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PRODUCTION OF GLUTAMIC

ACID FROM CORN COBS


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Alfaras, Alexander Allen S.

Calasanz, Billie Jean S.

Flores, Jernel G.

Flores, Mae Lyn R.

Fundano, Jerome D.R.

Granados, Paul Dillon A.

Layug, Kez M.

OCTOBER 13, 2018.

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CHAPTER 1

Product Description

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CHAPTER I

Product Description

1.1 INTRODUCTION

In the beginning of the 20th century, the demand for alternative energy
increased that made the development and innovation of industrial processes
increase competitively making use of the wastes as the raw material. Various food
industries produce a big amount of food wastes as their end products that have not
been recycled or used for other purposes. Most of these wastes can be converted
into valuable by-products by means of different processes given that the cost of
the process will not be expensive.

In Philippines, solid waste management is still a major challenge


especially in urban areas like Metro Manila [62]. Some of the reasons behind this
problem are improper waste disposal, inefficient wastes collection and lack of
disposal facilities. These wastes lead to some serious problem like health hazards
and serious environmental impacts. Water and ground contaminations, flooding,
air pollution and spread of diseases are some that are happening in our times.

The Philippines’ waste continues to rise with the increase in our


population. According to NSWMC, 37,427.46 tons per day of wastes are
produced in 2012 that gradually increased to 40,087.45 tons per day in 2016. The
biggest volume of wastes generated comes from the National Capital Region
(NCR) for the past five years due to the high number of people living in this area,
bigger number of establishments and modernized lifestyle. There is an estimated
population in Metro Manila of 12 million people that generates 9,212.92 tons of
wastes per day in 2016 that is followed by Region 4A with 4,440.15 tons per day
and Region 3 with 3,890.12 tons per day (NSWMC).

According to the Status of Agricultural Waste and Utilization in the


Philippines, the major sources of biomass in the Philippines are rice, corn,
coconut, sugarcane and manures from poultry and piggery farm. The biggest
number of wastes comes from rice husk and rice straw which is 3,966,130 and

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17,627,245 tons while the second source are from corns which are corn cob and
corn stalk having 1,949,080 and 28,875,264 tons respectively. There are different
conversion technologies that are being used in the Philippines namely direct
combustion, biomass carbonization and densification, gasification and biogas.
Open field burning is the process that is commonly used since it is the cheapest
and practical option though it releases harmful greenhouse gases.

Corn (Zea mays) is one of the top most produced grain crop in the
Philippines. Aside from rice, it is also considered as the staple food of the 20% of
the populace in Visayas and Mindanao. It is also a major ingredient for the
production of poultry feeds, syrups, fabrics, adhesives, and other fermented
products that are distilled for the production of alcohol [1]. Processing and
cultivation of corn results to a huge amount of waste (corn residues) wherein
around 15-20% of this corn residues are corn cobs [2]. According to Zhang, Y., et
al, 2012, there is about 0.15 kg cobs for every 1 kg of dry corn. For every 797 MT
of corn produced there is roughly 135 MT of corn cobs collected [3].

Corn cobs (CC) are an essential by product of the corn processing industry
[4]. CC is an agricultural residue that comes from maize and remains part of the
corn on which the kernels grows. In other countries CC is usually disposed and
burned in preparation for the coming season. Dumping and burning of CC
contributes in global problems such as air pollution [5]. In line with these,
researchers studied about the uses of corn cobs as a raw material for the
productions of sugars, activated carbons, bio-oils etc. to eliminate industrial
pollution [1].

Relatively, CC contains Cellulose/Glucan (28.04%), Xylan (19.15%),


Lignin (12.61%), Ash (3.93%), Extractives (16.27%) and moisture (20.0%). Due
to these chemical compositions, corn residues show great potential as a renewable
raw material to produce added-value chemicals, such as lactic acid, citric acid,
sugars, and ethanol [4].

Glutamic acid is one of the twenty amino acids that constitute proteins. In
the biosynthesis of glutamine, proline and arginine it acts as the precursor.
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Glutamic acid was discovered in the year 1856 by Rizzo Johnson. It is a crystal
with good flavor and is slightly soluble in water and soluble in hydrochloric acid
solution. Its isoelectric point is 3.22 and it plays an important role in the protein
metabolism in vivo and participates in many important biochemical reactions of
animals, plants as well as microorganisms. Glutamic acid was first produced in
Japan by hydrolysis using wheat, gluten or soya bean protein. Later, Kyowa
Hakko Kogyo discovered the process of producing glutamic acid by fermentation
process.
Glutamic acid has been the object of scientific study for over 150 years
and has been sold as chemical product for the last eight decades. The highest
produced amino acid approximately 900,000 tonnes per year is glutamic acid. L-
glutamic acid was the first amino acid produced commercially. All twenty amino
acids are sold in greatly different quantities, calling the amino acid business as a
multi-billion-dollar enterprise. Among of this, glutamic acid is one of the amino
acids that is accounted as the majority produced by weight with lysine and
methionine. Also, increasing popularity of health and dietary related products due
to the desire of a healthier lifestyle made an increase in the demands for amino
acids like Glutamic acid.
L-Glutamic acid (C5H9NO4) is one of the two amino acids that has a
carboxylic acid group in its side chains. This is commonly referred to as
“glutamate” wherein its carboxylic acid side chain will be deprotonated and
becomes negatively charged in its anionic form at physiological pH. Glutamic
acid in appearance is in white crystalline powders. In the body, human brain is the
only tissue which has the highest content of glutamate that is obtained from
glucose via Krebs cycle intermediate [6]. It is the principal excitatory
neurotransmitter in the Central Nervous System (CNS).

There are three different forms of glutamic acid including the L-handed,
right-handed and racemic body. The first one, the L-handed is the L-glutamate
which is the coding amino acid that is known for participating in protein
synthesis. It is a non-essential mammalian amino acid that can be produced from
the conversion of glucose. At room temperature, it is a white or colorless flaky

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crystal, slightly acidic, and is non-toxic. It is easily soluble in hot water and
almost in ether, acetone and acetic acid as well as ethanol and methanol but only
slightly soluble in cold water. It undergoes sublimation at 200 ℃ and decomposed
at 247 ℃-249 ℃ with a density of 1.538g/cm3 and optical rotation being + 37-+
38.9 (25 ℃). The process used in producing glutamate is based on the microbial
fermentation using carbohydrate as the raw material. Most of the glutamate that
are produced are by means of fermentation from molasses like sugar beet or sugar
cane, which is a process like that of making wine, beer, sauce and vinegar [6].

Corynebacterium glutamicum, a nonpathogenic species of Coryneform


bacterium is the bacteria used in producing glutamic acid and now used for
industrial fermentative production of various amino acids. There are also other
bacteria in producing glutamic acid aside from Corynebacterium glutamicum like
Brevibacterium, Arithrobacter and Microbacterium.

Glutamic acid can be used in various industries such as food,


pharmaceutical, industrial and cosmetics. In the food industry, Mono Sodium
Glutamate (MSG) is used as a food additive and flavor enhancer. It can also be
used for dietetic purposes or nutritional supplement.

In terms of pharmaceutical it can be symptomatic treatment for


achlorhydria or hypochlorhydria since glutamic acid releases hydrochloric acid in
the stomach and can also be used as mucosal protective for those who undergo
gastrointestinal surgeries.

For industrial purposes, it can be used as nutrition supplement in


Agricultural, Animal feed or Poultry feed and intermediate of various organic
chemicals. and lastly in cosmetic industry, it helps regulate acid base balance,
making the skin firm that is important for skin growth and wound healing.
Different personal care products that glutamic acids are baby products, bath
products, cleansing products, eye makeup and shaving preparations. It is also
used for skin conditioning, moisturizing properties and also acts as a neutralizer
also.

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1.2 Product Profile: GLUTAMIC ACID

L-Glutamic acid (2-Aminopentanedioic) is one of the two amino acid that


contains carboxylic group in its side chain. It is also known as “glutamate”, which
acts as an intermediary between ammonia and the amino acids. It has a molecular
weight of 147.13 g/mol and melts at 205˚C. L-Glutamic acid is soluble in water
and is produced both naturally which the brain uses for fuel and protein synthesis
and critical for proper cell function. It is acidic with a carboxylic acid component
to its side chain. There are wide range of uses of this product including food
industries, cosmetics, pharmaceuticals, and as well as industrial applications.

A. Technical Specification of Glutamic Acid

PRODUCT IDENTIFICATION
PRODUCT NAME L-Glutamic Acid
IUPAC NAME 2-Aminopentanedioic acid
CHEMICAL FORMULA C5H9NO4
FORMULA WEIGHT 147.13 gram per mole
COMMON SYNONYMS GLU
L-GLU
Aciglut
Glusate
H-GLU-OH
GLUTACID
Glutamic
Glutaton
L-Glu-OH
FEMA 3285

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PHYSICAL PROPERTIES
PKa VALUE 2.13
pH 3.0-3.5 (8.6g/l, H2O, 25℃)
PHYSICAL STATE Solid/Powder
COLOR White
ODOR/TASTE Odorless
BOILING POINT Sublimes at 175˚C
MELTING POINT 205˚C
DENSITY 1.54g/cm3 at 20˚C
ENTHALPY OF 83.83 kJ/mol
VAPORIZATION
SOLUBILITY IN WATER AT 8.6 mg/ml
25˚C
VAPOR PRESSURE AT 25˚C N/A

B. Glutamic Acid Sales Specification and Composition

INGREDIENTS CAS NO. EINECS NO. PERCENT


Glutamic Acid 56-86-0 200-293-7 ≥99%
Water 7732-18-5 231-711-2
Microorganism Corynebacterium glutamicum

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C. Uses of Glutamic Acid

Glutamic acid is one of the important industrial products that is widely used in
food, pharmaceutical, medical, analytical, industrial and in personal care products.

FOOD INDUSTRY Raw material to produce Mono


Sodium Glutamate (MSG).
Used as a food additive, flavor
enhancer and for dietetic purposes or
nutritional supplement.
PHARMACEUTICAL INDUSTRY Principal and classical excitatory
neurotransmitter in the Central
Nervous System (CNS).
It is used in the disposal of ammonia
that provides a nontoxic storage and
transport form of ammonia. It helps
regulate nitrogen balance in our body
and a metabolic intermediate in
Kreb’s cycle.
Regulates acid-base balance and
makes the skin firm that is important
for skin growth and wound healing.
INDUSTRY Can be used as nutrition supplement
in Agricultural, Animal feed or
Poultry feed. Used as an intermediate
of various organic chemicals
COSMETICS Used in cosmetics and personal care
product (baby products, bath
products, cleansing products, eye
makeup, shaving preparations) and
can also be used for skin
conditioning, moisturizing properties
and acts as a neutralizer also, used

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widely as hair restorer.

D. Glutamic Acid Transport, Packaging, Handling and Storage

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CONTAINER Double plastic bags or foil bags
PACKAGING Fiber Drums
CONDITION Cool and tightly closed
TRANSPORT Delivered in double plastic bags/foil
bags and fiber drums
DOT CLASSIFICATION Not regulated
HANDLING Wear personal protective equipment.
Ensure adequate ventilation. Avoid
contact with skin, eyes and clothing.
Avoid ingestion and inhalation.
Avoid dust formation.
STORAGE Keep containers tightly closed, store
in a dry area and room temperature.
CHEMICAL STABILITY Stable under normal conditions.
HAZARDOUS DECOMPOSITION Carbon monoxide (CO), Carbon
PRODUCTS dioxide (CO2), Nitrogen oxides
(NOx)
CONDITIONS TO AVOID Incompatible products. Excess heat.
INCOMPATIBILITIES Strong oxidizing agents
SHELF LIFE 36 months
FIRE AND EXPLOSION DATA
FLAMMABILITY May be combustible at high
temperature.
FLASH POINTS Not available.
COMBUSTION PRODUCTS Carbon monoxide, Carbon dioxide,
Nitrogen oxides.
FIRE FIGHTING MEDIA AND As in any fire, wear self-contained
INSTRUCTIONS breathing apparatus pressure-
demand, MSHA/NIOSH (approved
or equivalent) and full protective
gear.
RISKS ARISING FROM THE Dust can form an explosive mixture
CHEMICAL in air.

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E. Product Safety and Disposal of Glutamic Acid

SPILL OR LEAKAGE PROCEDURES


ENVIRONMENTAL PRECAUTIONS Should not be released into the
environment.
METHODS FOR CONTAINMENT Sweep up or vacuum up spillage and
AND CLEAN UP collect in suitable container for
disposal. Avoid dust formation.
SMALL SPILL Use appropriate tools to put the

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spilled solid in a convenient waste
disposal container. Finish cleaning by
spreading water on the contaminated
surface and dispose of according to
local and regional authority
requirements.
LARGE SPILL Use a shovel to put the material into a
convenient waste disposal container.
Finish cleaning by spreading water
on the contaminated surface.

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1.3 RAW MATERIALS PROFILE

1.3.1 Corn Cobs

One of the most important food crops in the Philippines is corn. Aside
from rice, it is the staple food of the 20% population primarily in the Southern
regions of Visayas and Mindanao [7]. Corn can be used in different industries
such as food, pharmaceutical, analytical and industrial. The global corn
production increased from 599.35-867.52 million tonnes ( 44.74% increase)
during the period of 2001-2011 but also produces most of the wastes in the
Philippines [8]. About 15 to 20% of aboveground corn residues (non-grain) is
corn cobs [2]. Wherein for every 1 kg of dry corn grains produced, about 0.15 kg
of cobs [8].
Corn cobs are an important byproduct of the sweet corn processing
industry and feed manufacturers [4]. These are agricultural wastes generated from
maize (Zea mays). Corncobs contain approximately 39.1% cellulose, 42.1%
hemicellulose, 9.1% lignin, 1.7% protein, and 1.2% ash. In most established
countries, corn cobs are usually disposed and destroyed by fire on the farms to
prepare for the next coming season. The dumping and burning of CC on the farms
constitute gross air pollution [5]. Due to their chemical composition, corn residues
show great potential as a renewable raw material for producing a variety of
added-value chemicals, such as lactic acid, citric acid, sugars, and ethanol [4].
Many researchers studied about the uses of these corn cobs to eliminate industrial
pollution [1]. Some products that were produced were xylooligosaccharide,
activated carbons and bio-oil etc. [1].

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A. Technical Specification of Corn Cobs

MATERIAL IDENTIFICATION
NAME Corn Cobs
COMMON SYNOYMS Cob Grit, Cob Pellets, Cob Bedding,
Corn Stoves

PHYSICAL AND CHEMICAL PROPERTIES


PHYSICAL STATE Tan granular to powder
COLOR Tan
ODOUR Odourless
SOLUBIITY IN WATER Practically insoluble
SPECIFIC GRAVITY (H2O=1) 0.8 - 1.2
MELTING POINT 2200-2400 F
STABILITY Stable: pH=7.3
YOUNGS MODULUS N/A
BULK DENSITY 160-210 kg/m3
HAZARDOUS DECOMOSITION OR Combustion byproducts may be
BY-PRODUCT CO2/H2O, typical wood smoke

B. Corn Cob Sales Specification and Composition

MATERIAL SPECIFICATION
GRADE Food grade
APPEARNACE Tan
MOISTURE 6.38%

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MATERIAL COMPOSITION
COMPONENT % BY WEIGHT
Cellulose/Glucan 28.04 %
Xylan 19.15 %
Lignin 12.61 %
Ash 3.93 %
Extractives 16.27 %
Sucrose 0.86%
Acetate 2.01%
Soluble Protein 3.44%
Soluble Solids 9.96%
Unknown Soluble Solids --
Moisture 20.0%
TOTAL 100%

USE OF CORN COBS


Corn cobs will be used to produce Glutamic acid. Glucose, which will be
extracted from this will be the chemical used in producing Glutamic acid.

C. Use of Corn Cobs

D. Corn Cobs Transport, Packaging, Handling and Storage

PACKAGING, STORAGE AND TRANSPORT


PACKAGING Super tote sacks with proper seals
TRANSPORT Store in dry area. Take care not to
puncture/tear paper bags or tote bags
used.
HANDLING AND STORING Store in a cool, dry, well ventilated
area.
FIRE AND EXPLOSION DATA
EXTINGUISHING MEDIA Use appropriate media for
surrounding fire (water, chemical

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foam, dry
chemical, or carbon dioxide)
FLAMMABILITY Not applicable

E. Product Safety and Disposal of Corn cobs

SPILL AND LEAKAGE PROCEDURE


SMALL SPILL Vacuum sweep or shovel; follow
normal clean-up
EXPOSURE CONTROL/ Pre-existing respiratory, skin, or eye
PERSONAL PROTECTION conditions. Nuisance dust may cause
coughing/sneezing or watering eyes.
ENGINEERING CONTROLS Ensure that enough ventilation is
available to keep dust below the TLV/
PEL.
PPE Respiratory Protection: lf bag is
broken or product spilled, a NIOSH or
MSHA approved respirator may be

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necessary to avoid inhaling dust.
Ventilation: None
Protective Gloves: None required
Eye Protection: Standard goggle if
necessary.
Other Protective Clothing or
Equipment: None required
Work/Hygienic Practices: Normal
and routine hygiene practices
recommended
DISPOSAL CONSIDERATION
Waste Disposal Dispose of in accordance with all
regulations. Reuse recovered product
where possible.

1.3.2 Raw Material: UREA

Urea (CH4N2O), also known as carbamide, is an organic compound. It is


commonly seen in nature since it comes from the urine of animals and in humans
where approximately 20–35 g of urea is excreted in human urine per day.
According to International Plant Nutrition Institute, it is used to reduce emission
of nitrous oxide (NOx) gases in power plants and diesel exhaust systems. Many
common industrial chemicals are made using urea as an important

Urea was the first organic compound to be synthesized from inorganic


reagents. In terms of the production processes of urea in U.S. react ammonia and
carbon dioxide at elevated pressure and temperatures to form ammonium
carbamate, which is then dehydrated to form urea. Urea comes in many forms like
granules, flakes, pellets, and crystals, and in solutions. It is pelletized to avoid
caking [9].

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A. Technical Specification of Urea

PRODUCT IDENTIFICATION
PRODUCT NAME Urea
IUPAC NAME Carbonic diamide
CHEMICAL FORMULA (NH2)2CO or CH4N2O
FORMULA WEIGHT 60.06 g·mol−1
COMMON SYNONYMS Carbamide
Carbonyl diamide
Carbonyldiamine
Diaminomethanal
Diaminomethanone

PHYSICAL PROPERTIES
PKa VALUE Not Available
pH 7.2 (10% aqueous solution)
PHYSICAL STATE Crystal solid
COLOR White
ODOR/TASTE Almost odorless; May gradually
develop slight odor of ammonia,
especially in presence of
moisture
BOILING POINT Not Available
MELTING POINT 132.7°C (270.9°F)
DENSITY 1.32 g/cm3 at 20˚C
SOLUBILITY IN WATER AT 119 grams per 100 grams water
25˚C
ENTHALPY OF VAPORIZATION Not Available
VAPOR PRESSURE AT 25˚C 1.2X10-5 mm Hg at 25°C

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B. Uses of Urea

There are various uses of Urea such as industry, agriculture, deicing


agent and as consumers’ product.

INDUSTRY Urea is used in adhesives, binders,


sealants, resins, fillers, analytical
reagents, catalysts, intermediates,
solvent, dyestuffs, fragrances,
deodorizers, flavoring agents,
humectants and dehydrating agents,
formulation components, monomers,
paint and coating additives,
photosensitive agents, fertilizers,
surface treatment agents.
In the manufacture of some
medicines, urea is used as the key
synthetic ingredient.
AGRICULTURE It is used as nitrogenous fertilizer
and animal feed supplement.
Urea is used at approximately 3% of
the grain ratio or 1% of the total
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ration.
CONSUMER PRODUCTS It can also be used in the production
of liquid soaps, detergents,
household cleaning products and in
cosmetics products (creams,
shampoos, hair conditioners, hair
dyes and dye removers, in
ammoniated dentifrices etc.).

