Xylitol Technology

INTRODUCTION

Xylitol is a naturally occurring sugar with a wide array of interesting

applications. The most significant fact about Xylitol is the possibility of its

extraction from bagasse, an abundantly available waste material in India. Xylitol can

be chemically characterized as a five-carbon sugar alcohol (1, 2, 3, 4, 5

pentahydroxy pentane) with a molecular formula: C5H12O5 (please see box for its

physical and chemical properties).

Xylitol can be found in small quantities in a various plants, fruits and

visitable - the primary sources are raspberries, strawberries, yellow plums,

cauliflower, spinach and others. Although widely distributed in nature, its presence

in low concentration makes it uneconomic to produce Xylitol on commercial scale

from such natural sources. In this context, the techno-economic feasibility of

extracting the Xylitol from bagasse, as established in Taiwan, is of important

commercial significance.

Xylitol with the sweetening property matching that of sucrose (sugar)

enjoys good applications as sugar substitute for food processing industry. Xylitol

produces a perceived sensation of coolness in mouth as it comes in contact with the

saliva for its negative heat of solution. This property makes it quite desirable in

certain food products, specially beverages.

Another significant property of Xylitol has been the prevention of

dental cavity as established by the dental caries prevention studies thus making it the

best nutritive sugar substitute with respect to caries prevention. Xylitol easily

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 Xylitol Technology

metabolizes (independently of insulin) in human body and produces the same

amount of energy (4 cal/gm) signifying its application in all diabetic foods.

Xylitol has been found particularly attractive as a non sugar sweetener

for chewing vitamins and gums, tablets, cough syrups, mouth washes, tooth pastes

etc. Hard candies, mints, sugar-less chocolates, gelatin, puddings, jams, baked

products, ice-creams etc. are also being marketed using Xylitol as the sweetener.

Apart from the above, the adhesive properties of Xylitol have been reported to

replace phenolic resin for plywood bonding.

As of late 1980s, 28 countries have been using Xylitol in commercial

products. In early 90s, an annual production of Xylitol has been reported as around

5000 tones in the world. Around 95% of the world's production belongs to two firms

from Finland and the balance quantity is distributed among four firms in Japan, one

in China and two in Switzerland. In addition to a number of companies in USA that

are interested in large-scale production of Xylitol in the future, similar interests are

also being pursued in Switzerland, Finland and Germany among others. Currently,

the major use of Xylitol has been in the manufacture of chewing gums.

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Physical and chemical properties of Xylitol

Molecular weight : 152.15

appearance : white, crystalline powder

odour : none

boiling point : 126° C (at 760 mm)

melting point : 92° to 96° C

solubility at 20° : 169 gms in 100 gms of water, sparingly

soluble in

ethanol and methanol

pH in water (1 gm/10 ml) : 5 to 7

heat of solution : - 34.8 cal/g (endothermic)

calorific value : 4.06 cal/gm

Process of manufacture

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1. Xylitol from Pentosans

The synthesis of Xylitol from natural products is based on the

chemistry of pentosans occurring in many plants. Xylan, a constituent of pentosan, is

a polysaccharide; this can be hydrolized into D- xylose. The synthesis reactions can

be summarized as under:

Hydrolysis Hydrogenation

(C5 H8 O4)n n(C5 H10 O5) n(C5 H12

O5)

Pentosans Xylose Xylitol

like xylan
Sud-Chemie AG, Munich, Germany in their patents granted in 1976

(U.S. Patent # 3980719) had described a process for preparing Xylitol by acid

hydrolysis of xylan to produce a solution containing xylose and acetic acid. The

solution was filtered for recovering unhydrolyzed acid. The solution was further

subjected to an adsorbent to remove proteins, tannins and pectins. The purified

solution was evaporated under vacuum to a viscous virtually water free syrup,

thereby removing all the acid acid from the said solution. The result and syrupy

solution was further diluted with water and pH maintained in the range of 6.5 to 7.5.

The diluted solution containing xylose was then hydrogenated using Raney nickel

catalyst, followed by the recovery of Xylitol from the solution.

Another U.S. patent (# 4008285), applied from Finland and granted in

1977, describes a maker of producing Xylitol on commercial scale by acid hydrolysis

of raw material containing pentosan. The process differs from the earlier one in the

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 Xylitol Technology

step after hydrolysis where the inorganic salts, organic impurities and colour are

removed by treating the solution with an ion exchange resin and activated carbon.

