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New Technology for Invert Sugar and High Fructose Syrups from Sugarcane

New Technology for Invert Sugar and High Fructose Syrups from Sugarcane

Indian Journal of Chemical Technology Vol. 8, January 200 I, pp. 28-32

New technology for invert and high from

J K Gehl awat Raha Gchlawat Sugar Academy, 248, R K Vihar, I P Extension, Delhi 110092, In dia Receil·ed 28 e 1998; accepred 13 No1'e111ber 2000

The in vert sugar is an cquimolar mixture of and fructose. It may be obtained on hydrolys is of under milder conditi ons using st rong cationi c res in s. The fru ctose contelll may be incre::tsed to about 60 per cent level by a partial removal of glu cose from invert sugar using th e tec hnique of column chromatography. The re sultant is called hi gh fructose syrups (HFS) whi ch is traditi onal ly produced from . HFS may be produced from sucrose wi th econom ic adva ntage by thi s novel process. The production of invert sugar and hi gh fructose sy rups from suc rose ( ) is cost effec ti ve. It has been co mmercialized in In dia . This paper discusses the sa li ent features of thi s novel technology, which results in an effective 25 per cent increase in the sweetener output from the same quantity of sugarcane as as a waste product is avoided.

In vert Sugar of high purity (+98 DE) starch hydrolysates usi ng In vert sugar finds applications for biscuits, immobilized glucose as th e catalyst. The , beverages, bakery , several other equ ilibrium mixture thu s obtained contain s about 42 and pharmaceutical formu lations. Traditionally, invert per cent fructose and 58 per cent glucose. sugar is produced from sucrose using minerals Commercially acceptable syrups must possess like H2S0 4 and HCI. This conventional method minimum 55 per cent fr uctose content. This is suffers from low conversion efficiency (65-70 per ach ieved by enrichment of fructose content in th e cent), hi gh ash content and undesirable products (7-8 mixture through column chromatography. Geh lawat per cent). Moreover, the invert thu s obtained is has been a strong supporter of production of HFS on dark in colour. In view of these drawbacks of the large scale in Indi a to supplement the supply of cane 8 10 traditional process, attempts have been made to sugar • • The production of hi gh fructose syrups from develop alternate methods to produce invert su gar sucrose through its cationic inversion has been 11 und er relatively milder process conditions. Enzymatic suggested • of sucrose with in ve rtase has been Cane juice is the principal source of sucrose. The 1 3 recommended in the literature • • Recentl y, the use of raw cane juice may be clarified by membrane an immobilized as a catalyst in a fixed-bed techniques like to el iminate organic reactor is claimed to produce invert sugar sy rups of impurities and by electrodialysis to remove inorgani c . I . ? 4 12 16 I11 g 1 punty-· . • • The sucrose soluti on (c larifi ed cane juice) thu s obtained may be inverted in a fix ed bed reactor Inversion of sucrose may be carried out using of strong cation res ins as di sc ussed by Seema and ca tioni c res in s. Strong cationic resin s behave as 17 18 Geblawat and Sinha and Gehlawat . Nea rly equ al catalysts in liquid media. They possess catalytic amou nts of glucose and fr uctose are formed with properties comparable to strong acids. Thus, by cation resins in H+ form. Interestingly, theCa++ form choosi ng a cation resin of· proper acidity and porosity, of the same res in is found to separate glucose from any degree of sucrose inversion could be achieved 9 fructose in column chromatography' . without the introd ucti on of any into the 5 6 syrup · . The inversion of sucrose usin g strong cation Inversion of sucrose present in refined cane juice is resins is a cheaper process for invert and hi gh the most economical meth od of obtaining eq uimolar 7 fru ctose syrups . mixtures of glucose and fru ctose which on enri chment through the column chromatographic technique High Fructose Syrups produces the cheapest and superior grades of hi gh During the past three decades, high fructose syru ps fructose syrups. Thus, in , HFS from cane juice (HFS ) have emerged as cheaper alternati ve may compete favou:·ab ly with the syrups obtained 17 20 sweeteners. They are manufactured by isomerization from corn in countries like USA ' . Fig. 1 shows two GEHLAWAT: INVERT SUGAR AND HIGH FRUCTOSE SYRUPS FROM SUGARCANE 29

c,z Hn o,, H~ /Invertase .+ + Sucrose INVERSION Glucose Fructose t Invert SugarT J

