UNIVERSITI TUNKU ABDUL RAHMAN

Faculty of Engineering and Green Technology

Bachelor of Engineering (HONS) Petrochemical Engineering

UGPA1193 Mass and Energy Balance

Assignment: Methanol synthesis from synthesis gas

Student(s) detail(s):
NAME ID YEAR/SEM Marks
LEE WEI HERN 1503476 Y1S1
SEOW KING WEI 1503477 Y1S1
KELVIN LIEW 1403152 Y1S1

Lecturer’s name: Dr. Sin Jin Chung

Date of Submission: 28/7/16

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Table of content:
1. Reaction Description Page1-7

2. Mass Balance Page 8-11

3. Energy Balance Page 12-13

4. Conclusion Page14-15

5. References Page 16

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SECTION 1

REACTION DESCRIPTION

Methanol can be produced by several ways. One of the way is produced from
the synthesis gas. Composition of synthesis gas is 6% of nitrogen (N2), 21% of carbon
dioxide (𝐶𝑂2 ) and 63% of hydrogen (𝐻2 ). In a steady state process, 100moles of
synthesis gas at 300℃ is supplied. Methanol (𝐶𝐻3 𝑂𝐻) and water (𝐻2 𝑂) is produced.
The optimum condition of this process is within the range of 300℃ to 380℃, and
pressure of 1atm.

CO2 + H2→CH3OH + H2O

Generally, methanol also known as methyl alcohol, wood alcohol, wood

naptha, methyl hydrate or even wood spirits. Methanol has a chemical formula
𝐶𝐻3 𝑂𝐻, but it is often abbreviated as MeOH. It is the simplest alcohol, with only a
methyl group attached to a hydroxyl group. It is a volatile, light-weight, colourless
and flammable liquid with a distinctive odour that very alike to but slightly sweeter
than ethanol. At room temperature, methanol is a polar liquid. The molar mass of
methanol is 32.04 g/mol. Methanol boils at 64.7℃ and melts at -97.6℃. (Donal

O'Leary, 2000)

Methanol is produced through the process according to chemical equation

CO2 + H2→CH3OH + H2O. The condition of the process was around 300oC and 1
atm. In this steady state process, 100 moles of mixture of 72% H2, 24% CO2 and 4%
N2 at 25oC reacts to form CH3OH and H2O while nitrogen is inert gas which does not
involve in the reaction. 100 moles of fresh feed and n3 of recycle stream are combined
in mixing point. The ratio of recycled stream to fresh feed is 5:1. The combined
stream enters the reactor. After reaction, the product forms two major streams which
leave the reactor. The first stream contains CH3OH and H2O. The second stream
contains CO2, H2 and N2 is spilted into two stream which are n3 recycle stream and n2
purge stream.

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 Figure 1: Uses of methanol in 2013

Based on Figure 1, in year of 2013, the major use for methanol is as a

feedstock for the plastic production industry. Methanol is used to produce methanal,
continued by react with other materials such as phenol, melamine and carbamide to
produce different types of plastics. The methanol also frequently used in the petrol
blending. Few years ago, only small amount of methanol is directly used as fuel in
cars. But this use is increasing rapidly nowadays since the advantage of methanol
which can produced from both coal and biomass via synthesis gas. 15% of methanol
is mixed with petrol for the engines without re-designation, while up to 85% methanol
can be used for the engines with some re-designation. This priority of using methanol
as fuel source is reflected in global annual production figure for methanol. Thus, the
use of methanol as fuel currently 14% is expected to rise up to 16% by 2016. Another
major use of methanol is to produce alkenes by the MTO and MTP process. The
figures are expected to increase from 6.6 million tonnes in 2013 to 20 million tonnes
in 2016. This indicates that a huge amount of plastics such as polyethene (PE) and
polypropene (PP) will be derived from the synthesis gas.

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 Table 1: Annual production of methanol in 2013

World 69.2 million tonnes

South America 10 million tonnes 14%
China 35 million tonnes 51%
South East Asia 4.8 million tonnes 6.9%
Middle East 14 million tonnes 20.2%
USA 2.8 million tonnes 4.1%
Europe 2.6 million tonnes 3.8%
As shown in Table 1, the worldwide production of methanol in 2013 is
approximately 69.2 million tonnes. From the table above, China produced the most
methanol around the world, 35 million tonnes. The percentage of methanol produced
is more than half, which is 51%. Middle East countries contributed 14 million tonnes,
percentage of 20.2%. Meanwhile, the South America produced roughly 10 million
tonnes annually. While the South East Asia, USA and Europe produced 4.8 million
tonnes, 2.8 million tonnes and 2.6 million tonnes respectively.

