tul'chinskii (72). Dorofeenko and I n t s u p o v a (18) reported a n overall yield of gluconic acid of 40y0 via oxidation with mercuric acetate. Biochemical Processes
I n general, these enzymatic oxidations take place at about 3OoC in aerated glucose solutions (up to 35 wt %) containing vegetable mycelia together with a number of nutrient salts.
Reactions last 10-30 hr and are sensitive to contamination. As early as 1880, Boutroux (12) described a biochemical process for the selective oxidation of glucose to gluconic acid. T h e first technical processes were based on surface techniques h number of working methods based with fungus molds (46). on this principle mere patented about 1930 (9, 16, 17, 29, 65), and other batchwise liquid-phase processes have been developed by use of rotary fermentors (21, 28,47, 75, 76). Aspergillus niger is often used as the biologically active material. Some other processes make use of a vertical fermentor for which the active mycelium is cultivated separately in a prefermentor (11 ) . Concentrated glucose solutions can be converted if borax is added to the reactor to prevent early precipitation of calcium gluconat'e (52). 1 semicontinuous process has been developed in which the mycelium is used a number of t'imes (60). -4fter the conversion of one batch, the mycelium can be separated from the solution by flotation, so t h a t about 80% of t h e liquid can be removed without appreciable loss of active material. Another method is the separation of the mycelium by filtration or in a centrifuge, after which it can be added t o a fresh glucose solution (59). I n 1959 a continuous process was patented to produce gluconic acid monohydrate (82). According to Baker and Sarett ( 4 ) , the difficulties with regard to the required sterilization can be avoided by using hydrogen peroxide as the oxidant together with glucose oxidase and catalase enzymes. .ittention has been given to several types of enzyme-producing bacteria, isolation of the enzymes and the mechanism and the kinetics of the reaction ( 8 , 1 9 , S S ,43, 67, 68,70,7l , 7 4 ) . T h e enzyme actually catalyzes a dehydrogenation of t h e glucose through the formation of a n enzyme-substrate complex which splits into gluconolactone and a reduced form of the enzyme. The latter is oxidized again by the dissolved oxygen. T h e rate-determining step in the overall reaction is either t'he hydrolysis of t h e lactone (25) or the formation of the complex which is affected by the steric configuration of the substrate (56). T h e oxygen transfer in a conventional fermentor was studied by Xiba et al. ( 1 ) . JIazza et al. (48) described a n airlift reactor in which the liquid is circulated by air injection. Heterogeneous Catalytic Procedures
As early as 1861, von Gorup-Besanez (24) oxidized mannitol in a n aqueous alkaline solution in the presence of platinum black to yield mannonic acid. I n 1953 Heyns and coworkers initiated a n extensive research program on the selective oxidation of carbohydrates by means of noble metal catalysis in alkaline solutions. -% survey is given by Heyns and Paulsen ( S I , 52). A catalyst prepared by reduction of chloroplatinic acid with formaldehyde is recommended to be the most effective for oxidizing glucose. The produced acids supposedly impede the reaction, because the oxidation proceeds slowly in neutral or acidic media. I n 1964 Levvy et al. (44) reported the platinum-catalyzed oxidation of manno,3e to 1,5-mannonolactone in a n acidic solution. More recently, his method has been applied to the prepInd. Eng. Chem. Prod. Res. Develop., Vol. 1 1 , No.
4, 1972 371
Table 1. literature Concerning Heterogeneous Catalytic Oxidation of Glucose to Gluconic Acid Reaction temp,
Ref no.
