BIOPOLYMER AND BIOCOMPOSITE

ESTERIFICATION

ESTERIFICATION
The basics of the reaction involve a process
called condensation in which a small molecule
of water is split out between two compounds,
leaving a linkage to form a larger molecule
from the original units:

Carboxylic Acid

Alcohol

Ester

Water

ESTER
Esters with low molecular weight are commonly used as
fragrances and found in essential oils and pheromones.
Substances associated with aromas and flavor essences. For
example, ethyl butanoate (aroma of pineapples):

Fats and oils are also esters. These are composed of the
triol glycerol, and long-chain "fatty" acids:

 The application of ester are:

Application

Example

Artificial flavours

Cold drinks, ice cream

Essences

Perfumes

Plasticizer

PVC

Table 1: application of ester

WHAT ARE ESTERS

Derived from carboxylic acids (R-CO-OH) with
an alcohol (R-OH).
Carboxylic acid contain the COOH group
Alcohol contain the OH group
R and R are either alkyl or aryl groups

MAKING ESTERS
Produced when carboxylic acids are heated
with alcohols in the presence of an acid
catalyst.
Water is remove during the reaction.
Catalyst is usually concentrated sulphuric acid.
Catalyst is needed to make the reaction occur
at a useful rate.

 Esterification reaction is both slow and

reversible
The equation reaction between acid R-CO-OH
and an alcohol ROH is:

Carboxylic acid

Ethanoic acid

alcohol

Ethanol

ester

water

Ethyl ethanoate
water
(colorless liquid with
sweet smell (similar to
pear drops))

pear drops

Advantages

Disadvantages

Most stable ester tends

to be product
Straight forward acid
condition can be used

Slow reaction rate

Corrosion of equipment

PROCESS:
PRODUCTION OF LEVULINIC ACID
AND LEVULINATE ESTER
( BIOFINE PROCESS)

WHY LEVULINIC ACID

Chemical which was identified as one of the most important sugar based
building blocks derived from lignocellulosic biomass*.
Levulinic acid was defined a versatile intermediate and one of the United
States Department Energys (DOEs) top 12 derivatives feedstocks.

levulinic acid is commonly prepared by heating the sucrose with

concentrated acid
This white crystalline solid is soluble in water and polar organic solvents. It
is also a potential precursor to biofuels. Levulinic acid is the precursor** to
pharmaceuticals, plasticizers, and various other additives.
*Source from National Renewable Energy Laboratory (NREL) and PNNL (Pacific Northwest National Laboratory).

** precursor is a compound that participates in the chemical reaction that produces another compound.

BIOFINE PROCESS

Is a commercialized technology that uses two step

dilute mineral acid hydrolysis to break down
biomass containing lignocellulose.

The Biofine Process is entirely chemical and does

not rely on the use of any form of microorganism
or Fermentation process
The process involves the use of dilute sulphuric
acid as a catalyst

Chemical conversion of cellulose to LA (Biofine process), producing formic acid

(byproduct) and tars (minor condensation products) in the 2 Biofine reactors

 Description of the process block diagram of Biofine process;

The waste is mixed with an acid-water solution to form a
slurry.
The chemical structure is broken down into three main
chemicals, furfural, levulinic acid, and lignin in a two-stage
chemical reactor (a high temperature tubular reactor into
which steam is injected followed by a second stage mixed
reactor).
The levulinic acid and furfural is concentrated and recovered.
In a complete Biofine plant, additional processing may then
occur, this depending on what final products are targeted. For
example, syngas production from the Biofine char may be
carried out in a gasification unit or the LA can be esterified with
ethanol to produce ethyl levulinate..

 After the 1st reaction, Hydroxymethylfurfural

(HMF) is produced. HMF is an intermediate
product before producing levulinic acid (LA).
Further reaction, 2nd reaction with HMF involves
several conversion process

LEVULINIC ACID
Levulinic acid is derived from lignocellulosic biomass
Levulinic acid, or 4-oxopentanoic acid, is the simplest
member of the comparatively rare class of organic
compounds known as gamma-keto acids.
Having both a ketonic carbonyl group and an acidic
carboxyl group, it reacts as a ketone and as a fatty acid.
The chemical structure of levulinic acid may be
represented as:
CH3 COCH2 CH2 COOH

 Levulinic acid is a starting product for the

preparation of organic chemicals, dyestuffs,
polymers, pharmaceutically active compounds,
and flavor substances.
Levulinic acid is an inhibitor of chlorophyll
synthesis.
It is utilized in edible compositions rigorous
purity, color and stability requirements must be
met.

