Tk14 Revised Assignment1
Tk14 Revised Assignment1
Tk14 Revised Assignment1
Report Assignment 1
GROUP 14
GROUP PERSONNEL :
AGUS AMANDA TANOYO
(1206254113)
CLAUDIA HARFIAN
(1206239876)
(1206202141)
ERICCO JANITRA
(1206249845)
ERWIN FIRMANSYAH
(1206202053)
EXECUTIVE SUMMARY
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synthesis in plug flow reactor with CuO/ZnO as it catalyst. The synthesis process
is produce the mixed of alcohol which needed to next separation by using
separator until got the pure ethanol.
The capacity of the plant will determine the mass and energy balance in
the process.The calculate our plant mass and energy balance for each process and
then overall are done. By calculating it, it give that our ethanol mass efficiency is
53.76%, overall mass efficiency is 69.85%, and energy efficiency is 88.02%.
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LIST OF CONTENTS
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LIST OF FIGURES
Figure 1.1 Worlds bioethanol production (1975 2005) ..................................... 1
Figure 1.2 Structure of cellulose, hemicellulose and lignin in plant cell ................ 4
Figure 1.3 Indramayu area .................................................................................... 12
Figure 1.4 Plant location ....................................................................................... 13
Figure 2.1 Alternative process diagram .................................................................. 2
Figure 2.2 Conceptual flow diagram of gasification............................................. 18
Figure 2.3 The result of process ............................................................................ 20
Figure 2.4 Flow diagram direct gasifier ................................................................ 23
Figure 2.5 Flow diagram indirect gasifier ............................................................. 24
Figure 2.6 Counter current fixed bed, counter current fixed bed .......................... 26
Figure 2.7 Fluidized bed gasifier .......................................................................... 27
Figure 2.8 Entrained bed gasifier .......................................................................... 27
Figure 2.9 Simplified process flow diagram of gasification area ......................... 30
Figure 2.10 Simplified process flow diagram of gas cleanup area ....................... 32
Figure 2.11 Simplified process flow diagram of alcohol synthesis area............... 34
Figure 2.12 Simplified flow diagram of the H2S/CO2 removal and sulfur ........... 35
Figure 2.13 Simplified process flow diagram of alcohol separation area ............. 37
Figure 2.14 Block flow diagram of cellulosic ethanol production........................ 45
Figure 2.15 Process flow diagram of pre-treatment and gasification process ...... 46
Figure 2.16 PFD of tar reforming, syngas cleanup, and compression .................. 47
Figure 2.17 PFD of alcohol synthesis, acid gas removal, sulfur recovery ............ 48
Figure 2.18 PFD of alcohol purification ............................................................... 49
Figure 2.19 PFD of steam system and power generation...................................... 50
Figure 3.1 Process simulation ............................................................................... 51
Figure 3.2 Hypothetical components of rice straw biomass ................................. 51
Figure 3.3 Conversion reactor for tar reformer modelling in Unisim ................... 53
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LIST OF TABLES
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CHAPTER 1
INTRODUCTION
1.1
Background
Cellulosic ethanol comes from biomass that contains cellulose. Almost
every stem, leaf and tree trunk in the world qualifies, from farm wastes to grass
clippings and recycled newspaper. Because cellulose makes up nearly half of all
plant biomass, cellulosic ethanol is considered as the largest potential source of
biofuel in the near future (Great Lakes Bioenergy Research Center, 2010).
Cellulosic resources are in general very widespread and abundant. For example,
forests comprise about 80% of the worlds biomass. Being abundant and outside
the human food chain makes cellulosic materialsrelatively inexpensive feedstocks
for ethanol production (P.C. Badger, 2002). Bioethanol is an environmentally
friendly alternative energy and being most produced rather than other alternative
energy, such as biodiesel. Worlds ethanol production is increasing along with the
fluctuations of oil price, as we can see in Figure 1.1 below.
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1.2
Basic Theory
1.2.1
Lignocellulosic Biomass
Lignocelluloses are composed of cellulose, hemicellulose, lignin,
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1.2.2
Rice Straw
Rice straw is a by-product of rice production and great bio resource. It is
the one of the abundant lignocellulosic waste materials in the world. It is annually
produced about 731 million tons, asia 667,6 million tons and europe 3,9 million.
Rice straw can potentially produce 205 billion liters bioethanol per year. It is the
largest amount from a single biomass feedstock. Rice straw predominantly
contains cellulose, hemicellulose,lignin and ash.
The moisture contents of the rice straw are between 10% - 20% which
harvested in summerwill be lower than that of rice harvested in fall. For rice straw
having high moisture contents, some problems may be countered during firing.
High moisture contents can lead to poor ignition, reduce the combustion
temperature. Which in turn hinders the combustion of the reaction products and
consequently affects the quality of combustion. The large quantity of flue gas is
formed during the combustion of high moisture content fuels which eventually
leads to large dimensions of the equipment for flue gas treatment.
The rice straw has low bulk densities around 50 -120 kg/m3. It is vey low
compared with the bulk densities of coals, which are in range of 560 600
kg/m3for brown coals and between 800 and 900 kg/m 3for bituminous coal. The
low densities of the rice straw complicate their processing, transportation, storage
and firing. Rice straw differs from most crop residues in its high content of
silicone dioxide (SiO2). Ash content on a dry weight basis ranges from 0,1% to
0,7%, varying according to the state of conservation of the straw after harvest.
Compares with coals and other agricultural residues, rice straw is
characterized by higher contents of volatile matter up to 85% dry basis. This
indicates that the rice straw is easier to ignite and to burn, although the
combustion is expected to be rapid and difficult to control. Experience showed
that the high volatile matter contents significantly affect the combustion process.
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(Source: www.scielo.br)
1.2.3
Bioethanol
Bioethanol has been used human since prehistoric times as a drunk in
alcoholic liquor. A mixture of bioethanol near purity for the first time discovered
by Jabir ibn Hayyan, Al- Kindi, and Al-Razi who developed the process of
distillation bioethanol. Jabir ibn Hayyan mentioned that steam from wine boiling
flammable. Al-Kindi with firm to explain about the process of distillation wine.
While bioethanol absolute obtained in the 1796 by Johann Tobias Lowitz using
distillation a sieve charcoal.
