The selective catalytic oxidation of D-gluconic acid to
2-keto-D-gluconic acid or D-glucaric acid
Citation for published version (APA):
Smits, P. C. C. (1984). The selective catalytic oxidation of gluconic acid to 2-keto-gluconic acid or D-glucaric acid. Technische Hogeschool Eindhoven. https://doi.org/10.6100/IR136409
DOI:
10.6100/IR136409
Document status and date: Published: 01/01/1984
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OF D-GLUCONIC ACID
TO 2-KETO - D-GLUCONIC ACID
OR D-GLUCARIC ACID
PROEFSCHRIFT
TER VERKRIJGING VAN DE GRAAD VAN DOCTOR IN DE TECHNISCHE WETENSCHAPPEN AAN DE TECHNISCHE HOGESCHOOL EINDHOVEN, OP GEZAG VAN DE RECTOR MAGNIFICUS, PROF. DR. S.T.M. ACKERMANS, VOOR EEN COMMISSIE AANGEWEZEN DOOR HET COLLEGE VAN DEKANEN IN HET OPENBAAR TE VERDEDIGEN OP
DINSDAG 24 APRIL 1984 TE 16.00 UUR
DOOR
PETER CAROLUS CORNELIS SMITS
prof. dr. ir. K. van der Wiele
Page
1. Introduction
1.1. Carbohydrates as a chemical feedstock 1
1.2. Oxidation of monosaccharides 4
1.3. Properties and applications of the
oxidation-products of glucose 6
1.4. Aspects of phosphate reduction 10
1.5. Choice of oxidation system 11
1.6. Aim and outline of this thesis 12
References 15
2. Literature survey
2.1. Introduction 17
2.2. Oxidation of D-glucose to D-gluconic acid 21
2.2.1. Homogeneous oxidation 21
2.2.2. Biochemical oxidation 22
2.2.3. Heterogeneous catalytic oxidation 24
2.3. Oxidation of D-glucose or D-gluconic acid to
D-glucaric acid 27
2.3.1. Homogeneous oxidation 27
2.3.2. Heterogeneous catalytic oxidation 27
2.4. Manufacture of 2-keto-D-gluconic acid 28
2.4.1. Oxidation of D-glucose or o-gluconic acid 28
2.4.2. Alternative oxidation methods 32
2.5. Oxidation of L-gulonic acid to
2-keto-L-gulonic acid 33
2.6. Discussion 33
3. Analysis
3.1. Introduction
3.2. Ion exchange chromatography 3.2.1. Introduction
3.2.2. Experimental 3.2.3. Typical results
3.3. Preparative ion exchange chromatography 3.3.1. Experimental
3.3.2. Typical results
3.4. l3c-nuclear magnetic resonance spectroscopy 3.4.1. Introduction 3.4.2. Experimental 3.4.3. Typical results 3.5. Isotachophoresis 3.5.1. Introduction 3.5.2. Experimental 3.5.3. Typical results
3.6. A specific detection method for a-keto carboxylic acids
3.6.1. Introduction 3.6.2. Experimental 3.6.3. Typical results References
4. Equipment and experimental methods 4.1. Introduction
4.2. The catalysts
4.2.1. The platinum on carbon catalyst 4.2.2. The lead platinum on carbon catalyst 4.3. Equipment
4.4. Experimental methods
4.5. Mass transfer in the stirred tank reactor References 43 44 44 45 46 52 52 53 55 55 55 56 60 60 61 61 65 65 65 66 67 69 69 69 71 74 75 76 76
S. Selective catalytic production of D-glucaric acid
S.1. Introduction 77
S.2. Exploratory experiments of the oxidation of
D-gluconic acid with Cu1II) and Co(!I) catalysts 81
S.3. Product distribution during the oxidation of
D-gluconic acid with a Pt/C catalyst 82
S.4. Oxidation of D-gluconic acid in the presence
of borate 86
S.S. Oxidation of D-gluconic acid, partly in the
form of o-lacton 93
S.6. Addition of Pb(II) to the oxidation formulation 98
References 99
6. Characteristics and scope of the Pb/Pt/C catalyst in ·the oxidation of carbohydrates and their monocarboxylic
ac~ds
6.1. Introduction 101
6.2. Experimental 102
6.3. The effect of lead on the Pt-catalyzed oxidation
of D-gluconic acid 102
6.3.1. Addition of a heterogeneous lead compound
to the Pt/C catalyst 102
6.3.2. Addition of a homogeneous lead compound
to a Pt/C catalyst 106
6.3.3. Addition of Pb3CP0
4)2
/c
to a Pt/Ccatalyst 108
6.3.4. Addition of EDTA to a Pt/Pb/C catalyst 110
6.4. Influence of the Pb/Pt ratio 111
6.S. Metal ions other than Pb2+ llS
6.6. Other substrates than D-gluconic acid 6.7. Deactivation of the catalyst
References
117
123 128
7. Selective catalytic production of 2-keto-D-gluconic
7 .1. Introduction
7.2. Influence of the catalyst concentration 7.3. Influence of the oxygen concentration 7.4. Influence of the pH
7.5. Influence of the temperature 7.6. Product distribution
8. Final discussion 8.1. Introduction
8.2. Coordination of Pb2+ with D-gluconic acid
acid 129 129 134 140 143 146 153 153 8.3. Reaction mechanism 157
8.4. Kinetics of the D-gluconic acid oxidation with
a Pb/Pt/C catalyst 160
8.5. Applications of the Pb/Pt/C catalyst References
Appendix I: Structure formulas Summary Samenvatting Dankwoord Levensbericht 161 163 165 167 170 173 175
Chapter 1
Introduction
1.1. Carbohydrates as a chemicai feedstock
Carbohydrates are produced every year in large quantities by photosynthesis, mainly in the form of the polysaccharides cellulose and starch, and the disaccharide sucrose. All can be hydrolyzed to monosaccharides, yielding glucose, while from sucrose also fructose is obtained. Starch and sucrose are almost exclusively used as food, while cellulose is mainly used for the manufacture of paper and rayon and in the form of wood as fuel and construction material. Only a very small part of the available carbohydrates is used as a feedstock for the chemical industry.
Since the publication of the first report of the Club of Rome (1) the awareness has grown that the reserves of oil, natural gas and coal are not unlimited, Therefore, it is
mandatory to look for alternative raw materials for the chemical industry. In certain instances carbohydrates can offer such an alternative, the more so because one can try to arrange that the rate of production by agriculture remains in equilibrium with the rate of conversion and consumption. Due to the
enormously increased price of oil also the economic attractiveness of processes based on carbohydrates is improving.
