Beruflich Dokumente
Kultur Dokumente
Draft Assignment 1
GROUP 05
GROUP PERSONNEL:
ALWENDO GUNAWAN (1506723452)
DIMAS RAHADI PITOYO (1506673473)
SAMSON PATAR SIPANGKAR (1506723774)
WIDA ADELIA PUTRI (1506673290)
YAZIDIE RIZQI ISNAINDI (1506728434)
ii Universitas Indonesia
LIST OF CONTENT
iv Universitas Indonesia
LIST OF FIGURES
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CHAPTER 1
INTRODUTION
1.1 Background
In moving toward sustainable clean technology regime, chemical and
biochemical process industries are gradually adopting bio-based production
strategies rather than pure chemical technologies. However, bio-based production
alone cannot ensure eco-friendliness of a process technology as downstream
separation–purification of the products often involves quite a few energy-intensive
steps that may require harsh chemicals also. This is where membrane-based
purification schemes are stepping in. In this context, development of a clean
technology for production of gluconic acid assumes significance. Being a
multifunctional organic acid, the gluconic acid (GA) has wide applications in food,
pharmaceutical and chemical industries.
Pentahydroxycaproic acid, 𝐶 𝐻 𝑂 or gluconic acid, naturally occur in
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plants, fruits, wine, honey, rice, meat, vinegar and other natural sources. The alkali
salt of gluconic acid such as calcium gluconate or sodium gluconate are extensively
used in chemical, pharmaceutical, food, beverages and construction industries
being a multifunctional carbonic acid. Due to multiple applications of metal
glutamates in different industries, the demand of gluconic acid is steadily increasing
globally. By virtue of low toxicity, low corrosiveness and high capability of
forming water-soluble complexes with divalent and trivalent metal ions, sodium
gluconate has been designated as GRAS (generally recognised as safe) by the US-
FDA (United States-Food and Drug Administration). Some specific properties of
gluconic acid permits its wide applications in preventing the deposition of milk
stone or in removing it in dairy industry and in preventing cloudiness in beverages.
Gluconic acid is also used as an additive in cement to control the setting and
increase the strength and water resistance. This organic acid can produce and
improve the taste and can form complexes with metal ions in various foods. It is
also used as water conditioner by removing alkali and protein films. The non-
corrosiveness nature of this acid may be used as gentle metal cleaning agent where
cleaning and degreasing of ferrous and non-ferrous metal ions like Ca2+, Fe2+,
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Al3+ and other heavy metals is possible. Sodium gluconate is used in the shampoo
and toothpaste as a chelator. In dishwashing and laundry detergent application, this
acid can replace toxic phosphates which are harmful to the bio-environment. It can
be used with artificial sweetener. For its non-corrosiveness nature, gluconic acid is
added in low concentration in water recirculation systems such as cooling towers
and heat exchangers. Gluconic acid finds application in tanning, textile industry and
in fermented tea for its anti-microbial activity.
In last 20 years, demand of gluconic acid has increased steadily reaching
60,000 tons per year. Market researcher Global Industry Analysts predicts that the
global market for organic acids will amount to EUR 1 billion by 2016, driven by
increasing demand in developing economies, stable demand for meat and meat
products from the developed economies and, a growing global population. And
some industry sources consider this figure as conservative. Use of gluconic acid
and its derivatives is currently restricted in many cases because of high prices which
is about USD 1.2–8.5/kg due to use of glucose as substrate and the system specific
requirements during fermentation. However, its increasing demand in different
industries has spurred interest in the development of an effective and economically
viable system for gluconic acid production.
1.2 Review of Literature
This report will mainly discuss about Fermentation, Glucose and Gluconic
Acid. Therefore, in this sub-chapter are some theories about it such as what is
Fermentation, Fermentation method and agent, what is glucose, the properties,
occurrence and also its application.
1.2.1 Fermentation
Fermentation is a metabolic process that consumes sugar in the absence of
oxygen. The products are organic acids, gases, or alcohol. It occurs in yeast and
bacteria, and also in oxygen-starved muscle cells, as in the case of lactic acid
fermentation. The science of fermentation is known as zymology.