Bioethanol is an ethanol derived from a source of biodiversity like,
glucose, starch and cellulose. Bioethanol is a clear, volatile, flammable and
colourless liquid. Bioethanol is a straight chain alcohol and its molecular formula
is C2H5OH. Bioethanol can be produced by biochemical or thermochemical
pathways. Production bioethanol through biochemical consist of several step such
as pretreatment, hydrolysis, and fermentation to convert biomass feed become
bioethanol. While, thermochemical ways convert biomass feed to syngas and then
syngas use to make bioethanol.
Bioethanol can produced from agriculture plant such as corn, sugarcane or
sweet sorghum. nowadays, bioethanol can derived from non food sources that
contain cellulose like trees and grasses. Bioetanol can be produced from different
raw materials in Indonesia, so it is very potential for processed and developed
because Indonesia is a agraris country.
1.2.4
Usefullness of Bioethanol
Bioethanol used as one of alternative fuel for vehicle because alcohol has a
high octane rating enabling high engine compression ratios that increase engine
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1.3
Analysis
1.3.1
analysis needs to be done to determine the potential of the product in the market.
Market analysis will determine capacity of the plant which will also affect the size
and amount of equipments, amount of raw materials, materials and energy
balance, and economic aspect of the product. Market analysis based by supply and
demand which consists of development in production, export, and import every
year. There are several companies in Indonesia that produce ethanol, which are:
Table 1.2 Bioethanol producer in Indonesia (2006)
Company
Salim Group
Medco
EN3 Korea
Angel Product
Sorini Tbk
RNI, PTPN
Mitsui Petrobras
Sampoerna
Molindo
Wilmar Group
Sugar Group
Sungai Budi
Location
South Sumatera
Lampung, West Java,
Kalimantan
South Sulawesi
North Sulawesi
North Sulawesi
North Sumatera, Lampung,
South Sulawesi, Java, NTT
Papua, Kalimantan
Madiun, Pawonsari
Lampung, Pacita, Kediri
Lampung, South Sumatera
Lampung, South Sumatera,
Kalimantan
Lampung
Production (KL/year)
70,000
270,000
180,000
10,000
200,000
200,000
500,000
375,000
100,000
70,000
500,000
120,000
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Year
2006
2007
2008
2009
2010
2011
2012
2013
2014
2015
2016
Production
(KL/year)
1,254,753
1,254,753
1,254,753
1,254,753
836,502
767,072
703,405
645,023
591,486
542,392
497,374
Export
(KL/year)
665,164
688,444
506,971
524,715
532,319
508,365
485,489
463,642
442,778
422,853
403,824
Import
(KL/year)
39,324
38,144
81,303
97,558
150,160
199,779
215,114
396,450
486,287
668,502
904,878
Demand
(KL/year)
628,913
604,453
829,085
827,596
454,343
458,487
433,031
577,831
634,995
788,042
998,428
1.3.2
Capacity Analysis
For determining the production capacity of our plant, we have to consider
and calculate the demand and supply of our product first, which has in the section
before. Our plant will be build approximately in 2016, therefore we will fulfill
several percentage of bioethanol demand in 2016. Based on the table, we know
that the demand of bioethanol for Indonesia in 2016 is 210,519 kilolitres per year.
Our plant will fulfill for about 35% of the demand in Indonesia, and we can
calculate our plant capacity.
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Working Time
10% of the demand
Production Capacity
1.3.3
source of biomass used in this plant design is rice straw. Tayeb (2012) reported
that rice straw contains 12.4% ash, 39.2% cellulose, 23.5% hemicellulose, 36.1%
lignin and 1.83% moisture. Generally, rice straw is a lignocellulosic biomass
because of high lignin and cellulose content. Lignocellulosic compounds
structure is a complex form of hemicellulose and cellulose which bonded in lignin
molecules. Lignocellulose has high availability, especially as agricultural waste.
Rice straw and husks offer an immense potential to create bioenergy, an
alternative renewable source of power, said Dr. Stephan Haefele, senior
researcher at the International Rice Research Institute (IRRI). He and his scientific
team have been exploring ways to turn rice residues into useful and valuable by
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1.3.4
investors to build a plant, such as capital and operating costs. The plant location is
also affects the continuity of the plant production, meanwhile the right chosen
location is the location where the unit cost of production and distribution either
raw materials or product will be low. In other hand, the price and volume sales of
our ethanol products will be able to generate maximum profits for our company.
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Transportation
There are potential industrial areas in Indramayu, likes Losarang,
Kadanghaur. In industrial area, transportation infrastructure will be
provided. In the presence of subway Cipali (Cikopo-Palimanan) it helps
the mode of transportation around the Java Island.
Labor
As a potential industrial area, Indramayuhas a reserve of human resources
reliable in quality and quantity.In addition, the availability of labor from
the area around and outsideIndramayu is also relatively large. Secondary
Factor
Government policy
Because of our plant location is in industrial area, the permits of plant
construction will be managed by the owner. In Indramayu the zone of
industry has been persistent and all of the administration in Bappeda
Indramayu, West Java is the most strategic location to build our plant, and Figure
1.4 shows the location of our plant.
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CHAPTER 2
PROCESS SELECTION
2.1
Alternative Process
Cellulosic ethanol is made from the cellulose, commonly in form of
biomass. In a source of biomass there is not contains cellulose only but also
contains lignin and hemicellulose. The cellulose could be converted to ethanol in
two main pathways either by biochemical or thermochemical conversion. In
biochemical process specialized enzyme or microbes is needed. The biomass goes
to pretreatment first to separate the lignin from cellulose and hemicellulose while
with the thermochemical conversion the biomass is processed into gaseous by
gasification process. In Figure 2.1 shows the alternative ways to process the
biomass into cellulosic ethanol.
As seen in Figure 2.1 there are three alternative processes to convert the
biomass into cellulosic ethanol, but in hydrolysis process there is alternative to be
chosen. Those are with enzyme or acid to hydrolysis process. Therefore, the
alternative process is become to four and for help to know each process in Table
2.1 is listed the process route.
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Alternative
Process Route
The process listed in table 2.1 would goes to selection process by scoring
each alternative in some criteria. Actually, the main different process to be
selected is in the conversion process, by biochemical conversion or
thermochemical conversion. The conversion is the key of this process pathway, it
would be differentiate the way to produce an ethanol.