C. Urea Transport, Packaging, Handling and Storage

CONTAINER Closed or sealed bags on pallets


PACKAGING Fiber drums
CONDITION Store in a dry area. Keep out of
direct sunlight. Keep container in a
well-ventilated place and tightly
closed.
TRANSPORT The majority of solid urea product is
bulk shipped in trucks, enclosed
railroad cars, or barges, but
approximately 10 percent is bagged.
DOT CLASSIFICATION Not regulated
HANDLING Keep locked up and away from heat.
Empty containers pose a fire risk,
ground all equipment containing
material and evaporate the residue
under a fume hood.
Wear suitable protective clothing. In
case of insufficient ventilation, wear
suitable respiratory equipment.
Avoid contact with skin and eyes.
Keep away from incompatibles such

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as oxidizing agents.

STORAGE Keep container tightly closed. Keep


container in a cool, well-ventilated
area. Do not store above 23°C
(73.4°F).
CHEMICAL STABILITY Stable under normal conditions.
HAZARDOUS Carbon monoxide (CO), Carbon
DECOMPOSITION dioxide (CO2), Nitrogen oxides
PRODUCTS (NOx)
CONDITIONS TO AVOID Incompatible products. Excess heat.
INCOMPATIBILITIES Strong oxidizing agents
SHELF LIFE 6 months
FIRE AND EXPLOSION DATA
FLAMMABILITY May be combustible at high
temperature.
FLASH POINTS 72.7 ± 22.6°C
COMBUSTION PRODUCTS Carbon monoxide, Carbon dioxide,
Nitrogen oxides.
FIRE FIGHTING MEDIA AND SMALL FIRE: Use DRY chemical
INSTRUCTIONS powder. LARGE FIRE: Use water
spray, fog or foam. Do not use water
jet.
RISKS ARISING FROM THE Risks of explosion of the product in
CHEMICAL presence of mechanical impact.

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D. Product Safety and Disposal of Urea

SPILL OR LEAKAGE PROCEDURES


ENVIRONMENTAL PRECAUTIONS Should not be released into the
environment.
METHODS FOR CONTAINMENT Contain and recover by physical
AND CLEAN UP means. Water contaminated with this
product may be sent to a sanitary
sewer treatment facility, or a
permitted waste treatment facility.
SMALL SPILL Use appropriate tools to put the
spilled solid in a convenient waste
disposal container. Finish cleaning by
spreading water on the contaminated
surface and dispose.
LARGE SPILL Use a shovel to put the material into
a convenient waste disposal
container. Finish cleaning by
spreading water on the contaminated
surface.
DISPOSAL CONSIDERATION
WASTE DISPOSAL METHOD Empty containers or liners may retain
some product residues. This material
and its container must be disposed of
in a safe manner.

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1.3.3 Raw Material: BIOTIN

Biotin, also known as vitamin B7 or vitamin H is a water-soluble vitamin


that serves as an essential cofactor for carboxylase enzymes in multiple metabolic
pathways. It has a molecular weight of 244.31 g/mol and melts at 232.5°C
(450.5°F). Biotin is water-soluble, and it has many important functions in the
body. It's necessary for the function of several enzymes known as carboxylases.
These biotin-containing enzymes participate in important metabolic pathways,
such as the production of glucose and fatty acids.

A. Technical Specification of Biotin

PRODUCT IDENTIFICATION
NAME Biotin
IUPAC NAME  5-[(3aS,4S,6aR)-2-oxohexahydro-
1H-thieno[3,4-d]imidazol-4-
yl]pentanoic acid
CHEMICAL FORMULA C10H16N2O3S
FORMULA WEIGHT 244.31 gram per mole
COMMON SYNONYMS (3aS,4S,6aR)-hexahydro-2-oxo-
1H-thieno[3,4-d]imidazole-4-
pentanoic acid
Bios
Coenzyme R.delta.-Biotin
D(+)-Biotin
D-Biotin; Meribin
NSC 63865; Rovimix H 2
Vitamin B7
Vitamin H

PHYSICAL PROPERTIES

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PKa VALUE N/A
pH 4.5 (0.01 %)
PHYSICAL STATE Solid/Powder
COLOR White
ODOR/TASTE Odorless
BOILING POINT Decomposes
MELTING POINT 232.5°C (450.5°F)
SOLUBILITY Very slightly soluble in water and
in alcohol, practically insoluble in
acetone. It dissolves in dilute
solutions of alkali hydroxides
DENSITY N/A
ENTHALPY OF 93.9±6.0 kJ/mol
VAPORIZATION
VAPOR PRESSURE AT 25˚C 1.07X10-8 mm Hg

B. Uses of Biotin
Biotin is one of the important industrial products that is widely
used in the pharmaceutical industry. It is needed for energy production
where in several enzymes are needed to function properly. These enzymes
are involved in the metabolism of protein, carbohydrates and fats that
initiate the most important steps in the metabolic processes of these
nutrients.
Biotin is often associated with increased hair growth, healthier and
stronger hair and may help in strengthening the nails. It also plays an
important role in the pregnancy and breastfeeding stages wherein there is
an increase need of these vitamins during these stages. Also, when
combined with chromium, biotin may help lower blood sugar levels in
people with type 2 diabetes [64].

C. Biotin Transport, Packaging, Handling and Storage

CONTAINER Plastic Bottle


CONDITION Cool and tightly closed
TRANSPORT Not available
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DOT CLASSIFICATION Not regulated as dangerous goods.
HANDLING Generally, when handling avoid all
contact and inhalation of dust, mists,
and/or vapors associated with the
material. Clean equipment and work
surfaces with suitable detergent or
solvent after use. After removing
gloves, wash hands and other
exposed skin thoroughly.
STORAGE Keep container tightly closed.
Upon receipt, store the biotin at -20
°C. The other components may be
stored at room temperature. I
CHEMICAL STABILITY Stable under normal conditions.
HAZARDOUS DECOMPOSITION carbon dioxide, carbon monoxide,
PRODUCTS nitrogen oxides, sulfur oxides
CONDITIONS TO AVOID Moisture. Light.
INCOMPATIBILITIES Strong oxidizing agents

FIRE AND EXPLOSION DATA


FLAMMABILITY This material is assumed to be
combustible. As with all dry powders,
it is advisable to ground mechanical
equipment in contact with dry
material to dissipate the potential

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buildup of static electricity.
FLASH POINTS Not available.
COMBUSTION PRODUCTS These products are carbon oxides
(CO, CO2), nitrogen oxides (NO,
NO2 etc.).
FIRE FIGHTING MEDIA AND As in any fire, wear self-contained
INSTRUCTIONS breathing apparatus pressure-demand
(NIOSH approved or equivalent), and
full protective gear to prevent contact
with skin and eyes.
RISKS ARISING FROM THE N/A
CHEMICAL

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D. Product Safety and Disposal of Biotin

SPILL OR LEAKAGE PROCEDURES


ENVIRONMENTAL PRECAUTIONS Take steps to avoid release into the
environment, if safe to do so.
METHODS FOR CONTAINMENT Wear approved respiratory
AND CLEAN UP protection, chemically compatible
gloves, and protective clothing. Wipe
up spillage or collect spillage using a
high-efficiency vacuum cleaner.
Avoid breathing dust. Place spillage
in appropriately labeled container for
disposal. Wash spill site.
SMALL SPILL Use appropriate tools to put the
spilled solid in a convenient waste
disposal container. Finish cleaning by
spreading water on the contaminated
surface and dispose.
LARGE SPILL Use a shovel to put the material into
a convenient waste disposal
container. Finish cleaning by
spreading water on the contaminated
surface and allow to evacuate
through the sanitary system.
DISPOSAL CONSIDERATION
WASTE DISPOSAL METHOD Collect and reclaim or dispose in
sealed containers at licensed waste
disposal site. This product, in its
present state, when discarded or
disposed of, is not a hazardous waste.

1.3.4 Product Profile: SODIUM HYDROXIDE

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Sodium hydroxide (NaOH), also known as lye and caustic soda, is an
inorganic compound. It is a white solid ionic compound that has sodium
cations Na⁺ and hydroxide anions OH−. It is highly caustic metallic base and
alkali of sodium which is available in pellets, flakes, granules, and as a
prepared solution for different concentrations. Many everyday products are
produced using sodium hydroxide like paper, aluminum, commercial drain
and oven cleaners, and soap and detergents.

A. Technical Specification of Glutamic Acid

PRODUCT IDENTIFICATION
PRODUCT NAME Sodium Hydroxide
IUPAC NAME Sodium Hydroxide
CHEMICAL FORMULA NaOH
FORMULA WEIGHT 39.997 gram per mole
COMMON SYNONYMS Caustic Soda
Sodium Hydrate
White Caustic
Soda lye
Lye
Aetznatron
Ascarite
Sodium hydroxi
Natriumhydroxi
CAS NUMBER 1310-73-2

PHYSICAL AND CHEMICAL PROPERTIES


PHYSICAL STATE Crystalline Solid (Deliquescent
solid)

30 | P a g e
COLOR White
ODOR/TASTE Odorless
BOILING POINT 1388˚C
MELTING POINT 318°C - 323˚C
PKa VALUE N/A
pH 12 (0.05%wt/wt solution)
13 (0.5%wt/wt solution)
13.5 (1% wt/wt solution)
14 (5%wt/wt solution)
SOLUBILITY Very soluble in water. Freely
soluble in ethanol
DENSITY 2.13 g/cm3 at 25°C
HEAT OF FORMATION -422 kJ/mol
ENTHALPY OF 175 kJ/mol at 1388°C
VAPORIZATION
VAPOR PRESSURE AT 25˚C 1.82x10-21

B. Uses of Sodium Hydroxide

Sodium hydroxide (NaOH) is a highly versatile substance used in a variety of


industries from food, pharmaceutical or production of medicines and in other
industrial manufacturing processes. It is a co-product of chlorine production.

FOOD INDUSTRY Used curing foods like olives or

31 | P a g e
helping to brown Bavarian-style
pretzels, giving them their
characteristic crunch.
It is used in the removal of skin of
tomatoes, potatoes and other fruits
and vegetables for canning.
Help prevent mold and bacteria to
grow in foods or used as a
preservative.
PHARMACEUTICAL INDUSTRY Needed it to produce variety of
medicines and pharmaceutical
products like common pain relievers
(aspirin), anticoagulants that can help
to prevent blood clots, to cholesterol-
reducing medications.
INDUSTRY It is used to manufacture rayon,
spandex, explosives, epoxy resins,
paints, glass and ceramics.
When it comes to textile industry, it
is needed make dyes, process cotton
fabric and in laundering and
bleaching, as well as in metal
cleaning and processing, oxide
coating, electroplating and
electrolytic extracting.
C. Sodium Hydroxide Transport, Packaging, Handling and Storage

CONTAINER Air tight containers to prevent


moisture.
PACKAGE High-density polyethylene
(HDPE) barrels and containers.
CONDITION Tightly closed
TRANSPORT Through tanks, drums or pipelines.
DOT CLASSIFICATION Not regulated

32 | P a g e
HANDLING Wear chemically protective gloves,
lab coat or apron to prevent prolonged
or repeated skin contact. Wash
contaminated clothes. Evacuate
unnecessary personnel. Keep
containers closed.
STORAGE Containers of lye must be tightly
closed to prevent conversion to
Sodium Carbonate by Carbon
Dioxide of air. Store in a well-
ventilated place above 60° F. Keep
only in the original container.
CHEMICAL STABILITY Stable under normal conditions.
HAZARDOUS DECOMPOSITION Sodium oxide. Thermal
PRODUCTS decomposition generates: Corrosive
vapors.
CONDITIONS TO AVOID Incompatible materials. Extremely
high or low temperatures.
INCOMPATIBILITIES Metals. Strong acids
SHELF LIFE 60 months

FIRE AND EXPLOSION DATA


FLAMMABILITY Not flammable
FLASH POINTS Not available.
COMBUSTION PRODUCTS Carbon monoxide, Carbon dioxide,
Nitrogen oxides.
FIRE FIGHTING MEDIA AND Use water spray or fog for cooling
INSTRUCTIONS exposed containers. Exercise caution
when fighting any chemical fire. In
case of fire, stop leak if safe to do so.
When cooling/extinguishing: no water
in the substance. Prevent fire- fighting
water from entering environment.
RISKS ARISING FROM THE May cause pH changes in aqueous

33 | P a g e
CHEMICAL ecological systems. Avoid release to
the environment.

D. Product Safety and Disposal of Sodium Hydroxide

SPILL OR LEAKAGE PROCEDURES


ENVIRONMENTAL Avoid release to the environment.
PRECAUTIONS Prevent entry to sewers and public
waters.
METHODS FOR CONTAINMENT Take up liquid spill into inert
AND CLEAN UP absorbent material. Carefully collect
the spill/leftovers. Clean
contaminated surfaces with an excess
of water. Wash clothing and
equipment after handling. Soak up
spills with inert solids, such as clay or
diatomaceous earth as soon as

34 | P a g e
possible. Collect spillage. Store away
from other materials.
SMALL SPILL Wear protective clothing and
carefully apply neutralization powder
or liquid, whichever is most
appropriate to the spill. Allow time to
neutralize, and then apply liquid
absorbent pellets or powder.
DISPOSAL CONSIDERATION
WASTE DISPOSAL METHOD Dispose of contents/container to
Comply with applicable regulations.

35 | P a g e
1.3.5 Raw Material: PENICILLIN G.

Penicillin G. or Benzyl Penicillin is one of the first pharmaceutical


chemical that is used widely as an antibiotic. In fermentation, secondary
metabolites which likely produce antibiotics that blocks the cell wall synthesis
of microorganisms reducing their growth.

A. Technical Specification of Penicillin G.

PRODUCT IDENTIFICATION
PRODUCT NAME Penicillin G Sodium.
IUPAC NAME 3,3-dimethyl-7-oxo-
[(2phenylacetyl)amino]-4-thia-1-
azabicyclo[3.2.0]heptane-2-
carbocylic acid
CHEMICAL FORMULA C16H18N2O4S
FORMULA WEIGHT 334.39 g/mol
COMMON SYNONYMS Benzylpenicillin
Monopotassium Salt

PHYSICAL PROPERTIES
PKa VALUE 2.74 at 25℃
pH 5.5-7.5 (10%; H2O)

36 | P a g e
PHYSICAL STATE Powder
COLOR White
ODOR/TASTE Odorless
BOILING POINT 663.3 ℃ at 1atm
MELTING POINT 214–217 ℃
SOLUBILITY Soluble in water (100 mg/ml),
alcohol, glycerol,DMSO (71
mg/ml at 25° C), and ethanol (< 1
mg/ml at 25° C)
DENSITY 1.42 g/cm3
ENTHALPY OF VAPORIZATION 102.51 kJ/mol
VAPOR PRESSURE AT 25˚C 1.69X10-18 mm Hg at 25°C

37 | P a g e
B. Uses of Penicillin G.
Penicillin G is a Beta-lactam type of antibiotics. It weakens the
lysis of the cell wall by binding the penicillin proteins like what other
penicillin uses. An increased bactericidal effect is observed when drug
concentrations are maintained above minimum inhibitory concentration
(MIC) values.

C. Penicillin G. Transport, Packaging, Handling and Storage

CONTAINER Glass container, Polyethylene or


polypropylene container
CONDITION Not dangerous goods.
DOT CLASSIFICATION Not regulated
HANDLING Should be handled by trained
personnel. When risk of exposure
occurs, wear protective clothing.
Empty containers may contain
residual dust which has the potential
to accumulate following settling.
Such dusts may explode in the
presence of an appropriate ignition
source.

38 | P a g e
STORAGE Store at: 2-8°C.
Store in original containers.
Keep containers securely sealed.
CHEMICAL STABILITY Product is considered stable.
HAZARDOUS carbon monoxide (CO), carbon
DECOMPOSITION dioxide (CO2), nitrogen oxides
PRODUCTS (NOx), sulfur oxides (SOx), other
pyrolysis products typical of burning
organic material.
CONDITIONS TO AVOID May emit poisonous fumes and
corrosive fumes.
INCOMPATIBILITIES Avoid contamination with oxidizing
agents i.e. nitrates, oxidizing
acids,chlorine bleaches, pool
chlorine etc. as ignition may result.
Incompatible with metal ions,
especially copper, zinc, mercury.
FIRE AND EXPLOSION DATA
FLASH POINTS 355 ℃
COMBUSTION PRODUCTS carbon dioxide, carbon monoxide,
potassium oxides, nitrogen oxides,
sulfur oxides
FIRE FIGHTING MEDIA AND Water spray, fog or foam.
INSTRUCTIONS Wear breathing apparatus plus
protective gloves.

D. Product Safety and Disposal of Penicillin G.

SPILL OR LEAKAGE PROCEDURES


METHODS FOR CONTAINMENT Vacuum up or sweep up.

39 | P a g e
AND CLEAN UP NOTE: Vacuum cleaner must be
fitted with an exhaust micro filter
(HEPA type) (consider explosion-
proof machines designed to be
grounded during storage and use).
SMALL SPILL Wear chemical-resistant gloves.
Absorb spill and place in closed
container for disposal. Wash area
thoroughly after clean-up is
complete.

DISPOSAL CONSIDERATION
WASTE DISPOSAL METHOD Puncture containers to prevent re-use
and bury at an authorized landfill.

40 | P a g e
1.3.6 Raw Material: Ammonium hydroxide

Ammonia hydroxide is also known as aqua ammonia, it is a solution of


ammonia gas in water and a common commercial form of ammonia. It is a
colorless liquid with a strong characteristic odor. Ammonia hydroxide when
concentrated can cause burns when made in contact with the skin on the other
hand the ordinary household ammonia can be used as a cleanser, it is a dilute
ammonium hydroxide. It has a chemical formula of NH4OH where the solution
has primarily large quantities of water and ammonia and smaller quantity of
ammonium ion and hydroxide ion [74].

A. Technical Specification of Ammonium Hydroxide

PRODUCT IDENTIFICATION
PRODUCT NAME Ammonium Hydroxide
IUPAC NAME Ammonium hydroxide
CHEMICAL FORMULA NH4OH
FORMULA WEIGHT 35.046 gram per mole
COMMON SYNONYMS Ammonium hydrate;
Ammonia solution;
Ammonia water;
Aqueous ammonia;
Aqua ammonia. 

41 | P a g e
PHYSICAL PROPERTIES
PKa VALUE N/A
pH 11.7 – 13.8 (Basic)
PHYSICAL STATE Liquid
COLOR Colorless
ODOR/TASTE Ammonia-like (Strong)
BOILING POINT 27.2˚C
MELTING POINT -74.4˚C
DENSITY 0.89 g /cm3

ENTHALPY OF N/A
VAPORIZATION
SOLUBILITY IN WATER AT Miscible in water
25˚C
VAPOR PRESSURE AT 25˚C 287.9 kPa

B. Uses of Ammonium Hydroxide

Ammonium hydroxide is added to the Ammonium Percolation


column reactor for the pre-treatment of the corn cobs. It causes swelling
and efficient delignation of biomass at high temperatures that increase
the efficiency of production of glutamic acid.

42 | P a g e
C. Glutamic Acid Transport, Packaging, Handling and Storage

CONTAINER Glass
PACKAGING SUITABLE MATERIAL: synthetic
material. Glass.
MATERIAL TO AVOID:
aluminum, Copper, Tin, Zinc,
Nickel, Bronze.
CONDITION Cool and tightly closed
TRANSPORT Delivered in glasses
DOT CLASSIFICATION Class 8: Corrosive material
HANDLING Containers of this material may be
hazardous when empty since they
retain product residues (vapors,
liquids). Observe all warnings and
precautions listed for the product
Use caution when combining with
water. DO NOT add water to
caustic. ALWAYS add caustic to
water while stirring to prevent
release of heat, steam, and fumes
STORAGE The chemical should be store in
tightly closed containers, which need
to be kept in a cool, well-ventilated
place. The temperature of the place
of storage should not exceed 25°C
(77°F). The containers should be dry
and kept locked up. They should be
kept away from incompatible
substances such as acids and metals.
CHEMICAL STABILITY Stable under normal conditions.
HAZARDOUS DECOMPOSITION Not available
PRODUCTS
CONDITIONS TO AVOID Incompatible materials, excess heat,
confined spaces. 