The high oxygen content of the sugars makes i t possible to produce, for some chemicals used at present, substitutes, that cause fewer environmental problems.
From the monosaccharides obtained by hydrolysis, glucose is the most important raw-material for the chemical indus~ry.
The main products which are of industrial interest are summarised in table 1.1. More detailed information is given in the literature (2-7) •
Biocatalytic processes Catalytic processes
ethanol glucitol
acetic acid mannitol (via fructose)
lactic acid gluconic acid
vitamin C (via glucitol) glucaric acid gluconic acid
fructose
Table 1.1. Produate and proaeesee of industrial interest, starting from gluaose
The processes can broadly be divided into catalytic and biochemical (biocatalytic) processes. In this thesis we will call processes using man made, mainly, although not exclusi-vely, inorganic catalysts catalytic processes, and processes that use microorganisms or enzymes biocatalytic or enzymatic processes. Their main features are compared in table 1.2. Although catalytic processes offer more advantages than disadvantages than biochemical processes, the former have yet found little application in the carbohydrate-industry. This is mainly caused by the fact that the selectivity of the catalytic processes is not high enough. In general, inorganic catalysts are less specific than biocatalysts, moreover a characteristic property of carbohydrate molecules is their rather high number of almost identical functional groups. Combination of these two factors will generally lead to a
lower selectivity when an inorganic catalyst is substituted for a biocatalyst in a carbohydrate process. This is especially true for processes involving conversion of only one hydroxyl group. Of these processes oxidation processes are commercially by far the most important.
process type catalytic biocatalytic
reaction time +
-concentration level of reactants +
-reactor volume +
-product separation from catalyst +
-continuous operation +
-reliability (resistance against poisoning) +
-selectivity
-
+product purification
-
++ : favourable less favourable
Table 1.2. Comparison between aataZytia and bioaataZytia aarbohydrate proaesses.
Improvement of the selectivity would take away this obstacle for the application of catalytic oxidation processes in carbohydrate industry. Therefore the main aim of the research work described in this thesis is the improvement of the selectivity of the catalytic oxidation of D-glucose to D-glucaric acid or 2-keto-D-gluconic acid.
0 II C-H I H-C-OH I HO-C,-H I H-C-OH I H-C-OH I CH 20H D-glucose TOOH H-T-OH HO-T-H H-C-OH I H-C-OH I CH 20H D-gluconic acid COOH I H-C-OH I HO-C-H I H-C-OH I H-T-OH COOH D-glucaric acid COOH I c = 0 I HO-C-H I H-C-OH I H-C-OH tH 20H 2-keto-D-gluconic acid
1.2. O~idation of monosaaaharides
Oxidation of monosaccharides is one of the main reactions that can be applied to carbohydrates. A well~known industrial example is the oxidation of L-sorbose to 2-keto-L-gulonic acid from which vitamin C (L-ascorbic acid) can be readily obtained:
0
.9]
HO-C II HO-C I H-C I HO-C-H I CH 20H L-sorbose 2-keto-L-gulonic acid L-ascobic acidWithout precautions the oxidation step is accompanied by many side reactions, so that a protection of the other, also reactive OH-functions by means of e.g. acetone is necessary. This oxidation requires therefore three reaction steps:
attachment of the protective groups, oxidation of the remaining target group, and removal of the protective groups, as shown below. fH 20H
f
0 HO-f-H H-f-OH HO-f-H CH20H L-sorbose 2,3:4,6 d1-D-isopropylidene 2-keto-L-gulonic acid 2,3:4,6 - d1-0-1sopropylidene -n-L-sorbofuranosef
OOHr
= o HO-C-H I H-C-OH I HO-C-H I CH20H 2-keto-L-gulonic acidThese three steps are part of the present industrial route for the production of vitamin C and are based on the work of Reichstein et al. (8) published in 1933 (!).It would be economically attractive if one could manage to oxidize
L-sorbose without the need of the introduction and subsequent removal of protective groups. In chapter 6 we will, on basis of our findings, propose an alternative route for the manu-facture of vitamin
c.
Another industrial example is the, at present mainly biochemical, oxidation of D-glucose to D-gluconic acid. In The Netherlands D-gluconic acid is produced by Glucona, a joint-venture of Akzo and AVEBE. At the moment they use two processes, one based on the fungus Aspergillus niger, and the other predicated the bacterium Gluconobacter oxydans. A logical development in this field is the use of the immobilized enzyme-system glucose oxydase-catalase from e.g. Aspergillus niger in a continuous process as described by Hartmeier and Tegge (9), Richter and Heinecker (10) and Tramper (30).
An important competitor of this process consists of the catalytic oxidation with palladium on carbon. An industrial process (with a high selectivity) is currently in operation in Japan. Dirkx (29) has found that this oxidation can be carried out with a high selectivity ( > 95%) too, using a trickle-bed reactor and (deactivated) platinum on carbon
(Pt/C) as catalyst.
The next step, the oxidation of D-gluconic acid to D-glucaric acid, is much more difficult. There is no bio-catalyst known for this reaction, while for the aqueous alkaline oxidation with oxygen and Pt/C as catalyst, the highest productivity reported is 50-55 %. For commercial application this is far from attractive. In this thesis we will describe some preliminary experiments to improve this productivity.
1. 3. Properties and appZiaations of the o:xidation-produats of g"luaose
The main product property of the oxidation-products of monosaccharides derives from their sequestering capacity, i.e. their ability to form soluble complexes with certain metal ions.
At a pH above 13 gluconic- , glucaric- , galactonic- , galactaric-, and xylaric acid are good sequestrants (12,13). Gluconic acid is the only sugar acid which is at present applied on a large commercial scale as a sequestrant. The sequestering capacity of glucaric acid is about a factor 5 higher than that of gluconic acid (3% NaOH, 25°C) (12). However, the relative high cost of production of glucaric acid by nitric acid oxidation of glucose has discouraged the widespread use of glucaric acid as a metal ion sequestrant (14).
In weak alkaline medium ( pH 8-13) the sequestering capa-city of the sugar acids is low, but on complexing the sugar acids with boric acid the sequestering capacity in a weak alkaline medium is much improved (15,16). For example, the sequestering capacity of disodium glucarate increases by a factor 9 by complexing it with 1 mol boric acid/mol glucarate
(pH= 9.5, 25°C) (15).