2.1.1
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In the alternative A and B, the separated cellulose is broke into the simple
molecule glucose by hydrolysis. The alternative A and B differ in here, the
alternative A used enzyme while the alternative B used acid in hydrolysis process.
a. Hydrolysis
Cellulose is one of polymer form from glucose, which the glucose unit is
connected each other. The cellulose need to be hydrolyzed before produce the
ethanol. There are two basic type of hydrolysis, using enzyme or acid. The
cellulosic material is converts into sugar first and the second reaction would
convert the sugar to other chemicals. Most of acid processes are limited to a
sugar recovery efficiency of round 50%. The advantage of acid processes is
their fast rate of reaction, which facilitates continuousprocessing yet low sugar
yield. Another process is by using enzymes. Enzymes are naturally occurring
plant proteins that cause certain chemical reactions to occur. However, for
enzymes to work, they must obtain accessto the molecules to be hydrolyzed.
For enzymatic processes to be effective, some kind of pretreatment process is
thus needed to break the crystalline structure of the lignocellulose and remove
the lignin to expose thecellulose and hemicellulose molecule. Depending on
the biomass material, either physical or chemical pretreatment methods may
be used.
b. Fermentation
Ethanol fermentation is the biological process in room temperature and
atmosphere condition.The main objective process is converts the glucose into
ethanol by using the microorganism like Saccharomyces cerevisia. that
classified to the yeast types. It common used in industry of ethanol production
and it has the good prosperity in ethanol fermentation. The fermentation of
carbohydrates into alcohol is one of the oldest known chemical processes.
The fermentation process is started by mixing the source of sugar, water,
and yeast and the yeast to act in an oxygen free environment. Bacterial
fermentation of CO, CO2 and H2 to ethanol using clostridium ljungdahlii
gives thefollowing equations
6 CO + 3 H2O C2H5OH + 4 CO2
G = -216 kJ/mol
(2.1)
G = -97 kJ/mol
(2.2)
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2.1.2
break cellulose into syngas (CO and H2) and reassemble it into products such as
ethanol. The cellulose with lignin-rich parts cannot be easily converted
biochemically. Cellulose in biomass is burned into syngas. This process is called
as gasification which also forms tar and sulfur. The gases formed then go to tar
reformer to be cleaned to get closer to pure CO and H2. The cleaned gas compress
and run across a catalyst that will make the gases back up into molecules likes
ethanol or hydrocarbons.
The process conversion biomass into ethanol is in catalytic synthesis
process. This process were differentiated the biochemical and thermochemical
conversion. The main different with biochemical is in catalyst used, the
biochemical conversion used the microorganism as catalyst while the
thermochemical conversion used the chemical catalyst. In the alternative, there is
only alternative D used the thermochemical conversion, but it has the same way
with the alternative C to form the syngas from biomass. With those alternative
gives the high capacity of ethanol that would be produced.
2.1.2.1 Gasification
The cellulose in form of biomass would be dried and goes to gasification
process. Biomass gasification means combustion of biomass resulting in
production of combusting gases consist of carbon monoxide (CO), hydrogen (H2)
and traces of methane (CH4). This mixture is called produces gas. Actually this
produces gas contain other contaminants too likes tar and sulfur, that must be
treated. The gasification process takes place at temperatures of about 1000C and
reactor used is called gasifier. The production of these gases from gasification
process is by reaction of water vapor and carbon dioxide through a glowing layer
of biomass. Thus the key to gasifier design is to create conditions such that
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Figure 2.2 Conceptual Flow Diagram of Gasification based Biomass to Fuel System
(Source: U.S Department of Energy, PNNL-19009)
Steam Gasification
The steam gasification reaction is endothermic which is requires heat input for
the reaction to proceed in its forward direction. This reaction is typical
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(2.3)
(2.4)
fouling
on
many
surfaces,
such
as
process
catalyst
Hydrogasification
The hydrogasification process is direct addition of hydrogen to biomass under
high pressure forms methane.
C + 2 H2 CH4
(2.5)
Partial Oxidation
Partial oxidation reaction is known as combustion process. The reactions for
partial oxidation are shown as follows.
C + O2 CO
(2.6)
C + O2 CO2
(2.7)
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From the Figure 2.3, we know the majority product conversion is ethanol. With
this conversion process the ethanol produced is about 70%.
2.2
Process Selection
In subchapter before in Table 2.1 there are the alternative process would
goes to be chosen. For the process selection we need some criteria to assess each
alternative process into get the best way to produce the cellulosic ethanol. As a
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Maturity
Maturity means the process we choose is proven and has been used in real
industry.
Product Conversion
The best process has a high conversion. It means the feeds which goes to the
process would be form the product, ethanol. Product conversion is the one of
selecting factor. When the conversion reach 80%, it means the process has
high conversion and would be given score 5.
Capacity
Sum of the feed or raw materials that could be processed is meaning of
capacity. The higher capacity that would form into the ethanol would be
chosen process.
Treatment Process
Some of the alternative needed an extra treatment before goes to process and
some of other produces the unneeded components like sulfur and tar which
needed to be removed. The extra treatment process and removal process may
give the adding of equipment, and impacts the cost needed.
Simplicity
Simplicity is how easy the process to convert the feed or raw materials to
become the final product, ethanol. The more complex the process, the
equipment needed to install and impact the all of the cost spent. If we see in
the step of each alternative, the process D has the few steps compare to the
other alternative. Alternative A and B have goes to pretreatment first before
the main process. It means the process A and B is more complex than another.
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Criteria
Maturity
Product
Conversion
Capacity
Treatment
Process
Simplicity
Weight
%
C
Score
Score
Score
Weight
20
Engineering Aspect
5
1
5
1
0.8
0.8
20
0.8
0.8
15
0.6
0.6
0.75
0.75
15
0.45
0.45
0.6
0.6
10
0.4
4
0.4
Economic Aspect
0.4
0.4
Capital
10
Expenditure
Operational
10
Expenditure
Total Score
Score
Score
Weight
Score
Weight
Score
Score
Weight
0.5
0.5
0.3
0.4
0.3
0.3
0.4
0.5
4.05
4.05
4.25
4.45
Based on the scoring process, the process with high score is the chosen
process. The process chosen is process D, biomass gasification catalytic
synthetic process ethanol. In this alternative, the main processes are gasification
and catalytic synthetic.
2.3
Technology Selection
The alternative chosen is alternative D with thermochemical conversion
through the gasification technology. It has the other alternative must be chosen,
like the technology used.