43 | P a g e
INCOMPATIBILITIES Strong acids, Silver nitrate, Strong
bases
SHELF LIFE 365 days
FIRE AND EXPLOSION DATA
FLAMMABILITY Non flammable
FLASH POINTS Not available.
COMBUSTION PRODUCTS Nitrogen oxides, ammonia fumes
FIRE FIGHTING MEDIA AND Cool tanks/drums with water
INSTRUCTIONS spray/remove them into safety. Do
not move the load if exposed to heat.
Dilute toxic gases with water spray.
Take account of toxic fire-fighting
water. Use water moderately and if
possible collect or contain it.

44 | P a g e
E. Product Safety and Disposal of Ammonium hydroxide

SPILL OR LEAKAGE PROCEDURES


ENVIRONMENTAL PRECAUTIONS Prevent further leakage or spillage if
safe to do so. Do not contaminate
water. Avoid discharge into drains,
water courses or onto the ground. In
case of large spill, dike if needed.
METHODS FOR CONTAINMENT Stop the flow of material, if this is
AND CLEAN UP without risk. Prevent entry into
waterways, sewer, basements or
confined areas. Dike the spilled
material, where this is possible.

Absorb spill with an inert material


(e.g. vermiculite, dry sand, earth,
cloth, fleece), and place in a suitable
non-combustible container for
reclamation or disposal. Do not use
combustible materials, such as
sawdust. Clean contaminated surface
thoroughly. Neutralize spill area and
washings with dilute acetic acid.
Never return spills in original
containers for re-use.
SMALL SPILL Dilute with water and mop up, or
absorb with an inert dry material and
place in an appropriate waste
disposal container. If necessary:
Neutralize the residue with a dilute
solution of acetic acid.
LARGE SPILL Corrosive liquid. Poisonous liquid.
Stop leak if without risk. Absorb with

45 | P a g e
DRY earth, sand or other non-
combustible material. Do not get
water inside container. Do not touch
spilled material. Use water spray
curtain to divert vapor drift. Use
water spray to reduce vapors. Prevent
entry into sewers, basements or
confined areas; dike if needed.
Neutralize the residue with a dilute
solution of acetic acid. Be careful
that the product is not present at a
concentration level above TLV.

46 | P a g e
1.3.7 Raw Material: Sulfuric Acid

Sulfuric Acid, a strong mineral acid having a chemical formula of H 2SO4


is also known historically as oil of vitriol. Pure sulfuric acid is highly corrosive,
colorless and a viscous liquid. Its salts ae called as sulfates. It is soluble in water
at all concentrations. Sulfuric acid has various applications in the industry
including lead-acid batteries used for cars and other vehicles, ore processing,
fertilizer manufacturing, oil refining, waste water processing and chemical
synthesis.

A. Technical Specification of Sulfuric Acid

PRODUCT IDENTIFICATION
PRODUCT NAME Sulfuric Acid
CHEMICAL FORMULA H2SO4
FORMULA WEIGHT 60.06 g·mol−1
COMMON SYNONYMS Oil of Vitriol
CAS NUMBER 7664-93-9

PHYSICAL PROPERTIES
PKa VALUE -3 / 2
pH 2.75/ 1nM
PHYSICAL STATE Clear,
COLOR colorless liquid
ODOR/TASTE odorless
BOILING POINT 337 °C
MELTING POINT 10 °C
DENSITY 1.84 g/cm³
SOLUBILITY IN WATER AT miscible, exothermic
25˚C
ENTHALPY OF VAPORIZATION 67.59 kJ/mol

B. Uses of Sulfuric Acid

47 | P a g e
Sulfuric acid is used in the hydrolysis process of corn cobs
to facilitate the conversion of cellulosic materials to fermentable
sugars for the production of glutamic acid.

C. Sulfuric Acid Transport, Packaging, Handling and Storage

PACKAGING Inner materials: glass, plastic or


metal
Outer materials: wood, fiberboard,
plastic and metal
IDENTIFICATION Sulfuric acid UNNA: 1830 PG: II
DOT CLASSIFICATION 8 - Corrosive
HANDLING Wash hands and other exposed areas
with mild soap and water before
eating, drinking or smoking and
when leaving work. Do not breathe
mist, vapors, spray. Avoid contact
during pregnancy/while nursing.

STORAGE Keep only in the original container


in a cool, well ventilated place away
from incompatible materials. Keep

48 | P a g e
container closed when not in use.
CHEMICAL STABILITY Stable under normal conditions.
HAZARDOUS Sulfur compounds. Thermal
DECOMPOSITION decomposition generates corrosive
PRODUCTS vapors.
CONDITIONS TO AVOID Direct sunlight. Extremely high or
low temperatures.
INCOMPATIBILITIES Metals, strong bases, cyanides.
SHELF LIFE 20 months from the date of
manufacture and must be stored at
10 - 25 °C
FIRE AND EXPLOSION DATA
FLAMMABILITY Non-flammable
FLASH POINTS Not applicable
COMBUSTION PRODUCTS Products of combustion are not
available since material is non-
flammable.
FIRE FIGHTING MEDIA Foam. Dry powder. Carbon dioxide.
Water spray. Sand.
RISKS ARISING FROM THE Thermal decomposition generates
CHEMICAL Corrosive vapors.

D. Product Safety and Disposal of Sulfuric Acid

SPILL OR LEAKAGE PROCEDURES


METHODS FOR CONTAINMENT Soak up spills with inert solids, such
AND CLEAN UP as clay or diatomaceous earth as soon
as possible. Collect spillage. Store

49 | P a g e
away from other materials.
SMALL SPILL Dilute with water and mop up, or
absorb with an inert dry material and
place in an appropriate waste disposal
container. If necessary: Neutralize the
residue with a dilute solution of
sodium carbonate.
LARGE SPILL Absorb with DRY earth, sand or other
non-combustible material. Do not get
water inside container. Do not touch
spilled material. Use water spray
curtain to divert vapor drift. Use
water spray to reduce vapors. Prevent
entry into sewers, basements or
confined areas; dike if needed.
DISPOSAL CONSIDERATION
WASTE DISPOSAL METHOD Sulfuric acid may be placed in sealed
container or absorbed in vermiculite,
dry sand, earth, or a similar material.
It may also be diluted and neutralized.

50 | P a g e
CHAPTER II

Review of Related Literature

51 | P a g e
CHAPTER II

Review of Related Literature

2.1 INTRODUCTION
L- Glutamic acid (C5H9NO4) is one of the most important type of
L-amino acid based on industrial application [10]. L-Glutamic acid,
known by the IUPAC systematic name, 2-Aminopentanedioic acid, is an
organic acid that belongs to the family of carboxylic acids. Glutamic acid
plays a big role in amino acid metabolism and helps in maintaining the
nitrogen balance in the body [6]. According to Kaiser Permanente (2015),
it is used by the body to build proteins and is the most common
stimulating neurotransmitter in the Central Nervous System (CNS). It is
commercially used as food additives, feed supplements, infusion
compounds, therapeutic agents and precursors for peptides synthesis or
agriculture-based chemicals. It is also the first amino acid that is
commercially produced [11]. The carboxylate ions and salts of glutamic
acid are known as glutamates [10].
Fermentation process played a crucial role in the progress of
technology wherein currently, amino acids represents the products
produced from biotechnology in both volume and value [12]. Production
of glutamic acid by means of microorganisms was developed in 1957 in
Japan where various amino acids were produced. Three different methods
were used in the production of amino acids namely, microbial
biotechnology, fermentation or enzymatic method.
In this study, corn cobs will be used as the main raw material in the
production of L-Glutamic acid. Corn cobs are composed of
Cellulose/Glucan (28.04%), Xylan (19.15%), Lignin (12.61%), Ash
(3.93%), Extractives (16.27%) and moisture (20.0%) wherein glutamic
acid will be derived through a series of processes like hydrolysis,
fermentation, separation and purification.

52 | P a g e
In this chapter, research studies and literature have been
collaborated that tackles about the production of L-Glutamic acid by using
corn cobs as the raw material and summarized according to the following
headings:
a.) Product Description, Properties and Applications
b.) Raw Materials Related Literature
c.) Process Description
d.) Equipment Overview

53 | P a g e
2.2 List/Reference of Related Literature

A. BOOKS

[25] T. Baj and E. Sieniawska, Chapter 13. Vitamins. Elsevier Inc.,


2017.

[42] P. Harmsen, W. Huijgen, L. López, and R. Bakker, “Literature


Review of Physical and Chemical Pretreatment Processes for
Lignocellulosic Biomass,” Food Biobased Res., no. September, pp. 1–49,
2010.

[44] G. Najafpour, “Biochemical Engineering and Biotechnology


Biochemical Engineering and Biotechnology,” no. November, 2015.

[47] C. Wittmann, J. C. Liao, and A. A, Related Titles Chemicals and


Fuels from Bio-Based Building Blocks Micro- and Nanosystems for
Biotechnology of Bioactive Compounds - Sources and Culture of Living
Cells Further Volumes of the Series : .

[51] G. Brown, “Unit Operations”.

[53] Coulson and Richardson, “Chemical Engineering” Volume 6 Third


Edition

[58] “PROCESS DESIGN MANUAL FOR CARBON ADSORPTION


U . S . ENVIRONMENTAL PROTECTION AGENCY Technology
Transfer October 1973,” no. October, 1973.

[63] J. Krugsman, “Product Recovery in Biopress Technology,” no.


1992

[65] M. Keanne, T. Marie, “Encyclopedia & Dictionary of Medicine,


Nursing & Allied Health,” no. March 2003.

54 | P a g e
B. JOURNALS

[1] J. Chutrtong, “Comparison of Corncob and Corn Using as Fungal


Culture Medium,” Procedia - Soc. Behav. Sci., vol. 197, no. February, pp.
797–800, 2015.

[2] N. Kaliyan and R. V. Morey, “Densi fi cation characteristics of


corn cobs,” vol. 91, pp. 559–565, 2010.

[3] R. I. Muazu and J. A. Stegemann, “Effects of operating variables


on durability of fuel briquettes from rice husks and corn cobs,” Fuel
Process. Technol., vol. 133, pp. 137–145, 2015.

[4] A. Ashour, M. Amer, A. Marzouk, K. Shimizu, R. Kondo, and S.


El-sharkawy, “Corncobs as a Potential Source of Functional Chemicals,”
vol. 2008, pp. 13823–13830, 2013.

[5] A. I. Anukam, B. P. Goso, O. O. Okoh, and S. N. Mamphweli,


“Studies on Characterization of Corn Cob for Application in a Gasification
Process for Energy Production,” vol. 2017, 2017.

[6] C. Kulkarni, K. S. Kulkarni, and B. R. Hamsa, “L -Glutamic acid


and glutamine : Exciting molecules of clinical interest,” vol. 37, no. 3, pp.
148–154, 2005.

[9] C. a S. No, “Toxicological Review of,” Toxicol. Rev. Urea, vol.


39, no. 110, pp. 759–786, 2011.

[10] Z. A. Mahmood, A. Zafar, and Mahmood, “Microbial amino acids


production,” Microb. Biotechnol. - Prog. Trends, no. JANUARY, p. 25,
2015.

55 | P a g e
[11] R. Shyamkumar, I. M. Ganesh Moorthy, K. Ponmurugan, and R.
Baskar, “Production of L-glutamic acid with corynebacterium glutamicum
(NCIM 2168) and pseudomonas reptilivora (NCIM 2598): A study on
immobilization and reusability,” Avicenna J. Med. Biotechnol., vol. 6, no.
3, pp. 163–168, 2014.

[12] R. Darshan and B. Priya, “Comparative Production of Different


Amino Acids by Pseudomonas Boreopolis MD-4,” Int. J. Sci. Res., vol. 2,
no. 9, pp. 57–60, 2013.

[13] M. Asif et al., “Amino acids : A review article Amino acids : A


review article,” J. Med. plants Res., vol. 5, no. 17, pp. 3997–4000, 2011.

[14] E. Institutions, “About OMICS Group,” 2007.

[15] A. Anschau, L. O. dos Santos, and R. M. Alegre, “A cost effective


fermentative production of glutathione by saccharomyces cerevisiae with
cane molasses and glycerol,” Brazilian Arch. Biol. Technol., vol. 56, no. 5,
pp. 849–857, 2013.

[16] J. Willy et al., “United States Patent ( 19 ) fermentation,” no. 19,


2000.

[17] P. Vijayalakshmi and D. Sarvamangala, “Production of L-


Glutamic acid by Corynebacterium glutamicum DSM 20300 T and
Arthrobacter globiformis MTCC 4299 using fruits of Muntingia calabura
Linn .,” vol. 2, no. May, pp. 116–121, 2011.

[18] T. Hirasawa and H. Shimizu, “ScienceDirect Recent advances in


amino acid production by microbial cells,” Curr. Opin. Biotechnol., vol.
42, pp. 133–146, 2016.

[19] L. Cole and P. R. Kramer, “Vitamins and Minerals,” Hum.


Physiol. Biochem. Basic Med., pp. 165–175, 2016.

56 | P a g e
[20] J. B. Marcus, Chapter 7 - Vitamin and Mineral Basics: The
{ABCs} of Healthy Foods and Beverages, Including Phytonutrients and
Functional Foods: Healthy Vitamin and Mineral Choices, Roles and
Applications in Nutrition, Food Science and the Culinary Arts. 2013.

[21] D. P. Patel, S. M. Swink, and L. Castelo-Soccio, “A Review of the


Use of Biotin for Hair Loss,” Ski. Appendage Disord., vol. 3, no. 3, pp.
166–169, 2017.

[22] C. Fernandez-mejia, “Biological Effects of Pharmacological


Concentrations of Biotin,” vol. 16, no. 1, pp. 40–48, 2011.

[23] G. F. Combs, “Biotin,” Vitam., pp. 325–338, 2012.

[24] C. Chazot and J. D. Kopple, Vitamin Metabolism and


Requirements in Renal Disease and Renal Failure. Elsevier Inc., 2013.

[26] S. R. Lipner, “Rethinking biotin therapy for hair, nail, and skin
disorders,” J. Am. Acad. Dermatol., vol. 78, no. 6, pp. 1236–1238, 2018.

[27] C. Higgins, “Urea and the clinical value of measuring blood urea
concentration,” no. August, pp. 1–6, 2016.

[28] A. Kapuścińska and I. Nowak, “The use of urea and its derivatives
in the cosmetics industry,” Chemik, vol. 68, no. 2, pp. 91–96, 2014.

[29] International Plant Nutrition Institute, “Urea,” Nutr. Source


Specifics, no. 1, p. 1, 2010.

[30] M. H. Andrew Gardinier, Quirine Ketterings, Bill Verbeten, “Uera


Fertilizer Application,” 2013.

[31] S. Testing, “Urea Fertilizer in Crop Production,” pp. 10–12.

57 | P a g e
[32] P. M. Glibert, J. Harrison, C. Heil, and S. Seitzinger, “Escalating
worldwide use of urea - A global change contributing to coastal
eutrophication,” Biogeochemistry, vol. 77, no. 3, pp. 441–463, 2006.

[33] P. Bakker, for the Tropics. .

[34] S. H. B. Yacob, “The Effect of Supplementation by different


Nitrogen Sources on the Production of Bioethanol from Sago Hampas By
Saccharomyces cerevisiae,” Zhurnal Eksp. i Teor. Fiz., p. 13, 2013.

[35] Sids Oecd, “Introduction Sodium Hydroxide Cas N ° : 1310-73-2,”


Unep Publ., pp. 1–112, 2002.

[36] N. A. M. Sani, Z. Man, R. M. Shamsuddin, K. A. Azizli, and K. Z.


K. Shaari, “Determination of Excess Sodium Hydroxide in Geopolymer
by Volumetric Analysis,” Procedia Eng., vol. 148, pp. 298–301, 2016.

[37] A. Rabieenezhad and A. Roosta, “Experimental study and


thermodynamic modelling of penicillin-G extraction using PEG 6000 and
K2HPO4 aqueous two-phase system,” J. Chem. Thermodyn., 2018.

[38] P. Information, P. Monitoring, S. A. Dosage, and L. A. Dosage,


“Penicillin G,” pp. 613–616.

[39] D. Li, M. Yang, J. Hu, Y. Zhang, H. Chang, and F. Jin,


“Determination of penicillin G and its degradation products in a penicillin
production wastewater treatment plant and the receiving river,” vol. 42,
pp. 307–317, 2008.

[40] D. Humbird et al., “Process Design and Economics for


Biochemical Conversion of Lignocellulosic Biomass to Ethanol,” Renew.
Energy, vol. 303, no. May, p. 147, 2011. [42] “Fermentation and
Other Uses of Microorganisms.”

58 | P a g e
[41] C. S. Yah, S. E. Iyuke, E. I. Unuabonah, and O. Pillay,
“Temperature Optimization for Bioethanol Production from Corn Cobs
Using Mixed Yeast Strains Chetty Vishanta and Samuel M . Tessa School
of Chemical and Metallurgical Engineering , Faculty of Engineering and
the Built Environment , University of the Witwat,” vol. 10, no. 2, pp. 103–
108, 2010.

[43] D. R. Walt, B. H. Davison, J. W. Lee, J. D. Mcmillan, and M.


Finkelstein, “Biochemistry and Executive Editor :,” no. 1, 2003.

[45] “Fermentation and Other Uses of Microorganisms.”

[46] I. Kusumoto, “Glutamine Metabolism : Nutritional and Clinical


Significance Industrial Production of L -Glutamine 1,” no. February, pp.
2552–2555, 2018.

[48] R. Kumar, D. Vikramachakravarthi, and P. Pal, “Ac ce p te t,”


Chem. Eng. Process. Process Intensif., 2014.

[49] H. Jagani, K. Hebbar, S. S. Gang, P. V. Raj, H. Chandrashekhar,


and J. V. Rao, “An Overview of Fermenter and the Design Considerations
to Enhance Its Productivity,” vol. 301, pp. 261–301, 2010.

[50] J. C. Merchuk and M. Gluz, Bioreactors, Air-lift reactors -


Encyclopedia of Bioprocess Technology: Fermentation, Biocatalysis and
Bioseparation, Volumes 1 - 5. 1999.

[52] J. S. Van Dyk and B. I. Pletschke, “A review of lignocellulose


bioconversion using enzymatic hydrolysis and synergistic cooperation
between enzymes-Factors affecting enzymes, conversion and synergy,”
Biotechnol. Adv., vol. 30, no. 6, pp. 1458–1480, 2012.

[54] R. Beck, A. Häkkinen, D. Malthe-sørenssen, and J. Andreassen,


“The effect of crystallization conditions, crystal morphology and size on

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pressure filtration of l -glutamic acid and an aromatic amine,” vol. 66, pp.
549–558, 2009.

[55] T. Koda, H. Ueda, and K. Sato, “(12) United States Patent,” vol. 2,
no. 12, 2005.

[56] C. Engineering and A. E. College, “ENHANCING THE


PERFORMANCE OF ROTARY VACUUM.”

[57] N. Supanchaiyamat, K. Jetsrisuparb, J. T. N. Knijnenburg, D. C.


W. Tsang, and A. J. Hunt, “Lignin materials for adsorption: current trend,
perspectives and opportunities,” Bioresour. Technol., 2018.

[59] D. Nabarlatz, A. Ebringerová, and D. Montané, “Autohydrolysis of


agricultural by-products for the production of xylo-oligosaccharides,”
Carbohydr. Polym., vol. 69, no. 1, pp. 20–28, 2007.

[60] S. Sakamoto and Y. Kawase, “Adsorption capacities of poly-γ-


glutamic acid and its sodium salt for cesium removal from radioactive
wastewaters,” J. Environ. Radioact., vol. 165, pp. 151–158, 2016.

[61] L. Cermakova, I. Kopecka, M. Pivokonsky, L. Pivokonska, and V.


Janda, “Removal of cyanobacterial amino acids in water treatment by
activated carbon adsorption,” Sep. Purif. Technol., vol. 173, pp. 330–338,
2017.

[62] Senate Economic Planning Office, “Philippine Solid Wastes,” no.


1, pp. 1–4, 2017.

[66] R, Havannavar, “Delignification and Bioethanol Production from


Agroresidues” pp. 1-68, 2006.