The solution is further fractionated by ion exchange chromatographic techniques to

yield a high purity xylose solution. The solution is then hydrogenated in presence of

a catalyst and subjected to ion exchange chromatographic fractionation again to

recover Xylitol of high purity.

2. Xylitol from Bagasse

Rice and cotton seed hulls, bagasse, corn stalks, coconut shells etc.

with rich Xylan contents can also be used for production of Xylitol.

Technology from Taiwan

The Taiwan Sugar Research Institute has dated out extensive

research work on the possibilities of commercial exploitation of Xylitol from

bagasse. A process for continuous production of Xylitol from bagasse on

commercial scale has been developed by the Institute.

The manufacturing process involves shredding of bagasse into smaller

particles (size: max. 1.5 cm long) and removal of pith, it is thoroughly washed with

water to remove the dissolved mineral matters. Drying of bagasse reduces its

moisture content to 10 percent and the ash content is maintained at maximum 1

percent.

Hydrochloric acid liquor found superior to sulphuric acid, which was

used earlier, and bagasse are fed into a mixer in a ratio of HCl : dry bagasse as 0.25

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 Xylitol Technology

to 12 percent. These are mixed thoroughly by agitation in a stirred tank reactor and

passed on to a rotary kiln (autoclave) fitted with a school feeder. The acid liquor and

bagasse are steam heated to 100-125 deg. C with a residence of 40-75 minutes in the

rotary kiln. This treatment helps in pre-hydrolysis of hemicellulose content of a

bagasse.

The output from the rotary kiln (the mixture of bagasse with acid

liquor) is post-hydrolized continuously on a screen conveyor where the mixture is

sprinkled with hot water (100 degree C) and leached the liquor. The leached liquor is

collected at conical bottomed vessels placed under the screen conveyor and it is

recycled. The post-hydrolysis step completely extracts the xylose content of

bagasse. The hydrolysate, collected at conical bottomed vessels, containing 17-20

percent of xylose, maybe further fermented for alcohol production of taken up for

xylose separation. Water is removed from the spent bagasse in a screw press and the

residue is used for pulp making. The following table presents various process

parameters for the extraction of xylose by acid hydrolysis of bagasse.

MANUFACTURING OF XYLITOL FROM BAGASSE (TAIWAN

TECHNOLGY)

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Xylose From Bagasse - A Schematic Diagram

Technology from China

A Chinese technology offer for producing Xylitol made available

through the Asian and Pacific Center for transfer of technology (APCTT), New

Delhi is also based on utilization of agricultural wastes such as bagasse or corn cob.

The process has little impact on environment and does not produce any waste gas.

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The waste dredge produce during the process can be used as fuel or culture for

mushroom cultivation. After neutralization, waste water can be drained away or an

aerobically treated if it contains organic substances. The process has been

commercialized in China.

Process description

Bagasse (corn cob) → hydrolysis and dredge removal →

decolorization → ion exchange → concentration → crystallization → separation

from mother liquor → finished product.

Inputs required

Steam - 9.5 tons/hr (P = 0.6 Mpa), building - 7800 sq.m., land – 4000

sq. m., water - 110 tons/hr, power - figure not known.

Manpower required

Total - 110, technicians - 12, skilled - 76, unskilled – 28

production capacity - 500 tons/year

Raw materials

bagasse (corn cob) -17,800 tons/year (6000 tons/year), sodium

carbonate 800 tons/year, sulphuric acid (not less than 92% conc. ) -1200 tons/year,

activated carbon - 90 tons/year.

Economic data

Machinery and equipment (FOB) : U.S. $4.1 million

Know-how fee : U.S. $650,000

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Training fee : U.S. $80,000

Operational cost/year : U.S. $ 1.8 million

Technology transfer details

Turnkey transfer, the technology supplier could also consider supply

of process plant and equipment, buyback arrangement.

Another Chinese process technology, offered through APCTT, for

making Xylitol involves safe and flexible process line with simple oppression and

low investment. The effluents can be simply treated within the battery limit. All

waste discharges from the plant are in accordance with international standards. The

solid waste residues can be used as fuel for brick manufacturing. The process has

already been commercialized in China.

Process description

Bagasse → hydrolysis → purification → hydrogenation →

concentration → crystallization → drying and packing.

Inputs required

Land – 4000 sq. m., building – 5000 sq. m., water – 2500 tons/ton of

product, power – 5500 KWH/ton of product.

Manpower required

Total - 200, technicians - 20

Production capacity

600 - 700 tons/year (300 working days).

Raw materials

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 Xylitol Technology

Bagasse, Sulphuric Acid, Caustic soda.

