Sugar Industry Technologists Sixty Six Annual Technical Conference

 

Baltimore, Maryland, USA- May 6 – 9, 2007

 

Value added functional foods from CMS and cane molasses

 
By

Dr. Wen Hong Gao, Associate Professor, South China University of technology**  

Mr. Jeng Yang, Managing Director, Vedan Enterprise Holding Corporation, Taiwan

Dr. Chung Chi Chou, visiting professor, South Chin University of Technology, China.

 

(I) Introduction

Recent research has demonstrated the relationship between the aging process and the damaging effects of free radicals on tissue cells, and the beneficial impact on blood plasma antioxidant capacity of the increased daily intake of antioxidant-rich foods. In recent publications (1, 2), the ORAC analysis was performed on a series of sugarcane products with the results ranging from some 5,000 (ORAC units/100g dried solids) to over 35,000, indicating strong antioxidant properties, comparable, if not superior, to those previously reported for the top-antioxidant-rich fruits.

USDA scientists have recommended a daily intake of 3,000 to 5,000 ORAC units. The Oxygen Radical Absorbance Capacity (ORAC) method, to quantify the antioxidant property, was developed by USDA research laboratories several years ago, and since has then been used to rank (ORAC units/100g) common foods. Prunes (5,770), raisins (2,830), and blueberries (2,400) top the list, trailed by such health food industry favorites as kale (1.770), spinach (1,260) and Brussels sprouts (980) (3).

Antioxidants in concentrated sugarcane extracts obtained from cane juice, using the Cti process was found to contain over one million ORAC units/100g dried solids (1, 2). Table below shows analysis of antioxidant for three extracts (2 from USA and 1 from China). Besides ORAC units, analysis was also performed on polyphenols and cathechin. The % of polyphenols is comparable to that of grape seeds extract. The extraction of antioxidants from cane juice has been reported (8)

The increasing demand for production of safer foods is accompanied by the need for cleaner production processes. The food industry will have to sustain increasing costs for treating solid and liquid wastes. This is particularly true for sugar and glutamic acid production. The industry produces a substantial volume of solid organic by products and /or wastes such as molasses and CMS. In this research we focused our attention on extracting antioxidant from molasses and CMS for a possible future application in functional food industry.

 

**All experiments were conducted by graduates students: Miaomiao Li, Huiming Qin, Jianjun Zhang, and Jiancheng Zeng during 2006 school year. Thanks are due to them.

 

 

(II) Extraction of Antioxidants from Sugarcane Using Cti Process

The extraction process includes the following steps:

Decolorization of clear liquor, and removal of antioxidants, being part of colorants, by filtering through an adsorbents resin. The decolorized and antioxidants depleted clear liquor is returned back to the factory for crystallization to produce various food sugar products.

Recovery of antioxidants from and regeneration of, adsorbent resin by washing the resin with aqueous sodium hydroxide solutions (and/or ethanol), etc., producing antioxidant extract solution containing color, antioxidants, sodium and hydroxyl ions.

Removal of sodium and hydroxyl ions by filtering the above antioxidant extract solution through cationic exchange resins, producing antioxidant enriched functional food products.

Regeneration/reactivation of spent cationic exchange resins by passing hydrochloric acid solution through spent cationic exchange resins.

The yield of antioxidants range from 0.01% to 0.02% on the weight of cane depending on the color of feed material to the Cti process.

The use of adsorbent resin in studies of the nature of sugar colorants and for decolorization has been previously reported (6, 7)

Antioxidant Analysis

ORAC unit on dried basis, other on samples as received basis at about 67 brix

 

Extracts (origin)

ORAC unit/100 grams

Polyphenols %

Total cathechin %

#1 (USA)

1.26 million

19.05

1.26

#2 (USA)

1.36 million

   

#3 (China)

2.61 million

17.47

0.80

In two Japanese studies published in 2001 and 2002 Sugar Technologists Technical Proceedings (4, 5), sugarcane extracts were found to have many other beneficial physiological functions as shown below:

Phylactic Effects (promotion of resistance against virial and bacterial infections)

Vaccine Adjuvant Effect (stimulates the immune response and increase effectiveness of the vaccine)

Protection Effects on liver injuries

Antioxidative Activities (one gram contains 12,000 ORAC units)

Enhanced Growth of animal

Anti-coccidial infection in chickens

 

(III) Antioxidants extract as functional foods

Antioxidant as dietary daily supplement

Based on USDA scientists: about 4000 ORAC/day/person

ORAC = Oxygen Radical Adsorption Capacity

Concentrated sugarcane extracts = 12,000 ORAC/g

1 g = 3 capsules (soft gels)

4,000 ORAC/capsule/person/day

1Kg. = 3000 capsules

1 gram of concentrated antioxidants also contains about 250 mg of polyphenols.

1 gram can make into 3 capsules (soft gels).

Each capsule would contain about 80 mg of polyphenols, comparable to the popular grape seed extract.