[68] Mani, “Ethanol from Agricultural Crop Residues” Canada: University


of Saskatchewan.

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C. INTERNET SOURCES

[64] H. Palsdotirr, ‘What are the health benefits of biotin?’ 2018.


[Online]. Available:
https://www.medicalnewstoday.com/articles/318724.php. [Accessed: 18-
Sept- 2018].

[67] A. Michel, A. Koch-Koerfges, K. Krumbach, M. Brocker and M.


Bott ‘Anaerobic Growth of Corynebacterium glutamicum via Mixed-Acid
Fermentation’ 2015. [Online]. Available:
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4592858/. [Accessed: 18-
Sept-2018].

[69] M. Garg, ‘Fermentor (Bioreactor): History, Design and Its


Construction’. [Online]. Available:
http://www.biologydiscussion.com/industrial-microbiology-2/fermentor-
bioreactor-history-design-and-its-construction/55756. [Accessed: 18-Sept-
2018]

[70] N. Khan, ‘Glutamic Acid Fermentation’ 2018. [Online].


Available: https://www.slideshare.net/NOMIKhanS/glutamic-acid-
fermentation. [Accessed: 18-Sept-2018]

[71] J. March, W. Brown, ‘Carboxylic Acid’ 2018. [Online]. Available:


https://www.britannica.com/science/carboxylic-acid. [Accessed: 18-Sept-
2018]

[72] The Gale Encyclopedia of Science, ‘Sulfuric Acid’ 2018. [Online].


Available: https://www.encyclopedia.com/science-and-
technology/chemistry/compounds-and-elements/sulfuric-acid. [Accessed:
9-Oct-2018].

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[73] Chemical Compounds, ‘Ammonium Hydroxide’ 2018. [Online].
Available: https://www.encyclopedia.com/science/academic-and-
educational-journals/ammonium-hydroxide. [Accessed: 9-Oct-2018].

[74] The Editors of Encyclopaedia Brittanica, ‘Ammonium Hydroxide’


2018. [Online]. Available:
https://www.britannica.com/science/ammonium-hydroxide. [Accessed: 9-
Oct-2018].

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2.3 Review of Related Literatures on Glutamic Acid and its Raw Materials
2.3.1 L-GLUTAMIC ACID
A. Properties and Utilization

The amino acid business is a multi-billion-dollar enterprise where


there are all twenty amino acids that are sold in greatly different quantities.
Glutamic acid is one of the amino acids that is accounted as the majority
produced by weight with lysine and methionine. L-Glutamic acid
(C5H9NO4) is a type of amino acid that is responsible for enhancing flavor
for food known as monosodium glutamate (MSG) [6]. In pharmaceutical
industry, glutamic acid is used for the synthesis of glutathione. It is also
converted to alpha ketoglutaric acid in transamination reactions [13]. In
cosmetics industry, it regulates acid-base balance and makes the skin firm
that is important for skin growth and wound healing. It also has
moisturizing properties and acts as a neutralizer. It is widely used as hair-
restorer.

It is a dibasic amino acid used widely for the distribution of protein


and a neurotransmitter in the central nervous system where its
hydrochloride salt is used as a gastric acidifier. L-glutamic acid is a
nonessential amino acid that means it is produced in the body and does not
need to be obtained from outside sources [65].

Glutamate can be found in both free and bound forms in all natural
food stuffs like meat, poultry, cheese, fish, milk (including human breast
milk), tomatoes, mushrooms, and other vegetables [6].

Glutamate used in food is a free form of glutamate called MSG.


MSG is a derivative of glutamic acid, found to be a naturally occurring
nutrient in many foods, and is widely used in processing of food and home
cooking. It is commercially used to give or produce pleasant or agreeable
taste for humans. The presence of free form of glutamate, not linked to
protein is said to enhance flavor that gives a fuller taste to many foods.
MSG is called as ‘palate pleaser’ because of its ability to enhance food and
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can produce a unique taste sensation that is called ‘UMAMI’. Studies
shown that food containing glutamate is said to be 10 times more in breast
milk compared to cow’s milk that is why it is enjoyed by infants to adults
[6].

The bound form of glutamate is connected to other amino acid in


proteins present in, muscles, hair, and skin. In the human body, it is
considered essential for protein repair, regeneration and growth. The
average glutamate content in the body of an adult is around 1.5-2 kg. The
only tissue that has the highest glutamate content is the brain, it acts as a
neurotransmitter that is distributed in the central nervous system (CNS) and
maintains nitrogen balance in the body. It is obtained from glucose via
Krebs cycle intermediate. It is stored in synaptic vesicles, released by
calcium-dependent exocytosis and is said to act as an endogenous agonist
of the receptors mentioned. It also has a stimulating effect on the
metabolism of the cerebral cortex that improves mental performance and
memory function [10]. Glutamate is also synthesized in the body through
transamination of α-ketoglutarate by accepting amino groups from amino
acids, first step in metabolism of amino acid [6].

The most abundant amino acid present in the body is glutamine. It


is also called as levoglutamide, L-GA 5 amide, L-(+)-2-aminoglutamicacid.
It is produced by an energy requiring reaction catalyzed by glutamine
synthase using glutamic acid and ammonia in the body. Glutamine is said
to be nonessential in health, but it is essential for stress and illness. It is
commonly found in the skeletal muscle of the body making up to 60% of
free amino acid pool in the skeletal muscle [6].

An example of product where glutamic acid was used as an


intermediate is glutathione. Glutathione is the body’s primary antioxidant
and is one kind of a liver drug. It is a small protein composed of three
amino acids namely Cysteine, Glutamic acid and Glycine. The body uses
up its supply of glutathione faster when the body is exposed to greater

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toxins. It is called the master antioxidant since it is the most powerful anti-
oxidant that is naturally occurring in all 70-100 trillion cells that make up
the human body [14]. In humans, glutathione deficiency leads to various
diseases like liver cirrhosis, pulmonary diseases, gastrointestinal and
pancreatic inflammations, diabetes, neurodegenerative diseases and aging
[15].

Glutamic Acid Properties

CAS No. 56-86-0


EINECS NAME:
EC No. 200-293-7
Molecular Formula: C5H9NO4
IUPAC Name: 2-Aminopentanedioic acid
Mol. Weight: 147.13 gram per mole
Physical Status: Solid/Powder
Color: White
Odor: Odourless
Boiling Point: Sublimes at 175˚C
Decomposition Temperature: 247 ˚C or 476.6 ˚F
Density: 1.54g/cm3 at 20˚C
Stability: Stable under normal temperatures and pressures.

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REACTIVITY PROFILE

Glutamic Acid is incompatible with materials that are strong


oxidizing agents. Also, hazardous polymerization will not occur with it
and is non-corrosive with the presence of glass. Excessive heat and dust
formation should be avoided. There are different hazardous products that
will be formed when it decomposes like carbon monoxide (CO), carbon
dioxide (CO2), nitrogen oxides (NOx). Aqueous glutamic acid solutions
will form pyrrolidonecarboxylic acid slowly at room temperature and
more rapidly at 100 °C.
L-Glutamic acid (C5H9NO4) is one of the two amino acids that has
a carboxylic acid group in its side chains. This is commonly referred to as
“glutamate” wherein its carboxylic acid side chain will be deprotonated
and becomes negatively charged in its anionic form at physiological pH
(Sigma). Glutamic acid in appearance is in white crystalline powders.
Amino acids are known as the building blocks of proteins where they have
a carboxylic acid group because of having a weak acid and a weak base,
they exist as salts. Proteins play an important role in continuing
functioning of life and catalyze most chemical reactions that occur in the
cell [71].

Carboxylic acid is an organic compound that contains a carboxyl


group where its general formula is R–COOH. The R in the formula refers
to the rest of the molecule. It occurs widely that includes acetic acids and
amino acids. It is bonded to an oxygen atom by double bond and to a
hydroxyl group by a single bond. They are weaker than the familiar
mineral acids but are more acidic than organic compounds containing
hydroxyl groups [71]. Carboxyl groups donate hydrogen ions if a base is
present to accept them. They react with bases, both organic like amines
and inorganic. Neutralizations happen with them when they react with
bases where evolution of substantial amounts of heat happens. The
product produced when neutralization happens between an acid and a base

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are water plus a salt. Soluble carboxylic acids dissociate in an extent in
water to yield hydrogen ions. The pH of carboxylic acids is therefore less
than 7.0.

Carboxylic acids react rapidly with aqueous solutions containing a


chemical base and dissolve as the neutralization generates a soluble salt. It
forms gaseous hydrogen and a metal salt when the aqueous solution and
liquid or molten carboxylic acids reacts with active metals. Such reactions
also occur with solid carboxylic acids also, but the reaction is slower if the
solid acid is dry. Like other organic compounds, carboxylic acids can be
oxidized by strong oxidizing agents and reduced by strong reducing
agents. These acids are also often used as catalyst that increase the rate of
reaction and they may also initiate polymerization reactions.

Amino acids are crystalline solids with relatively high melting


points, so they decompose rather than melt when heated. They have the
amphoteric character which is an important characteristic of an amino acid
where they contain both acidic and basic functional groups that’s why they
can act as a base or an acid. In aqueous solutions, they act as neutral
dipolar ions or also called as zwitterions. The predominant form of the
amino acid present in solution depends on the pH od the solution and on
the nature of the amino acid. In strongly acid solutions, they are present as
cations, in strongly basic solutions they are present as anions while at
intermediate pH values, and more specifically at the isoelectric point (pI),
the concentration of the dipolar ion is at its maximum.

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Application Areas of Glutamic Acid

1. Food

Glutamic acid in the form of an odorless white crystalline powder.


It is the raw material that is used in the production of Mono Sodium
Glutamate (MSG). It is mainly used as a flavor enhancer and can also be
used for dietetic purposes or nutritional supplements.

2. Pharmaceutical

This is the principal and classical excitatory neurotransmitter in the


Central Nervous System (CNS). In the body, it is serves as the signal of
cutaneous barrier homeostasis and epidermal hyperplasia. It also helps
regulate nitrogen balance in our body and in the disposal of ammonia that
provides a nontoxic storage. This the intermediate used in the Kreb’s
Cycle. Glutamic acid is also used in the regulation of acid-base balance
and makes the skin firm. It can also be used for skin growth and wound
healing.

3. Industry
Glutamic acid is used as a nutrition supplement in Agricultural,
animal feed or poultry feed. It is also used as an intermediate for
various organic chemicals.

4. Cosmetics

In cosmetics, Glutamic acid is used for skin conditioning,


moisturizing properties and acts as a neutralizer also, used widely as hair
restorer. It is also found in cosmetics and personal care product (baby
products, bath products, cleansing products, eye makeup, shaving
preparations.

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DIFFERENT PROCESSES IN PRODUCING GLUTAMIC ACID

There are different advantages seen by using the solid-state


fermentation where its vital feature is the growth of microorganisms on a
pre-dominantly insoluble substrate without a free liquid phase. On the
other hand, extraction of amino acid by means of protein hydrolysate
method became of only limited importance though it is still relevant to
produce Lserine, L-proline, L-hydroxy-proline, and L-tyrosine.
L-Glutamic acid is made commercially by using the fermentation
process. Micrococcus glutamicus, Brevibacterium divaricatum,
Brevibacterium aminogenes, Brevibacterium flavum, Bacillus megaterium
and Microbacterium salicinovorum are the microbial strains that can be
used for the production but the species belonging to the genus
Corynebacterium is used to obtain glutamic acid by fermentation [16]. The
British patent GB 993,699 uses a novel Strain of Microbacterium
ammoniaphilumnin producing L-glutamic acid where it is mentioned that
a wheat protein hydrolysate can be used as an amino acid source that is
used as a growth nutrient where urea on the other hand is used as the
nitrogen source.
Other process that is used is via hydrolysis of glutamic acid rich
proteins. Glutamine rich protein that is isolated will be hydrolyzed using
acid and/or enzyme-conversion under a specific pH and temperature
conditions. The disadvantage of using this method is that the other amino
acids released during hydrolysis requires the product to be extensively
purified about three times crystallization and the other amino acids are lost
as nitrogen containing wastes.
There are also factors affecting the production of glutamic acid like
the carbon sources, nitrogen source, growth factors (biotin) and oxygen
supply where high concentration of oxygen inhibits growth while low
supply leads to lactic acid and succinic acid production.

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B. Current Market and Demand

According to Glutamic Acid Market: Global Industry Analysis


2012 – 2016 and Opportunity Assessment; 2017 – 2027 (2018), a
substantial growth to produce glutamic acid is anticipated due to the
growing applications in different industries. Also, the usage of processed
foods is expected to bolster the glutamic acid market growth across the
globe. The glutamic acid market is segmented by regions into North
America, Latin America, Western Europe, Eastern Europe, Middle East &
Africa (MEA), Asia-Pacific excluding Japan (APEJ), and Japan. In
Europe, the rising health concerns and the government regulations
regarding public health and feed additives are supposed to impact the
market significantly.

According to the Department of Trade and Industry there are


40,992 kilograms of glutamic acid that was imported in the current year,
2018 that amounted to 388,078 pesos. The prominent players in the global
glutamic acid market are Global Bio-chem Technology Group Company
Bachem AG, Ningxia EPPEN Bioengineering Stock Co., Ltd, Kyowa
Hakko Bio Co., Ltd Sichuan Tongsheng Amino Acid Co., Ltd, Iris
Biotech GmbH, Suzhou Yuanfang Chemical Co. Ltd., Ajinomoto Co.,
Inc., Limited, Akzo Nobel N.V., and Evonik Industries AG,.  To ensure
product differentiation and to gain a considerable share of the market,
major vendors are adopting creative strategies and are constantly
developing innovative products.

As stated by Global Market Insights, glutamic market was


estimated at over 2.9 million tons in 2014 and is likely to reach more than
4 million tons by 2023. Revenue is likely to be worth more than USD 15.5
billion by 2023 growing with an estimated CAGR of above 7.5% up to
2023.

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Monosodium glutamate (MSG) market size was estimated over 3
million tons in 2014 and is likely to surpass 4 million tons by 2023. MSG
is the sodium salt of glutamic acid which is an amino acid.
Approximately 64% and 88% for glutamic acid and MSG respectively of
the total volume in 2014 was consumed by the Asia Pacific. More
than 85% of the total volume in 2014 comes from the food & dietary
supplements. Pharmaceutical application is likely to witness highest gains
over the forecast period. The growing awareness with increasing health
consciousness favors the growth of glutamic acid production wherein it is
used as natural additive. It is also used in diary applications as it increases
the taste and shelf life of the product. This factor is likely to favor MSG
market growth. On the other hand, the major application of glutamic acid
in livestock production is the swine animal feed followed by poultry.
Glutamic acid as of now do not share a big quantity in
medical/pharmaceutical applications but was anticipated to increase over
the period. congenital metabolic diseases, parenteral nutrition and
hypertention neuroregulators are some of its medical application.

Due to the hectic lifestyles, processed food is seen as an easy


availability to consumers with the increase in middle class disposable
income levels. Glutamic acid and MSG, both are used as flavor enhancers
and additives in food applications. Major end-users for this particular
application include food processing industry (manufacturers of snacks,
convenience & functional food, condiments, seasoning blends, soups and
instant noodles), institutional food service providers and restaurants.

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2.3.2 CORN COBS
A. Properties and Utilization
According to the Status of Agricultural Waste and Utilization in
the Philippines, the major sources of biomass in the Philippines are rice,
corn, coconut, sugarcane and manures from poultry and piggery farm. The
biggest number of wastes comes from rice husk and rice straw which is
3,966,130 and 17,627,245 tons while the second source are from corns
which are corn cob and corn stalk having 1,949,080 and 28,875,264 tons
respectively. There are different conversion technologies that are being
used in the Philippines namely direct combustion, biomass carbonization
and densification, gasification and biogas. Open field burning is the
process that is commonly used since it is the cheapest and practical option
though it releases harmful greenhouse gases.

Corn (Zea mays) is one of the top most produced grain crop in the
Philippines. Aside from rice, it is also considered as the staple food of the
20% of the populace in Visayas and Mindanao. It is also a major
ingredient to produce poultry feeds, syrups, fabrics, adhesives, and other
fermented products that are distilled for the production of alcohol [1].
Processing and cultivation of corn results to a huge amount of waste (corn
residues) wherein around 15-20% of this corn residues is corn cobs [2].
Accor ding to Zhang, Y., et al, 2012, there is about 0.15 kg cobs for every
1 kg of dry corn. For every 797 MT of corn produced there is roughly 135
MT of corn cobs collected [3].

Corn cobs (CC) are an essential by product of the corn processing


industry [4]. CC is an agricultural residue that comes from maize and
remains part of the corn on which the kernels grows. In other countries CC
is usually disposed and burned in preparation for the coming season.
Dumping and burning of CC contributes in global problems such as air
pollution [5]. In line with these, researchers studied about the uses of corn

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cobs as a raw material for the productions of sugars, activated carbons,
bio-oils etc. to eliminate industrial pollution [1].

Relatively, CC contains 42.1% hemicellulose, 39.1% cellulose,


9.1% lignin, 1.7% protein, and 1.2% ash. Due to these chemical
compositions, corn residues show great potential as a renewable raw
material for the production of added-value chemicals, such as lactic acid,
citric acid, sugars, and ethanol [4].

A. Current Sources, Supply and Prices

The corn plants are part of the grass family or graminae and s
called as Zea mays Linn. Other crops that belong to this group are rice,
sugar cane, and sorghum. In the Philippines, corn is also considered as our staple food
next to rice. Almost 70% of the corn produced are consumed as human food while the
rest are used for livestock and poultry needs. There are many by-products produced
from corn such as corn starch, textile, paints, corn oil, paper, etc.

Corn bran, corn glutted fees and corn oil meal or corn oil cake are
some of the by-products of corn. Corn bran is the outer part of the corn
kernel after milling. Corn gluten feed is obtained from the manufacture of
cornstarch or syrup but has a low-quality protein. Lastly, corn oil meal or
corn oil cake comes from the wet milling of corn starch and corn syrup as
a by-product. It contains 22 % protein and 10% fiber.
Almost all the parts of the corn are used in the industry. Corn
stalks are used for manufacturing wallboard, fuel gas and paper. Corn ear,
for making oil and corn starch wherein this oil goes t the manufacturing of
soap, paint varnish, and rubber substitute. It can also be processed to make an edible oil
for salad or into oil cakes.
According to Corn: An Investment Opportunity, Region IV-B
(MIMAROPA) has vast agricultural resources which are highly suitable
for almost types of crops particularly corn. In the region, Palawan has the
biggest agricultural area of corn but in terms of production Occidental
Mindoro has the highest production. Almost 90% of the corn produced in
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the region are yellow corn while white corn is very much important to the
region.
According to the Philippine Statistics Authority (2018) “Rice and
Corn Stocks Inventory”, the total corn stocks inventory level was 480.86
thousand metric tons (Figure 2) as of July 2018.There was an decrement
29.66% in comparison with the last year’s level of 683.62 thousand metric
tons. Relative to the last month’s stocks inventory level of 592.01
thousand metric tons, this showed an increase of 18.78 percent (Table 2).

Corn
stocks

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inventory level in all sectors declined with regards to last year's level. A decrease
of 7.03 percent, 31.42 percent, and 100.00 percent was observed in the
households, commercial warehouses and NFA depositories, respectively (Table
2).

Household corn stocks inventory level grew by 29.25 percent from the last
month's inventory level while a drop of 22.88 percent was observed in
commercial warehouses (Table 2).

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B. Alternative Raw Materials

In the production of glutamic acid, glucose is one of the major


sources of carbon. There are different kinds of raw materials used for
producing glutamic acid via submerged fermentation.

L-amino acids are major biological components commercially used


as additives in food, feed supplements, infusion compounds, therapeutic
agents and precursors for peptides synthesis or agriculture-based
chemicals. After antibiotics, the second most important category are the
amino acids with fermentation products exhibiting the highest growth
rates. L-glutamic acid was the first amino acid produced commercially.