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There are two main types of gasifiers, indirect and direct gasifier. In direct
gasifier the fees is heated directly or partial oxidation gasifier will be generated
the heat required for gasification inside the reactor. Heat would be used from the
partial combustion of the feedstock. In other hand, indirect gasifier transfer heat
from an external source into gasifier. The heat from external source came from the
heat generated through the combustion of by product created during gasification.
In the direct gasifier the heat required is supplied by burning a portion of
biomass with flow of oxygen in the reactor. In order to purify the oxygen, a
pressurized cryogenic air separation unit is needed. The feed into the reactor then
sealed and filled with pressurized CO2recovered from the gas purification and
conditioning section of the plant. The raw untreated gas from the gasifier is sent to
a primary cyclone separator where char is captured and sent to the char
combustor.he char is combusted in char combustor and the hot flue gas is sent to
the biomass drying unit. The gas from the primary separator is then sent to a
secondary cyclone separator to remove the ash and residual fines. The completely
process flow diagram is shown in Figure 2.4.
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fulfilled the heat, another heat is supplied by circulating hot olivine particles
between the gasifier and the separate combustorA series of cyclone separators are
used to remove particulates and char from the raw gas leaving the gasifier then the
majority of the olivine, char, and ash is separated in the cyclone separator and
then sent to the char combustor.The gas from the primary gasifier cyclone is sent
to the tar reformer while the char is burned in the char combustor to reheat the
olivine. The flue gas from char combustor is sent to primary combustor cyclone
separator which almost 99.9& of olivine will returned to the gasifier while the flue
gas then sent to a secondary combustor cyclone separator to remove the solid such
as fines and ash. The wet solids are transported to a landfill and the hot gas is then
cooled by boiler in order to use for biomass drying. All of these completely
process can be seen in Figure 2.5.
Factor
Direct
Indirect
Feed (mtpd)
2200
2200
Products (mmgal/y)
45
43
14.5
34.7
26.8
30.2
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Factor
Direct
Indirect
Fuel Products
30.1%
28.7%
Thermal Efficiency
44.8%
42.5%
480
356
3.07
2.71
From the data U.S Department of Energy we can give score to each
technology alternative to get the right chosen. The technology selection through
several criteria, such as yield product, energy consumption, costs needed. The
score is given from 1 to 5.
Table 2.5 Gasification technology scoring
Criteria
Weight %
Product Yields
Energy Efficiency
Equipment Needed
Cost
Total Score
25
25
25
25
Direct Gasifier
Score
Score
Weight
4
1.00
4
1.00
4
1.00
4
1.00
4.00
Indirect Gasifier
Score
Score
Weight
4
1.00
5
1.25
4
1.00
5
1.25
4.5
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gasifier consist of a fixed bed biomass with counter current flow of steam, oxygen
and air flowing upward through the fuel bed while the Co-current fixed bed
reactor (downdraft) gasifier the steam, oxygen and air flows downward with the
fuel. Gas exit temperaturesforn updraft gasifier are low, which improves thermal
efficiency, but increases tar and methane impurities in the gas. In other hand,
because the gas passes through the hot char at the bottom of the bed before exiting
in downdraft gasifier, some impurities such as tars are trapped in the char and the
final product has a higher purity. The exit temperature of the gas is higher,
resulting in a lower overall efficiency.
Figure 2.6 (a) Counter Current Fixed Bed (Updraft), (b) Counter Current Fixed Bed (Downdraft)
(Source: FAO Corporate Document Repository)
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In entrained flow gasifiers, the fuel is fed either as a dry pulverized solid
or the fuel slurry in tandem with oxygen or air. Gasification takes place in a dense
cloud of fine particles and is particularly useful for coals which can be easily
pulverized into fine particles. This gasifier has the highest operating temperature
and pressure, which decreases the amount of tars and methane formed during
gasification.Because of the entrainment requirement, high space velocity of gas
stream and fine powdery coal particles are very essential to the operation of this
type of process. Because of the very short residence time (i.e., high space
velocity) in the reactor, a very high temperature is required to achieve
good conversion in such a short period of reaction time. This can also be assisted
by using excess oxygen.
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Criteria
Weig
Fixed Bed
Fixed Bed
Fluidized
Entrained
(Updraft)
(Downdraft)
Bed
Bed
-ht %
Score
Product
Yields
Energy
Efficiency
Equipment
Needed
Cost
Score
Weight
Score
Score
Weight
Score
Score
Weight
Score
Score
Weight
25
0.75
0.75
0.75
1.00
25
0.75
1.00
1.00
1.00
25
1.00
1.00
1.25
0.75
25
1.00
1.00
1.25
0.75
Total Score
3.50
3.75
4.25
3.50
Overall, fluidized bed reactors have greater potential for use with biomass
conversion than fixed bed reactors or other types of gasifier.The gasification of
carbonaceous biomass occurs via three main reactions, partial oxidation, complete
oxidation, and the water gas reaction
C + O2 CO
(2.8)
C + O2 CO2
(2.9)
C + H2O CO + H2
(2.10)
In addition, the water gas shift reaction plays an important role in the composition
of the CO, CO2, and H2
CO + H2O CO2 + H2
(2.11)
Syngas can also contain a number of other compounds such as methane (CH4),
acetylene, ethylene, ethane, nitric oxide (NO), sulfur dioxide (SO 2), tars, and ash
which can have complex effects on the metal catalyst.
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2.4
Process Description
2.4.1
to plant use trucks. Before the feedstock brought to plant, it will feed into the
hammer mill for reduction its size. Biomass feedstock will has a size reduction
use hammer mill until the size is 0,1-0,3 mm.Pneumatics may be integrated into
the hammer mill, which would increase grinder efficiency and provide additional
drying beyond that which is accomplished in the absence of pneumatics. Chips are
ejected from the hammer mill directly into a flat floor chip trailer, and once the
truck reaches capacity the material is taken to the plant.At the plant, the trucks are
weighed and a truck dumper unloads the truck contents into a hopper. A dust
collection system is present during unloading to prevent excessive dust
accumulation and to limit dry matter losses. Before the biomass are converted to
syngas, the feedstock is dried by rotary drum dryer to reduce moisture content
until 10 wt% moisture using hot flue gases from the char combustor and tar
reformer catalyst regenerator.