One of the main applications of sequestrants nowadays is in the formulation of detergents. The most important sequestrants used for this purpose are citric acid, ethylene diamine tetra-acetic acid (EOTA), nitrilo tri-tetra-acetic acid (NTA), and scdium tripolyphosphate.
The choice of the sequestrant for a specific application depends, among other factors, upon the type of ion to be com-plexed, pH and temperature. Table 1.3. gives the sequestering capacity (defined here as g Ca2+ complexed per 100 g seques-trant) for a number of sugar acids and the four other se-questrants. The data are adopted from work described by Heesen
(16) and van der Steen (17).
sequestrant mol boric acid/ sequesterin9 capacity
mol sequestran t 9 Ca2•;100 9 sequestrant (pH
=
9.5, 25•c1 sodium gluconate 0 0.5 1 6.5 disodium glucarate 0 La 1 16.5 disodium galactarate 0 1.3 1 14.0 L(+) sodium tartrate 0 2.0 1 a.a trisodium citrate 0 5.5 1 5.2 Na-NTA 0 16.2 K4-EDTA 0 4.9 sodium tripolyphosphate 0 12.3table 1.3. Sequestering aapaaity towards ca 2+
for some sequestrants
From table 1.3. is concluded that the sequestering capa-city of the sugar acid/boric acid complexes can easily compete with that of the more conventional sequestrants.
Sodium tripolyphosphate is used on a large scale in syn-thetic detergents, but it causes serious environmental pollu.-tion. Therefore, considerable research is carried out by various industrial laboratories to find alternatives for sodium tripolyphosphate (1826). A computersurvey over the years 1971 -1981 by International Research Service S.D.C. (20) showed that no less than 400 patent applications were filed world-wide by about 40 companies: detergent manufactures, oil-com-panies, chemical industries, and others.
To judge the potential alternatives, the following pro-perties have to be compared: sequestering capacity, bio-degradibility, toxicological- and cancerous properties and of course the price.
From all the possibilities suggested in The Netherlands only two serious candidates (20) remained: zeolite and NTA. The zeolite used is a special sodium-aluminium-silicate. It is a crystalline water-insoluble ion- exchanger that
exchanges its sodium ions with the metal-ions from the solution. A more recent study at our laboratory (27), however,
showed that the oxidation mixture of D-glucose, prepared by the use of Pt/C as catalyst and oxygen as oxydant, offers a clear alternative. The main constituent of this mixture is D-glucaric acid, which, in combination with boric acid, is a very good sequestrant (table 1.3.). The detergents in use nowadays already contain borates, consequently they need not to be added separately. According to this study the price of the so-called "Glucombinaat" is as low as, or even lower than the other alternatives.
Akzo successfully (21,26) introduced another alternative, the so-called "washing-bag", in which a mixture of dicarboxylic acids (succinic- , glutaric- and adipic acid) is used as phosphate-substitute.
The sugar acids and their complexes with boric acid not only are an alternative for sodium tripolyphosphate, but also are potential alternatives for other sequestrants for other applications, e.g. bottle washing, cleaning of metal-surfaces, tanning in the leather industry, and as carrier of certain metal ions in pharmaceutical applications.
The other oxidation reaction described in this work is that leading to 2-keto-D-gluconic acid. This product is an important intermediate. It can be converted into its ascorbic acid analog D-a~aboascorbic acid (!so-vitamin C) (28) :
TOOH
c
=
0HO-~-H
I H-C-OH I H-C-OH I CH20H2-keto-D-gluconic acid D-araboascorbic acid
(!so-vitamin C)
This iso-vitamin C has only a very low anti-scorbutic activity, but it is potentially a very good anti-oxydant in e.g. food.
The a-keto carboxylic acid can also be transformed into a dicarboxylic acid. Thus 2-keto-D-gluconic acid reacts with cyanide and hydrolysis of the product gives a 2-carboxy-D-gluconic acid. 2-keto-D-gluconic acid
f
OOH HO-C-COOH I HO-C-H I H-C-OH H-t-OH I CH 20H +f
OOH HOOC-C-OH I HO-C-H H-h-oH I H-C-OH I CH20H 2-carboxy-D-gluconic acidThese two 2-carboxy-D-gluconic acids are poly-hydroxy-di-car-boxylic acids. Based on table 1.3. it can be expected that, eventually in combination with boric acid, the product is a
good sequestrant too. The addition product is subject of extensive industrial research.
1.4. Aspects of phosphate reduction
Phosphates can cause serious environmental pollution by cutrofication of the surface-water. In The Netherlands the situation around the phosphate-load of the surface-water is rather complex (20). Only 52% of it results from activities in The Netherlands. The rest comes into our country via the big main rivers, especially the Rhine. From the internal phosphate load 70% is from domestic origin. Half of it comes from feaces and urine and the other half from synthetic de-tergents. The latter quantity amounts to about 10 000 ton of phosphate per year.
To reduce the phosphate content of the surface-water there are three possibilities:
- replacement of the phosphates in the synthetic detergents by other sequestrants
- obviation of the need for sequestrants by central water-softening
- or dephosphatation of the waste water
In the Netherlands at the moment the best solution for this problem is still under discussion. From the above mentioned percentages it is clear that the reduction of the phosphate load, due to the complete replacement of phosphate in the detergents in The Netherlands will only be about 18% of the total load. However, if the surrounding countries would take the same measure, the reduction would be about 35%. From these figures it is clear that replacement of the phosphates in the detergents will alleviate the phosphate problem considerably. It will be just a matter of price and policy which solution or combination of solutions will be chosen. The phosphate
substi-tutes have in their favour the intention of the Dutch government to completely eliminate the phosphates in the detergents by 1987.
Any possible substitute of the polyphosphates must not only have good sequestering properties, but must also be able to compete pricewise. Therefore a process to manufacture such a substitute must be as simple as possible.
1.5. Choice of oxidation system
We have investigated only catalytic oxidations of mono-saccharides, because the non-catalytic oxidations by chemical oxidants are in general much slower, more costly, and less selective than the catalytic oxidations. In section 1.1. we already discussed the choice between an inorganic catalytic and a biocatalytic process. We will now examine the economic aspects of the inorganic catalytic processes in some detail,
First we have to consider the choice of the oxidizing agent. In chapter 2 we will discuss some of the possibilities, and show that there is no oxidizing agent that posseses a higher selectivity than low pressure oxygen in combination with a noble metal catalyst. Consequently the process can use air, the cheapest oxidizing agent available.
The price of the catalyst is in general not so important, at least when the catalyst losses are low and the catalyst does not deactivate or can easily be recovered and regenerated.