Adsorp-tion . , Chromatography~

c::Y + (/) ...... 0 c::Y u (/) :J c 0 L.. 0 u c lL ·-...... ~ 0 1J u <-9:;: c::Y a .r:. L.. c::Y u .~ lL '-- a L.. :J L.. c Q_ lL w

Enzymatic ~ High Fructose Isomerization Syrups Jl l.__. For- Sates Glucose ~ t (C6 H1005) n H .fd•[3Amytases rtC6H1206 + Starch HYDROLYSIS Glucose

Fig. !-Chemistry and method of productionof fructose and high fructose syrups alternate schemes for the production of fr uctose and a reasonably fast reaction and complete inversion high fructose syrups. occurs within about 30 min under optimum This paper describes recent developments for the conditions. This technology has been commercialized 22 production of invert sugar and high fructose syrups. with excellent results . The details of the process 20 Table 1 gives data on relati ve of common have been reported elsewhere . Invert sugar is sugars and Table 2 provides typical composition of obtained on hydrolysis of sucrose. The final syrup commercial grades of high fructose syrups. contains about 75-80 per cent dry solids (mixture of glucose and fructose). It has a relative sweetness of New Technology for Invert Sugar 120 as compared to sucrose as 100 (Table I). Fig. 3 India has taken a lead in developing new processes for shows the process flowsheet. Scheme A is for the invert sugar. The National Research and Development production of syrtip from refined cane juice during the Corporation (NRDC) is marketing the season. Scheme - B is with crystal sugar as the raw process developed by Bhabha Atomic Research material that may be used during the off season. Centre (BARC). A few have been set up based 1 on thi s technolog/ • lndian I~stitut e of Technology, Cheaper Syrups from Cane juice Kanpur, has developed a novel process based on resin Traditionally high fructose syrups are produced 7 20 technolog/·' · . Fi g. 2 shows the kinetics of from the hydrolysates of starch. The extracti on of hydrolysis of sucrose usin g strong cati onic resins. lt is starch from corn () is a complex process. 30 INDIAN J. CHEM. TECHNOL., JANUARY 2001

lOQr------, Table I - Relative sweetness of sugars; 15 °C, 15 % solution Sugar Relative sweetness Glucose Fru ctose Cane sugar (sucrose) 100 X Sue rose Fructose (crystalline: 100%) 178 l> Glucoso D-glucosc (crystalline: I 00 %) 70 (I) 0 Fructose Invert sugar ( 100 %) 123 0 E 60 Medium invert (50 %) 110 c HFS (90 wt %) 125-130 0 HFS (55 wt %) 105- 110 Ill HFS (42 wt %) 95- 100 0 Q_ 40 42 DE 45 E 0 u 35 u Res in : RDL-90-7 t5 ::J Flow ra\e.SOml(min Table 2-Typical compositions of commerci al grades of HFS "8 20 pH•S.3 ;Temp = 60'C '- Q_ Suc r ose soln. 300fo(w/v 55 to60 % HFS 90 % HFS