1.2.1.1 Fermentation Method
There are so many ways to ferment but we have shrunk to 2 sections which
is Solid State Fermentation and Submerged Fermentation.
a) Solid-State Fermentation
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Solid State Fermentation has been widely used and has gained
renewed attention as an alternative for submerged fermentation. It
provides the opportunity for economical production of fermented food,
amino acids and flavor inducing compounds by inducing the natural
growth on water- insoluble solid support in the absence or near absence
of free liquid medium. SSF is better than submerged culture due to less
variation of osmotic pressure, DO concentration, availability of water
and nutrients. Buckwheat substrate was used as SSF medium for the
production of spores of Aspergillus niger and these entrapped spores
were used for the bioconversion of glucose to gluconic acid with
conversion rate of 1.06 g per mass of glucose without any nitrogen
source.
b) Aerobic Submerged Fermentation
Submerged fermentation is a process involving the development of
microorganisms in a liquid broth. This liquid broth contains nutrients
and it results in the production of industrial enzymes, antibiotics or other
products. The process involves taking a specific microorganism such, as
fungi, and placing it in a small closed flask containing the rich nutrient
broth. A high volume of oxygen is also required for the process. The
production of enzymes then occurs when the fungi interact with the
nutrients on the broth resulting in them being broken down. At industrial
level this production of yeasts has become a major output of
microbiological industries as a result of improved fermentation
technologies. Fermentation in industries is carried out using fermenters
which are large vessels which can store huge volumes. In an effort to
reduce nitrogen and carbon levels, microorganisms secrete enzymes in
the selected medium. There are two common methods by which
submerged fermentation takes place; they are batch-fed fermentation
and continuous fermentation. In batch-fed fermentation sterilised
growth nutrients are added to a culture. It is most common in bio-
industries as it occurs during the growth of bio-mass in the fermenter. It
helps raise the cell density in the bioreactor and it is typically highly
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maize, but A. niger can be isolated from almost any type of stored
commodity. Dried, smoked and cured fish and meat products are other
common sources.
Growth temperatures for Aspergillus niger are minimum, 6–8 °C,
maximum, 45–47 °C and optimum 35–37 °C. A. niger is a xerophile:
reported germination at 0.77 aw at 35 °C. A. niger is able to grow down
to pH 2.0 at high aw.
Until relatively recently, Aspergillus niger was regarded as a benign
fungus, and has been widely used in food processing.
1.2.2 Gluconic Acid
Gluconic acid is produced from glucose through a simple dehydrogenation
reaction catalysed by glucose oxidase. Oxidation of the aldehyde group on the C-1
of b-D-glucose to a carboxyl group results in the production of glucono-d-lactone
and hydrogen peroxide. Glucono-d-lactone is further hydrolysed to gluconic acid
either spontaneously or by lactone hydrolysing enzyme, while hydrogen peroxide
is decomposed to water and oxygen by peroxidase. The conversion process could
be purely chemical. However, the most commonly involved method is the
fermentation process.
pH; its action is comparatively better than EDTA, NTA and other chelators.
Aqueous solutions of sodium gluconate are resistant to oxidation and reduction at
high temperatures. It is an efficient plasticizer and a highly efficient set retarder. It
is easily biodegradable (98% at 48 hours). It has an interesting property of inhibiting
bitterness in foodstuffs. Concentrated gluconic acid solution contains certain
lactone structures (neutral cyclic ester) showing antiseptic property. The
characterisitics are described in Table 1.1.
pKa 3.7
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application as an additive to cement, controlling the setting time and in- creasing
the strength and water resistance of the cement. It helps in the manufacture of frost
and crack resistant concretes. It is also used in the household cleaning compounds
such as mouthwashes.
Calcium gluconate is used in pharmaceutical industry as a source of calcium
for treating calcium deficiency by oral or intravenous administration. It also finds a
place in animal nutrition. Iron gluconate and iron phosphogluconate are used in iron
therapy. Zinc gluconate is used as an ingredient for treating common cold, wound
healing and various diseases caused by zinc deficiencies such as delayed sexual
maturation, mental lethargy, skin changes, and susceptibility to infections.
1.2.3 Glucose
Glucose is a simple sugar with the molecular formula 𝐶6 𝐻12 𝑂6. Glucose is
the most abundant monosaccharide, a subcategory of carbohydrates. Glucose is
mainly made by plants and most algae during photosynthesis from water and
carbon dioxide, using energy from sunlight. There it is used to
make cellulose in cell walls, which is the most abundant carbohydrate. In energy
metabolism, Glucose is the most important source of energy in all organisms.