As already mentioned in section 1.3. it is for certain applications not necessary to purify the oxidation mixture (27). When a complexing agent has to be produced, the reaction mix-ture needs only little purification, because almost all of the by-products act as a sequestrant too, although their sequestering capacity i~ lower than that of the desired product. This is one of the main reasons for us to investigate methods to im-prove the selectivity for the component with the highest
sequestering-capacity. A higher selectivity of course also facilitates, in general, an eventual purification, thus making the process cheaper.
The only by-product from our oxidation-mixtures that has to be removed, if the mixture is to serve as a sequestrant, is oxalate. This is easily removed by precipitation as calcium oxalate convertable with sulphuric acid to oxalic acid. For this oxalic acid, currently mostly imported from abroad, there exists a good market in our country. The only product that may have a negative value is calcium sulphate.
The utilization of 2-keto-D-gluconic acid as a source of iso-vitamin C, applicable as a food anti-oxidant will necessi-tate extensive purification either of the keto acid or the iso-vitamin
c.
1.6. Aim and outiine of this thesis
Biocatalytic oxidation of monosaccharides have found extensive applications in the carbohydrate industry, while the
(anorganic) catalytic oxidations have found as yet hardly any application, although recently there is improvement in this respect (11). The main reason why the catalytic processes, with their potential advantages, lag behind the enzymatic processes, is the lower selectivity of the former processes. For this reason we have investigated potential possibilities to improve the selectivity of some of the catalytic oxidation processes. Hardly any data are available in this respect. We have chosen the oxidation of D-glucose, because it is very readily available and because of its potential applicability of its oxidation products. From the literature it is known that the first step in the oxidation-process (D-glucose + D-gluconic acid) can be
carried out with a high selectivity ( > 95%) both catalytically (29) and with the aid of enzymes (9,10).
the oxidation of D-gluconic acid to D-glucaric acid or 2-keto-D-gluconic acid in aqueous solution with Pt/C and modified Pt/C catalysts. Dirkx (29) also studied the
kinetics of the oxidation of D-gluconic acid to D-glucaric acid, and the present thesis is in certain respect a continuation of that work.
In chapter 2 a survey of the literature data on the pre-paration of D-glucaric acid and 2-keto-D-gluconic acid is given.
The analysis of the various reaction mixtures is described in chapter 3. For this purpose mainly ion-exchange chromato-graphy is used. At times isotachophoresis, 13c-nuclear magnetic resonance and a specific detection method for a-keto-carboxylic acids are used to help the identification and quantification of the various components of the reaction mixtures. For identifica-tion purposes we have also made use of preparative liquid chro-matography for the isolation of certain components out of the product mixtures.
In chapter 4 a description of the stirred tank reactor, the preparation of a number of catalysts, and the basic experi-mental procedure is given.
Some explorative experiments to improve the selectivity for D-glucaric acid are discussed in chapter 5. During one of these experiments we discovered the selective catalytic produc-tion of 2-keto-D-gluconic acid with a lead modified Pt/C
catalyst. As this compound is of potential industrial interest, we decided to study its manufacture more closely.
In chapter 6 we describe investigations into the potentials of this oxidation reaction, e.g. with respect of the catalyst preparation and also in respect to various monosaccharides as substrate.
In chapter 7 we dis.cuss the experiments to improve the selectivity of the reaction described in chapter 6 and experi-ments that are the basis of a reaction model.
Finally in chapter 8 an attempt will be made to give a consistent description of the factors that determine the
charac-teristics of the Pb/Pt/C catalyst. The description will be based on the results presented in chapter 6 and 7 and a literature studie on the complexation of D-gluconic acid with Pb2+.
References
1. Rapport van de Club van Rome, Het Spectrum, Utrecht, Au1a Pocket 500 (1972)
2. van Ling, G., Polytechnisch Tijdschrift, 386 (1970) 3. Dewar, E.T., Manuf. Chemist., 29, 458 (1958)
4. Machell, G., Manuf. Chemist.,
l!r
520 (1960)5. Korf, D., Ph.D. thesis, University of Technology, Delft, The Netherlands (1963)
6. Van Velthuijzen, J.A., Seminar on Sucrochem. (1973) 7. Van der Baan, H.S., Kuster, B.F.M~, Innovation study,
University of Technology, Eindhoven, The Netherlands (1982) 8. Reichstein, T.H., Griissner, A., Oppenauer, R., Helv. Chim.
Acta,~, 561/1019 (1933)
9. Hartmeier,
w.,
Tegge, G., Starch,l!•
348 (1979) 10. Richter, G., Heinecker, H., Starch,;!_!, 418 (1979) 11. Kuster, B.F.M., private communication12. Mehltretter, C.L., Alexander, B.H., Rist, C.E., Ind. Eng. Chem., !2_, 2782 ( 1953)
13. Yufera, E.P., Easas, C.A., Carrasco, A.A., Rev. Agroquim. Technol. Alimentos,
!•
40 (1961) i C.A. 57, 16384g (1963) 14. Mustakas, G.C., Slatter, R.L., Zipf, R.L., Ind. Eng. Chem.,46, 427 (1954)
15. Peters, H., Dutch Patent, 99,202 (1961) 16. Heesen, J., Dutch Patent, 7,215,180 (1972)
17. Van der Steen, H.C., Internal report, University of Techno-logy, Eindhoven, The Netherlands (1974)
18. Chemisch Weekblad, 72 (24) , 1 ( 1976) 19. 20. 21. 22. 23. 24. 25. Chemisch Weekblad, 73 (30/31), 1 Van Reede, D.' Chemisch Weekblad, ibid., 77, 353 ( 1 981) ibid.' 78, 139 ( 1 982) ibid., 78, 214 (1982) ibid. I 78, 330 ( 1982) ibid., 79, 225 ( 1983) ( 1977) 77, 336 ( 1 981 )
26. ibid,
22..1
379 (1982)27. "Glucombinaat", Internal report, University of Technology, Eindhoven, The Netherlands (1982)
28. Maurer, K., Schiedt, B., Ber., 66, 1054 (1933)
29. Dirkx, J.M.H., Ph. D. thesis, University of Technology, Eindhoven, The Netherlands (1977)
30. Tramper, J., Luyben, K.C.A.M., Van den Tweel, W.J.J., Eur. J. Appl. Microbiol. Biotechnol., ..121 13 (1983).
Chapter 2
Literature Survey
2.1. Introduation
In this chapter we present a survey of the literature concerning the oxidation of D-glucose to D-gluconic acid and of D-gluconic acid to D-glucaric acid or 2-keto-D-gluconic acid. Furthermore we will pay attention to some other routes for the production of 2-keto-D-gluconic acid. Because of the commercial importance of L-ascorbic acid (vitamin C) we also present literature data on the production of 2-keto-L-gulonic acid, a precursor of vitamin
c.