Glutamic acid is of industrial importance since it is widely used in


food, pharmaceutical, medical biochemical and analytical industries [17].
L-glutamic acid was mainly produced by microbial fermentations and the
chemical mode of synthesis is not widely preferred due to the formation of
racemic mixture. By means of submerged fermentation, L-glumatic acid is
produced per year by using a Corynebacterium species. Several
fermentation techniques have been used to produce glutamic acid.
Glutamic acid was produced with various kinds of raw materials using
submerged fermentation of palm waste hydrolysate, cassava starch, sugar
cane bagasse, date waste [11]. Cheapest saccharin materials are usually
used for producing glutamic acid like molasses, cane juice, beet juice,
cassava roots, sago etc. Based on the research reported on 2011, a high
amount of glutamic acid was excreted from date waste juice by
Corynebacterium glutamicum CECT 690. Later, a research was conducted
by Das et al. wherein he concluded that palm waste hydrolysate is the best
substrate which gives an elevated concentration of glutamic acid 88g/l
using submerged fermentation [17].

There are numerous raw materials that can fit into the above-
mentioned category, but some present study introduces another novel
substrate for glutamic acid fermentation- fruits of M. calabura. M.calabura
76 | P a g e
L. is an ever-green tree found commonly on wastelands and its fruits
become unutilized and left for natural degradation by soil microbial flora.
The fruits were used as substrates in current researches and subjected to
glutamic acid submerged using OFAT method produces appreciable
quantities of product i.e., 88.8% of glutamic acid higher than the yield
acquired by the earlier studies on glutamic acid production from the
substrates like sugarcane baggase (3.86%) by Jyothi et al., cassava starch
(75.7%) by Amin et al., Mexican lime waste (13.7%) by Islas-Murguia et
al. (1984), biotin rich beet molasses (55%) by (Haruo Momose and
Takashi Takagi, 1978) , Palm waste hydrolysate (88g/l) by Das et al.

The fruit sample consists of 17.0g of sugars per 100g of substrate


as per the analysis report obtained from spectrophotometric phenol
sulphuric acid method read at 490nm. Nearly 15.1g of sugars out of 17.0g
were converted to glutamic acid. Qualitative sugar analysis reports of the
fruit sample showed the presence of glucose, fructose and sucrose.

2.3.3 MICROORGANISM (Corynebacterium glutamicum)

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Corynebacterium glutamicum (C. glutamicum) is a model
organism in microbial technology, is known to metabolize glucose under
oxygen-deprived conditions to l-lactate, succinate, and acetate without
significant growth [67]. C. glutamicum, a gram-positive soil bacterium is
widely used for the production of various amino acids like glutamic acid.
Analysis reveals that marginal growth take place anaerobic conditions
with glucose, fructose, sucrose, or ribose as a carbon and energy source
but not with gluconate, pyruvate, lactate, propionate, or acetate. Some of
the important roles of amino acids with a high ATP, a demand for
biosynthesis and amino acids of the glutamate family is for growth
stimulation that indicates ATP limitation and restricted carbon flux into
the oxidative tricarboxylic acid cycle toward 2-oxoglutarate.

The nonpathogenic coryneform bacterium, Corynebacterium


glutamicum, was isolated as an L-glutamate-overproducing
microorganism by Japanese researchers and is currently utilized in various
amino acid fermentation processes. Production of glutamate by means of
Corynebacterium glutamicum is induced by the limitation of biotin and
addition of fatty acid ester surfactants and β-lactam antibiotics [18].
Corynebacterium glutamicum, is a short, aerobic, Gram-positive rod that
can grow on a simple mineral salt medium with glucose, provided that
biotin is also added. Biotin is an important factor in the production of
glutamic acid where deficiency of biotin affects fatty acid biosynthesis,
membrane formation alters, permeability is affected and intracellular
export of glu is altered.

After the discovery of this bacterium, many researchers


investigated the mechanism underlying in the production of glutamic acid
with respect to the cell surface structures of this organism.

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2.3.4 BIOTIN

Vitamins (and other minerals) play an important role in bodily


functions such as metabolism, digestion and immunity. It is generally
required in little amounts as supplement for a healthy body. Vitamins are
important organic molecules that cannot be integrated by the body.
Vitamins are grouped into two categories, the water-soluble and fat-
soluble categories. Fat soluble vitamins are stored in the body’s fatty
tissue while water-soluble vitamins are the vitamins that the body must
use right away [19]. Water-dissolvable vitamins incorporate all the B
vitamins, also called as B-complex and vitamin C. B-complex vitamins
includes thiamine, riboflavin, niacin, folic acid, pyridoxine, biotin,
cobalamin and pantothenic vitamins. These B vitamins work as
coenzymes with the help of enzymes to act as a catalyst to accelerate
reactions. Every one of these B vitamins works intimately with different
vitamins and related compounds in an associated web of chemical and
organic activities [20].
Biotin (otherwise called vitamin B7 or vitamin H) is vitamin that
belongs to the water-soluble category, it fills in as a basic cofactor for
carboxylase catalysts in various metabolic pathways. Because of its
abundance and cheapness as a cosmetic grade, it has become famous for
consumers to have healthier and longer hair and nails [21]. Vitamin B7
also functions as a prosthetic group of carboxylases. Inconsequential to
this role as a carboxylase prosthetic unit, pharmacological centralizations
of biotin influence both the transcriptional and the translational levels and
have a wide collection of impacts on fundamental procedures such as
metabolism, development and reproduction [22].
Biotin also works in gluconeogenesis, amino acid and fatty acid
metabolism as key steps involving the exchange of covalently bound,
single-carbon units in the most oxidized shape, CO 2 [23]. Biotin mostly
goes about as a "CO2 transporter" being the coenzyme for carboxylases
(propionyl CoA carboxylase, pyruvate carboxylase, B methyl crotonyl,
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CoA carboxylase, CoA carboxylase,). Biotin is covalently bound to the ε-
amino classification of a lysine deposit of carboxylases. In this manner, it
assumes an essential part in the metabolism of starches, amino acids and
saturated fats [24].

Biotin is mostly found at very low concentrations in food and


foodstuff. Only few foods such as calf kidney (100 μg/100 g), Rapeseed
meal (98.4 100 μg/100 g), soybeans (60 100 μg/100 g) etc., contain
considerable amounts of biotin. Some of the most common sources of
biotin are liver, milk, egg (egg yolk) and other vegetables. Dried seed,
alfafa and oilseed meals, are the most important sources of vitamin B7 for
the feeding of mammals. The biotin contents food are highly variable,
cereal grains are influenced by the variety of plant, yield and ratio [23].

Biotin is a white crystalline substance, in dry frame and is stable to


light, heat and air. In arrangement, however, it is delicate to degradation
under basic or acidic conditions its structure comprises of a collapsed
tetrahydrothiophene (thiophane) core and a planar ureido core, which
results in an arrangement with a plane of symmetry going through the S-1,
C-2′, and O positions so as to raise the sulfur particle over the plane of the
four carbons. The atom has three awry focuses; be that as it may, of the
eight possible stereoisomers, just the d-biotin has natural movement.
Biotin is covalently bound to its chemicals by an amide attach to the ε-
amino gathering of a lysine deposit and C-2 of the thiophane core. This
bond is adaptable, enabling the coenzyme to move between the dynamic
focuses of a few proteins. The biotin particle is actuated by polarization of
the O and N-1′ molecules of the ureido core. This prompt expanded
nucleophilicity at N-1′, which advances the development of a covalent
bond between the electrophilic carbonyl phosphate shaped from
bicarbonate and ATP and enables biotin to fill in as a vehicle specialist for
CO2 [23].

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Vitamin B7 is an important nutrient that plays an important role in
the initial steps of metabolism. Biotin works as the carboxyl carrier during
carboxylation reactions. Pyruvate carboxylase, b-methyl crotonyl-CoA
carboxylase, acetyl coenzyme A (CoA)-carboxylase-1 and -2 and
propionyl-CoA carboxylase are five biotin-dependent carboxylases that
are found in mammals. In carboxylases, biotin is connected to the e-amino
faction of lysine through the action of synthetases of holocarboxylase in a
twostep ATP (adenosine triphosphate) dependent reaction. It is followed
by the transferring of biotinyl group to carboxylase apoenzyme forming a
lysine bond that is semi peptic. Biotin-dependent carboxylase take part in
various metabolic pathways, the only mammalian carboxylase, acetyl-
CoA carboxylase1, is located in the cytoplasm, it speeds up the binding of
bicarbonate to form acetyl-CoA that creates malonyl-CoA, a carboxylase
that is needed in the fatty acid synthesis. For the synthesis of fatty acids,
carboxylase take place in the mitochondrial matrix. Propionyl-CoA
carboxylase catalyzes fundamental strides in the digestion of amino acids,
cholesterol, and odd-chain unsaturated fats, and b-methylcrotonyl-CoA
carboxylase takes an interest in leucinemetabolism; pyruvate
carboxylase,which changes over pyruvate to oxalacetate, is basic in
gluconeogenesis and tricarboxylic corrosive anaplerosis; and acetyl-CoA
carboxylase-2 partakes in the direction of unsaturated fat oxidation and
can likewise fill in as a biotin supply [22].
According to Baj, T. and Sieniawska, E. (2017), through bacterial
activity in the intestine, biotin is produced. Insufficiencies in biotin result
in hair loss and dry skin, languor, anorexia, despondency, and
hypercholesterolemia. Biotin insufficiency in people prompts confined
aggravation of the skin around the eyes, nose, mouth, conjunctivitis,
strange nails, and hair development, notwithstanding irregular fat
digestion. Biotin bolsters the procedures of development of keratin and the
separation of epidermal cells and hair and nails, enhancing their condition
[25].

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Combs, G. F. (2017), stated that at oxidizing conditions, biotin is
destroyed by heat particularly under conditions that help concurrent lipid
peroxidation because it is not stable. In addition, the poisonous quality of
biotin has appeared to be low. No cases have been accounted for of
antagonistic responses by people to high level of doses (Combs, G. F,
2012). While there are no settled day by day intake for biotin, the Food
and Nutrition Board of the Institute of Medicine suggests 30
micrograms/day for fully grow individuals [26].

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2.3.5 UREA

Urea is said to be the first organic chemical to be synthesized using


inorganic chemicals. The synthesis and research were headed by Friedrich
Wohler in 1828. Because of this, it marked the history as the birth of
organic chemistry and raised the first doubts about the popular belief of
many that an undefined “vital force” was required to synthesize chemicals
involved in the process of living organisms [27]. All production processes
of urea involve reaction with ammonia and carbon dioxide, it only differs
in the method of handling unreacted ammonia and carbon dioxide [9].

Urea, also called as carbamide, which means the diamide of


carbonic acid, is a natural chemical compound that can be found and
produced by the human body. It is formed in the liver from ammonia and
can be found in all organs, tissues, body fluids, and in the surface of the
skin [28]. It is considered as the principal nitrogenous waste product of
metabolism and is generated from protein breakdown [27]. Less than 10%
of urea is found in sweat and most of the remaining urea produced in the
liver is transported in blood going to the kidneys where it is released from
the body in urine [27].

I. Uses of Urea
Urea is preferred by fertilizer manufacturers because it is
easy to manufacture compared to ammonium nitrate. It also has a
high content of nitrogen needed for plant growth. It is commonly
mixed with soil or applied directly to the soil surface [29]. It is
popular to the farmers because it is said to have lower cost, ease of
storage and suitability for use in solid or liquid formulations [30].
Urea is considered as a stable product to store and transport, for
this reason the transportation of it is considered very cost effective
in comparison to its most common alternative, ammonium nitrate.
It is because ammonium nitrate is now classified as a hazardous

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product, there are many restrictions and potential additional costs
related to its transportation [31].

Another direct application of urea to land is as urea-based


herbicides or pesticides (sulfonyl urea pesticides). In this case, urea
is chemically synthesized with a poison or inhibitor. Sulfonyl urea
is one of the preferred herbicides for broadleaf and grassy weeds.
Urea-based herbicides potentially have a large impact by both
increasing urea inputs and reducing the potential for local uptake
[32].

Urea can also be used in some direct applications to


seawater. It is used in the growing world aquaculture industry. In
intensive shrimp culture, for example, ponds may be fertilized with
urea and superphosphate to initiate an algal bloom that eventually
serves as food for the commercial resource. A significant
proportion of such nutrients are subsequently discharged to local
waters with pond effluent as only a small fraction of added
nutrients ultimately winds up in marketable product [32].

Urea can also be used to prevent, stop or clean bodies of


water. In example, urea will be spread on coastal oil spills, to break
down the oil by stimulating the growth of natural bacteria
populations [32].

Urea is widely used and very popular in dermatology but it


is still considered unstable with water. It has been used for skin
diseases for more than a century. Urea is a potent emollient and
keratolytic agent, making urea an effective monotherapy for
conditions associated with dry and scaly skin [33]. Urea has
strong moisturizing properties and has keratolytic and antimitotic
effects. It is very useful for the thickening of the outer layer of the
skin problems. Urea is used in dry skin problems for example in
ichthyosis, but epidermal thinning may occur which is the side
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effect of using the product, especially with long-term use. Urea
having higher concentration can cause stinging. Urea can also be
used in combination with lactic acid [33].

II. Urea as a source of nitrogen for fermentation


Urea is one of the organic compounds that is considered to
have high nitrogen content. Assimilation of nitrogen is considered
the most important component in the fermentation medium.
Addition of urea in fermentation helps to accelerate the process
and it is considered as the most suitable in terms of economic and
yield product [34].

Global Production and Consumption

Urea is an organic compound that is widely used in different


industries. Commercial production of urea started in 1920s using Haber-
Bosch process. It is produced by reaction of carbon dioxide and anhydrous
ammonia at high temperatures. Global production capability of urea is
now approximately 70 million metric tons per year [32].

Seventy-five percent of the manufactured urea is used as nitrogen


fertilizer and the remaining are other significant uses of urea, which are
increasing globally. These other significant used are categorized based on
their pollution impact especially those who are applied directly to land or
sea [32].

Urea as a reductant in catalytic and non-catalytic reduction of


combustion products in vehicles is one of the applications of urea that is
considered to greatly expand through the years [32].

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2.3.6 SODIUM HYDROXIDE

The Sodium Hydroxide (NaOH) can be in a solid or liquid form.


When it comes to solid form its color is white. NaOH melting point is
318°C and the boiling point is 1388°C, it also solidifies at 20°C in such
condition that the concentration is more than 52% (by weight) and it can
contemplate the maximum water solubility at the temperature of 20°C.
When it comes to the vapor pressure of NaOH it is very low (< 10-5 hPa
at 25°C). The NaOH is a strong alkaline substance that completely
separates in the water to sodium and hydroxyl ions. It is powerfully
exothermic in the dissociation in water, therefore when the NaOH is added
to water there will be a dynamic reaction [35].

Sodium Hydroxide has a lot of use to human exposures such as


ingestion, inhalation and for the eyes and skin in domestic and industrial,
it is also accessible in the public. There are a lot of medical cases and
reports for the treatment of the burns caused by NaOH that are presented.
The pH of the blood increases when there is an exposure in NaOH.
Though the blood pH is controlled between narrow ranges to keep its
homeostasis. When there is a contact to low concentrations, the NaOH that
should approve is expected to be low because of the low absorption of
ions. It needed to uptake under normal conditions. There is a danger for
some accidental and intentional contact to the solid NaOH. Most of the
ingestion incident are linked with children especially that occurs at home
[35].

In the cleaning of the recyclable bottles in beer and other drinking


companies that are in large industries they used NaOH for
decontamination and cleaning determinations. The enterprises that are in
small and medium sized also used NaOH. The use of NaOH could result
in an aquatic emission of NaOH and it can also rise the concentration of
the sodium and the level of pH in the aquatic environment [35].

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When it comes to geopolymers synthesis the Sodium Hydroxide is
one of the most usually used alkaline activators, some of the reason why it
is commonly used is because of its cheap cost, its abundance and low
viscosity. The role of NaOH as an activator is because NaOH hastens the
reaction more swiftly. The NaOH offers both hydroxide anion and sodium
cation. The hydroxide anion act as a catalyst and the sodium cation act as
a structure-forming component that balance the negative charge
framework. NaOH was expressively that can affect the compressive
strength and also the geopolymers constructions [36].

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2.3.7 PENICILLIN G.

Penicillin G also known as Benzyl penicillin is one of the first


pharmaceutical chemicals that has been used widely as an antibiotic for
many infections, such as pneumonia, diphtheria, syphilis, strep throat,
necrotizing enterocolitis, leptospirosis, cellulitis, gas gangrene, and
tetanus. Fermentation process has secondary metabolites which most
likely produced antibiotics that block the cell wall synthesis of
microorganisms in result to reduce their growth. The production yield can
be enhanced during the extraction of antibiotics from fermentation
medium [37] .

I. Penicillin G in pharmaceutical industry

Penicillin G is a Beta-lactam type of antibiotics. It weakens


the lysis of the cell wall by binding the penicillin proteins like what
other penicillin uses. An increased bactericidal effect is observed
when drug concentrations are maintained above minimum
inhibitory concentration (MIC) values. The spectrum of penicillin
G is limited to gram-positive bacteria, anaerobic bacteria, and a
few highly susceptible gram-negative bacteria. Practically all
bacteria of the Enterobacteriaceae and beta-lactamase–producing
Staphylococcus spp. are resistant. Penicillin sodium or penicillin
potassium when injected intravenously has a half-life of 1 hour or
less in most animals. However, the same dose of procaine
penicillin given intramuscularly may produce more prolonged
concentrations and a half-life of 20-24 hours because of slow
absorption from the injection site [38].

II. Penicillin G production

Penicillin G produced by North China Pharmaceutical


Group Corporation (NCPGC), top producer of penicillin G in Asia
for having an annual production of about 7000 tons . The

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following biological treatments like anaerobic treatment, primary
aerobic treatment, hydrolyzation, acidification and secondary
aerobic treatment is to be done after the discharged of penicillin G
into the Wangyang River from the factory of penicillin G in the
city of Shijiazhuang. To recover the extracted solvent of penicillin
G before of these treatments, the raw wastewater is to be stored in
storage tank with the temperature of 75°C. Before and after the
anaerobic treatment, the extracted solvent of penicillin G diluted
with sewage wastewater and some other chemical production
wastewater including some kinds of antibiotics. Short fibers are
used in the two aerobic systems as biological support media. The
average time for hydraulic residence for each unit is 30 hours and
the annual output of excess sludge, which has been in operation
since the 1990s, is 1200 tons in dry weight [39].

III. Penicillin G availability and prices

The international stakeholders such as WHO, UNICEF and


World Heart Federation (WHF) calls by communiqué to address
the supply of benzathine penicillin G to be accessible to all
countries with high quality of product (RHD Action).

The price for BPG shows at the table below. Fixed price
implemented by own government for some countries (RHD
Action).

Table 1.

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2.3.8 Sulfuric Acid

Sulfuric acid, also known as oil of vitriol is a colorless, odorless,


extremely corrosive and an oily liquid. Pure sulfuric acid when subjected to heat
loses sulfur trioxide gas, SO3. Concentrated sulfuric acid is a weak acid that is a
poor electrolyte due to its little dissociation in to ions at room temperature. When
it is cold, it does not react with common metals like iron or copper but when hot,
it acts as an oxidizing agent where the sulfur in it is reduced and sulfur dioxide
may be released [72].

Concentrated sulfuric acid has a strong affinity with water and a high
boiling point that is used to release more volatile acids from their salt when
chemicals such as NaCl is heated with can also be used as a drying agent and to
dehydrate many compounds like carbohydrates [72].

In terms of diluted sulfuric acid, it should be slowly added to cold water


with constant stirring for limiting the buildup of heat. It reacts with water that
forms hydrates that have distinct properties. The diluted sulfuric acid is a strong
acid, good electrolyte, highly ionized where heat is released in the dilution that is
from the hydration of hydrogen ions. When placed in a litmus paper, the blue
color turns to red. It releases hydrogen gas when reacted with metals that forms
the sulfate of the metal [72].

Sulfuric acid has various uses in the chemical industry wherein it is almost
used in all manufactured goods. Its major use is in the fertilizer production and
manufacture of chemicals like hydrochloric acid, nitric acid, sulfate salts etc. It is
also used for washing impurities in petroleum refining [72].