Glucose for metabolism is partially stored as a polymer, in plants mainly
as starch and amylopectin and in animals as glycogen. Glucose circulates in the
blood of animals as blood sugar. The naturally occurring form of glucose is D-
glucose, while L-glucose is produced synthetically in comparably small amounts
and is of lesser importance.
1.2.3.1 Glucose Chemical Properties
With six carbon atoms, it is classed as a hexose, a subcategory of the
monosaccharides. D-Glucose is one of the sixteen aldohexose stereoisomers.
The D-isomer, D-glucose, also known as dextrose, occurs widely in nature, but
the L-isomer, L-glucose, does not. Glucose can be obtained by hydrolysis of
carbohydrates such as milk sugar, (lactose), cane sugar (sucrose), maltose, cellulose,
glycogen, etc. It is commonly commercially manufactured from cornstarch by
hydrolysis via pressurized steaming at controlled pH in a jet followed by further
enzymatic depolymerization. Unbonded glucose is one of the main ingredients
of honey. All forms of glucose are colorless and easily soluble in water, acetic acid,
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and several other solvents. They are only sparingly soluble in methanol and ethanol.
Glucose is a monosaccharide with formula 𝐶6 𝐻12 𝑂6 or H-(C=O)-
(CHOH)5-H, whose five hydroxyl (OH) groups are arranged in a specific way
along its six-carbon back. Glucose is usually present in solid form as
a monohydrate with a closed pyran ring (dextrose hydrate). In aqueous solution, on
the other hand, it has an open-chain to a small extent and is present predominantly
as α- or β-pyranose, which partially mutually merge by mutarotation. From aqueous
solutions, the three known forms can be crystallized: α-glucopyranose, β-
glucopyranose and β-glucopyranose hydrate. Glucose is a building block of the
disaccharides lactose and sucrose (cane or beet sugar), of oligosaccharides such as
raffinose and of polysaccharides such as starch and amylopectin, glycogen or
cellulose. The glass transition temperature of glucose is 31℃ and the Gordon-
Taylor constant (an experimentally determined constant for the prediction of the
glass transition temperature for different mass fractions of a mixture of two
substances) is 4.5. Glucose is no toxic chemical compound and have highly
combustible. This compound also finely dispersed particles that become explosive
when exposed to air.
1.2.3.2 Glucose Physical Properties
The physical properties of glucose can be used to characterize matter and
energy also their interactions. The phase of glucose can be solid or liquid depending
from the source. This compound has a sweet taste, but not have an odor. Glucose is
soluble in water and acetic acid. All forms of glucose are colorless also clear. The
another of glucose physical properties are described in Table 1.2.
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of 7.2% based on Global Market Insight Report. The calculation shown in Table
1.4.
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aerobic environment.
Aspergillus niger should be activated before the reaction start called as
incubation process. Incubation process provide a condition for the filamentous
fungi to inoculate its spore inoculum. Driouch, H. et al. (2010) has been inoculate
Aspergillus niger by growing thawn spores from the maintenance culture at 30 °C
for 3 days on Potato Dextrose Agar (PDA). Spores are harvested as spore
suspension from the plate into 20 mL 0.9 % NaCI solution, which is spreaded onto
the plate. After filtration (Miracloth, 25 μm pore size, CalBioChem, Darmstadt,
Germany) the spore concentration is determined photometrically then make a
calibration between spore number and optical density to precisely inoculate with a
well-defined spore concentration. Cultivations for enzyme production are
typically inoculated to an initial spore concentration of 106/ml.
Another study also revealed Aspergillus niger culture activation in inoculum
in fermentation media containing molasse which shows the best result in the
concentration of 30% at 30˚C for 4 days. The spore of mutant A. niger from slant
were harvested in 5 ml of sterile 50 mM sodium phosphate buffer (pH 6.8)
containing 0.1% presterilized Tween 80. The spores in inoculums were maintained
at 108 -1010 spores per ml (Nilesh, K. et al., 2012).
Aspergillus niger is the most applicable fungi that usually used for
converting glucose to gluconic acid. Besides, these filamentous fungi are easily
obtained and available in powder and granule which have purity of 97% – 99%.