In this literature survey we mainly review those methods of preparation that are of potential industrial interest. As we have already pointed out in chapter 1, processes will be only of interest if they are not too costly. In our survey, therefore, we pay special attention to the use of air and gaseous oxygen as oxidizing agents and to the selectivity of the various processes.
The oxidation reactions can in general be grouped in three main processes: homogeneous oxidation, heterogeneous catalytic oxidation, and biochemical oxidation. Each of which we discuss shortly below.
Homogeneous oxidation
In the group of homogeneous oxidation we have· gathered the non-catalytic oxidation with oxidizing agents other than oxygen and the electrochemical oxidations.
For the oxidation of a hemiacetal or an aldehyde to an acid or a lactone we have, besides oxygen, in general the following oxidizing agents to our disposal:
- halogens - nitric acid - Ag!
- CuII - Fe!II
For the homogeneous oxidation of a primary hydroxyl to a carboxyl, nitric acid or NOx is often used (119,120). In this reaction the corresponding aldehyde is formed as an intermediate. In general this type of oxidation is not so very selective be-cause of concurring side- and consecutive reactions. E.g., with D-gluconic acid the oxidation of the hydroxyls on
c
2 andc
5 to keto groups, followed by cleavage of the carbon chain causes serious reduction of the selectivity towards L-guluronic acid.The selective oxidation of one of the.secondary hydroxyl-groups of a hexose to a carboxyl group is rather difficult. The aldehyde (or hemiacetal) function is almost always oxydized first, the primary hydroxyl groups thereafter. To avoid this, these groups have to be protected first e.g. by the formation of glycosides or acetals. This also goes for those secundary hydroxyls which we don't want to be oxidized.
Oxidizing agents other than oxygen have the disadvantage that they are relatively expensive and their products have to be removed from the reaction mixture.
Heterogeneous catalytic oxidation
This group of reactions mainly consists of the noble-metal catalized oxidations with oxygen. This procedure offers, to-gether with the biochemical oxidation, the best possibilities for application on a commercial scale. The selective oxidation of D-glucose to D-gluconic acid can be carried out with
palladium on a carrier in an aqueous solution. For the manu-facture of D-glucaric acid platinum on a carrier is to be prefered. The oxidation of the a-hydroxyl of D-gluconic acid can only be carried out selectively, with platinum on a carrier, if the other hydroxyls are protected.
Biochemical oxidation
Aerobic microorganisms usually oxidize their organic substrates completely to carbon dioxide and water. During this degradative process, energy and intermediary metabolites re-quired for biosynthesis are generated. Under special circum-stances, however, such as (i) an excess of carbon substrate in the growth medium, (ii) inhibition of certain metabolic path-ways by the presence of inhibitory compounds and (iii} abnormal physiological conditions (e.g. extremes of pH or temperature), oxidation of the substrate may be incomplete, leading to the accumulation of intermediate metabolite in the medium. This type of incomplete oxidation is not genotypically determined, but simply reflects a changed phenotypic expression of the organism, induced by environmental conditions.
Microorganisms have been described, which possess only a very limited capacity to oxidize certain substrates, more or less independent of culture conditions. In many cases, these organisms are not even able to assimilate carbon from the sub-strates that they convert, and are able to grow only at the expense of other organic nutrients present in the medium.
carried out by enzymes, that may be present constitutively or induced by the substrate. On the other hand they may be effected by other "essential" enzymes of intermediary meta-bolism acting non-specifically. A survey of the enormous diversity in oxidative microbial transformations has been published by Kieslich (1) in 1976.
An important group of aerobic bacteria, which are parti-cularly characterized by their ability to oxidize organic substrates incompletely, are the acetic acid bacteria. These organisms have been used since ancient times f.or the manu-facture of vinegar. In this connection especially members of the genus Gluconobacter are known for their relatively rapid and imcomplete oxidation of a wide range of organic compounds and the near quantitative excretion of the oxidation products into the reaction medium. Today, commercial biochemical
processes, such as the production of L-sorbose from D-glucitol and D-gluconic acid from D-glucose, are carried out with mem-bers of this genus.
Besides bacteria, fungi are used for the selective oxidation of monosaccharides. For the manufacture of D-gluconic acid from D-glucose fungi of the genera Aspergillus and Penicillium are used.
In general, biochemical oxidations take place in a narrow pH-range at about 30°C in aerated substrate solutions containing mycelia together with a number of nutrient salts. The process requires relatively long reaction times and is sensitive to contamination. The isolation of the products is generally rather complicated and expensive. This is the main reason why at present much research is devoted to the immobilization of the active enzyme species of the fungi and bacteria.
2.2. Oxidation of D-gZucose to D-gZuconic acid
The oxidation of aldoses to the corresponding aldonic acids has been the subject of numerous publications (2-5), some of which are related to preparative methods on a labo-ratory scale only.
2.2.1. Homogeneous oxidation
Considerable attention has been given to studying the mechanism and kinetics of the oxidation by means of halogen compounds. In acid solution the free halogen or hypohalous acid is the active oxidant, whereas in alkaline media the hypohalous anion plays the major role (6). The most widely used homogeneous method is oxidation with bromine in aqueous solution having been first used by Hlasiwetz in 1861 (7). The hydrobromic acid formed as a by-product lowers the rate of oxidation. To minimize this effect buffered solutions (pH 5-6), are used, or barium carbonate or barium benzoate is added to the system (8). According to Isbell and Pigman (9), the primary oxidation product from the reaction of D-glucose with bromine in the presence of barium carbonate is D-glucono-o-lactone. Grover and Mehrotra (10,11) found that the oxidation of D-glucose to D-gluconic acid by means of bromine in a strongly alkaline solution can be described as a bimolecular second order reaction between the monosaccharide and the hypobromite ion. From the influence of the pH on the reaction rate, it is concluded that the hypobromite ion is the actual oxidizing agent. Analogous conclusi9ns have been reported by Ingles and Israel (12,13) for hypoiodite oxidations. More recently, Perlmutter-Hayman and Persky (14) concluded from the dependence of the reaction rate on the molecular bromine
The dependence of the reaction rate on pH can be explained by the assumption that the anionic form of glucose is more reactive than the glucose molecule.