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2.3.9 Ammonium Hydroxide

Ammonium hydroxide is a clear aqueous solution that has ammonia gas


dissolved in water produces a strong pungent odor caused by the ammonia in the
solution. Normal concentration of ammonia in ammonium hydroxide is about one
percent to 35 percent wherein most of the commercial purposes have a
concentration of about 10 percent ammonia in water [73].

The advantage of using ammonium hydroxide instead of ammonia is that


ammonia is easily controlled when it is dissolved in water unlike when it is
available as a gas. Ammonium hydroxide can be used as a cleaning agent,
refrigerant, food additive that maintains the level of acidity in foods, production
of soaps and detergents, pharmaceutical, ceramics, explosives, inks and
fireproofing of wood [73].

Production of bio-fuel (bio-ethanol) from biomass (pteris) by fermentation


process with yeast

When it comes to the use of ammonium hydroxide in the pre-treatment of


biomass, it was observed by Saha, P. et al. (2013) that it is the best for the
treatment when compared to sulfuric acid and sodium hydroxide since it produced
the highest amount of reducing sugar concentration.

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2.4 Review of Related Literature on Glutamic Acid Production

2.4.1 RAW MATERIAL PREPARATION

Glutamic acid can be produced through microbial fermentation and enzymatic


methods. Raw materials undergo hydrolysis to convert starch or cellulose to
fermentable sugars. In the case of lignocellulosic materials, pretreatment is
necessary to remove lignin which hinders successful hydrolysis of the biomass.
Fermentations involving the production of glutamic acid are then carried out to
convert monosaccharide such as glucose, fructose, galactose or disaccharides such
as sucrose or lactose into glutamic acid.

A. Pretreatment of Feed

According to Kim and Lee from the journal entitled “Pretreatment and
Fractionation of Corn Cobs/Stover by Ammonia Percolation Process”; the
pre-washed corn cobs with water is treated with aqueous ammonia in a flow
through column reactor to remove soluble that can hinder the reaction where
this process is called as Ammonia Percolation Process (ARP). At high
temperatures, aqueous ammonia causes swelling and efficient delignification
of biomass. The ARP process solubilizes about 80.5% of hemicellulose but
remains more than 99.6% of the cellulose content. Enzymatic digestibility of
ARP-treated corn cobs is 93% with 10 FPU/gglucan enzymes. Low-liquid
ARP can reduce the liquid throughput and residence time to 3.3 ml/g-biomass
and 10-90 min, without adversely affecting the overall effectiveness. The low-
water ARP achieved 97.1% delignification and 88.5% digestibility with 15
FPU/g-glucan. Successive operation of a hot-water treatment and the ARP
was applied as a method of biomass fractionation. The two-stage process
separated xylan in the first stage (84%) and lignin in the second stage (98%),
resulting treated solid that contains 94% glucan.

According to Humbird, D. et al., pretreatment process converts most


of the hemicellulose carbohydrates in the feedstock to soluble sugars (xylose,

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mannose, arabinose, and glucose) by hydrolysis reactions. Acetyl groups in
the hemicellulose are liberated as acetic acid [40].

Downstream enzymatic hydrolysis is facilitated in the breakdown of


biomass in pretreatment by disrupting cell wall structures, driving some lignin
into solution, and reducing cellulose crystallinity and chain length. The nature
and extent of such changes are highly dependent on the pretreatment
chemistry and reactions severity (define by residence time, temperature, and
catalyst loading). Furfural and 5-hydroxymethyl furfural (HMF) are the sugar
degradation products that can also be formed in the pretreatment. Adverse
effects on the fermenting organisms are can be made by these compounds in
sufficiently high concentrations [40].

The first stage in the pretreatment process have a short residence time
(5-10 minutes) and is a horizontal screw-feed reactor. The second stage, lower
temperature/ longer residence time is called the ‘oligomer conversion’ step. In
here, the xylose oligomers leaving the first stage are converted to monomeric
xylose without generating significant additional degradation products. After
the pretreatment reactors, flash cooling is done with the hydrolysate slurry
that vaporizes large amount of water along with some of the acetic acid and
furfural. The flash vapor is condensed and sent to the wastewater treatment
area. After that, the hydrolysate slurry is cooled by dilution water and sent to a
conditioning reactor, where ammonia is used to raise its pH from 1 to 5-6.

In previous designs, the pretreated biomass was separated into washed


solid liquid fractions, and the liquor and wash water were conditioned by an
”over liming” process in which the pH was increased from 1~10 with lime
and then readjusted to ~5 with additional sulfuric acid. Gypsum is formed
when the lime and sulfuric acid is precipitated which is removed in another
solid-liquid separation step. Cellulosic solids are used to reslurry the
conditioned liquid before proceeding to enzymatic hydrolysis. A significant
amount of sugar in the liquor (as much as 13%) could be lost to side reactions
occurring at high pH when using ammonia in the over liming process so that

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the hydrolysate is simply adjusted to enzymatic hydrolysis pH in one step.
Ammonia is more expensive than lime, but the economic benefits of reduced
sugar loss and reduced capital cost make ammonia the more economical
alternative. There is also a possibility that ammonia could reduce nitrogen
requirements in fermentation but is currently not modeled.

In the study made by Havannavar from the article “Delignification and


Bioethanol Production from Agroresidues”, it was stated that pretreatment is
essential to improve enzyme digestibility and obtain soluble sugar since
lignocellulosic biomass is naturally recalcitrant to enzymatic hydrolysis.
Physical, chemical and biological pretreatment methods are employed.
Examples of physical pretreatment method are ball milling and compression
milling decreases the degree of crystallinity and molecular weight if cellulose.
Dilute acid hydrolysis of certain softwood species is found to be suitable for
obtaining maximum soluble sugars [66].

An experiment was conducted by Kim et al. 2005 on pretreatment of corn


stover by aqueous ammonia was found that it is highly effective in
delignifying of the biomass, reducing the lignin content by 70-85 per cent. In
the first 20 minutes of the process, most lignin removal occurred. About 40-60
per cent of the hemicellulose was solubilized but left the cellulose intact. The
conversion of cellulose to glucose obtained is 99 percent upon enzymatic
hydrolysis.

In the pretreatment of raw dairy manure, 3 percent sulfuric acid is used at


110˚C for 1 h by Wen et al. (2004) and found that the hemicellulose was
completely degraded into mainly arabinose, galactose and xylose and when
pretreated material was subjected to enzymatic hydrolysis they obtained
glucose of 11.32 g/100 g raw dairy manure, which corresponds to about 40
percent cellulose conversion.

In the article by Yah et al., “Temperature Optimization for Bioethanol


Production from Corn Cobs Using Mixed Yeast Strains”; ammonium
hydroxide steeping of the corn cobs can be used to release lignin from it. An

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ammonium hydroxide ratio of 1:5 is used in the ammonia steeping by using
2.9M ammonium hydroxide. The delignified corn cobs give better yield in
acid hydrolysis and fermentation process [41].

In the utilization mixture of ammonia and ethanol for treating


lignocellulose-containing material under relatively mild temperatures
(preferably around 140˚C), showed improvement in the carbohydrate yield
and removal of lignin was promoted compared to, e.g., corresponding
methods only using ammonia. (Yongming Zhu). In the delignification,
ammonium serves as the catalyst while ethanol is used to facilitate the
solubilization and removal of lignin from the solid phase, in addition, not
being bounded by any theory, the addition of ethanol is believed to help the
preservation of carbohydrates in the solids probably by reducing their
solubility [41].

In a preferred embodiment, the lignocellulose-containing material is


subjected to 0.02-40 g ammonium per g lignocellulose substrate. In general,
the delignification catalyst may be present during treatment in a concentration
in the range from 1-30 wt.%, preferably 2-10 wt.%, especially around 5 wt.%
per g treating solution. In a preferred embodiment ammonium is dosed so that
the treating solution comprises from 0.02-40 g ammonia per g lignocellulose
substrate [41].

Hammer mill that is equipped with a screen having 5-mm holes is used to
ground corn stovers. The feedstock used for the experiment are the undersized
particles. The particles contains a moisture content of 8.9 wt%. Autoclave
reactors which are constructed out of 1.905 cm (0.75”) (Monel tubes sealed
with 316 stainless steel caps) are used for the delignification treatment and a
sand bath was used to provide heating for the treatment. At the beginning of
the experiment, 2.2 grams of corn stover particles (containing 2 grams of dry
matter) and 18 grams of aqueous treating solution were loaded into each
reactor. The corn stover is soaked in the reactors at room temperature for one
hour before heat-up [41].

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The treatment is made at 140˚C, using 5 wt% aqueous ammonia, 40 wt%
ethanol where results indicates a high degree of lignin removal at small
expense of carbohydrate loss. After two hours of cooking, only approximately
22% of initial lignin is left in the solids while approximately 84% of initial
xylan was recovered. A substrate formed when the treatment was done
without ethanol addition containing approximately 37% of initial lignin and
approximately 68% of initial xylan. Under all conditions in this experiment,
the recovery of cellulose was constantly higher (approximately 95-97%) [41].

Another desired pretreatment process was suggested by Harmsen et al.


from the article “Literature Review of Physical and Chemical Pretreatment
Processes for Lignocellulosic Biomass”. In the alkaline pretreatment, the
major effect is the removal of lignin from the biomass that improves the
reactivity of the remaining polysaccharides. In addition, alkali pretreatments
remove acetyl and the various uronic acid substitutions on hemicellulose that
lower the accessibility of the enzyme to the hemicellulose and cellulose
surface. It is reported that alkaline hydrolysis mechanism is based on
saponification of intermolecular ester bonds cross linking xylan
hemicelluloses and other components such as lignin. It was also observed in
the pretreatment of biomass using aqueous ammonia at elevated temperatures
reduces lignin content and removes some hemicellulose while decrystallizing
cellulose. Ammonia pretreatment techniques include the ammonia fiber
explosion-method (AFEX), ammonia recycle percolation (ARP) and soaking
in aqueous (SAA) [42].

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B. Hydrolysis

There are three major compounds of lignocellulose are the


cellulose, hemicellulose and lignin. Water and proteins are the main
components of lignocellulose that do not affect in the material structural
arrangement. The crystalline fibrous structure holds by hemicellulose
within the lignocellulose complex and appears as the core of the complex.
Hemicellulose can be found between the cellulose’s micro and
thermicrofibrils. Cellulose and hemicellulose embedded by the structural
role provided in lignin [42].

Chemical pretreatment is a significant process that breaks the


structures of some raw materials containing biomass and it helps the
preparation of fermentation process as well to obtain high monomeric
sugar yield. There are many pretreatment methods that are widely used for
cellulosic biomass. Many pretreatment processes have been used for
biomass conversion. They are physical, physio-chemical, chemical and
biological processes. Different methods used in pretreatment of biomass
can affect the rate of hydrolysis and the level of enzymatic action for
maximum theoretical yield of ethanol [68].

Chemical methods used for pretreatment of biomass are


ozonolysis, acid hydrolysis, alkaline hydrolysis, and oxidative
delignification and organosolv process. Among these methods, acid
hydrolysis and alkaline hydrolysis are commonly used to treat biomass
[68].

Liquid hot water (LHW) process is also known as


hydrothermolysis, aqueous fractionation, solvolysis, and hydrothermal
pretreatment. LHW is a process in biomass pretreatments of water at high
pressure and temperature. Water interacts with biomass by solvolysis
process or hot compressed water. Temperature ranges between 200–230
°C and dissolved the 40 – 60% amount of biomass, the process lasts for up
to 15 minutes. During the process for dissolving of biomass, cellulose with

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4-22%, lignin with 35-60% and all hemicellulose is detached. Throughout
the process of hydrolyzing of resulting liquid, 90% of the hemicellulose is
being recovered. The acid catalyst used for polysaccharide hydrolysis is
the acetic acid formed in the process. The production of monomeric sugars
is one of the outcome of the treatment and the type of biomass that has
very high lignin solubilization is considered as a major component that
affects the recovery of hemicellulose sugar [42].

Dilute acid treatment is also a type of chemical pretreatment which


is considered as one of the most effective pretreatment methods for
lignocellulosic biomass. High temperature and continuous flow process
for low-solids loading (T> 160 °C, 5-10 wt% substrate and concentration)
and low temperature and batch process for high-solids loading (T≤160 °C,
10-40% substrate concentration) are the two types of weak acid
hydrolysis. The most commonly used as a dilute acid is the sulphuric acid
that sprayed in the raw material and turns into a mixture. The mixture at
160-220 °C is held constant for up to few minutes. From the cell wall
matrix, the soluble oligomers and monomeric sugars are released into the
hydrolysate and hydrolysis of hemicellulose occurs but then removed to
increase and improve the porosity and enzymatic digestibility respectively.
The removal completion of hemicellulose can be eventually obtained with
high enzymatic digestibility. Dilute acid pretreatment can also use organic
acids as an substitute for inorganic acids. The treatment is good and
effective in terms of recovering hemicellulose sugars but there are also
some disadvantages. The hemicellulose sugars might be further degraded
to furfural and hydroxymethyl furfural, strong inhibitors to microbial
fermentation. Furthermore, acids that are used in the formation of solid
waste can be corrosive and neutralization. The method is especially
suitable for biomass with low lignin content, as almost no lignin is
removed from the biomass [42].

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Concentrated strong acids such as H2SO4 and HCl are considered
as strong agents for cellulose hydrolysis and have been widely used for
treating lignocellulosic materials because they are powerful agents (Sun
and Cheng, 2002), and enzymes are not needed subsequent to the acid
hydrolysis. High conversion of hemicellulose or xylan to xylose yields
when less critical conditions are produced by dilute acid hydrolysis
pretreatment. The total ethanol production method is enhanced given that
the hemicellulose content of biomass is up to one third of the total amount
of carbohydrates. High temperature continuous flow process foe low
solids loading which is containing 5-10% of hemicellulose in biomass and
low temperature batch process for high solids loading containing 10-40%
of hemicellulose in biomass are the two types of dilute acid pretreatment.
Advantages of using concentrated acid hydrolysis are the flexibility in
terms of feedstock choice, high monomeric sugar yield as well as mild
temperature conditions that are needed. Disadvantages of using
concentrated acids are corrosive nature of the reaction, toxic, harzardous
and the need to recycle acids in order to lower cost. To date, several
companies are in the process of commercializing strong acid hydrolysis of
lignocellulosic biomass for microbial fermentation purposes (BlueFire
Ethanol, 2010; Biosulfurol, 2010) [42].

Ozonolysis is also a type of chemical pretreatment used to degrade


lignin and hemicellulose in many biomass materials such as crop residues,
bagasse, wood chips, etc. This method is usedto increases the rate of
enzymatic hydrolysis by the factor of 5 when 60% of lignin is removed
from wheat straw. It effectively removes lignin and the process does not
produce any toxic residues despite of being an expensive type of
pretreatment. These processes are commonly used in many industries
since they are efficient in converting cellulosic materials into its
monomeric sugars [42].

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Corn stovers considered as a domestic feedstock and has high
amount of biomass. It can produce significant quantities of fuel ethanol
and other bioenergy and bio based products. However, availability of
comprehensive yield and carbon mass balance information and validated
kinetic models for dilute–sulfuric acid (H2SO4) pretreatment of corn stover
have not been reported. Because of this, estimation of process economics
and limited the ability to perform techno-economic modeling to guide
researchis hindered. To better characterize pretreatment and assess its
kinetics, corn stoverwas pretreated in a continuous 1 t/d reactor. Itwas
pretreated at 20% (w/w) solids concentration over a range of conditions
encompassing residence times of 3–12 min, temperatures of 165–195°C,
and H2SO4 concentrations of 0.5–1.4% (w/w). Xylan conversion yield and
carbon mass balance data were collected at each run condition. The
performanceresults were used to determine kinetic model parameters
assuming biphasic hemicellulose hydrolysis and a hydrolysis mechanism
incorporating formation of intermediate xylo-oligomers. In addition,
simultaneous saccharification and fermentation (SSF) process was used to
some of the pretreated solids to measure the reactivity of their cellulose
component to enzymatic digestion by cellulase enzymes. Monomeric
xylose yields of 69–71% and total xylose yields (monomers and
oligomers) of 70–77% were achieved with performance level depending
on pretreatment severity. Cellulose conversion yields in SSF of 80–87%
were obtained for some of the most digestible pretreated solids. In general,
the cellulose and xylan conversion results obtained under these conditions
are similar to those achieved in the lower-temperature pretreatments.
However, a particularly high total glucose yield of 87% was achieved,
which was performed at 180°C and 0.10% (w/w) acid and a residence time
of almost 90 minutes [43].
Corn stover is the raw material used which was obtained directly
from Biomass AgriProducts (Harlan, IA). The tub- ground material was
approx. 9mo old (harvested in fall 2000) when received at National

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Renewable Energy Laboratory (NREL) (summer 2000) and was then used
over a period of 9 mo. The fresh corn stover was dried to approx. 10%
moisture before grinding to produce small particles. The corn stover was
then washed by mixing with water (3 m3 / ton of corn stover) at 60°C in an
agitated 6000-L conical tank to remove dirt, solubles and extractives.
Filtration of the mixture was appliedto separate the cellulosic feedstock
from the water-extractives solution. The composition of the washed corn
stover (with negligible amount of extractives) from an average of five
randomly selected samples was 40.2% cellulose, 26.8% xylan, 20.7%
lignin (acid soluble and insoluble), 5.2% ash, and the balance is water
[43].

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C. Fermentation Process
The term fermentation came from the Latin verb ‘fervere’ that
describes the action of yeast or malt on sugar or fruit extracts and grain.
The ‘boiling’ is due to the production of carbon dioxide bubbles from the
aqueous phase under the. Fermentation is defined as the chemical
transformation of organic compounds with the aid of enzymes. Glycolytic
or Embden-Myerhof-Parnas pathways is done after the degradation of
carbohydrates by microorganisms. Fermentation process involves
biochemical reaction mechanism for the extraction of energy and
formation of products under anaerobic conditions [44].
Fermentation process by natural occurrence plays a vital role in the
human development and the oldest form of food preservation.
Fermentation process happens when microorganisms consume susceptible
organic substrate as part of their own metabolic processes. Interactions
like this is fundamental to the decomposition of natural materials. In some
cases, growth of microorganisms in some foods are undesirable and
considered a form of spoilage. Some examples of fermentation in foods
are the production of alcohol from fruit and fruit juices, milk that is mildly
acidic eventually forms cheese etc. [45].
Various preservation methods are being done based on the
application of heat, cold, removal of water, application of radiation and
other principles, having the common objective to decrease the numbers of
living organisms that is in contrast with the fermentation principle. In
fermentation whether it is for preservation purposes or not, multiplication
of microorganisms is the process being done but only selected organisms
are used [45].
There are different meanings associated with the word
fermentation, but the derivation of the word indicates a gentle bubbling
condition. The bubble formation is due to the conversion of the sugars to
carbon dioxide gas. Early researches dealing with this process became
associated with microorganisms and later with enzymes where it dealt

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with carbohydrates and reactions that forms carbon dioxide. In present
time, fermentation is described as the breakdown of carbohydrates under
anaerobic conditions. Reactions involving conversion of carbohydrates
and carbohydrate-like materials (true fermentations) to alcohol, acids, and
carbon dioxide are classified as “fermentative” while those proteinaceous
materials are referred to as “proteolytic or putrefactive” that gives the
putrid ad rotten odors and flavors that is undesirable beyond certain low
levels and the breakdown of fatty acids are called as lipolytic. Materials
that undergo fermentation results to different products due to their nature,
types of microorganisms present and environmental conditions that may
affect the growth and metabolic patterns [45].
Microorganisms are not just catabolic that breaks down more
complex compounds but also are anabolic and synthesize several complex
vitamins and other growth factors. Milling processes release nutrients by
physically rupturing cellulosic and hemicellulosic structures surrounding
the endosperm which is rich in digestible carbohydrates and proteins. On
the other hand, crude milling is used in many less developed regions that
is often inadequate to release full nutritional value. In terms of certain
molds in fermentation, physical and chemical breakdown happens with the
indigestible coatings and cell walls. Molds are known to be rich in
cellulose-splitting enzymes [45].
In large scale productions, a major problem observed is the
contamination. Microorganisms uses various sources of nutrients to be
able to do a wide range of metabolic reactions that makes fermentation
process suitable for industrial applications by using inexpensive nutrients
[45].
In the fermentation process, the addition of microorganism for the
conversion of one substance into another is a science that man is studying
and energetically applying. Fermentation was already known decades ago
from the fermentation of fruits to alcohol, making of various beverages out
of fruits and grains, it is only during the past generation that the wider

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application of this procedure has been recognized. In the present time,
usage of yeasts, bacteria and molds to the production of chemicals ae
being studied. Alcohol can be viewed as having been produced in this
way from the earliest times, but the making of acetone and butanol, acetic
acid lactic acid, citric and many antibiotics is a recent technical
accomplishment (SHREVE).