2.4.2
Gasification
In this stage, biomass feedstocks that already dried will enter gasification
processes to produce syngas. The design includes two parallel gasifier trains, each
with a biomass processing capacity of 1000 dry metric tonnes per day.
Gasification process use heat source from steam so called indirect gasified. The
heat for the gasification reactions is supplied by circulating synthetic olivine sand
that is pre heated in a char combustor and fed to the gasifier. In this case the
medium is synthetic olivine (calcined magnesium silicate) consisting of Enstatite
(MgSiO3), Forsterite (Mg2SiO3), and Hematite (Fe2O3). A small amount of
magnesium oxide (MgO) is added to the fresh olivine. The MgO rejects the
potassium
present
in
biomass
as
ash
by
forming
high
melting
(~2,370F/1,300C) ternary eutectic with the silica, thus sequestering it. Without
MgO addition, the potassium will form glass (K2SiO4) by interacting with the
silica in the system. K2SiO4 has a low melting point (~930F/500C) and its
formation would cause the bed media to become sticky, agglomerate, and
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The operation of the gasifier and char combustor resembles that of a fluid
catalytic cracker (FCC), a common oil refinery unit operation. Like an FCC, the
gasifier and char combustor will remain in heat balance by producing (gasifier)
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and burning (char combustor) enough char to satisfy the energy requirements of
the operation. The gasifier and combustor reach thermal equilibrium based on the
amount of char formed in the gasifier. If the gasifier temperature is lower than the
equilibrium temperature, then more char is formed and more heat is generated by
char combustion. This results in more heat transfer from the combustor to the
gasifier, thus bringing the gasifier temperature up toward equilibrium. gasifier
temperature is 1,596F (869C) and the char combustor temperature is 1,808F
(987C). The char combustor is operated with 20% excess air (based on the
stoichiometric requirement) to ensure complete oxidation of char components. The
(2.12)
( ) + 2
(2.13)
( ) + 2
(2.14)
( ) + 2
+ 2
+ 32
2 + 2
(2.15)
4 + 2
(2.16)
There are water gas shift reaction on gasifier which functions to decrease
CO and increase the amount of H2. It is useful to get H2/CO ratio near 2. Within
the gasifier, biomass thermally deconstructs to a mixture of syngas components
(CO,H2,CO2,CH4,etc), tars, and solid char containing residual carbon from the
biomass and coke deposited on the olivine. At the exit of the gasifier, there are
cyclones that separate the char and olivine from the syngas. The solids flow to the
char combustor where the char is burned in air in a fluidized bed, resulting in
olivine temperatures greater than 1800oF (982oC). The hot olivine and residual ash
is carried out of the combustor by the combustion gases and separated using a pair
of cyclones. The first cyclone captures olivine while the second cyclone captures
ash and olivine fines. Hot olivine flows back into gasifier, completing the
gasification loop. The hot flue gas from the char combustor is utilized for heat
recovery and feedstock drying. Ash and olivine fines are cooled, moistened to
minimize dust, and removed as waste.
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2.4.3
Gas Cleanup
After gasification, there are other components beside syngas like tars,
Similar to the gasification area, the heat for tar conversion is supplied by
circulating catalyst (Ni/Mg/K supported on alumina) between the tar reformer
reactor and the catalyst regenerator. The reactions in tar reformer can be seen in
the below:
10 8 + 102
4 + 2
+ 32
(2.17)
(2.18)
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2 6 + 22
2 4 + 22
2 + 52
(2.19)
2 + 42
(2.20)
As we can see, the reaction in tar reformers produce hydrogen more than
carbon monoxide, so the ratio H2/CO will increase. The catalyst regenerator burns
carbon (coke) deposits off the catalyst particles, regenerating the catalyst activity
and providing heat for the tar reforming reactions. Because the rate of coke
formation in the tar reformer is not sufficient to sustain the endothermic reforming
reactions, supplemental combustion gases are supplied to the catalyst regenerator
from various process areas. Air is supplied to the catalyst regenerator by the
combustion air blower to provide the oxygen for combustion.
The spent catalyst from the tar reformer is separated from the syngas in a
two-stage cyclone separator and flows to the catalyst regenerator). The
combustion flue gas and catalyst from the regenerator are sent to a cyclone
separator system. A two-stage cyclone separates the regenerated catalyst from the
combustion gases and the catalyst flows back to the tar reformer. The flue gas is
then utilized for heat recovery before it is mixed with flue gas from the
gasification area. The combined flue gas stream is used for the feed drying system
and then sent to a flue gas scrubber.
Hot syngas from the tar reformer is cooled to 140F (60C) through heat
exchangers, which are used to heat other process streams. A syngas scrubbing
system removes impurities such as particulates, ammonia, halides, and residual
tars. The scrubbing system consists of a venturi scrubber, cyclone separator, and a
quench water circulation system. The syngas exits the quench system at a
temperature of 130F (54C).Scrubber water is purged and treated continuously
an on-site wastewater treatment facility.
2.4.4
Alcohol Synthesis
Cooled low-pressure syngas enters a six-stage centrifugal compressor
system where the pressure is increased to approximately 3,000 psi (207 bar). Each
inter-stage cooler includes water, air, and process stream exchangers. These
exchangers are deliberately oversized to minimize pressure drops to an average of
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6 psi (0.41 bar) per inter-stage. Minimizing pressure drop in the coolers will
minimize electrical consumption.
The compressed fresh syngas is mixed with recycled syngas and methanol
and pre heated to 595oF (313oC) before entering the alcohol synthesis reactor. The
pressurized syngas is fed to the tube sides of two vertical tubular reactors (shell
and tube type) operating in parallel. CuO/ZnO catalyst is packed within the tubes
of the reactor, which is oriented in a down-flow configuration. Then, reactions at
above 570F (300C) convert a portion of the syngas to oxygenate and
hydrocarbon products. The overall stoichiometric reaction for alcohol synthesis is
summarized in equation 2.12 :
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+ 2 2
(2.21)
2 +1 + 1 2
(2.22)
2 + 2
Heat from the reactions is removed by steam generation in the shell side of the
tubular reactor. Heat must be removed from the reactors because the synthetic
reaction is exothermic. Steam is generated at 1336 psia and 581 oF (305oC). The
reactor effluent consisting of mixed alcohols, gaseous by-products (such as CO2
and methane), and unconverted syngas is cooled through heat exchanger with
other process streams. As the reactor effluent cools, alcohols and water are
condensed and sent to downstream separation and purification equipment.