Economic data

Total Project Cost -U.S. $ 5.5 million, Machinery and Equipment

(FOB)-U.S. 3.0 million, Know-How fee-U.S.$ 400,000, Training fee-U.S. $ 50,000,

Operating cost - as per local labor and material costs.

Technology transfer details

Transfer of know-how, offer of consultancy, technical assistance,

supply of process plant and equipment, training of personnel.

3. Other processes

A search of the IBM site on the Internet on patents applied for and

granted by the U.S. patent and trademark office(USPTO) reveals the following

processes:

Xylitol from Hemicellulosic materials

A patent (# 3627636) granted to Hoffman-La Roche, New Jersey in

December, 1971 describes a process for producing Xylitol from lignin-free

Hemicellulosic materials. In this process, the polysaccharides of Hemicellulose have

been converted to monosaccharides which on fermentation with a hexose

fermentation yeast and further hydrogenation of the aqueous medium produces

Xylitol.

Xylitol by Fermentation

A Finnish patent (# 50 81,026) granted by USPTO in January, 1992

deals with the method of preparing Xylitol by fermenting an aqueous solution

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 Xylitol Technology

containing xylose and other free hexoses with a yeast stram. While the yeast

converts xylose to Xylitol, it converts hexoses to ethanol. The Xylitol-rich fraction

is then separated from the fermented solution by chromatographic method.

Manufacturing Xylitol by using recombinant microbial hosts

A resent Finnish patent (# 5631150 ) granted in May, 1997 by USPTO

reports production of Xylitol from a recombinant microbial host. The process

involves growing an arabitol producing yeast or fungus under the conditions suitable

for synthesizing Xylitol. The arabitol producing yeast or fungus is modified to

Xylitol in a single fermentation step. The recombinant microbial post is transformed

with a DNA encoding a D- xylulose forming D- arabitol dehydrogenase and with a

DNA encoding Xylitol dehydrogenase. Xylitol is then recovered from the above

solution.

Xylitol: potential applications

Xylitol has been used in a wide range of products. It can be used as

an additive in food industry, in pharmaceutical industry, health food, beverage

industry, cakes, gums as sweetener and in light industry as raw material. A search of

international the literature and also the patents on various applications of the Xylitol

is summarized in the following sections.

Xylitol in food products

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 Xylitol Technology

A chewing gum with improved storage qualities was patented (# 4

000320) by general foods corporation, New York, U.S.A. in December, 1976. The

patent relates to a chewing gum comprising gum base, sweetener, flavor and Xylitol.

The Xylitol content, less than 50 percent of the total gum composition is effective in

improving the storage quality and stability.

The U.S. patent (#34105801) awarded to an Italian company in 1978

describes a coated edible product and its preparation. The product consists of a core

portion and a shell enveloping the core. The shell comprises of a mixture of Xylitol

microcrystals with solid fat (selected from the group consisting of mono-,die-and

triglycerides of palmitic-, stearic- and oleic acids and cocoa butter) in a proportion of

0.50 to 15 parts by weight of fatty substance to 100 parts by weight of Xylitol.

A Japanese patent, granted in 1990, describes the application of

Xylitol in a granular quality improver for frozen fish and meat products. The

granular quality improver is manufactured by mixing sugar, sugar alcohol (Xylitol),

phosphate salts and optional fats - this is pressure moulded and pulverized. The

granules prevent denaturation by freezing, give firm texture and maintain whiteness;

these are more convenient than the conventional additives.

A patent for a low calorie artificial honey using Xylitol was applied

for in 1992 in U.S.A. The honey based food product having taste and texture

resembling to that of pure honey while having a low-calorie content has been

reported. The formulation contains low-calorie polysaccharides such as polydextrose

and a polyol (sorbitol, maltitol, Xylitol etc.).

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In a Chinese patent application of 1993, the use of Xylitol in the

preparation of medicinal chewing gum for oral hygiene and treatment of oral disease

has been reported. The chewing gum is prepared by mixing bactericides, powdered

sugar, gum base and a pre-heated starch syrup. It may also contain other ingredients

such as softeners and fragrance. The bactericides are chosen from chlorhexidine

citrate, chlorhexidine fluoride and ribavirin.