Author
(2) Ashida (13) Buckley (14) Busch (30) (41) (49) (54) (55) (58)
Heyns Johnson, Matthey Mehltretter Okada Okui Poethke (77) de Wilt 5
PH
O C
25-55 25 22 40-60 50 40 65 20 25-65
Catalyst type
8-11
8-9 7-14 8 7-14
8 8-12
Raney N i 2% P d / C Pd/CaCOs 5% P t / C 1% Pd/A1208 10% P t / C 0.5% Pd/BaSOd Adams Pt Pd/MgO : Pd/BaS04 10% P t / C
Continuous trickle bed reactor. * Glucanic acid
$711.
literature Cited
S.,Hara, AI., Someya, J., Hakko Kogaku Zasshi, 41, 74-81 (1963) (Jap.); CA, 62, 15382g;. (2) Ashida. K.. Nakamura. S..Bebeko. T.. J . Aar. Chem. SOC. j a p a n , 23, 231-7 (195Oj; Sugar Ind: A h - . , li, 210 (1950); C A , 45, 562g. (3) Atmasui, A., Oprescu, G. AI., Bull. Inst. ,Yatl. Cercetar,’ Technol., 3, 400-12 (1948) (Fr.); CA, 43, 8904e. (4) Baker, D. L., Sarett, B. L., U.S. Patent 2,651,592 (Sept. 8, 1953); CA, 48, 334h. (5) Balasundaram, S.,Hirani, R . K., Subrahmanyan, V., J . Sci. Ind. Res. (India), 9B, 295-8 (1950); CA, 45, 6512a. (6) Barker, I . R. L., Overend, W.G., Rees, C. W., Chem. Ind. (London), 1960, 1297-1298 (1960); CA, 55, 16432~. (7) Barker, I. R. L., Overend, W. G., Rees, C. W., J . Chem. SOC., 1964, pp 3254-62; CA, 61, 13395. (8) Bentley, R., Seuberger, A,, Biochem. J., 45, 584-90 (1949); CA, 44, 40351; Bentley, R., -Yature, 176, 870-3 (19j5); CA, 50, 7918f. (1) A h a ,
Ind. Eng. Chem. Prod. Res. Develop., Vol. 1 1 , No. 4, 1972
Glucose concn., mmol/l.
Glucose conversion,
%
Reaction time, hr
45
1000-2500
20 7 3-7
100 50-2000 150 50-300
30
12 0.1-0.3
0-1.6
2500 50-250
100
1-2
+ glucmaccharic acid (547,).
aration of 1,5-lactones of some other pyranoses. I n these studies the ratio of the catalyst concentration to the sugar concentration is considerably higher than under alkaline conditions (15). I n general, the selectivity of the platinumcatalyzed oxidation is lower than t h a t of the enzymatic processes. According to Poethke (58), the selectivity can be affected by a consecutive oxidative degradation of the produced gluconic acid-probably by a Ruff mechanism. Furthermore, in strongly alkaline solutions the oxidative degradation of glucose becomes more important as a nonplatinumcatalyzed side reaction. Glucosaccharic acid has been reported as a n important consecutive reaction product, depending on the catalyst quality (41, 49). A schematic survey of the literature concerning t h e heterogeneous catalytic oxidation of glucose to gluconic acid is given in Table I. Most publications noted in Table I give only phenomenological descriptions of the methods used. One exception is t h e recent work of Okada et al. (54) who reported a mathematical description of the oxidation reaction up to a conversion of 30% in a continuously stirred tank reactor and a vertically mounted multistage countercurrent gas-liquid contractor. The catalyst was always kept in suspension and was transported through the reactor system together with the reactants. Their calculations are based on a n empirically determined, bimolecular second-order kinetic model of t h e catalytic reaction, modified by a logarithmic term describing catalyst deactivation during t h e reaction. D e Wilt (77) developed a kinetic model which is based on a dehydrogenation mechanism and a Langmuir-Hinshelwood type adsorption of the substrate and acidic products on a platinum-carbon catalyst.
372
Cat. concn.,
%
7-10
80-90
5-10
70 90
90-100
Stirred tank reactor
Yield, Note
a
b C
90
+ continuous multistage contactor.
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RECEIVED for review March 11, 1971 ACCEPTED September 14, 1972
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