Figure 2.12 Simplified Flow Diagram of The H2S/CO2 Removal and Sulfur
(Source: NREL/TP-5100-51400,2011)
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2.4.5
Alcohol Separation
Cooled crude alcohols are de-pressurized and de-gassed in a flash
separator. The evolved gases are recycled to the gas cleanup section as a feed to
the tar reformer. The depressurized liquid stream is dehydrated using a molecular
sieve system. The molecular sieve dehydrator consists of two parallel vessels
containing fixed bedsof porous alumino-silicate pellets, which are designed to
selectivity adsorb water. One molecular sieve vessel is in alcohol drying service
while the material in the other vessel is being regenerated by recycled methanol.
This can be seen in Figure 2.13 below:
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15% (in the base case design) is sent to the molecular sieve system, which is
adequate to regenerate the molecular sieve beds by flushing the adsorbed
water. The resulting methanol/water mixture is returned to the gasifier as a
source of steam for fluidization.
From 0% to 15% (11% in the base case design) is chilled and mixed with an
H2Srich stream from the sulfur recovery system. H2S dissolves in the cold
methanol and the resulting solution is pumped to the inlet of the alcohol
synthesis reactor, providing sulfur for catalyst activity management. The
amount of H2S is adjusted to maintain an average concentration of 70 ppmv at
the reactor inlet. It should be noted that a range of 0% to 15% is specified
because the required amount of H2S recycle will depend on the amount of H2S
(from sulfur present in the biomass feedstock) entering the alcohol synthesis
reactor with fresh syngas.
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The remaining material (69% in the base case design) is recycled to the
alcohol synthesis reactor to improve ethanol yields.
2.4.6
Cooling Water
A cooling water system is included to determine the requirements of each
cooling water heat exchanger within the biomass conversion process as well as
makeup water and power requirements. In a version of the design that includes
additional water optimization, process condensate is treated and combined with
the cooling water makeup to reduce fresh water consumption.
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39
2.5.1
Hammer Mill
Hammer mill is a crusher that can grind, pulverize, and crush a wide range
of materials. In our plant hammer mill used in handling feed section to crushing
the rice straw to size 0.1mm until 0.3 mm. Hammer mills work on the principle
using a simple four step operation:
1. Material is fed into the mills chamber typically by gravity.
2. The material is struck by ganged hammers which are attached to a shaft which
rotates at a high speed inside the chamber. The material is crushed or shattered
by the repeated hammer impacts, collisions with the walls of the grinding
chamber as well as particle impacts.
3. Perforated metal screens or bag grates covering the discharge opening of the
mill retain coarse materials for further grinding while allowing properly sized
materials to pass as finished product.
4. Hard, heavy materials such as glass, stone or metals exit the mill via gravity.
Pneumatic suction us used to assist in the discharge of lighter materials such
as wood, paper or other low bulk density products.
2.5.2
Rotary Dryer
Dryer use to reduce moisture content of biomass feedstock until 10% wt.
Type of waste heat dryer (M-101) that used is rotary drum dryer. Wet biomass
material goes into the feeding hopper by dryer feed screw conveyor (C-101), then
through the feeder goes into the feed pipe. The feed pipe slope is greater than the
natural inclination of the materials, so that the material can inflow the rotary dryer
smoothly. There is supply hot flue gas from char combustor and tar reformer
torotary dryer. The rotary dryer cylinder is tilted slightly compared with
horizontal. Materials and hot flue gas goes into the rotary dryer cilinder from the
higher end. During the rotation of the cylinder, the material by gravity goes into
the lower end. When the wet material is in the process of moving forward in the
rotary dryer cylinder body, the lifting plates inside the rotary dryer cilinder makes
the material up and down to contact with the hot flue gas completely. Thus, the
moisture inside the wet material is evaporated into water vapour, and finally we
get the dried materials.
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2.5.3
flows upward through the bed and fluidizes the biomass particles. Owing to the
ascent of particles and fluidizing gas, larger biomass surface area is made
available. It can promote the gas solid chemical reaction, which in turn results in
enhancement in carbon conversion.
This type of reactor allows intimate contact between gas and solid biomass
fines and at the same time providing relatively longer residence times than
entrained flow reactor. We use indirect heat biomass gasifier (R-201) because we
want to produce syngas with high H2/CO ratio. The indirect gasifier also do not
require an air separation unit to separate oxygen and nitrogen. While, the direct
gasifier needs air separation unit because they have partial oxidation reaction
(POX). A source of heat required gasifier in distributed by char combustor (R202). From char combustor, steam may be generated and used for biomass
gasification in gasifier.
2.5.4
Cyclone
Cyclone separators utilize gravity and a vortex to remove particulates from
2.5.5
methane, and other hidrocarbons from gasification unit to become syngas. Tar
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2.5.6
2.5.7
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2.5.8
that form like tubular reactor which has a shell and tube section. The feed will be
fed to tube section which filled with CuO/ZnO packed catalyst. The reaction of
synthesis alcohol is a exothermic reaction that produce heat. The heat will transfer
through surface between shell and tube to generate steam for others process. The
material that used in tubular reactor is SA 213. The operation condition of this
reactor is 570oF (300oC) and the pressure is around 3000 psi (207 bar).
2.5.9
Heat Exchanger
In the plant, heat exchanger have function to help transfer heat in several
section. One of function heat exchanger that used in our plant is cooling the
methanol/water mixture that resulted from the molecular sieve regeneration.
Moreover, we use heat exchanger for tar reformer effluent (HE-301), syngas
quench inlet (HE-302), alcohol synthesis effluent (H-403), ethanol product, higher
alcohols product, steam turbine exhaust, catalyst regenerator flue gas and char
combustor flue gas. The type of heat exchanger is shell and tube.