In fact, methanol is one the most versatile compounds developed. It is the

basis for hundreds of chemicals and thousands of products that get involved in our
daily lives. Moreover, methanol is the second most in the world in amount shipped
and transported around the globe every single year. (Centre for Industry Education
Collaboration [CIEC], 2014)

As methanol is the most basic alcohol, it is widely used as transportation fuel.

It is easy to transport, readily available and has a high octane rating that allows for
superior vehicle performance when compared to gasoline. Other than that, methanol
has a lower price compared to gasoline or ethanol and it is eco-friendly since it
produces less toxic emissions than reformulated gasoline, since lesser particulate
matter and smog forming emissions.

Other than that, methanol is used by the wastewater treatment facilities to

carry the process of removal of nitrogen from effluent streams. Initially, wastewater
contains high levels of ammonia, and it is converted into nitrate through the bacterial
degradation process. If the wastewater is directly discharged into the environment, the
nutrient rich nitrate in sewage effluent can have a calamitous effect on the water

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ecosystems, which leads to occurrence of long way of algae blooms that vitiate
oxygen and sunlight from the aquatic life. Methanol is an effective and affordable cost
method to help revitalize waterways tainted by the effects of nitrates.

Furthermore, methanol plays a key role in the development of different types

of fuel cells. From large-scale fuel cells to power vehicles, provide back-up power to
remote equipment to portable fuel cells for electronics and personal use, methanol is
used as it is an ideal hydrogen carrier. The reason is with a formula of 𝐶𝐻3 𝑂𝐻 ,more
hydrogen atoms contains in each gallon when compared with other liquid which is
stable in standard conditions. (BYJU’s Chemistry,2016)

The other importance of methanol is in the processing of biodiesel fuel, it used

as a vital component in a part called transesterification. The transesterification process
reacts methanol with triglyceride oils contained in various type of oils such as
vegetable oils, animal fats and recycled greases and forms fatty acid alkyl esters
(biodiesel) and the side product, glycerin.

Moreover, nowadays many institutes are also exploring and researching the
use of methanol to drive the turbines to generate electricity. This is a great option for
those areas which rich in resources other than traditional sources.

Methanol is also often converted into formaldehyde, acetic acid and olefins.
This leads to many types of materials can be made from methanol such as plastics,
synthetic fibres, safety glass laminate, paints, pigments and dyes and many others.

However, methanol is a highly toxic colourless liquid. You are exposed to

methanol in our daily life. At home, you might expose to methanol when using
consumer products such as wall, spray paint, adhesives, cleaners, pesticides,
antifreeze and many more. Exposure can occur in different ways, from inhaling and
exhaling of air that contains methanol from natural sources or vehicle exhaust to
drinking and eating contaminated water and food. During work, you might experience
exposure to methanol when using solvents, inks, wood fungi treatments, alternative
fuels and windshield washer fluid. Working at a pharmaceutical or semi-conducting
manufacturing facility, mortuary or oil recovery facility also can be exposed to
methanol. Sometimes even the geographic locations will cause you exposed to the
methanol when you are around those places such as area that near to volcano that has
erupted or near decomposing organic material, sewage or sludge. (John J. Clary,2013)

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 Swallowing, inhaling and exhaling or absorbing huge amount of methanol
through the respiratory system or skin, in an industrial setting can cause death. The
amount of methanol is approximately 30mL. Other than that, exposure to methanol
(approximately 10 mL) can cause visual problems and may lead to permanent
blindness. It can cause convulsions, coma, loss of consciousness, kidney failure, liver
damage and even harm the central nervous system. Chronic exposure to methanol will
cause methanol poisoning, leads to inflammation of eyes, headaches and insomnia.
Meanwhile, short-term exposure to methanol can affect in difficult breathing,
dermatitis, confusion, nausea, diarrhea, leg cramp, vision problems and over-
sweating. (Tox Town, nd)

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SECTION 2

MASS BALANCE

Fresh feed
100mol/h (250C)
0.72mol H2/mol
0.24mol CO2/mol
0.04mol N2/mol

Mixing stream
ṅo
yN2= 0.3mol (mol N2/mol)
yCO2 (mol CO2/mol)
0.9- yCO2 (mol H2/mol) Recycled
ṅ3
y3, N2 (mol N2/mol)
y3, CO2 (mol CO2/mol)
1–y3, N2 – y3, CO2 (mol H2/mol)