1.4.2.2 Gluconobacter oxydans
Gluconobacter oxydans is a genus of bacteria which also has the ability for
converting glucose to gluconic acid. Gluconobacter oxydans is an aerobe bacterial
which has oxygen as a terminal electron acceptor. The highest growth rate occurs
at temperatures between 25 ˚C – 30˚C and it could not withstand high temperatures
above 37 ˚C (Comprehensive Macrobial Resource). Gluconobacter oxydans was
grown in mannitol medium (Buchert and Viikari, 1998) or ethanol medium
(Mostafa et al., 2002) which were adjusted to pH 5.0 or pH 6.0 by hydrochloric acid
on a shaker at 130 rpm.
Gluconic acid is derived from glucose by a simple oxidation reaction.
Bacterial gluconic acid production has limited success at industrial scale as the
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CHAPTER 2
PROCESS SELECTION
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hydrated structure as well as its low lignin content. These properties of potato pulp
make it easier to hydrolyze into sugar (Jiang. 2018). But, usually buried as feed or
waste disposal for the processing costs of this waste is high. In Indonesia the waste
potato potential represented from the number, annually Indonesia could produce 1.3
million ton of potato (Kementrian Pertanian, 2016). Thus, potato pulp is a suitable
resource for producing gluconic acid, but it will involve more complex raw material
pretreatment.
From explanation above, the raw material that will be used in the production
of gluconic acid is sugarcane. Sugar cane is used because this source of carbon has
simpler pre-treatment process and been readily accepted by the food industries.
Also, sugarcane juice is easily available in Indonesia for it is annually produced
about 2.4 million ton (Kementrian Pertanian, 2016)
2.1.1 Sugarcane
Sugarcane may be used as carbon source without the necessity of much pre-
treatment, saccharification and liquefaction. The use of sugarcane juice has been
encouraged for the production of gluconic acid through fermentation with suitable
micro-organisms. Gluconic acid which obtain from fermentation of sugarcane juice
has the highest concentration among all the available raw material, about 76.3g/L.
This type of carbon sources has been readily accepted by food industries and the
consumers as raw materials and is derived from biological origin. Sugarcane juice
is also easily available throughout the year in Indonesia
2.1.2 Carbohydrate-Containing Waste
[khuy tar]
From explanation above, the raw material that will be used in the production
of gluconic acid is sugarcane. Sugarcane is used because this source of carbon has
simpler pre-treatment process and been readily accepted by the food industries and
the consumers as raw materials. Also, sugarcane juice is also easily available in
Indonesia for Indonesia annually produce about 2.4 million tonnes of sugarcane
(Kementerian Pertanian, 2016).
2.2 Process Synthesis
There are mainly three different methods for the commercial production of
gluconic acid like; chemical methods, enzymatic catalysis and fermentation. Each
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method consists of three main process, those are: raw material preparation; glucose
to gluconic acid reaction, and purification. Each method is used in production of
gluconic acid based on the product specification that is required and the raw
material that is used. In this plant design, gluconic acid product specification that
will be produced is 3131 tonnes/year and the raw material that will be used is
sugarcane juice.
There are plenty of alternative process from each step in each methods of
production of gluconic acid. The methods and the process steps then will be
analyzed and selected to find the most suitable production process to produce the
xspecified gluconic acid.
Pt, Pd or Au nanoparticles as catalysts and oxygen from air as oxidant under mild
conditions. Although the conversion is a simple one-step process, the chemical
method is not at all favored due to its limited selectivity towards gluconic acid,
environmental toxicity and biological hazards; whereas the rapid increase in the
cost of electrical power in the recent years has turned electrolytic process costly.
Different oxidizing agents are used in this process, but still the process appears to
be costlier and less efficient than fermentation method.
2.2.1.3 Enzymatic method
Enzymatic method is developed for the commercial production of gluconic
acid. Various enzymatic processes have been described in the technical
bibliography, aiming in the replacement of commercial fermentation processes
suffering under difficulties including the removal of glucose and separation of
gluconic acid from fermentation broths. However, enzymatic production of
gluconic acid is economically unfeasible for large-scale industrial production due
to enzyme’s instability and resulting very high cost.
From explanation above, the gluconic acid production plant will use
fermentation method for it is the most reliable method for large-scale production.
This method is also the most economically method among other methods. For the
weakness of this method such as difficulties in the separation, new superior
fermentation processes system has been developed. Membrane-based separation
processes are considered as viable alternative to some traditional separation
processes. This system can largely overcome these problems due to high cell
density and continuous removal of products and ensures reduced energy
consumption as it involves no phase change (except pervaporation).