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2.5.14 Pump
A pump is a device that moves fluids or sometimes slurries by mechanical
action. Pumps can be classified into three major groups according to the method
they use to move the fluid: direct lift, displacement, and gravity pumps. In our
plant, there are a lot of pump like quench water recirculation pump (P-301), crude
alcohol column reflux pump, methanol column reflux pump, condensed methanol
pump, crude alcohol column bottoms pump,etc. all of pump is centrifugal pump
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2.6
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2.7
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Figure 2.16 Process flow diagram of tar reforming, syngas cleanup, and compression
(Source: Authors personal data)
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Figure 2. 17 Process flow diagram of alcohol synthesis, acid gas removal, sulfur recovery
(Source: Authors personal data)
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Figure 2.19 Process flow diagram of steam system and power generation
(Source: Authors personal data)
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MASS AND ENERGY BALANCE
3.1
Process Simulation
The process mainly involves biomass gasification, tar reforming and
mixed alcohol synthesis. The simulation was done in Unisim Design. This is the
simplified Unisim process flow diagram:
51
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(3.1)
Variable
X Units
Dry syngas
28.993
-0.043325
0.000020966
CO
133.46
-0.1029
0.000028792
CO2
-9.5251
0.037889
-0.000014927
CH4
-13.82
0.044179
-0.000016167
C2H4
-38.258
0.058435
-0.000019868
C2H6
11.114
-0.011667
0.000003064
H2
17.996
-0.026448
0.00001893
C2H2
-4.3114
0.0054499
-0.000001561
Tar (C10H8)
0.045494
-1.9759E-05
This equation can used in temperature range from 1280-1857 F and pressure
from 2.4 to 14.4 psig. This equation and material balance equation used to
model the gasifier in unisim. Where gasifier modeled as subflowsheet, and the
outlet stream calculated from above equation and material balances.
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b. Tar Reformer
Tar reformer was modeled using a conversion reactor. In this reactor, some regasification of many components (hydrocarbon of gasifier outlet) occur. The
reaction are as follows:
10 8 + 102
10 + 142
(3.2)
+ 32
(3.3)
2 6 + 22
2 + 52
(3.4)
2 4 + 22
2 + 42
(3.5)
4 + 2
The conversion of the four reactions was set to the value of NREL (National
Renewable Energy Laboratory)s pilot scale conversions in tar reformer under
the same exact conditions as the simulation was. The conversion is as follows:
Table 3.2 Tar reformer conversion
Compound
Conversion
Methane (CH4)
80%
Ethane (C2H6)
99%
Ethylene (C2H4)
90%
Tars (C10H8)
99%
(Source :Process Design and Economics for Conversion of Lignocellulosic Biomass to Ethanol,
NREL)
These conversion data was used in the tar reformer model. The output of this
reactor is tar-free syngas. The gas is then compressed before processed in
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alcohol synthesis reactor. This conversion reactor also represent the separation
of the ash from the gas after the reactions. Ash were separated in nonvolatile
stream.
c. Alcohol Synthesis Reactor
The reactor modeled in unisim as plug flow reactor with many tubes (tubular
reactor). In this reactor, the synthesis of some alcohols and water gas shift
reaction happened. The catalyst used in this reactor (CuO based) were very
selective to produce ethanol and produce very little the other alcohols. The
reactions are as follows:
+ 22
2 + 42
+ 2
(3.6)
2 5 + 2
(3.7)
2 + 2
(3.8)
(3.9)
= / 2
(3.10)
= / 2
(3.11)
Reaction
Ea (J/mol)
A (mol/gcat/h/MPa)
Methanol Synthesis
72190
59.40
2.00
Ethanol Synthesis
81450
268.00
1.50
WGS
144.80
144.80
-0.57
1.00
60
9579
42.2
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1.5
0.16
The reactor outlet was ethanol mixed with unreacted reactants. Then, the reactor
must be distillated to have the desired product, which is pure ethanol. The first
distillation use 10 stages, and the second one used 15 stages. With
this
3.2
Mass Balance
The is calculations of mass balance is determined by the product capacity,
which is 100,000 KL per year. Therefore, the mass balance must require that amount
of capacity:
3.2.1
discussion of mass balance of ethanol production. From the final result of market
share, the maximum capacity that needs to be prepared for our manufacturing unit is
74,000 KL per year. In this mass balance, will be described details of components
needed to produce in one cycle.
Gasification
Table 3.5 Gasification unit mass balance
Components
Ash
Cellulose
Hemicellulose
Lignin
Hydrogen
CO2
CO
H2O
Methane
Ethane
Acetylene
1 - Mass (kg/h)
10,914
83,985
41,026
58,430
0
0
0
0
0
0
0
2 - Mass (kg/h)
0
0
0
0
0
0
0
103,623
0
0
0
3 - Mass (kg/h)
45,449
0
0
0
0
61,756
125,723
0
26,368
1,561
935
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Components
Ethylene
Benzene
Ammonia
H2S
Nitrogen
Naphthalen
Methanol
Ethanol
1-Propanol
1-Butanol
1-Pentanol
Selexol
TOTAL
1 - Mass (kg/h)
0
0
0
0
0
0
0
0
0
0
0
0
194,355
2 - Mass (kg/h)
0
0
0
0
0
0
0
0
0
0
0
0
103,623
3 - Mass (kg/h)
13,459
0
0
0
0
4,505
0
0
0
0
0
0
279,756
Tar reformer
Table 3.6 Tar reformer unit mass balance
Components