Extensive kinetic studies on the oxidation of D-glucose in acidic chlorine solutions has been reported by Lichtin and Saxe (15), Grillo (16), and Urquiza (17).
Processes have been patented in which glucose is oxidized by bromine-bromate (181 and by bromic acid together with sodium chlorate (19). Biniecki and Moll (20) reported the oxidation by potassium chlorate.
The main drawback of the above processes is the difficulty of separating the gluconate from the large amounts of salts and the regeneration of the letter. This disadvantage is partly overcome by indirect electrolytic oxidation in which bromine or iodine is formed electrolytically from a small quantity of the hydrohalic acid (20-28). Recently yields of 77% (29) and 70% (30) have been reported. 'l'he direct electrooxidation of D-glucose to D-gluconic acid on Pt electrodes has been studied by Rao and Drake (31) in neutral solution.
Besides the oxidation with halogens, other homogeneou~
methods have been described (2). As they are of no great industrial importance, they will not be discussed here.
2.2.2. Biochemicai oxidation
This is nowadays one of the most widely applied industrial procedures for manufacturing D-gluconic acid. This acid, the simplest oxidation product of glucose, is produced by many microorganisms, particularly by bacteria of the Acetobacter and Pseudomonas genera and by molds of the Penicillium and Aspergillus genera. Previous publications (32,33) have re-viewed some of these oxidations, which will not be discussed in detail here.
As early as 1880, Boutroux (34) described a biochemical process for the selective oxidation of D-glucose to D-gluconic
acid. The first technical processes were based on surface techniques with fungi (35). A number of methods based on this principle were patented about 1930 (36-40), and subsequently other batch-wise liquid-phase processes have been developed, that use rotary fermentors (41-45). Aspergillus niger is often used as the biologically active material. Other processes make use of a vertical fermentor for which the active mycelium is cultivated separately in a prefermentor (46). Concentrated D-glucose solutions can be converted if borax is added to the reactor to prevent early precipitation of calcium gluconate
(47). A semicontinuous process has been developed in which the mycelium is separately used (48): after the conversion of one batch, the mycelium can be separated from the solution by flotation, so that about 80% of the liquid can be removed without appreciable loss of active material.
Another method is separation of the mycelium by filtration or centrifugation, after which it can be added to a fresh
glucose solution (49). In 1959 a continuous process was pa~
tented to produce D-gluconic acid monohydrate (50). In this field much attention has been devoted to the study of various types of enzyme-producing bacteria, the isolation of the
enzymes and the mechanism and kinetics of the reaction (51-67). The following reaction-scheme is a combination of the work of Gibson et al.(68) and Tsukamoto et al. (69).
1. E0x + D-glucose + Ered glucono-6-lactone + Ered + glucono-6-lactone
3. glucono-6-lactone +
u
2
o
+ gluconic acidThe enzyme in step 1 and 2 is glucose oxidase. This enzyme catalyzes a dehydrogenation of the glucose through the
formation of an enzyme-substrate complex which splits into glucono-o-lactone and a reduced form of the enzyme. The latter is oxidized again by dissolved oxygen and hydrogen peroxide is formed. This peroxide is decomposed by the second vital enzyme catalase. Glucono-o-lactone can hydrolyze to gluconic acid
either spontaneously or catalyzed by the enzyme gluconolactonase. The rate-determining step in the overall reaction is dependent on several factors and can be e.g. the formation of the complex or the hydrolysis of the lactone.
In enzyme catalysis where the reaction is run in a homo-geneous batch reactor, it is necessary to separate enzymes from the reaction mixture at the end of the reaction, for example, by ultrafiltration, affinity chromatography, etc. In order to avoid these tedious recovery processes, increasing attention has been given in recent years to the preparation, utilization, and stability of immobilized enzymes (70-87). There are still problems with the stability of the immobilized enzymes.
n
2o
2 causes severe deactivation, and the intraparticle mass transfer of oxygen can easily be rate-limiting, making the immobilized enzymes less effective than the homogeneous enzymes. In general the selectivity is very high (90-100%), but the reaction-rate is rather low. Reactions still require at least several hours.Another recent development in the field of biochemical oxidation is the combined hydrolysis and oxidation of e.g. sucrose (88), maltose (89), starch hydrolysate (90), molases
(90,91), and starch (92) for the manufacture of D-gluconic acid.
2.2.J. Heterogeneous catalytic oxidation
As early as 1861, von Gorup-Besanez (93) oxidized mannitol in an aqueous alkaline solution in the presence of platinum black to yield mannonic acid. In 1953 Heyns and co-workers initiated an very extensive research program on the selective oxidation of carbohydrates with oxygen by means of noble-metal catalysis in alkaline solution. This work is
( 100) Acres et al. 45 1%Pd/o.-Al2o3 1000 92 a)
( 101) Asahi Chem. Ind. 70 Pt/C 57 2 49 b)
{ H.'2) Buckley et al. 25-55 e-11 2%Pd/C 45 1000-2500 7-10 80-90 (103) Dirkx 45-65 9-10.3 5%Pt/C 500-1000 60-90 es a) ( 104) Hattori et al. 45-55 9.3-9.7 5%Pt/C 1.5 650 99.2 1. 7 94
(105) Heyns et al. 22 B-9 5%Pt/C 20 100 5-10 70 (99) Johnson Matthey 40-60 7-14 1%Pd/Al
2o3 50-2000 90-100 90 al
(106) Kao Soap lo. 5%Pd/C 94
(107) !<awaken F.C. Pd:Pt=J,5:1,5 6 800 14 93 ( 108) 'Kimura et al 40 9-10 2%Pd/C 1600 2 96 ( 109) Kiyoura et al. 70 7,0-7,5 Pd/C 1. 5 94 { 110) Nakagawa et al. 35 10 2%Pd/C 2500 10,5 88 c) ( 111) Nakayama et al. 50 l?d/C 1. 7 95 d) (112 I Nishikido et al. 50 5%Pd/C 15 95 61 2 56 b) ( 113) Nishikido et al. 70 21%Pb0/5%Pd/C 40 200 98 83 bl
( 114) Okada et al. 40 7-14 0,5%Pd/BaS04 3-7 50-300 30 0,1-0,3 el (97) Poethke 20 e Pd/MgO:Pd/BaS0
4 2500
( 115) Saito et al. 75-85 ~7 ~,5%Pd+1,5%Pt)/C 94 15 85 (116) De Wilt et al. 25-65 8-12 10%Pt/C 0-1,6 50-250 100 1-2 90
(117) De Wit et al. 25 13-14 5%Pt/C 10 70 97 0,67 96 fl
al Continuous tricklebed reactor bl Non-aqueous solvent c)1,3% o3 in air as oxidizing-agent d) Reactor with circulating pipe el Stirred tank reactor + continuous multistage contactor
fl oxygen free + hydrogen. production
sununarized in three comprehensive reviews (94-96). They have given selectivity-rules, which we will discuss in detail in chapter 5. A catalyst prepared by reduction of chloroplatinic acid with formaldehyde is reconunended as the most effective for oxidizing glucose. The produced acids impede the reaction, because the oxidation proceeds fastest at a pH of about 9. To avoid this, pH-control by buffers, or (stepwise) addition of hydroxide are applied.