LA potential
LA is a valuable platform chemical due to its
particular chemistry it has two highly reactive
functional groups that allow a great number of
synthetic transformations.
LA can react as both a carboxylic acid and a
ketone.

APPLICATION OF LIVULINIC ACID

Comparison Biofine process vs Conventional

Lignocellulosic Technologies
Biofine Process
Lignocellulosic biomass as feedstock.
Approximately 30 minutes for conversion
of cellulose to levulinic acid.
Allows a wider range of heterogeneous
lignocellulosic feedstocks to be utilised,
including those (e.g. cellulosic municipal
solid waste, sewage) that contain
contaminants that might inhibit
fermentation.
The lignin content of biomass has no
inhibiting effect on biofine process.
High yield of levulinic acid

Enzymatic Hydrolysis
Enzymatic hydrolysis and in conventional
dilute/concentrated acid hydrolysis
technologies use of biological agents to
convert sugars, fermentation process
takes a significant time.
Cellulase enzyme and fermentation
organisms require about 7 days to bring
about the conversion to ethanol.
lower range of feasible feedstocks.
Steric hindrance, caused by ligninpolysaccharide linkages, limits access of
fibrolytic enzymes to specific
carbohydrate moieties
Resulting in lower yields or the need for
steam-explosion pre-treatment

Feedstock

Sources

Waste plant material: hard wood or beech bark

Kin et al., 1978

Fiber board industry waste water

Pajak and Kryczko, 1979

Bagasse pity, bagasse, molasses

Nee and Yse, 1975

Post-fermentation liquor

Mel'nikov et al., 1972

Furfural still residues

Badovskaya et al., 1972

Aqueous oak wood extracts

Prosinski et al., 1971

Rice hull

Sumiki, 1948)

Oat residues

Rodriguez, 1973

Wood sugar slops

Faerber, 1943

Fir sawdust

Haworth, 1966

Naphtha

Kikuchi and Ikematsu, 1974

Corncob furfural residue

Dunlop and Wells, 1957

Cotton balls, rice, straw, soybean skin, soybean oil residue, corn husks

Sumiki and Kojima, 1944

Cotton stems

Minina et al., 1962

Cottonseed hulls

Akmamedov, 1962

Molasses

Rao et al., 1959

Starch

Hands and Whitt, 1947

Potatoes, sweet potatoes, lactose

Takahashi, 1944

Waste wood pulping residues

Wiley et al., 1955

Sunflower seed husks

Shil'nikova, 1967

Tapioca meal

Chapman, 1971

TABLE 1. BIOMASS FEEDSTOCKS OF LEVULINIC ACID PRODUCTION

PROCESS FLOW DIAGRAM OF LEVULINIC ACID

Hydrolysis reaction

Crushing
Lignocellulosic
Material

Separation

CRUSHING
The biomass (lignocellulosic
undergoes crushing process.
Function:
Reduce the size ( 0.5-1.0 cm)
Efficient hydrolysis
Optimum yield

material)

HYDROLYSIS PROCESS

1) MIXING TANK
The biomass is move to high pressure air
injection system to a mixing tank
Sulphuric acid (HSO) being added as catalyst
Addition of some sodium/potassium sulphate
(to prevent coagulation)

2) TUBULAR REACTOR
The mixture is move to tubular reactor
Condition :
Temperature (210-220C)
Pressure (25 bar)
Time (12 s)

Function :
Depolymerise the polysaccharides onto the
soluble monomer (eg: hexose)

3) STIRRER TANK
Moved to continuous stirred tank reactor
Condition:
Time ( 20 min)

Product :
Furfural
Formic acid

SEPARATION

 To separate the bran and left over mix of

Levulinic acid
Insoluble mix will go to the hydration unit and
being cracked to give powdery substance
(char)

FILTRATION

 Remove Levulinic acid from solid by product

In filter press, crude Levulinic acid product be
purified up to 98%

References
http://www.chemtopics.com/aplab/ester.pdf
http://www.academia.edu/3203706/A_roadmap
_for_conversion_of_lignocellulosic_biomass_to_c
hemicals_and_fuels
Daniel J.Hayes et al. Production of Levulinic Acid,
Furfural and Formic acid from Lignocellulosic
Feedstock.
Anna Maria Galletti et al. Conversion of Biomass
to Levulinic acid, A New Feedstock for Chemical
Industry.