Antioxidants fortified/enriched dietary syrup

Add antioxidants into edible molasses to make 1500 ORAC per table spoon (15 ml). One table spoon a day will meet 50% of daily requirement (3000 ORAC/person)

Antioxidant fortified/enriched soft/brown sugar

1 kg antioxidants to mix with 3000 lbs of soft sugar

Soft sugar fortified with 4,000 ORAC/lb soft sugar

(VI) Extraction of antioxidant from Molasses and condensed molasses fermentation soluble (CMS)

1. Scope

The increasing demand for cleaner environment requires more friendly process for production of safer foods. The food industry will have to sustain increasing costs for treating solid and liquid wastes. This is particularly true for sugar and glutamic acid processing which produce a substantial volume of solid organic by product and/or wastes such as molasses and CMS. In this research we focused our attention on extracting antioxidant from molasses and CMS for a possible future application in functional food industry.

2 Methods

2.1.Preparation

2.1.1 Molasses pretreatment

The molasses were diluted to 10°Brix with water

Clarification

a. Heating to 70 degree Centigree.

b Add H3PO4(500ppm) to the molasses, take the pH.

c Adjust the pH to 7.2 with Ca(OH)2,write down the dosage.

d Laying aside for about 1~2 hr, discard the precipitation

e Centrifuge the supernatant, then 0.5 Kieselguhrs were added , filter it.

f Take the Brix, pH, color and conductivity of the supernatant.

2.1.2 Pretreatment of macroporous adsorbent resin ZG SD300

Water-rinsing

The resins were soaked in distilled water for 12hr. Water was decanted after the resins swelled fully. The resins were repeatedly rinsed with distilled water to remove the impurity completely, until the eluent became clear.

Ethanol-washing

2Bv 95% ethanol was added, stir constantly for 1hr, then the ethanol was decanted, washing with water, until the elute become clear and flavorless.

Acid-alkaline treatment

a 4% HCl was added until the liquid level was about 5cm over the surface of the resin. Soak for 1hr, stir constantly. The acid liquor was drained off and the resins were washed for several times. When the eluent was about pH 4-5.

b the resins were soaked in 5 % NaOH for 1hr. Stir constantly. The alkaline solution was discharged. Rinse with distilled water for several times. Stop rinsing when the eluent was about pH8-9.

2.2 Experimental Design

2.2.1. Adsorption

Feed

a Column preparation: fill the column with resin-water mixture, and the resin volume was 100 ml. Drain off the water with vacuum.

b The Jacketed column was kept at 65oC with water bath.

c Feed up-flow until slightly over the surface of the resin, then down-flow at 2Bv/hr for 4.5hr (the total volume10Bv), take the Brix , pH, color and conductivity of the effluent every 2Bv.

Washing

a Drain off the molasses with vacuum.

b Feed the water up-flow until slightly over the surface of the resin, then down-flow at 2Bv/hr for 2hr.

c Soak for 1hr after washing.

d Wash again for another 2 hr.

2.2.2 Desorption

Drained the water off with vacuum.

Feed 2%NaOH solution up-flow until slightly over the surface of the resin, then down-flow at 2Bv/hr, recycle for 2hr, save the eluent, then neutralize it.

Feed 2% fresh NaOH solution up-flow until slightly over the surface of the resin, then down-flow at 2Bv/hr, recycle for 2hr, save for next cycle.

Drain off the secondary eluent with vacuum.

2.3 Regeneration

After drain off the 2% NaOH solution with vacuum, wash with water at 2 Bv/hr, keep washing until the pH less than 9.0.

2.4 Neutralization

Take the pH and conductivity of the first 2%NaOH eluent.

Feed the eluent into the column, neutralize with acidic resin ZG C258.

After neutralization, take the pH, conductivity and weight of the effluent every 0.5Bv. If the pH>7, then feed the eluent into another column.

2.5 Concentration

The eluent was concentrated to 67°Brix with Rotary-Evaporator at 70 oC. Then dry it with vacuum drier at 70.

3 Results

3-1. Extract from cane molasses using 80% ethanol

a. The first cycle

Feed each column with 4Bv (400cc) 10.25Brix diluent molasses

So the input dry matter of the two column is:

400×1.04127(apparent specific gravity)×10.25%(Brix of molasses)×2=85.38g

The weight of eluent after evaporation with rotary-evaporator at 70:21.77g

Dry matter of 80% ethanol eluent: 8.61g

Weight of 1%NaOH eluent after neutralization: 293.8g

Weight of 1%NaOH eluent after evaporation with rotary-evaporator at 70:17.8g

Dry matter of 1% NaOH eluent after drying with vacuum drier at 70:0.89g

So the total weight of dry matter is: 8.61+0.89=9.50g

Yield (Dry Solid basis): 9.50/85.38×100%=11.13%

 

Polyphenol(%): (33.72+33.98)/2=33.85% ( too high %, because original blank color was not subtracted)

b. After one resin generation, ethanol extraction (the calculation according to the above-mentioned method )