%sol ids 77.00 80.00 0~----~~--~~~~==~--~ % ash (sulphated), DS 0.03 0.03 o.o 30.0 % Fructose, DS 55-60 90.00 Tim<2 (min) % D-glucose, DS 4 1-36 7.00 Fig. 2- ln vc rsion of sucrose in a resin bed % other saccharides. DS 4.00 3.00 Moreover, the subsequent processes such as As regards the economics of invert sugar from enzymati c hydrolysis of starch to glucose and its refined cane juice, it may be mentioned that there is partial isomerization to fructose are far more complex no loss of sucrose, like it takes place to the extent of reactions. On the other hand the extraction of sucrose about 2 per cent in molasses in th e case of crystal either from sugarcane or sugarbeet and its inversion to sugar. Consequently the yield is hi gher by about 2 per obtain equ imolar mixtures of glucose and fructose are cent. Moreover, invert syrup contains about 20 per rel atively simple operations. Fig. 4 shows a schematic cent and possesses higher sweetness. Hence, flow diagram for a commercial process. invert sugar from cane juice is much cheaper than It may be note.d that realizable starch content in crystal sugar. mai ze is about 60 per cent. At its current price of Rs.S,SOO per metric tonne, the material cost of starch Huge Market Potential for In vert Sugar and HFS work s out to about Rs.9,000 per metric tonne. As sweeteners, invert sugar and hi gh fructose Similarly, the practical range of sucrose content in sy rups can replace sucrose 1n almost all its mature cane is 13- 15 per cent. About 2 per cent sucrose appl ications. Functionally, they possess more is lost with during juice extraction. Hence, the desirable properties than sucrose and are much realizable sucrose content in refined juice may be 12 sweeter. In fact, chemically, invert sugar is same as per cent on an average. At the current sugarcane price and replaces honey in herbal cosmetics and of Rs.800 per metric tonne, the raw material cost in simi lar other applications. Its property terms of sucrose amounts to Rs . 6,500 per metric increases shelf life of processed fr uits, bread, cake tonne. Jn the southern zone, where the sugar content in and pastry. It is used by bakers and biscuit cane is much hi gher, the effective raw material cost manufacturers as carameliser and it lends texture to will be lower at Rs.6,000 per metric tonne. the product. In bread, it hastens . It This analysis shows that as compared to starch, does not crystall ize even at high concentrations and sugarcane is cheaper by about Rs .2,500 per metric low temperatures. Hence, it is ideal for cough syrups, tonne for the production of high fructose syrups. condensed , sq uashes and icecreams. Being much Further in view of the complexity of the process from sweeter than sugar, it helps in masking the bitterness starch the investment in and equipment as well of tonics and pharmaceutical preparations. It is good as the cost for the traditional process for soft drinks and . It releases instant for HFS is much higher th an from sugarcane as an as it is readily assimilated by the human body. alternative route for the given capacity. Hence, under Hence, it is good for th e kids and the sports persons. Indian conditions, sugarcane is a cost-effective raw It emerges from the above th at invert sugar and 20 material for the production HFS . HFS are ideally suited for the non-domestic market GEHLAWAT: INVERT SUGA R AND HIGH FRUCTOSE SYRUPS FROM SUGARCANE 31

Crystal ~ SCHEME - B

Cation resin Eva porators reactor Ac tiva t ed To vac/ car bon Fil ter press ~ condenser

ClarifiedJ cane juice (15-20'/, [). ~

SCHE ME-A 1 Holding Holding Holding Demineralising Holding tank tank t ank unit t a nk

Fi g. 3 - A Schemati c now sheet for th e producti on of in ve rt sy rup from cane juice/sugar crystals

(j) H olding ta n k (I)Inver sion /Isomerisalion colu mns G) Fil t er press 55% High Fructose syrup (!;)Fr uctose enr i chm ent unit ,---__.....JL-~-, 300fo Glucose • 70 oro ®Ble nding un it F r uctose Water ( Oesorbent) (0 Solid D

Cation resins 1-( 70°fo Fructose (A) Desorpti o n lmmo b illsed (A• D) 3 o f Fructose (A) Isome rase 1 1 ~ Enzyme L------~--~ ~------..... Deso r p t ion 0 2 0 of Gl ucos e (B) Refined Cane j u ic e Feed 1 I ~( '-A.:._•.:._B:,_) __+- ~--1 -~- -~ ~ Hi ~ h DE syr up 1 .2 1 g of Fruc t ose(A) 98 °fo Glucose (B•D) lL lL

