Simultaneous Acid-Catalyzed Reaction of Coconut (Cocos nucifera) Coir

Dust in Ethanol Media for the Production of Ethyl Levulinate

Raw Material: Coconut coir dust

During the processing of the thick, fibrous

mesocarp (husks) of the coconut fruit to produce

coir fiber, a spongy, peat like residue is

simultaneously generated. This waste stream

which is typically consists of short fibers (<2cm)

around 2%-13% of the total and cork-like particles

ranging from granules to fine dust are called coir

dust. The fiber is used for the manufacturing of

ropes, carpets, mats and related products while the fall off materials (coir dust)

remain available as waste stream of no industrial value and are normally

incinerated or dumped without control (Israel et al., 2011).

Table 1. Typical Chemical Composition of Coconut Husk (Dry Basis)OLD NUT (%)

YOUNG NUT (%)

VERY YOUNG NUT (%)

Water soluble substancesPectin, others soluble in boiling waterHemicellulosesLignin Cellulose

2614. 25

8.529. 3323. 87

2914. 85 8.15

31. 6419. 26

38. 5015. 259. 00

20. 1314. 39

Reference: Tejano, E. A., 1985

Intensive researches were currently developed in order to utilize this

agricultural by-product and in the Philippines, the Philippine Coconut Authority

(PCA) in Diliman, Quezon City took the major step in exploiting the potential of coir

dust. Among these were extended fillers for plywood adhesives ( Chan, F.D., 1985),

cement additives (Lauricio, F.M., 1984), biosorbent (Manas et al., 1990), particle

board (Mari, E. L., 1985)

In 2012, the Philippines exported more than 1.5-million metric tonnes of

copra, coconut oil, copra meal, desiccated coconut, coco shell charcoal, activated

carbon and coco chemicals, a slight 1.49 per cent increase compared to the volume

exported in 2011. There are 3.5 million hectares dedicated to coconut production in

the Philippines, which accounts for 25 per cent of total agricultural land in the

country. The Philippines ranks near the top in global coconut production with over

15 billion nuts produced per year (Philippine Coconut Authority, 2012). For coconut

farm producing 10,000 nuts annualy has the potential of 3,600 kg of husks and

2,300 kg of coir dust (Philippine Coconut Authority, 2001). From this figure, a total

of 3.45 x 109 kg coir dust can be produced and this quantity is of great significance

for the said waste stream to be utilized into useful products.

Cellulose and hemicellulose fraction of this biomass feedstock (old nut

is much preferred, see Table 1) was the main properties needed for the

production of ethyl levulinate. This fraction will produce value-added sugar,

glucose and hexose, respectively that will undergone through series of acid-

catalyzed reaction in an ethanol media in order to produce ethyl levulinate.

List of Coconut Processing Industry in the Philippines

SC Global Food Products Inc.

Address (office): 2601 Jollibee Plaza

Building, F. Ortigas Jr. Road, Ortigas

Center, Pasig City, Philippines 1605

Telephone: (632) 635-4020

Fax: (632) 635-4007

Peter Paul Philippine Corp.

Address: Barrio Pahinga, Candelaria,

Quezon Province

Telephone: (02) 633-5978/ 79

(02) 633-6391/ 92

Fax: (02) 633-9883/ 84

Email: salesinq@peterpaul.com.ph

United Coconut Chemicals, Inc.

(COCOCHEM)

Address: CAIP-SEZ San Antonio, San

Pascual Batangas, Philippines

Trunkline: (6343) 727-1511

(6343) 984-1602-03

Email: www.cocochem.ph

Tantuco Enterprises, Inc.

Address: 663 J. Rizal Street cor. C.

Castanada Street, Mandaluyong City,

Philippines 1501

Telephone: (632) 531-9071 - 74

Fax: (632) 532-1722

Email:tantuco@mindgate.com.ph/

tantuco_ent@yahoo.com

Reference: PLDT yellow pages

Experimental Flow Chart

Coconut coir dust was collected and washed to remove adhering dirt and

sand and undergone size reduction. Testing, such as Thermal Gravimetric Analysis

Coconut Coir Dust Collection and Chemicals Preparation

Pre-Conditioning of Raw Material

Drying of Conditioned Coconut Coir Dust

Acid-Catalyzed Hydrolysis of Coconut Coir Dust on

Ethanol Media

Testing for the Composition of Dried Bagasse, TGA

Centrifugation for the Removal of Insoluble Materials, Humins

Testing of the Solution Components by HPLC

Solvent Extraction Acid Catalyst and Solvent is Recovered via Evaporation and Recycled back to the Process

Purification of Ethyl Levulinate

Quality Product Assurance

(TGA), is employed to determine the chemical composition (cellulose,

hemicelluloses, lignin, and ash).

Simultaneous acid-catalyzed reaction will be employed. The first phase

will be the delignification of the biomass feedstock via acid-catalyzed hydrolysis in

order to remove the lignin content of the material. The cellulose and hemicelluloses

content will be synthesized by the same acid catalyst to yield glucose and hexose,

respectively. These sugars will then undergone dehydration reaction to produce 5-

hydroxymethylfurfural and by decomposition reaction will yield levulinic acid, an

intermediate chemical in the production of ethyl levulinate. Each run of tests started

the ethanol medium heated to a salt bath to the desired temperature. After a

specified reaction time, the reaction was terminated by rapid immersion of the

reactor into a cool, ice water bath. The liquid phase was separated from the solids

by filtration. Afterward, a sample was neutralized and subsequently centrifuged to

obtain a particle-free solution. The composition of the particle-free solution was

determined (using high performance liquid chromatography, HPLC).

The aqueous mixture containing the acid catalyst and ethyl levulinate

is then contacted with a water-immiscible solvent to obtain the extract containing

the product and raffinate having the acid catalyst. The latter will be recycled to be

used in the hydrolysis of raw material. The extraction solvent is separated from the

ethyl levulinate by evaporating it and collecting its condensate, and recycling back

to extraction column. Further concentration and purification of ethyl levulinate is

carried out in a fractionation unit (vacuum distillation). Almost two-third (approx.

66.67% conversion) of the carbohydrate content of the feedstock is expected to

be converted to ethyl levulinate, the remaining is for the formation of insoluble

material, humins.

Bibliography

Chan, F. D., (1985). Development of Extender Filler for Plywood Adhesives

from Coconut Coir Dust. Terminal Report. FPRDI.

Lauricio, F. M., (1984). Utilization of Coconut Coirdust as Building Material

(Hollow Block). Terminal Report. FPRDI.

Manas, A. E., M. S. S., Romana, and A. S. Torres, (1990). Utilization Coconut Coir

Dust for Water Treatment and Recovery of Heavy Metals. Terminal Report.

FPRDI.

Mari, E. L., (1985). Development Coco-Coil' Dust Wood Particle board by

Graft Polymerization. Terminal Report. FPRDI.

Philippine Coconut Authority. Official Page. www.pca.da.gov.ph/

Philippine Coconut Authority (2001). Utilization of Cocopeat in Coconut

Production. Zamboanga Research Center, Davao City.

Tejano, E.A.,(1985). State of the Art of Coconut Coir Dust and Husk Utilization. Philippine Journal of Coconut Studies, Quezon City.

Xu, G.Z, C. Chang, W. Zhu, B. Li, X. Ma and F. Du (2013) A Comparative Study on the Direct Production of Ethyl Levulinate from Glucose in Ethanol Media Catalyzed by Different Acid Catalyst.

http://link.springer.com/article/10.2478%2Fs11696-013-0410-0#page-1