Purge

Product (300oC) ṅ2

ṅ1 y2, N2 (mol N2/mol)

y1 ,CH3OH (mol CH3OH/mol) y2, CO2 (mol CO2/mol)

1-y1 ,CH3OH (mol H2O/mol) 1–y2, N2–y2, CO2 (mol H2/mol)

Condition : 1 atm, 25℃ - 300℃

Recycle ratio: 5mol recycle mol / mol fresh feed
0.3 mol ratio of N2 in mixing point

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Recycle ratio= 5:1
ṅ 3= 5 (100 mol/h) ṅ o= 500 mol/h + 100mol/h
= 500 mol/h = 600 mol/h

N2 balance
ṅ o (0.1 mol N2/mol) = 0.06(100mol/h) + y3,N2 (n3)
600 x 0.3 = 0.04 x 100 + y3, N2 (n3)
y3, N2 (ṅ 3) = 176 mol/h
y3, N2 = 176/500 mol N2/mol
= 0.352 mol N2/mol

Overall mass balance of N2

Mol ratio of N2 in ṅ 3= ṅ 2
100 x 0.06 = 0.352 (n2)
ṅ 2 = 17 mol/h

Atomic Species Balance

C balance
1𝑚𝑜𝑙 𝐶 1 𝑚𝑜𝑙 𝐶
(0.24 x 100 mol CO2/h ) x ( 1 𝑚𝑜𝑙 𝐶𝑂 ) = (y1 ,CH3OH) ṅ 1 x1 𝑚𝑜𝑙 𝐶𝐻 + (y2, CO2) ṅ 2 x
2 3 𝑂𝐻

1 𝑚𝑜𝑙 𝐶
1 𝑚𝑜𝑙 𝐶𝑂2

(y1 ,CH3OH) ṅ 1 =24 - (y2, CO2) ṅ 2 Equation 1

O balance
2 𝑚𝑜𝑙 𝑂
(0.24 x 100) mol CO2/h x (1 𝑚𝑜𝑙 𝐶𝑂 )
2

1 𝑚𝑜𝑙 𝑂 1 𝑚𝑜𝑙 𝑂 2 𝑚𝑜𝑙 𝑂

= (y1 ,CH3OH) ṅ1x(1 𝑚𝑜𝑙 𝐶𝐻 ) + (1 - y1,CH3OH) ṅ1 x 1 𝑚𝑜𝑙 𝐻 𝑂+ (y2, CO2) ṅ2x 1 𝑚𝑜𝑙 𝐶𝑂
3 𝑂𝐻 2 2

1 𝑚𝑜𝑙 𝑂 2 𝑚𝑜𝑙 𝑂
= ṅ1 x 1 𝑚𝑜𝑙 𝐻 + (y2, CO2)n2 x 1 𝑚𝑜𝑙 𝐶𝑂
2𝑂 2

(y2, CO2) ṅ2 = 24-0.5 ṅ 1 Equation 2

Substitute equation 2 in to equation 1
(y1 ,CH3OH) ṅ 1 =24-(24-0.5 ṅ 1)

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(y1 ,CH3OH)n1 = 0.5 ṅ 1
(y1 ,CH3OH) = 0.5
H balance

2mol H
(0.72 x 100) mol H2 x1mol H2

= [(y1 ,CH3OH) ṅ 1 x (1mol

4mol H
CH3OH
) ] + [ (1–y2, N2 – y2, CO2) ṅ 2 x (1mol
2mol H
H2
) ] + [ (1 –0.5)
ṅ 1 x (1mol
2mol H
H2O
)]

=[(y1 ,CH3OH) ṅ1 x (1mol

4mol H
CH3OH
) ] + [ (1–0.352 – y2, CO2)n2 x (1mol
2mol H
H2
) ] + [(y1 ,CH3OH)
ṅ1 x (1mol
2mol H
H2O
)]

= 6 x (y1,CH3OH) ṅ1 + (0.648– y2, CO2)(17mol/h)x (1mol

2mol H
H2
)

=6 x [24-(y2, CO2)( ṅ2)] + (22.02-34y2, CO2)