In the fermentation process, it is essential to maintain a clean and


sterile fermentation tank. Compared with wild-type strains, l-Gln-
producing strains are weak and are compromised in a contaminated
environment. Furthermore, it is important to maintain the tank under
positive pressure by aeration during fermentation to prevent contamination
by other microorganisms and external materials. The fermentation
medium consists of glucose as a carbon source, ammonia as a nitrogen
source, a small amount of minerals and vitamins as growth factors.
Control factors during fermentation are pH, temperature and dissolved
oxygen [46].

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D. Separation and Purification Process

The downstream process of glutamic acid fermentation include


separation and purification of L-gluytamic acid from the culture broth,
decolorization and crystallization. Separation and purification of glutamic
acid from the culture broth is completed through crystallization. Low
solubility, isoelectric point (3.2) and decreasing pH affects the
crystallization process of the glutamic acid, hence, at low solubility, acid
phase and 3.2 isoelectric point, glutamic acid is easily crystallized. After
the conversion of α crystal types to β crystal types, neutralization with
alkali, decoloration with the addition of active carbon and concentration
are performed, these results to the collection of crystallized pure glutamic
acid. Glutamic acid fermentation produces culture wastes such as
ammonia, phosphates, cells, magnesium and potassium, these wastes are
also used as fertilizers [47].

In the midst of environmental consciousness and severe disposal


regulations, chemical and allied process industries are seeking for a
cleaner process as a replacement for the traditional and polluting processes
of the fermentation of glutamic acid. In connection with this, the
production and purification of amino acid such as glutamic acid presumes
to be important. Concerned traditional process includes fermentation,
centrifugation, crystallization, evaporation, carbon adsorption, ion
exchange and other processes that involves the production of glutamic
acid [48].

The properties of the products that includes molecular size,


solubility and attraction to adsorbent and the charge characteristics may be
used to separate the amino acids from the fermentation broth. The
expected to be the one of the most auspicious candidates is the membrane
separation when it comes to successful separating of amino acids from the
great amounts of other amino acids. The other method that uses an anion-
exchange and cation exchange is called Electro dialysis but it has not been

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successful because of the substantial changes in the pH in the feed
solutions, that became unwanted for the reactions of enzymes when the
electro dialysis separation process is merged into the reactors. An anion-
exchange membrane separation was found to be a without difficulty when
it comes to contamination this is perhaps due to a reaction that is oxidative
of sulfhydryl group that amino acids have [48].

The cells can possibly be filtered by the use of a rotary drum filter
and it is done after the fermentation process. By the used of filter aids the
filtration can have a better-quality. Kiesselgur, the usual filter aids that is
based on diatomaceous earth, can enhanced the absorbency of the ensuing
filter cake that leads to the flow rate that is faster. A thin layer is applied
as a precoat of the filter (usually the standard filter) before the filtration
process proceeds. The level of purity in the product was the dependent for
the extraction of the amino acids from the filtrate. There were two
methods that are commonly used, one is the chromatographic (ion
exchange) method and the other one is the concentration-crystallization
method [70].

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2.5 Review of Related Literature on Production Equipment

2.5.1 Equipment Literatures

A. Fermenter (Bioreactor)

The Fermenter or also called bioreactor is a sealed vessel with


enough arrangement for temperature and pH control, agitation, aeration
and overflow or drain vent to dispose the waste biomass of cultured
microorganism alongside with their corresponding products [69].

It is used for commercial production in industries that involves


fermentation and also fermenter is an equipment which a substrate of low
value is used by enzymes or living cells to create a product of higher
value. Fermenters are extensively utilized for fermentation, waste
treatment, food processing, etc. [69].

The bioreactor is a specially designed vessel which can support the


cultivation of high concentration of microorganisms. The design of the
bioreactor must be able to operate at optimum environmental and
conditions that will specifically support the growth of the microorganism
[49].

The difference of bioreactor and chemical reactor is that the


bioreactor supports and control the biological entities. This equipment
must be constructed and designed to give a higher degree of control over
the process upsets and contaminations, since the organisms are more
sensitive and less stable than chemicals. By nature, biological organisms
have the ability to mutate which alters the biochemistry of the bioreaction
or the physical properties of the organism. However the majority of the
elementary bioreactor engineering and design issues are the same,
preserving the desired biological activity and minimizing and removing
undesired activities often presents a significant challenge than traditional
chemical reactors usually require [49].

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The fermenter or bioreactor is the central system of any
biochemical process in which mammalian, plant cells, microbial, enzymes
are used for large scale manufacturing of useful biological products. The
fundamental purpose of a correctly designed bioreactor is to give a
controlled environment to attain optimal growth and/or product formation
in the particular cell system employed [44].

Materials of Construction

The significant option that must be made are (1) the kind metal to
be used for nozzles and vessel, and (2) the kind of elastomer to be used for
the static seals. The selection must be based form the compatibility with
the welding characterictics, corrosion resistance, cleanability, organism to
be used and its product and also to the durability and cost. These
characteristics should be determined during the stage of process
development. Mostly in al cases, the metal selected will fall into stainless
steel (usually SS304, SS304L, SS316, or SS16L). The selection is usually
related with the value and nature of the product, although some of the
other factors earlier mat be considered. For lower value and unlicensed
products, SS304 are usually will suffice but for higher value and licensed
products, SS316L is the suitable material of choice. If corrosion resistant
vessel and well multipass welding characteristics are needed, L grade is
selected but it adds about 15 percent to the cost of the vessel [50].

In metal selection it is important to keep in mind that WFI, purified


water, clean steam are all highly corrosive. In static seal materials such as
EPDM, silicone, Teflon and Viton are used. EPDM and silicone are the
materials of choice for the headplates and elsewhere, respectively. When it
comes to temperature resistance Teflon is much better compared to sither
silicone and EPDM, but Teflon cold flows and it doesn’t stretch while The
viton hardens on use [50].

Lastly, some O-ring gaskets-forming processes might leave tiny


amount of metals in the seals. These might not be enough to disrupt the
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fermentation process or cause product problems, but it can cause
considerable corrosion [50].

Agitation System

Through magnetic coupling and direct mechanical coupling


agitation can be done. Magnetic coupling has been recommended for cases
that high levels of containment are required. There is also a concept that
magnetic drives are fit for maintaining more stringent levels of cleanliness
and asepsis compared to direct drive. Neither of the said claims has any
substantive basis; yes, it is somewhat reasonable to believe that existing
magnetic drives must be placed at the bottom of the vessel and in addition
the power transfer is quiet low [50].

When it comes to popularity, direct drive is predominant choice at


mostly in any scale of operation. The main altercation for bottom drive are
the shorter shafts, lower overall height, less support structure and the ease
of maintenance. These arguments revolved primarily on the possibility of
catastrophic spills resulting from the failure of the bottom seal, grinding of
the seal as a result of broth particulates operating into a bottom seal and
the greater difficulties in cleaning. If these seals are maintained and
designed properly, problems stated earlier can be prevented. We hardly
seen any legit difference in aseptic operability between the bottom and top
drives, and we are indeed certain that the organisms don’t actually care.
The selection would probably rely on personal preference [50].

It should be noted that there is also some cases in which double


mechanical seals should not or totally not be used in fermenters. The
details of individual seal designs and seal orientation caused a major
debate. But inline is much more recommended because we discovered that
it operates more cleanly and it require a much simpler lubricating and
sterilizing system [50].

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The lubrication of the seal is generally provided by means of
sterile steam condensate. It is really important that the condensate are
particulates free, because their presence will result into rapid seal failure,
hyperactive maintenance program and contaminated fermentations. It
should not be forgotten that during the sterilization the live stream flows
through the seal housing [50].

Fermenter
vessel schematic and terminology

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B. Evaporator

Evaporation is a type of unit operation that concentrates a solution by


boiling to separate the solvent from the mixture, which means that it is
dependent on the heat transfer for their operation [49]. The process is usually
stopped before the solute begins to precipitate from the solution. The
equipment itself must consist of a heat exchanger that can boil the solution
and can separate the vapor phase from the boiling liquid. In the industry,
evaporator is usually used for a continuous operation, the surface area of the
heat exchanger is vastly increased, boiling is much more violent, and the
evolution of the vapor is faster. Some problems might be encountered such as
foaming, scaling, heat sensitivity, corrosion, and space limitation. Because of
these problems, improvements and refinement in the design of the evaporator
are done to meet different combinations of solution properties and economic
conditions. The size, behavior and design of an evaporator are usually based
on the heat and material balance of the equipment itself [49].

Types of Evaporators

Evaporators can be designed in different types based on the specific


applications. Some of the types of evaporators are Natural Circulation
Evaporators, Falling- film Evaporators, Plate Evaporators or Multi-effect
evaporator [63].

Natural circulation evaporator is dependent on the nastural circulation


of the product, which is caused by the difference generated by heating. The
vertical tubes serve as the boiling area of the liquid. The circulation of the
liquid will start, which is caused by the rising bubbles. The separation of the
liquid and vapor will also start at the top of the heating tubes. The remaining
liquid will recirculate to the evaporation section so that only part of the total
evaporation occurs in one pass. This type of evaporator has low residence
time, high steam consumption, hence, it is a good heat transfer for liquids with
high temperature differences [63].

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Falling film evaporators have large number of long tubes
(approximately 4-8 meter in length), which is surrounded by a steam jacket.
The liquid will enter at the top of the tubes and distribute itself over the
heating surfaces as a thin film. The distribution of the liquid must be uniform
to have proper evaporation [63].

Plate evaporators are different from the other types of evaporator, it is


because the surface area of the evaporation section is relatively large despite
of having small volume. Corrugated metal plates are usually supported by
metal frame. During the evaporation process, the free space between the two
plates serves as the channels for the flow of the heat carrier or the steam. It
alternately climbs and falls parallel to the concentrate in co-current, counter-
current mode. The vapor and the concentrate are fed to a vapor/liquid
separator. Plate evaporators are usually used in the dairy and fermentation
industry. It is because it has small construction volume and flexibility.
However, the possibility of treating viscous and solids containing products is
limited [63].

In single evaporator, such as those already considered, the energy


(steam) consumption is rather high. Theoretically, we need 1 kg of steam for
the removal of 1 kg of water. To reduce the high consumption, multi-effect
evaporators of up to seven effects may be used [63].

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C. Hydrolysis Reactor
According to “Process Design and Economics for Biochemical
Conversion of Lignocellulosic Biomass to Ethanol: Dilute-Acid
Pretreatment and Enzymatic Hydrolysis of Corn Stover” by D. Humbrid et
al., most of the hemicellulose carbohydrates in the feedstock in a
pretreatment process is converted to soluble sugars (glucose, arabinose,
xylose and mannose) by hydrolysis reactions. The reactor pretreatment
system consists of a feedstock receiving system, a vertical vessel for
potential acid impregnation of the biomass and steam-heating with a long
residence time. Next to it is the horizontal pretreatment reactor which has
a short residence time and operates at a higher pressure. The configuration
for the horizontal reactor permits tighter residence time distribution
control than a reactor that is vertical that is why it is chosen. It is important
to minimize “over-cooking” or “under-cooking” portions of the biomass,
which could lower the overall yield [40].
At the pretreatment reactor inlet, milled corn stover is fed to the
receiving bins. The rectangular bins have a bottom-drag conveyor that
moves the feedstock pile inside the bin to the doffing rolls (special scraper
shafts with radial pins that spread material uniformly onto the discharge
belt conveyor). To ensure first-in/first-out material handling, the receiving
bins have a top-rake belt installed just under the cover of the bin to move
the incoming material towards its end. At the discharge of each bin, the
transfer conveyor lifts the material to the distribution screw conveyor,
which supplies ( ̴10%) slightly more feedstock than each pin drum feeder
requires. The speed of the pin drum feeders controls the flow rate of the
material in each plug screw feeder when overfeeding and ensures that the
feeders maintain a maximum fill. The excess feedstock is transferred back
to the storage bin by a series of conveyors that are connected in series
[40].
There is no significant hydrolysis reaction that occur in the pre-
steamer because in the current model it only operates at 100 deg C where

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the vertical pre-steamer of biomass is designed for a retention time of up
to 10 minutes and up to 165 deg C. Also, a single vertical is adequate with
a 2,205 ton/day throughput and 10 minute retention time. With uniform
temperature throughout, the feedstock flows downward through the
vertical reactor and the reactor is discharged through a dual screw outlet
device to two plug screw feeders. The feeders meter the feedstock to the
reactor for pretreatment and control both the pressure and temperature
between it and the pre-steamer. The transport conveyor combines the
feedstock from both plug screw feeders and delivers it to the pretreatment
reactor. Acid is added for the pretreatment reaction at the discharge of
each plug screw feeder.
The pretreatment reactor is a horizontal, single reaction vessel and
is designed for fairly severe conditions up to 190֯ C (374֯F) and about
1.1wt% sulfuric acid. The reaction conditions are milder at 158֯ C (310 ֯ F)
and 18 mg acid/dry biomass. High pressure steam is injected in to this
vessel wherein acid is metered to the reaction chamber proportional to the
rate of the feedstock. The pressure inside the reactor is held at the bubble
point for the mixture and heat losses are not accounted from the reactor in
the energy balance calculations. Lastly, the residence time in the
pretreatment reactor is normally 5 minutes.
There are four enzymatic reactors namely batch stirred tank
reactors, continuous stirred tank reactors, fixed bed column (immobilized
enzyme is packed remaining stationary while the substrate solution is
pumped through it) and fluidized bed column reactor (immobilized
enzyme is kept suspended by means of recycling of the substrate solution
pumped through) The enzymatic design of reactors requires knowledge in
mechanisms of mass transfer, hydrodynamics of the system, and reaction
kinetics. The reactor’s performance is crtically dependent on the properties
of the biocatalyst employed that will determine the mode of operation and
reactor flow characteristics. The configuration of the reactor also depends
in different factors like the effect of glycerol, the homogeneity of the

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reaction mixture, product solubility in alcohol, the type of alcohol, enzyme
recovery, enzyme stability, limitations in diffusion and the immobilization
of the system that can give highly productive processes [40].
An ideal support must have high resistance to compression in
operations at high flow rates PBR, frictional resistance in STR, and
resistance towards settling velocity in FBR. Furthermore, for continuous
operation, rigid supports with spherical and uniform particle size are often
more appropriate because these particles will produce little to no
variations in operational pressure, and allow good flow characteristics of
the interstitial fluid. The thermal, operational, and mechanical stability
may limit the long-term application of the biocatalyst in the process. The
mechanical strength of biocatalysts must allow the use of filtration,
centrifugation, and stirring because continuous and repeated uses
sometimes require these operations. Therefore, the mechanical stability of
the support is crucial for many applications of immobilized enzymes in
reactors. Depending on the support material, the effect of mechanical
stress can cause disintegration of the biocatalyst, further complicating the
downstream processing. The agitation speed in STRs influence yields of
reaction, because it is closely related to the mechanical stability of the
support. Immobilized T. lanuginosus lipase on silica gel was used in the
synthesis of palm oil esters (POE) via alcoholysis of palm oil (PO) and
oleyl alcohol (OA) in a batch reactor. An important parameter tested was
the stirring speed of the reactor, which ranged from 250–350 rpm. The
conversion and system productivity were slightly enhanced increasing
impeller speed up to 325 rpm, which caused substantial improvement in
the specific interfacial area between the substrate and enzyme observed in
the non-aqueous phase, as consequence of reduced droplet sizes. However,
the yield and productivity decreased at 350 rpm (maximum tested
agitation) is caused by the high shear and support disintegration. In
enhancing the mass transport for this kind of reactor, some alternatives can

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be done like reducing the particle size at a constant fluid stirring speed for
it to imcrease [40].
Based on “A review of lignocellulose bioconversion using
enzymatic hydrolysis and synergistic cooperation between enzymes—
Factors affecting enzymes, conversion and synergy” by Van Dyk J.S. and
Pletschke, B.I, mixing, pH and temperature are the conditions that affects
hydrolysis. To achieve optimal hydrolysis of substrates, reactor conditions
must be met because enzymes are active optimally at specific temperature
and pH. Complications occur in situations in SSF or simultaneous
saccharification and fermentation wherein processes take place within the
same bioreactor and CBP or consolidated bioprocessing which refers to
the use of a single organism to produce enzymes required and to perform
both the hydrolysis and fermentation when conditions for the
microorganisms are not met. An enzyme that is not operating at optimal
conditions affects the overall process cost and higher enzyme loadings
may be required to achieve the same level of hydrolysis efficiency [51].
Suspension and mixing of the substrate in the analysis or reactor
may have an impact on hydrolysis especially when dealing with
lignocellulosic insoluble substrates. In large reactions, mass transfer are
important and increased in agitation had an impact on Avicel conversion.
The intensity of agitation had no effect as long as solids are remained in
suspension. The compounds such as glycerol maybe added to reduce
particle settling. High intensity mixing has a synergistic effect with
enzyme hydrolysis. Mixing speeds up to 400 rpm are recommended since
mixing above 200 rpm resulted in decrease in hydrolysis as the activity of
the enzyme is lowered. Intense or continuous mixing is not required to
overcome mass-transfer limitations for efficient hydrolysis, but flask
mixing studies are inadequate.

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D. Rotary Dryer
Based on the book “Coulson and Richardson’s Chemical
Engineering” Vol 6 3rd Edition by Coulson and Richardson, Drying is the
removal of water, or other volatile liquids by evaporation. In the
production, most solid materials require drying at some stages. One
common type of dryer is the rotary dryer wherein here, the solids are
conveyed along the inside of a rotating, inclined, cylindrical and are
heated and dried by having a direct contact with hot air gases flowing
through the cylinder but in some cases, cylinders are indirectly heated. It is
fabricated in carbon, stainless steel and MS+ rubber lined with flights or
lifters that are welded or bolted internally to produce cascade of particles
falling through the hot gas stream. The parts of the rotary dryer are mainly
the hot air generator, feeding equipment and the dust collection equipment
[52].
Rotary dryers are used for drying free-flowing granular materials,
suitable for continuous operation at high throughputs, have a high thermal
efficiency and relative low capital and labor costs. Some of the
disadvantages of using this type of dryer are the formation of high noise
levels, dust generation and non-uniform residence time [52].
It was stated by Coulson and Richardson that rotary dryers are
suitable for continuous drying of materials on a large scale around 0.3 kg/s
(1 tonne/h) or greater that is driven by a low speed of around 0.4 Hz. A
small angle to the horizontal supports the shell so that the material fed in
at the higher end will travel through the dryer under gravity and the drying
medium that will be used like air or hot gases will be fed at the upper end
of the dryer to give co-current flow or at the discharge end of the machine
to give countercurrent flow. The mechanical lifting of the material allows
drying of materiasl from filter cake to coarse minerals through the hot gas
stream that helps in the breaking up lumps for uniform drying. The drum’s
length may range from 4 to 10 times of its diameter and usually operates
with 12-15% of their volume filled with the material.