In general, the selectivity of the platinum catalyzed oxidation is lower than of the enzymatic processes. According to Poethke (97), the selectivity can be affected by a consecutive oxidative degradation of the produced Dgluconic acid -probably by a Ruff mechanism. Furthermore, above pH 12 the oxidative degradation of D-glucose becomes more important as a non-platinum catalyzed side reaction. D-glucaric acid has been reported as an important consecutive reaction product depending on the catalyst quality (98,99). For the selective production of D-gluconic acid, this consecutive reaction has to be supres-sed, e.g. by using palladium instead of platinum. A schematic survey of the literature concerning the heterogeneous catalytic oxidation of D-glucose to D-gluconic acid is given in Tabel 2.1.
The selective manufacture of D-glucono-o-lactone requires oxidation in non-aqueous media (101,112,113). In aqueous media the lactone would hydrolize spontaneously.
Table 2.1. shows that the oxidation of D-glucose to D-gluconic acid with oxygen can be carried out selectively and fast by means of a Pd/C catalyst. The highest selectivities reported approach the biochemical ones. This is substantiated by the recent start in Japan of the industrial production of D-gluconic acid by means of a palladium catalyst (118).
2.3. Oxidation of D-gluaose or D-gluaonia aaid to D-gluaaria aaid
For the manufacture of D-glucaric acid, only two methods are known, viz. the homogeneous oxidation with nitric acid, and the heterogeneous catalytic oxidation with noble-metal catalysts. As far as we are aware, no selective biochemical method for the preparation of D-glucaric acid exists yet.
2.3.1. Homogeneous oxidation
D-glucose can be oxidized to D-glucaric acid with nitric acid (119,120). Mustakas et al. (121) studied this process on a pilot plant scale and obtained a yield of 44% (as K-H-gluca-rate). According to Truchan (122), pretreatment of the glucose with ammonia, followed by the oxidation with nitric acid, would give a yield of 65%.
Another possible route for the manufacture of D-glucaric acid is the oxidation of starch to polyglucuronic acid by N0
2 (123-125). Although glucuronic acid can be oxidized very selec-tive to D-glucaric acid, yields are low, due to the extensive degradation during the hydrolysis of the polymer.
2.3.2. Heterogeneous aatalytia oxidation
Platinum and palladium are used as catalyst for the oxidation of aqueous solutions of carbohydrates with oxygen. The use of a palladium catalyst for the further oxidation of D-gluconic acid in alkaline solution leads to many degradation products, including D-arabinonic acid, D-erythronic acid, and no D-glucaric acid is obtained at all (97).
Among others, de Wilt (116) has studied the oxidation of D-glucose to D-gluconic acid with Pt/C as catalyst. The maximum selectivity for D-gluconic acid was about 95%, which was
At a somewhat higher pH (pH 9-10) and/or temperature (55°C), attack on the primary hydroxyl group at C-6 of D-gluconic acid results; thus, a 55% yield of D-glucaric acid is obtained from D-glucose (98,103,126).
2.4. Manufaature of 2-keto-D-gluaonia aaid
From the literature various methods for the manufacture of 2-keto-D-gluconic acid are known (127). Those with D-glucose or D-gluconic acid as substrate will be discussed in section 2.4.1. Some alternative methods, starting from other mono-saccaride-derivatives, will briefly be discussed in section 2.4.2.
2.4.1. Oxidation of D-gluaoae or D-gluaonia aaid
Oxidizing-agents other than oxygen
Since the molecule of D-gluconic acid contains many reactive groups, it is obvious that chemical oxydizing agents must be highly selective in their action if they are to de-hydrogenate only the second carbon atom. D-gluconic acid or its lactones can be oxidized with chlorates in the presence of vanadium pentoxide and phosphoric acid (128-132) to produce 2-keto-D-gluconic acid. When the oxidation is carried out in a mildly acidic aqueous medium (pH between 3 and 4) after 40 hours a yield of 50% is obtained (130). Improvement of the yield and a simpler recovery of the product is possible by the addition of a water miscible organic solvent which is
sub-•
stantially inert to the oxidizing action of the chlorates in the presence of the vanadium catalyst. Thus, ammonium-D-gluconate is converted in an aqueous methanol (50%) medium in 24 hours to the methyl ester of 2-keto-D-gluconic acid with a yield of 72% (131).
The same authors also patented the specific oxidation with chromic acid (133). The oxidation is catalyzed by the addition of small amounts of substances such as nickel, cerium, iron, platinum and their salts. According to this patent, the oxida-tion of D-gluconic acid with chromic acid in the presence of feric sulphate at 0°C, yields 40% of 2-keto-D-gluconic acid after 12 hours.
The electrochemical oxidation of D-glucose to D-gluconic acid with bromide solution as the electrolyte, have been dis-cussed in section 2.2. There was no evidence that the 2-keto acid was formed as a byproduct. However, Pasternack and Regna
(134) have found that an electrolytic process involving the combined action of a halide, other than an iodide, and soluble chromium compounds will convert the aldonic acid to the corres-ponding 2-keto-acid. The relatively small amount of chromium required in this process compared to the above mentioned chromic acid oxidation is of great advantage, because of the easier purification of the product and the lower costs of the oxydizing agent. Thus, the electrochemical oxidation of calcium-D-gluco-nate with calcium bromide and chromium trioxide at 20°C gave a yield of 80% of calcium-2-keto-D-gluconate after about 6 hours.