The hard coated chewing gum with improved shelf life with Xylitol

and polyol coatings was patented (# 5376389) by Wrigley Jr. Co., Chicago, U.S.A. in

1994. The patent relates to a duel composition hard coated chewing gum which

comprises 35-90 percent by weight of gum center (a chewing gum base + flavoring

agents) and 10-65 percent by weight of an outer coating (containing 50-100 percent

by weight of Xylitol and non-Xylitol polyol). The duel composition hard coated type

is suitable for chewing gum pellets which have improved shelf life with respect to

atmospheric moisture.

A Japanese patent, awarded in 1995, describes the method for

manufacturing chocolate containing sugar substitute. The mouth-feel of the plates

having sugar alcohol impacted Xylitol) as sugar substitute has been improved by

using diglycerides.

'Xylifresh' is a new chewing gum launched by Leaf Inc., Chicago,

U.S.A. The gum is being promoted as the first to curb bacteria and reverse early

decay. Xylitol, the active ingredient of xylifresh, has been long accepted as cavity

fighter in parts of the -Europe.

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Xylitol for Dental and Medical Applications

Colgate Palmolive company, New York, U.S.A. patented (# 3970747)

a humectant sweetener in 1976. This is a dentifrice containing non-calorigenic

humectant sweetener. A dentifrice is nothing but an aqueous dental cream

(toothpaste) containing at least 10 percent water and a humectant. The humectant

comprises about 10 percent by weight of a Xylitol solution in water in combination

with other polyols.

The use of Xylitol in pharmaceutical preparation allowing it to

penetrate the blood-brain barrier has been reported in a Japanese patent of 1993. Of

pure sugar combination selected from a group of comprising meso-erythritol,

Xylitol, galactose, lactose, fructose, glucose and others had been used.

In an European patent application of 1994, the use of Xylitol has been

cited for medicament for topical application to the eye for treatment of increased

intraocular pressure. It has been reported that the intraocular pressure was lowered

by application of ophthalmic solution containing a polyol (0.5 -10 percent by weight)

such as sorbitol, mannitol or Xylitol. In clinical trials, the application of one drop of

five percent sorbitol solution twice daily to a group of patients decreased the mean

intraocular pressure from 27 to 19 mm Hg within seven days.

A Finnish paper, published in 1994, reported the retention of calcium

from various Xylitol-calcium combinations in rats. Xylitol increases the intestinal

absorption of calcium been tested in rats. In the study, and optimum Xylitol: calcium

molar ratio for calcium absorption and retention was determined in 10 weeks. The

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 Xylitol Technology

highest retention rate of radioactive calcium (45Ca) was found when 114 mg of

Xylitol was given with calcium (Xylitol : Ca molar ratio of 1:5). For companies and,

the selection of 45Ca was determined from 4-lactose : CaCl2 combinations and from

calcium lactate and calcium citrate salts. The results favor the use of a Xylitol: Ca

molar ratio of 1:5 in Ca supplements.

In June, 1995 Colgate Palmolive company of U.S.A. patented (#

5424059) the application of Xylitol as an antibacterial and antiplaque dentifrice. It

is reported that the Xylitol used in the dentifrice inhibits plaque information, reduces

gingivitis and caries. The dentifrice essentially consists of an orally acceptable

aqueous humectant Xylitol vehicle, about 20-75 percent by weight of a dentally

acceptable and water insoluble Ca or Mg alkaline earth metal (as polishing agent)

and a non toxic to fluoride compound to release 25-5000 ppm of fluoride ion. The

dentifrice also contains an effective antiplaque (selected from halogenated diphenyl

ethers, halogenated salicylanilides, benzoic esters, sesquiterpene alcohols,

halogenated carbanilides and phenolic compounds) and about 0.1 percent by weight

of Xylitol.

Another antimicrobial oral composition containing Xylitol has been

patented (# 553 1982) by, Colgate Palmolive, U.S.A. in July, 1996. It is reported that

the older composition is effective in reducing dental caries and fissures even without

a fluoride ion source. This contains about 10-30 percent by weight of a water

insoluble and dentally acceptable siliceous polishing agent, an antiplaque and

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 Xylitol Technology

noncationic antimicrobial agent, an antibacterial agent (0.05-4 percent by weight)

and at least about 0.1 percent by weight of Xylitol.

An antimicrobial mouthwash of pleasant taste was patented (#

5560906) by Oral Technology Laboratories, U.S.A. in October, 1996. The

mouthwash has been reported to be effective in removing dental plaque. It does not

content any alcohol, sugar or artificial sweetener making it safe for use by diabetics,

alcoholics and others. The formation consists of water, glycerin, sodium benzoate,

cetylpyridinium chloride, citric acid, maltol, Xylitol, a flavoring agent (for pleasant

but biting taste) and a coloring agent.