Ash
Cellulose
Hemicellulose
Lignin
Hydrogen
CO2
CO
H2O
Methane
Ethane
Acetylene
Ethylene
Benzene
Ammonia
H2S
Nitrogen
Naphthalen
Methanol
Ethanol
1-Propanol
1-Butanol
1-Pentanol
3 Mass
(kg/h)
45,449
0
0
0
0
61,756
125,723
0
26,368
1,561
935
13,459
0
0
0
0
4,505
0
0
0
0
0
4 -Mass
(kg/h)
0
0
0
0
0
0
0
53,423
0
0
0
0
0
0
0
0
0
0
0
0
0
0
5Mass(kg/h)
29,078
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
5a Mass
(kg/h)
0
0
0
0
13,836
923,524
96,239
0
2,977
0
598
86
0
0
0
0
3
0
0
0
0
0
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Components
Selexol
TOTAL
3 Mass
(kg/h)
0
279,756
4 -Mass
(kg/h)
0
53,423
5Mass(kg/h)
0
29,078
5a Mass
(kg/h)
0
1,037,263
Alcohol Synthesis
Table 3.7 Alcohol synthesis unit mass balance
Components
Ash
Cellulose
Hemicellulose
Lignin
Hydrogen
CO2
CO
H2O
Methane
Ethane
Acetylene
Ethylene
Benzene
Ammonia
H2S
Nitrogen
Naphthalen
Methanol
Ethanol
1-Propanol
1-Butanol
1-Pentanol
Selexol
TOTAL
19 - Mass (kg/h)
0
0
0
0
13,835
92,332
96,237
0
2,973
0
591
71
0
0
0
0
0
0
0
0
0
0
0
206,038
Separator
Table 3.8 Separator mass balance
Components
Ash
Cellulose
Hemicellulose
21 -Mass (kg/h)
0
0
0
23 - Mass (kg/h)
0
0
0
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Components
Lignin
Hydrogen
CO2
CO
H2O
Methane
Ethane
Acetylene
Ethylene
Benzene
Ammonia
H2S
Nitrogen
Naphthalen
Methanol
Ethanol
1-Propanol
1-Butanol
1-Pentanol
Selexol
TOTAL
21 -Mass (kg/h)
0
0
92,352
116
30,910
2,977
0
598
86
0
0
0
0
270,441
0
79,045
0
0
0
0
476,527
23 - Mass (kg/h)
0
0
25,227
3
30,896
223
0
139
3
0
0
0
0
3
0
78,977
0
0
0
0
135,470
T-100
Table 3.9 T-100 mass balance
Components
Ash
Cellulose
Hemicellulose
Lignin
Hydrogen
CO2
CO
H2O
Methane
Ethane
Acetylene
Ethylene
Benzene
Ammonia
22a - Mass
(kg/h)
0
0
0
0
0
1.267
0.002
0
0.052
0
0.009
0.002
0
0
23 Mass
(kg/h)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
24a - Mass
(kg/h)
0
0
0
0
0
57,898
104
0
2,688
0
388
75
0
0
24b - Mass
(kg/h)
0
0
0
0
0
9,222
1
13
66
0
72
8
0
0
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Components
H2S
Nitrogen
Naphthalen
Methanol
Ethanol
1-Propanol
1-Butanol
1-Pentanol
Selexol
TOTAL
22a - Mass
(kg/h)
0.000
0.000
0.000
0.000
0.001
0.000
0.000
0.000
0.000
1.332
23 Mass
(kg/h)
0
0
0
0
0
0
0
0
100
100
24a - Mass
(kg/h)
0
0
0
0
0
0
0
0
15
61,168.521
24b - Mass
(kg/h)
0
0
1
0
67
0
0
0
445,154
454,603.731
Distillation
Table 3.10 Distillation mass balance
Components
Ash
Cellulose
Hemicellulose
Lignin
Hydrogen
CO2
CO
H2O
Methane
Ethane
Acetylene
Ethylene
Benzene
Ammonia
H2S
Nitrogen
Naphthalen
Methanol
Ethanol
1-Propanol
1-Butanol
1-Pentanol
Selexol
TOTAL
25 - Mass (kg/h)
0
0
0
0
0
25,227
3
30,896
223
0
139
3
0
0
0
0
3
0
78,977
0
0
0
0
135,470
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3.2.2
Components
Ash
Cellulose
Hemicellulose
Lignin
Hydrogen
CO2
CO
H2O
Methane
Ethane
Acetylene
Ethylene
Benzene
Ammonia
H2S
Nitrogen
Naphthalene
Methanol
Ethanol
1-Propanol
1-Butanol
1-Pentanol
Selexol
TOTAL
(kg/h)
1 Mass (kg/h)
10,914
83,985
41,026
58,430
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
194,355
104,483
31,272
3.3
Energy Balance
3.3.1
Equipment
R-101
-52.354
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Equipment
R-102
K-101
E-101
K-102
E-102
K-103
E-103
7
Q3
8
9
Q5
10
K-104
11
Q7
E-104
12
K-105
E-105
K-106
E-106
E-107
13
Q9
14
-21.12
-19.94
3.232
-16.708
-16.71
-16.71
-19.42
3.261
-16.159
-16.16
-16.16
-19.94
3.412
-16.528
-16.52
-16.52
-19.41
3.453
-15.957
-15.95
16
-15.95
-18.86
2.771
-16.089
-16.09
17
-16.09
-19.85
15
Q11
7
Q2
8
9
Q4
10
11
Q6
12
13
Q8
14
15
Q10
16
17
Q12
18
-21.12
-19.94
-1.176
-21.116
-16.71
-16.71
-19.42
2.714
-16.706
-16.16
-0.002
-0.004
0.002
-0.004
-16.16
-19.94
3.772
-16.168
-16.52
0.001
-16.52
-19.41
2.884
-16.526
-15.95
-0.008
-15.95
-18.86
2.902
-15.958
-16.09
-0.007
-16.09
-19.85
3.763
-16.087
-22.39
0.001
0.008
0.006
0.008
-0.003
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Equipment
R-103
E-108
V-101
T-101
T-102
-0.004
0.3089
-0.673
-0.3681
3.1.1
Equipment
R-101
R-102
K-101
E-101
K-102
E-102
K-103
-19.94
3.232
-16.71
9
Q5
-19.42
3.261
-23.4
2.996
-21.12
7
Q2
8
-19.94
-1.176
-16.71
9
Q4
10
-19.42
2.714
-16.16
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63
Equipment
E-103
K-104
-19.94
3.412
-16.52
13
Q9
14
-19.41
3.453
-15.95
E-106
15
Q11
16
-18.86
2.771
-16.09
K-107
17
-19.85
R-103
19
-22.39
E-108
20
-33.11
V-101
21
-40.31
T-101
23
22a
22b
-0.9371
-13.67
-26.64
E-104
K-105
E-105
K-106
T-101
TOTAL
Input - Ouput
-19.41
2.884
-15.95
15
Q10
16
-18.86
2.902
-16.09
17
Q12
18
Q13
20
Q14
21
Q15
22a
22b
24a
24b
27a
27b
-19.85
3.763
-22.39
2.542
-33.11
10.72
-40.31
7.204
-26.64
-13.67
-3.096
-11.82
-20.62
-5.347
-387.478
-440.2041
-52.7261
3.4
main product produced in this plant. It can be done by dividing amount main
product produced with raw material used.
mass efficiency ethanol =
ethanol produced
104,483
=
x100% = 53.76%
biomass feed
194,355
product produced
135,755
=
x100% = 69.9%
biomass feed
194,355
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64
Total output
387.478
=
x100% = 88.02%
Total input
440.204
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CHAPTER 4
CONCLUSION
conversion.
Based
on
the
scoring
process,
the
65
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REFERENCES
66
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67
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