144=144 + 22.02+( -34 y2, CO2-102 y2,CO2)

y2, CO2= 0.162 mol CO2/mol

y2, CH2 = 0.486 mol H2/mol

(y2, CO2) ṅ2 = 2.75mol CO2/h

(y2, H2) ṅ2 = 8.25mol H2/h

From Equation 1

(y1,CH3OH) ṅ1 =24-(0.162)17

=21.25 mol CH3OH/h

Since y1,CH3OH= 0.5,

ṅ1=42.5mol/h

y1, H2O = 0.5

(y1, H2O) ṅ1 =21.25mol H2O/h

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Overall conversion of methanol

24−2.77
x100% = 88.5%
24

Table 1:Summary of each composition

ṅo 600mol/h
ṅ1 42.5mol/h
ṅ2 17mol/h
ṅ3 500mol/h
y1 ,CH3OH 0.5
1-y1 ,CH3OH 0.5
y2, N2 0.352
y2, CO2 0.162
1– y2, N2 – y2, CO2 0.486
y3, N2 0.352

y3, CO2 0.162

1–y3, N2 – y3, CO2 0.486

yCO2 0.175
0.9- yCO2 0.525
Mol/h of CH3OH produced 21.25mol CH3OH/h
Mol/h of H2O produced 21.25mol H2O/h
Mol/h of CO2remained 2.75mol CO2
Mol/h of H2remained 8.25mol H2

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SECTION 3
Energy balance
Table 2:INLET-OUTLET ENTHALPY TABLE

Substance nin (mol) Hin (kJ/mol) nout (mol) Hout (kJ/mol)

CO2 24 0 2.75 H1

H2 72 0 8.25 H2

H2O - - 21.25 H3

CH3OH - - 21.25 H4

CO2 (g. 300℃) : H1 = 11.58 kJ/mol (getting from specific enthalpies appendix)
H2 (g. 300℃) : H2 = 7.96 kJ/mol (getting from specific enthalpies appendix)
H2O(g. 300℃) : H3 = 9.57 kJ/mol (getting from specific enthalpies appendix)
CH3OH(g.300℃) : H4= Cp [ kJ/mol ∙℃ ]
= a + bT + cT2 + dT3
= 42.93 x 10-3 + 8.30 x 10-5T + (-1.87 x 10-8 )T2 + (-8.03x10-12)T3
(getting from specific enthalpies appendix)

𝑇2
△H = ∫𝑇1 𝐶𝑝d T
300
H3 = ∫25 42.93x 10-3 + 8.30 x 10-5T + (-1.87x10-8)T2 + (-8.03x10-12)T3
8.30 x 10^−5 2 −1.87𝑥10^−8 −8.03𝑥10^−12
= [ 42.93x10-3T + T + T3 + T4 ]300
25
2 3 4

= [(12.879kJ/mol + 3.7355kJ/mol + (-0.1683kJ/mol) + (-0.065kJ/mol) ] -

[(1.073kJ/mol + 0.0266kJ/mol + (-9.7395x10-5) + (-7.842x10-7)]
= 15.282 kJ/mol

ṅ𝐶𝑂2,𝑜𝑢𝑡 – ṅ𝑐𝑜2,𝑖𝑛 2.75−24.0

ζ= = | |= 21.25 mol/h
Vco2 1

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⍙Ĥor = ∑ | vi| ⍙ Ĥfio - ∑ | vi| ⍙ Ĥfio
Product reactants
= [(1 x (-201.2) kJ/mol + 1 x (-241.83)kJ/mol) ] – [(1 x (-393.5) kJ/mol +
3 x 0kJ/mol ) ]
(Getting from physical property data appendix)
= -49.53kJ/mol

⍙Ḣ = ζ⍙Ĥor + ∑ ṅout Ĥout -∑ ṅin Ĥin

=ζ(H∘r) + ( ṅ CH3OH out H4 out + ṅ H2O out H3out + ṅ CO2 out H1 out +
ṅ H2 out H2 out )– (ṅ CO2in H1 in + ṅ H2 in H2in )
= (21.25 mol x (-49.53)kJ/mol) + (21.25mol x 15.282kJ/mol + 21.25 mol x
9.57kJ/mol +2.75 mol x 11.58kJ/mol + 8.25 x 7.96kJ/mol) – (24 mol x 0 kJ/mol + 72
mol x 0 kJ/mol)
= -1052.51 + 628.20
= -424.31 kj/h (Exothermic Reaction)

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CONCLUSION:

Methanol is a material that has been used widely in our daily life. One of the
most major use is as a feedstock for the plastic production industry. Besides that,
methanol also mainly used in the petrol blending field. This use of methanol is
increasing rapidly within this few years since methanol can be produced from coal
and biomass via synthesis gas. Moreover, methanol can be used to produce alkenes by
MTO and MTP process.