A fluoride toothpaste with Xylitol has been launched by Digitemp

Industries Sdn. Bhd., Malaysia. The manufacturer in their advertisement reports that

Xylitol fights tooth decay and control is bad breath by resisting fermentation by

mouth bacteria, neutralizing acid produced by fermenting carbohydrates, inhibiting

plaque accumulation and calorigenic bacteria and by promoting demineralization.

The dental benefits of Xylitol have been demonstrated as such in numerous field

studies and this has led to official endorsements by the dental associations in Finland,

Norway and Sweden.

Other Applications

A paint composition containing Xylitol was patented (# 3925278) by

new Japan chemical company Ltd., Japan in 1975. The coating composition

essentially contains a film forming binder selected from the group consisting of tar

epoxy, alkyd and modified alkyd resin. The binder properties have been improved

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 Xylitol Technology

by adding a thickening agent (0.001-10 percent by weight) consisting of a

condensation product of 1 to 3 moles of a polyhydric alcohol (Xylitol, sorbitol,

heptitol) and one mole of aromatic monoaldehyde (benzaldehyde, methyl

benzaldehyde, nitrobenzaldehyde, aminobenzaldehyde, napthylaldehyde and several

others). Xylitol as a reusable heat device has also been reported. In a patent (#

4295517) awarded by USPTO to a group of Swiss scientists in 1981 describes a

method of providing the heat source by adding Xylitol as a heat storage material.

The process involved heating Xylitol in a container to a temperature above its

melting point, then cooling the resulting melt to a temperature below the melting

point of Xylitol without crystallizing it and further initiating the crystallization of

Xylitol thus releasing the heat of crystallization of Xylitol as the source of heat.

In a French patent application of 1993, the use of a number of simple

polyols such as Xylitol and their combinations in cosmetic preparations has been

claimed. The selected polyols help restore the balance of skin flora while inhibiting

pathogenic germs.

Conclusion

India with over 400 sugar mills produces around 70 million tons of

bagasse every year. The TIFAC reports on 'Use of Biomass (Bagasse) for Paper

and Pulp Industry' and ' System Approach to Bagasse Utilization' in detail the

national and international trends and scenarios on various means of bagasse

utilization. As one of the reports, the global trends in bagasse utilization is mostly

concentrated in two areas: a) generation of power has practiced in Mauritius,

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Hawaii, U.S.A. etc. and b) paper manufacture, India has carried out extensive

research on bagasse utilization for paper and pulp of making and successfully solved

many problems by implementing design improvements and proper mix of chemical

and mechanical processes along with using 10-50 percent bagasse with hardwood

pulp or waste paper pulp.

The TIFAC studies for the recommend that a detailed techno-

economic evaluation should be carried out for improved utilization of bagasse by

various means. It is suggested that at least 10 percent of bagasse available maybe

diverted to pulp and paper manufacture and further 10 percent may be consumed for

manufacturing various types of particle boards.

The TIFAC studies also cover Xylitol as an important product from

bagasse. Xylitol has been identified as a critical raw material for producing feed

yeast, food industry, pharmaceutical and chemical industries. It is evident from this

article based on patent searches and other technology trends that Xylitol enjoys the

excellent potential for commercial applications. Xylitol has been categorized as a

degree (on safety scale) for its use as a food additive.

The process details for extracting Xylitol from bagasse as described in

the Taiwanese experiment covered in this article do not appear complicated and it

definitely merits experimentation on a pilot-scale so as to establish the optimal

process parameters. Such a project maybe taken up in right earnest by the industries

with venture capital financing or funding support under various technology

development schemes of the Government of India. It is inferred by TIFAC study that

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sugar mills already manufacturing or any chemicals should seriously consider

seeking up the plant for the Xylitol extraction. At least 2-5 plants for Xylitol should

be set up in the near future with a national plan of setting up 20 plants in the next

five years.

The demand for Xylitol may be much in the country today due to lack

of awareness and availability. The techno- economic feasibility for extracting

Xylitol from bagasse (and using the residues for paper making or boiler fuel) may

lead to a cheaper cost of the product compared to one obtained from birch wood or

hard wood chips as practiced in the European countries. This may help in

developing an export market for Xylitol produced in India.

References

1. www.Xylitol.org

2. www.xclear.com

3. www.Xylitoltechnology.com

4. A journal 'Chemical Engineering World'

- Jan. 98 , Vol. XXXVIII, Page No. 103-108

5. Organic Chemistry By Bahl.

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