Glucose Partial (EJ deso rption o f D Rec cle stock

Fig. 4-A Schemati c now diagram fo r the CO illlllercial process fo r HFS li ke th e food processin g in dustry, soft drinks and sugar. 25 per cent ex tra qu anti ty , that is about 1.0 armaceuti cals. It is es tim ated th at the industri al million tonnes add iti onal in vert sy rup can be sector consum es about 30 per cent of cutTent sugar produced from the same qu antity of sugarcane since co nsumption th at is about 13.0 million tonnes. Thus, the loss of sugar in molasses is eliminated. Th is th e potenti al market for in ve rt sugar is of the order of additional 1.0 million tonn e equi va lent of sugar 4.0 million tonnes, whi ch is indeed a hu ge market. produced annuall y is worth about Rs. l ,500 crores. The surplus sugar thus produ ced will imp rove the Effective Sweetener Output could be up by 25 per cent profitab ility of sugar . It emerges fro m the above analys is th at in vert syrups can substitute crystal sugar in the industri al Conclusion sec tor with advantage. Presentl y the non-domestic The need to increase prod uct range sector co nsumes about 4.0 million tonnes of crys tal to im pro ve its pro fit ability. The production of in ve rt 32 INDI AN J. CHEM. TECHNOL., JAN UA RY 200 1 sugar and hi gh fructose syrups by this new 9 Gchlawat J K, J Sci lnd Res, 50 ( 199 1) 989. tech nology, particularly for the non-domes tic sector, I 0 Gehlawat J K, Chemical Weekly, 39(20) ( 1994) 135. II Schoenrock, Karlheinz W R, Kearney, Michael M, Rearick & is in the national interest. The corresponding sugar 1 Enge ne D, US Appl. 267, 065, 26 h May ( 198 1), 33 pp ; Chem. output will increase by about 25 per cent. The Ab.11r, 98 (1983) 9135lc. integration of cane splitting technique for juice 12 Anon, Chemical Weekly, April 13 ( 1993) 114. 6 extraction as discussed elsewheret in details, makes 13 Kum ar R, Singh V, Sastogi, S, Brar, P, Mehta R N & Raina P, this process ideally suited for the mini-sugar plants. ?roc. 54'" STAI, Convenrion, ( 1992) I. The development and implementation of such cost­ 14 Sarma M V J, Mal she V C & Gehlawat J K, Studies in effective tec hnologies should be promoted in the ultrafiltration of sugar cane juice, ?roc. CHEMCON- '93, large r national interests. Bombay (Dec. 15-1 8) ( 1993). 15 Gehlawat J K, Clarification of cane juice by the membrane techn ology, Proc. STA I Seminar, Bhubancshwar, April 29 References ( 1995). & I Mo nson P Combes D, Biotechnol. /Jioeng, 26( 1984) 347. 16 Gchlawat J K, J Sci lnd Res, 57( 1998), 490. 2 Mansfield J, Schellenberger A & Rombach J, Biotechnol 17 Ge hl awat Secma and Gchlawat J K, Hi gh fructose sy rups /Jioeng, 40 (1992) 997. from cane juice, ?roc ISSCT Con Carragena, Columbia. 3 Kumar V, Kumar N R & Upadhyay S N, Indian J Chem Scpl. 8- 17 ( 1995). Techno/, 2(1995) 179. 18 Sinha Chitra & Gehlawat J K, In dian J Chem Tecllllol , 2 4 Anon , Business Line, 2 June (1993) 126. (1995) 171. 5 Kulhanek, MiLos & Tadra Mil anc Czech CS 206, 710, 15 19 Niranjan T & Gchlawat J K, In dian Ch em Engr, 35(4) ( 1993) Scpi., ( 1983) Chem Abstr I 00 ( 1984). I 0545 lj. 217. 6 Tadra Milan, Tuma Jan, Kulhanek Mi Los L C & Listy 20 Kumar Satendra & Gchl awat J K, J Set lnd Res, 55 ( 1996) Cukrov, I 0 I ( I), I 0-15 ( 1985) (CLcc h) ; Chem. Absrr. I 03 490. (1985) 72842 . 7 Gehlawat Sccma & Gchlawat J K, Chem lnd News, 40 ( 1995) 21 Chandrashekar S, Sucrose faces the boot as in vert suga r 595. smil es sweetly, Economic Tim es, Nov. 4 (1997). 8 Gc hl awat J K, (Ed), Modemizarion of l11dian sugar induslt)', 22 Product Bulletin, Highlights of Vistas Liquid Cold, VISTA (A rnold Publishers, New Delhi ), 1990. Invertase Ltd., Dhampur, India, 1997.