Methanol bring a lot of benefits to us. Firstly, it is used as transportation fuel

as it is easy to transport, readily available and has a high octane rating. One of the
benefits that methanol bring to us is carry the process of removal of nitrogen from
effluent streams in the wastewater treatment facilities. Next, methanol acts vitally in
the development of various types of fuel cells, from large-scale fuel cells to power
vehicles and back-up power to remote equipment to portable fuel cells for electronics
and personal use. The reason methanol has been chosen is because it is an ideal
hydrogen carrier. Methanol is extremely important in the processing of biodiesel fuel,
especially in the transesterification part. Other than that, methanol is also often
converted into formaldehyde, acetic acid and olefins. With this, many types of
materials can be made from methanol. Lastly, nowadays exploration and research
works are carried out to drive the turbines with methanol to generate electricity.

Nevertheless, every single thing has its own good and bad. Methanol is a
highly toxic colourless liquid. We are exposed to the methanol in daily life.
Swallowing, inhaling or absorbing large amount of methanol can cause death if the
amount of methanol exceeds 30ml. For exposure around 10ml, visual problems,
convulsions, coma, loss of consciousness, kidney failure, liver damage and even harm
the central nervous system. While chronic exposure to methanol will leads to
inflammation of eyes, headaches and insomnia. Moreover, short-term exposure to
methanol can affect in difficult breathing, dermatitis, confusion, nausea, diarrhea, leg
cramp, vision problems and over-sweating.
Methanol can be produced by synthesis of synthesis gas. This process
typically involves exothermic equilibrium reactions. The equation of exothermic
equilibrium for methanol synthesis from synthesis gas with the equation as below:

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 CO2 + H2→CH3OH + H2O

The reaction has overall conversion of 88.5% and 12.5% is recycled back to
the mixing point for continuous reaction. The temperature of the process is 25oC and
the outlet temperature is raised to 300 oC. The reaction is carried out in pressure of
1atm.100mol/h of fresh feed is combined with 500mol/h of recycle stream in the
mixing point. 30% of N2 is found in the mixing point. N2 is inert gas and it does not
involve in the whole process. After the chemical reaction of 24mol/h CO2 and
74mol/h H2, 21.25mol/h of CH3OH and 21.25mol/h of H2O are produced while
2.75mol/h of CO2 and 8.75mol/h of H2 are remaining/unreacted. The unreacted
component in the product stream is recycled back to the mixing point. However, the
unreacted components are not fully recycled. They are spilt into 17mol/h of purge
stream and recycled stream to prevent accumulation of nitrogen which disrupt the
process.
The synthesis of methanol is an exothermic reaction. The enthalpy of CO2, H2,
CH3OH and H2O are 11.58kj/mol, 7.96kj/mol, 9.57kj/mol and 15.282kj/mol
respectively. The total enthalpy changes obtained for this process is -49.53kj/mol. The
overall heat energy released from this process is -424.31kj/h

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REFERENCES:

1. The essential chemical industry. (2014). Methanol. Available from:

http://www.essentialchemicalindustry.org/chemicals/methanol.html
[Accessed: 15 August 2016]
2. IHS Markit. (2014). Chemical Economics Handbook: Methanol. Available
from: https://www.ihs.com/products/methanol-chemical-economics-
handbook.html [Accessed: 15 August 2016]
3. Tox Town. (2014). Methanol. Available from:
https://toxtown.nlm.nih.gov/text_version/chemicals.php?id=77 [Accessed: 15
August 2016]
4. BYJU’s Chemistry. (2016). Uses of methanol and ethanol in everyday life.
Available from: http://byjus.com/chemistry/uses-of-methanol-and-ethanol/
[Accessed: 16 August 2016]
5. Donal O’Leary. (2000). Methanol. Available from:
http://www.ucc.ie/academic/chem/dolchem/html/comp/methanol.html
[Accessed: 16 August 2016]
6. Merchant Research and Consulting Ltd. (2016). Methanol:2016 World Market
Outlook and Forecast up to 2020. Available from:
http://www.researchandmarkets.com/research/2x4tzg/methanol_2016
[Accessed: 16 August 2016]
7. Bionomic Fuel (n.d.). Pros and cons of methanol fuel. Available from:
http://www.bionomicfuel.com/pros-and-cons-of-methanol-fuel/ [Accessed: 16
August 2016]

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