2.2.2 Selection of Fermentation Process
The plant will produce gluconic acid through fermentation. Based on the
mode of 𝑂2 supply, two types of culture conditions have been defined for GA
fermentation: including aerobic submerged fermentation (ASF) and solid-state
fermentation (SSF).
2.2.2.1 Solid-State Fermentation
Solid-state fermentation (SSF) is a process of growth of microorganism in
an SSF solid medium (substrates). The main advantage of using these substrates is
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that nutrient-rich waste materials can be easily recycled as substrates. SSF is better
than submerged culture due to less variation of osmotic pressure, DO concentration,
availability of water and nutrients. In this fermentation technique, the substrates are
utilized very slowly and steadily, so the same substrate can be used for long
fermentation periods. Hence, this technique supports controlled release of nutrients.
However, it cannot be used in fermentation processes involving organisms that
require high aw (water activity), such as bacteria.
2.2.2.2 Aerobic Submerged Fermentation
Aerobic Submerged Fermentation (ASF) is a process of growth of
microorganism in a free-flowing liquid medium (substrates). This fermentation
technique is best suited for microorganisms such as bacteria that require high
moisture content. An additional advantage of this technique is that purification of
products is easier. However, oxygen supply in the center of large pellets sometimes
lack enough oxygen supply, leading to autolysis of the fungus or bacteria, which
further negatively affects fermentation. Submerged fermentation is usually
employed for commercial production of gluconic acid which is sensitive to process
control parameters, demands investment and is an energy intensive process.
Shown in the Table 2.1 below is the scoring for selection process based on
the comparison of fermentation time, yield, and applicability.
each criteria. Processes are rated through a comparison to the reference design
process. Representative ratings or ranks are valued from 1 to 3, indicating much
worse to much better process that the reference, this would be explained here after.
Once all the concepts are rated, a total score for each design concept is calculated.
The calculation is shown in Table 2.2 below.
The table shows that each fermentation process has advantage and
disadvantage, but one alternative has to be chosen. From scoring in the table 2.2,
Submerged fermentation is chosen as the fermentation process in the production of
gluconic acid. ASF is the most reliable method for large-scale production for it is
the most used method in the production of gluconic acid. Also, this technique has
easier products purification.
2.2.3 Fermentation Agent
Based on the literature, there are a few microorganisms that has been used
for gluconic acid production. Each one of them has their own benefits and
challenges. To produce gluconic acid in the most economical way, which
fermentation agent used should be considered. To choose which one is the best
fermentation agent to be used, there are few parameters to be considered which are
related to the fermentation process and ability for the conversion of glucose to
gluconic acid. The parameters are tabulated in Table 2.3 below.
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For purpose of process selection, the weight factor of the criteria was
determined subjectively by our team from our rational intent. The total weight
factor has to be 100% and it is normally used to assign the weight factor value of
each criteria. Processes are rated through a comparison to the reference design
process. Representative ratings or ranks are valued from 1 to 3, indicating much
worse to much better process that the reference, this would be explained here after.
Once all the concepts are rated, a total score for each design concept is calculated.
The calculation is shown in Table 2.2 below.
The table shows that each fermentation process has advantage and
disadvantage, but one alternative has to be chosen. From scoring in the table 2.2,
Submerged fermentation is chosen as the fermentation process in the production of
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gluconic acid. ASF is the most reliable method for large-scale production for it is
the most used method in the production of gluconic acid. Also, this technique has
easier products purification.
2.2.4 Process Selection
2.2.4.1 Reaction
2.2.4.3 Incubation
2.2.4.4 Purification
2.3 Block Flow Diagram
2.4 Process Flow Diagram
2.4.1 Pre-Treatment Process
2.4.2 Incubation Process
2.4.3 Fermentation Reaction Process
2.4.4 Purification Process
2.4.5 Drying Process
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CHAPTER 3
MASS AND ENERGY BALANCE
3.1 Mass Balance
3.2 Energy Balance
3.3 Product Conversion Efficiency
3.4 Product Yield
3.5 Energy Consumption of Unit Product
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CHAPTER 4
CONCLUSION
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REFERENCE
https://www.marketwatch.com/press-release/production-and-market-of-
sodium-gluconate-in-china-2018-09-06
https://www.gminsights.com/pressrelease/gluconic-acid-market)
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