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The rotary dryer’s shell is usually made by welding rolled plate
that is thick enough for the transmission of torque required to cause
rotation and to support its own weight and the weight of the material in the
dryer. Large tires usually support the shell which run on wide rollers. The
usual material of construction used in rotary dryers are mild steel and
some alloy steels are still used and if necessary, the shell is coated with
plastic material to avoid contamination of the product [52].
In a countercurrent operation, gases are often exhausted by a fan
there is a slight vacuum in the dryer and dust-laden gases are in this way
prevented from escaping. Arrangements like these are suitable for sand,
salt, ammonium nitrate and other inorganic salts and is particularly
convenient when the product is discharged at a high temperature. Gas or
oil firing are used in these cases but when air s used as the drying medium,
this may be filtered before heating to minimize contamination of the
product. Some form of cyclone or scrubber is usually fitted when gases
leaving the dryer carry away very fine material. Since there is an
immediate contact between the hot gases and the dried material, the
moisture content may be reduced to a minimum, though the charge may be
excessively heated. A great deal of space is taken up with heating the
material since the rate of heat transfer is a minimum at the fees-end [52].
On the other hand, for co-current flow, the gas is travelling in the
same direction that makes the rate of passage of the material through the
dryer tends to be greater. Rapid surface drying rises when there is a
contact between the wet material and the inlet gases. This is an advantage
if the material sticks to the wall and this rapid surface drying is helpful
with materials containing water of crystallization. Another advantage in
co-current is that the temperature of the product leaving the tower is lower
and the rapid lowering of the gas temperature is a result of the immediate
contact with the wet material that enables sensitive materials to be handled
more satisfactorily.

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Drying action arises mainly from the direct contact with hot gases
and some form of lifter is essential to distribute the material in the gas
stream that may take the form of light or louvres. In former cases, the
flights lift the material and then shower it across the gas stream then the
gas stream enters the shell along the louvres. In the rotary louvre dryer,
hot air enters the louvre and carries away the moisture at the end of the
dryer. This is not strictly a co-current flow unit but rather a through
circulation unit since the material continually meets fresh streams of air.
The rotation of the shell at about 0.05 Hz (3 rpm), maintains the material
in agitation and conveys it through the dryer. Rotary dryers are 0.75-3.5 m
in diameter and up to 9 m in length [52].
The efficiency of the rotary dryer is dependent on the differential
between the inlet and exhaust temperatures although heat transfer rate is
influenced by the relationship of design flights and speed of rotation.
However, irrespective of the gas and material temperature, drying or
residence time may be critical as it is governed by the rate of diffusion of
water from the core to the surface of the material.
Rotary dryers are still known as the workhorse of many process
industries despite of the new technologies introduced. That is suitable for
wide variety of products that can be granular, powdered or crystalline
materials. The powerful yet simple construction with the combination of
its flexibility with reliability enables this type of dryer to handle wide
range of materials [52].

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E. Crystallizer

Crystallization parameters allows the regulation of necessary crystal


properties that affects the down-stream process such as the filtration, washing,
drying, storage and transport. Crystallization is viewed as the most vital unit
operation process in the production of pharmaceutical ingredients, which
allows the control of the basic properties of the crystal. Crystallization is
commonly followed by filtration which is utilized to separate the crystals from
the mother liquor [53].

Morphology, structure, crystal hardness, size and other properties of


crystals are the result of growth phenomena, nucleation, breakage and
aggregation. The most imperative parameters that influences growth and
nucleation of crystals are the temperature, supersaturation (chemical potential
and the type of substance used. As an addition, type and amount of seed
crystals, mixing conditions, pH and time are also considered as parameters
that can influence nucleation and growth of crystals [53].

All in all, supersaturation is directly proportional to nucleation and


crystal growth of new crystals, where in a higher supersaturation results to an
increase of crystals in both processes. Furthermore, lower supersaturations
results to larger crystals with a more uniform crystals size distribution higher
than of higher supersaturation. Crystal growth is mostly influenced by
supersaturation inside the metastable zone. The expansion in the development
rate can make particles to form by spherulitic development [53].

L-glutamic acid are commonly produced through fermentation


process, wherein the crystals of L-glutamic acid are acquired by culturing a
microorganism that can form and accumulate L-glutamic acid, followed by
the separation of the collected crystals from the fermentation broth which may
contain in several cases, different kinds of impurities. Consequently,
monosodium salt of L-glutamic acid is manufactured by neutralization of
crystals as they are the primary crystals that may apply a large load of de-

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coloration, filtration and crystallization of monosodium salt of L-glutamic
acid in the fabrication process in the monosodium salt of L-glutamic acid [54].

Along these lines, as a method of purification of primary crystals


(crude crystals) of L-glutamic acid there has been a previously proposed way
of heating the crystals (crude) of L glutamic acid in an aqueous solvent to
transform the C. Crystals into the β crystals.

Purification of L-glutamic acid is usually carried out when crude


crystals of L-glutamic acid containing C crystals of glutamic acid are
maintained in an aqueous solvent at 50 ℃ to the boiling point of the aqueous
solvent in the coexistence of about 30% of carbon or majority of the crystals
of L-glutamic acid are transformed into in β crystals, the quantity of the said
aqueous solvent is not more than the amount adequate to develop a saturated
solution of the crystals of L-glutamic acid. According to this method, purified
crystals of L-glutamic acid are obtained in high yields easily and rapidly on an
industrial scale, compared to the previously used purification method of L-
glutamic acid, the conventional transformation recrystallization [54].

Crude crystals containing C. Crystals of L-glutamic acid is acquired by


culturing a microorganism has an ability to form and accumulate L-glutamic
acid binder neutral pH and at low pH condition to produce L-glutamic acid
followed by the addition of L-glutamic acid to the fermentation broth in order
to crystallize L-glutamic acid. These crystals are samples of crude crystals that
is usually subjected to the recrystallization method, including not only
primary crystals but as well as crude crystals obtained in the succeeding
process or crystals acquired by a process other than the fermentation process
[54].

The entire or part of such crystals of L-glutamic acid is essentially


made out of C. Crystals thereof, however the content these crystals is not
particularly restricted at the extent of the purification effect by the purification
method for the recrystallization is accomplished. Mostly, β crystals and only
parts of the crystals are C crystal *(in some cases 1% of the total glutamic
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acid), the purification effect can be accomplished similar to the case of most
crystals are C crystals. In line with these, C. Crystals are acquired from crude
crystals of the L-glutamic acid [54].

Aqueous solvent to be used may be water, an aqueous solution of


potassium glutamate, calcium glutamate, sodium glutamate, ammonium
glutamate and glutamic acid hydrochloride.

The amount of solvent needed should be capable of maintaining the


crude crystals as a slurry. In addition, the quantity of the solvent is not
particularly constrained the extent that the amount falls inside the range.
Generally, crude crystals that have a larger amount of impurities are to be
treated, slurry at lower concentrations are preferred. Nevertheless, if the
purification is performed in a dilute slurry state, there is a larger amount to be
treated hence it becomes expensive. On the other hand, if it is performed in a
high concentration state, stirring may cause structural viscosity, this may
result to an increase in energy cost [54].

The active carbon to be utilized in recrystallization is not limited, any


active carbon that is commercially available can be appropriately used. As to
the measure of active carbon to be used, the aimed-at effect can be
accomplished even in an amount of 0.1wt % relative to the amount of crude
crystals of L-glutamic acid that is needed to be purified, generally, a larger
amount is added preferably when a slurry with larger amount of impurities is
to be treated. However if it is viewed economically, an excessive addition of
active carbon is not necessary and the addition of amount should be controlled
because it can be easily determined [54].

The temperature of purification (transition recrystallization


temperature) is ideally a consistent or varying temperature inside the scope of
from 50° C up to the boiling point of the solvent used. By stirring or leaving
the mixed system under such temperature conditions, the transition of C
crystals of glutamic acid into β crystals proceeds. With regards to its
transformation rate, purification effect may be achieved even if the
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transformation proceeded only a little, but it is preferred to stir or leave the
mixed system above the range of temperature until approximately 30% or
more of the C. Crystals are converted into β crystals [54].

After the recrystallization processes have been completed, it is not


really necessary to separate the active carbon from the purified L-glutamic
acid crystals because it may properly be separated in the de-coloration
process. The active carbon added to the recrystallization process also shows
de-coloring action, however, when it is separated with the crystals of glutamic
acid, the purified L-glutamic acid crystals are neutralized and dissolved
through the addition of sodium hydroxide aqueous solution that does not
desorb the adsorbed impurities. In this case, de-coloration happens without
separation through the addition of active carbon [54].

According to the book “Coulson’s & Richardson’s Chemical


Engineering” Vol. 6, 3rd Edition, p. 435, crystallization is mainly utilized for
the manufacture, recovery and purification of solids. Crystalline items are free
flowing, have an attractive appearance, easily handles and packaged. The
process is used in a wide range of industries: from the small scale production
of chemicals such as in pharmaceutical industry to a large scale production of
products such as salts, fertilizers and sugar.

Crystallizers are classified by the technique use to acquire super


saturated liquor, furthermore by the strategy used to suspend crystals that are
growing. Super saturated liquor is obtained by cooling or evaporation. There
are four essential kind of crystallizers [52].

Types of Crystallizer

The simplest kind of industrial crystallizing equipment is the tank


crystallizer. Tank crystallizers are normally used for small scale production
and is generally operated in a batch production process. Crystallization is
started by cooling the mother liquor in tanks, which may be a stirred and is
provided with cooling jackets (coils).

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The second type of crystallizer is the scraped-surface crystallizer, this
crystallizer works similarly with the tank crystallizer. In this type, the cooling
surfaces are agitated continuously to inhibit fouling by deposited crystals and
to encourage heat transfer. Scraped-surface crystallizers are appropriate for
liquors that are high in viscosity. This type of crystallizer is also operated
batch wise, with distribution of the mother alcohol, or ceaselessly. A
disadvantage of this variety is that it produces very small crystals.

Circulating magma crystallizer is the third type of crystallizer, it is the


most essential type of crystallizer used in the large scale production in the
chemical process industry. This type makes liquor and the growing crystals
circulate in the zone in which the super saturation occurs. Designs are in
which super saturation is accomplished by dissipation or evaporative cooling
under vacuum or by direct cooling.

Lastly, the circulating liquor crystallizer circulates the liquor through


the cooling and heating equipment wherein the crystals are held in the
suspension in the crystallizing zone by the up-flow of liquor. This type of
crystallizer fabricated crystals of normal size. The basic outline comprises of
three components; a method of producing super saturation through
evaporation or cooling, a vessel wherein the crystals are suspended, grown
and removed; and a means of mingling the liquor.

Temperature and solubility relationship of solute and solvent is the


main factor in selecting a crystallizer. A vacuum cooling unit or a simple
cooling unit is the appropriate crystallizer for solutions that produces a
considerable amount of crystal on cooling. An evaporating crystallizer would
be used for arrangements that has an alteration in composition on cooling and
salting out would be utilized in specific cases. The size, size distribution and
shape of the products also plays an important role in choosing the appropriate
type of crystallizer. A controlled suspension unit fitted with proper devices for
fines, allowing the release of a partially classified product is suitable for large
uniform crystals. This means that washing, drying and screening of products

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may not be required. Simple cooling-crystallizers are relatively cheaper,
however the initial cost of a mechanical unit is relatively high albeit low cost
vacuum or condensing equipment is needed. Crystal slurries that are heavy are
handled in cooling units without the use of liquor circulation, however cooling
surfaces coupling surfaces becomes covered with crystals resulting to a
reduced heat transfer efficiency. If the liquor has a high boiling point
elevation, vacuum crystallizers with no cooling surfaces are not used.

There are many factors in deciding what type of crystallizer should be


used, the decision depends on the space available, type and size of product,
initial operating cost, composition and characteristics of the liquor, the need of
corrosion resistance and etc. Since the circulation of loops contains may
regions wherein the flow streams of different composition and mixture
combines, specific attention must be given to liquor mixing zones. These are
the points at which a high value of super saturations may occur that may cause
heavy nucleation, therefore causes poor performance, operating instabilities
and encrustation. It is important that the enthalpies of mixer streams are
always at equilibrium wherein only one phase exists under the standard
conditions of pressure and temperature [52].

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F. Rotary Drum Filter

The Rotary Vacuum Drum Filter is one of the most practical and
oldest filters used in chemical process industry. It is therefore commonly used
in the best part of separation of solid liquid processes. It can be used when
there is a continuous separation of solid from liquid stream. It is also can be
used in the application of process when either the solid or the liquid is the
product (some cases that both phases are the product). Lastly, it can be used
to dewater a variation of sludge or for the clarification of wastewater and this
is called the applications for wastewater [55].

Due to the versatility and simplicity of the rotary drum filter, it is one
of the most vacuum filters used and a filter of this type was originated from
England in 1872 by William and James Hart. The design differs with different
manufacturers, though all drum type vacuum filters can be divided into two
categories which are:

(a) Those where vacuum is made in partitions formed on the edge of the
drum.

(b) Those where vacuum is useful to the entire interior of the drum.

The most often used drum type filters that is continuous is the first
category. It gives the versatility in maximum, the unit area in cheap price and
the individual time period in filtration, washing and drying is in wide
discrepancy. A multi-compartment drum type vacuum filter is compromised
of a drum that is rotating on a horizontal axis, so that the drum is somewhat
submerged in the trough where the material to be filtered is fed. The drum’s
edge is divided into sections, each of this is offered with a certain number of
drain lines. It can pass through the inside of the drum and can sack as a ring of
ports that is covered by a valve called rotary valve, through which the vacuum
is applied. The filter fabric covered the surface of the drum, it rotates at low
speed and it is frequently ranging from 0.0016-0.004 Hz (0.1-0.25 rpm) or up
to 0.05 Hz (3 rpm) for the material used in filtering. Each of the compartment

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undergoes then same cycle operations as the drum begin its rotation and the
drum speed is the one that determine the duration of each cycles. Filtration,
Drying and Discharge is one of the normal cycles. It can possibly introduce
other basic cycles such as: (a) Separation of initial filtrate- can be a gain if the
filter that is open is used. (b) the filter cake washing. (c)Th filter cake
mechanical dewatering and (d) cloth cleaning [52]

Figure (a) shows a typical layout of a rotary drum installation and Figure (b)
shows the sequence of cake formation, washing and dewatering.

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Materials of Construction

The modern plant use drums that have a surface of 60-100m 2 unlike to the
older version of cast iron drum that is 20m 2. The common materials that used in
construction such as titanium, stainless steel, plastics and epoxy resins has a
longer life because it’s corrosion resistance for slurries was enhanced. The knife
system auxiliary by some form of belt has given an improved cake discharge and
is allowed to use filtering media that is thin such as synthetic fibers. The support
for the cake is provided by the belt and it assists materially to the effect of air that
is compressed for lifting off the cake. The drying process can be improved by
covering the filter with a hood. For reducing cake cracking, techniques in
improvements need also to be completed [52].

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G. Carbon Adsorber

From the article presented by Supanchaiyamat, Jetsrisuparb,


Knijnenburg, Tsang and Hunt entitled “Lignin Materials for Adsorption:
current trend, perspectives and opportunities”, Lignin is used as the
adsorbate which will be adsorb through a layer of activated carbon in
lignin adsorption process of experiment. The temperature and lignin
concentration were imitated as the conditions in pulping and pulp
washing, lignin adsorption kinetics and isotherms were investigated.
Under defined operating conditions, lignin adsorption was found on both
the carbon surface and in the activated carbon bulk. The carbon surface
takes place in reaching maximum more faster compared to the carbon
bulk. The solution has lignin concentration which dominantly affects the
surface lignin adsorption. When lignin adsorbed and materialize to be a
monolayer on the carbon surfaces, it accords with more that 1% of lignin
concentration. The huge increase of the maximum concentration of surface
lignin affected by the presence of calcium ions due to coagulation and
precipitation of lignin aggregates on the carbon [56].

The physical capacity, contact time, hydraulic loading, pre-


treatment, feed characteristics, relative economics mode of operation and
product quality are the basis for the selection of the size, shape, number
and configuration of the vessel in contaminating of carbon [57].

The continuous fabricating over field-erected vessels is shown and


manifested by the economic analysis. The transportation clearance
imposed that the maximum diameter for shop fabricated vessels is 13 feet,
in order to minimize the required carbon to fulfil the spare contacting
vessel and to lessen the required inter-vessel piping and the offsetting of
valves [57].

The approximate total carbon volume that actively contacts the


wastewater together with the required contact time will set by the desired
product quality. The selected hydraulic loading affects the total carbon bed
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depth and the total cross-sectional area. The overall bed depth may be
converted into more than one bed depths in series, on the other hand, the
total cross-sectional area of the carbon bed comes to be in parallel, these
conclusions can be defined be the manufacturers [57].

During backwash in a down flow bed, expansion of the carbon bed


allowed if each vessels have sufficient height, appropriate expansion also
happens in an up flow bed during the process. To make sure that
accumulated suspended solids can be detached from the carbon particles
surface, the vessel is being designed to allow the 50% expansion [57].

In order to accommodate the internal and external system of


distributors and piping, the inlets and outlets of vessels need to be
arranged properly. Distribution during backwash operation and service is
more efficient for dish-shaped bottoms while slurry discharged removed
the carbon in vessels conical bottoms [57].

To retain carbon in 60 to 80 mesh range, screening should be done


in nozzles that used as the means of collecting the wastewater after it
passes through the carbon bed.

Using flat porous bottoms, funnels arrangement at the bottom of


the vessels can be in used in removal of carbon for regeneration. Carbon
contactors considered the filter bottoms designs used in rapid sand filters.

Bed depth at minimum diameter ratio of 1-3 (L/D) may consider


better distribution with sufficient protection to back mixing. Higher
pressure drop may happens by using deeper beds with diameter ratio
larger than 1 (L/D).

Manufacturer of beds has major problems in terms of corrosion in


treatment system of carbon. Given that the oxygen and water are presents,
activated carbon is a reactive material and it is in a risk to take corrosion.
Using particular coating materials, the contacting vessels can easily be
protected. Designer also needs to give special consideration to other

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equipments that are more vulnerable to corrosion like piping, valves, and
pumps.

The importance of selecting of application and method of the


corrosion protective lining is also considered to be prioritized. Typical
coating materials are calibrated and ranged from a painted coal epoxy to
laminated rubber linings. Testing of some coatings like polyethylene
coatings is being done for this application [57].

The precipitation using non solvent is one of purification methods


tested for the separation or removal of impurities in different molecular
weight fractions; it yields to 85% to 95% recovery of the xylo-
oligosaccharides from almond shells and corncobs, the process obtained at
169 degree Celsius and 25 minutes of reaction. Since oligomers and
monomers were soluble in the ethanol-water mixture at low molar mass,
higher reaction times attain a much lower yield of product precipitated
[58].

For the separation of different molecular weight fractions and


removal of low molar mass impurities, the ultra-filtration using polymeric
membranes is the most in demand to be used.

Activated carbon is being tested for adsorption of impurities and it


results that activated carbon has more lignin-related product than xylo-
oligosaccharides. Some part of lignin is limited because of being linked to
the xylo-oligosaccharides [58].

The poly-γ-glutamic acid offers an alternative to conventional


technologies of removal and recovery of metals from aqueous solution
such as precipitation, coagulation, activated carbon adsorption, solvent
extraction and ion exchange [59].

Recovery of heavy metals of biosorption process in industrial


applications have been barely known because of economic constraints.
When the poly-y-glutamic acid purity is getting higher, the cost of

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wastewater treatment is being lowered or can be negligible compare to
other applications in medicine, food industries and cosmetics [59].

There were several conclusions came from recent adsorption


experimentation. Molecular weight of amino acid together with their size
or geometry of molecules affects their adsorption efficiency. Amino acid
has polarity, solubility and functional groups content that can also be
accountable for its adsorption ability. The adsorption is not only affected
by the adsorbate properties, it has also governed by the solution properties
(ionic strength (IS), pH, temperature, initial adsorbate concentration) and
adsorbent nature (surface charge, pore structure, functional groups on the
adsorbent surface). These factors combined to finally determines the
adsorption character and also the mechanisms [60].

As a replicate for activated carbon, there are more common


mechanisms in amino acid adsorption, electrostatic interactions,
hydrophobic interactions and hydrogen bonds.

The presence of sodium chloride in background electrolytes reduce


the amino acids removal. The added salt screened the removal of amino
acid in the occurring of adsorption by attractive electrostatic interactions.
The initial solution concentration also affects the adsorbed amount of
amino acid. Direct interaction between the amino acids and carbon
surfaces affects the adsorption as the initial concentration is higher. The
forces in the adsorbate molecules is also being affected [60].

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