Oxygen as oxidizing-agent
In their comprehensive review of the heterogeneous cata-lytic oxidation of carbohydrates with oxygen at a platinum catalyst, Heyns et al. (96) conclude that for the oxidation of the secondary hydroxyl groups of open-chain polyhydroxy mono-saccharide-deri vates, almost no selectivity is to be expected. This is in agreement with our observations. D-gluconic acid must suitably be protected to direct the platinum catalyzed oxidation to 2-keto-D-gluconic acid. Some examples of the oxidation of protected monosaccaride-derivatives will be given in section 2.4.2. In thi~ thesis, however, we will describe a catalytical method with which it is possible to oxidize D-gluconic acid
temp % hrs % •c
(135) Agapova et al. Pseudomonas
( 136) Banik et al. Bacillus firmus
B. circulans
B. subtilis
(137) Bernhauer et al. Bacterium gluconicum 80 (138) Bernhauer et al. A. suboxydans
( 139) Blais ten Ps. fluorescens a)
Ps. fragi a)
Ps. reptilivora a)
( 14 0) Bull et al. Serratia marcescens NRRL B-486 a) ( 141) F!!rber 27 Cyanococcus chromospirans 20 .. 100
( 14 2) F!!rber et al. Ps. chromospirans
Ps. aeruginosa
( 143) F'ewster A. suboxydans
( 14 4) Ikeda Ps. fluorescens a)
Serratia marcescens
(145) Knobloch et al. A. orleanense 720 56
A. ascendens 720 39
(146) Kozhobekova et al. 5 100 12
(147) Kulhanek Ps. aeruginosa 74 b)
(148) Lockwood et al. 30 Ps. aeruginosa 192 70 a) ,c)
Ps. fluorescens 82 948 88 949 84 142 75 frag11 4973 86 graveolens 4683 77 4684 82
30 Ps. mil de nberg i1 795 192 100 al ,cl oval1s 950 55 pavonacea 951 77 putida 4359 85 schuylk1111ensis 82 vendrelli 7700 81
( 149) Misenheimer 30 Serratia marcescens NRRL B-486 16-32 100 al (1501 Neijssel et al. Klebsiella aerogenes NCTC-418 al (151) Norris et al. Ps. aerug1nosa
(152) Pfeifer et al. Ps. fluorescens al
Ps. fragi a)
Ps, reptilivora a)
(153) Stoutharner A. suboxydans
(154) Stubbs et al. 25 Bacterium gluconicurn 25 82 al
(155) Vondrova-Hovezova et al. Ps. chrornospirans
(1561 Yamazaki 5 Ps. fluorescens 168 40 d)
(1571 l:'okosawa Ps. fluorescens a)
a) glucose oxidation instead of gluconic acid oxidation c) the numbers in the column yield are selectivities b) 10 strains of Ps aeruginosa are examined d) simultaneous oxidation of D-gluconate and L-idonate
A,~ Acetobacter B.= Bacillus Ps. Pseudomonas
table 2.2. Literature concerning the biochemical oxidation of D-gZucose or D-gZuconic acid acid to 2-keto-D-gluconic
w
to 2-keto-D-gluconic acid selectively, obviating the use of protective groups.
Biochemical oxidation
Special bacteria are cultivated for the fermentative oxidation of D-glucose or D-gluconic acid to 2-keto-D-gluconic acid. A schematic survey of the literature concerning this oxidation is given in table 2.2. In this table we again encounter the characteristics of a biochemical process: the yields are generally high, but the processes are slow. In section 1.1. we already discussed this matter.
2.4.2. Aiternative oxidation methoda
Besides the oxidation of D-glucose or D-gluconic acid, there are some alternative methods for the manufacture of 2-keto-D-gluconic acid:
- Oxidation of D-glucosone (D-arabino-hexos-2-ulose) with bromine in water under the influence of light (158,159). After 3-4 days at room temperature the yield is 68%. - Direct oxidation of D-fructose, with oxygen in an aqueous
alkaline medium. Heyns (160) describes this reaction u~ing
platinum as catalyst.(The analogous oxidation of L-sorbose to 2-keto-L-gulonic acid has been the subject of more
investigations, as this product is a precursor of vitamin C). - Oxidation of a D-fructose derivative substituted in such a
way that only the neighbouring
ce
2
oe
group remains free. Thus, 2,3-4,5-di-0-isopropylidene-D-fructopyranose(S - diacetone-D-fructose) is oxidized with potassium permanganate to the diacetone derivate of 2-keto-D-gluconic acid (161-163). The same oxidation can also be carried out with air in aqueous alcohol with Pt/C as catalyst with a yield of more than 90% in 2-5 hours (164).
2.5. Oxidation of L-gulonia acid to 2-keto-L-gulonic acid
The lead/platinum/carbon catalyst is also active in the oxidation of L-gulonic acid to 2-keto-L-gulonic acid. The latter product is a direct precursor of vitamin C, and for this
reason this oxidation step can be of great industrial impor-tance. We want to find out whether our oxidation method can compete with others. For comparison we will review the litera-ture concerning the oxidation of L-gulonic acid to 2-keto-L-gulonic acid shortly:
- Oxidation with chl?rate in the presence of vanadium pentoxide and phosphoric acid. After 20 hours the yield is 68% if the reaction is carried out in an aqueous solution (130).
- Oxidation with chromic acid. The yield for
2-keto-L-gulonic acid is 41% and the selectivity is about 70% after 24 hours of reaction (133).
- Electrochemical oxidation with a combination of mainly bromide and a little chromium trioxide. No yield is stated (134).
- Biochemical oxidation. Aerobic fermentation with Pseudo-monas aeruginosa leads to a conversion of 44% after 8 days (165) and with Xantomonas translucens a yield of minimal 85% is achieved after more than 72 hours at
28-30°C (166).
2.6. Disaussion
In section 1.6 we have given our motivation for investiga-ting possibilities to improve the selectivity of the catalytic oxidation of D-glucose to the commercially attractive products
D-glu~onic acid, D-glucaric acid and 2-keto-D-gluconic acid. From the literature survey in this chapter it is clear that the oxidation of D-glucose to D-gluconic acid can be carried out with a high selectivity (~95%) either with the aid of enzymes or with noble metal catalysts. Such a selectivity is not ob-tained for the oxidation of D-gluconic acid to D-glucaric acid or to 2-keto-D-gluconic acid, with two exceptions: The micro-bial manufacture of 2-keto-D-gluconic acid and the electrochemi-cal oxidation of electrochemi-calcium-D-gluconate to electrochemi- calcium-2-keto-D-gluco-nate. We have already discussed the disadvantages of the bio-chemical process in section 1.1. The latter process is slow and makes use of relatively expensive oxidants. Therefore we
have directed our efforts towards improving the selectivity of the catalytic oxidation of D-gluconic acid to either D-glucaric acid or to 2-keto-D-gluconic acid with air as oxidizing agent.
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