 

Column

Column

Volume(cc)

Brix

Dry matter content(g)

Volume(cc)

Brix

Dry matter content(g)

400

10.25

42.69

400

10.25

42.69

Weight of 80% ethanol eluent (g)

179.2

179.2

Weight of 80% ethanol eluent after evaporation with rotary-evaporator at 70(g)

17.16

10.49

Weight of dry matter of 80% ethanol eluent after drying with vacuum drier at 70 (g)

2.23

2.48

Weight of 1%NaOH eluent after neutralization

127.1

120.3

Weight of 1%NaOH eluent after evaporation with rotary-evaporator at 85(g)

6.71

2.42

Weight of dry matter of 1%NaOH eluent after drying with vacuum drier at 70 (g)

0.17

0.26

Yield(Dry Solid basis)(%)

(2.23+0.17)/42.69=5.62

(2.42+0.26)/42.69=6.42

Polyphenol(%)

(35.22+35.54)/2=35.38% ( too high %, because original blank color was not subtracted)

 

3-2. Extract from cane molasses using 2% NaOH (the calculation according to the above-mentioned method )

 

Column

Column

Volume(cc)

Brix

Dry matter content(g)

Volume(cc)

Brix

Dry matter content(g)

1000

10.5

109.42

1000

10.5

109.42

Weight(g)

Brix

Weight(g)

Brix

243.7

0.75

265.6

0.75

Weight of Eluent after evaporation with rotary-evaporator at 85(g)

8.3

17

Weight of dry matter after drying with vacuum drier at 70 (g)

3.03

3.76

Yield(Dry Solid basis) (%)

2.77

3.43

 

3-3. Extract from CMS using 2% NaOH (the calculation according to the above-mentioned method )

 

Column

Column

Volume(cc)

Brix

Dry matter content(g)

Volume(cc)

Brix

Dry matter content(g)

600

10.25

64.04

600

10.5

64.04

Weight(g)

Brix

Weight(g)

Brix

244.0

0.5

251.2

0.5

Weight of Eluent after evaporation with rotary-evaporator

at 85(g)

11.6

7.5

Weight of dry matter after drying with vacuum drier at 70 (g)

1.92

3.06

Yield(Dry Solid basis) (%)

3.00

4.78

 

 

(V) Summary of results

 

Table I % Extract, yield on feed (on dried solid basis -average of two columns parallel tests)

 

Molasses

(a) Molasses

(b) Molasses

CMS

 

Ethanol Extract

NaOH extract

NaOH extract

NaOH extract

Fresh adsorbent

11.13

3.19

5.32

3.89

After one re-generation

6.02

 

4.10

 

Four observations can be made from the table I data:

(a) The extraction yield using ethanol is higher than those by NaOH, most likely due to higher affinity/solubility of ethanol for "coloring" matter,

(b) The extraction yield for fresh adsorbent is higher than those of once regenerated adsorbent. This probably indicate that the resin is not fully regenerated resulting in lower adsorption capacity for "coloring" matter.

(c) The variation in yield between NaOH extracts from (a) & (b) molasses could be explained in terms of the difference in feed loadings,

(d) There is no significant difference in yield between Molasses and CMS.

Table II. Polyphenol Content (% on dried solid basis) in extract

 

Molasses

Cane Juice

 

Ethenol Extract

NaOH Extract

Test I

3.947

2.137

17.24

28.43

Test II

 

 

15.66

26.19

* CMS: Molasses Fermentation Soluble.

The polyphenol content in both CMS and molasses on "as received" basis are 3.947% and 2.137 respectively. However, the % polyphenol on extract, which has no other solid such as sucrose, are very small indicating only a fraction of polyphephenol are been extracted.

 

References Cited

Saksa and Chou, Antioxidant Properties of Sugarcane Extracts, First Biennial World Conference on Recent Development in Sugar Technologies, May 16-17, 2002, Florida, USA.

Koge, Saska and Chou, Asian Functional Food (Nutraceutical Science & Technology Series) Marcel Dekker Publishing Company – pending, 2004

Top antioxidant foods, USDA Agriculture Research Magazine, Feb 1999 Issue

Nagai, Mizutani and Iwabe, 2002 Physiological Functions of Sugarcane Extracts. Proc. Sugar Ind. Technol. pp 97-104

Koge, Nagai, Ebashi and Ewabe, Physiological Functions of Sugarcane Extracts-Growth Promotion, 2002. Proc. Sugar Ind. Technol. pp 285-292

Chou and Rizzuto, The acidic Nature of Sugar Colorants, Proceedings of the1972 Technical Session On Cane Sugar Refining Research, Agricultural Research Service, U. S. D. A.

Rothchild, Decolorization by Adsorption with A non-Functional Resin, 1993 Proc. Sugar Ind. Technol. pp 305-324.

                    (8) Chou and kwok, Sugar Industry Technologists Sixty Six Annual Technical Conference. 2004