Energy balance

Introduction to energy balance (written by Firdaus Al-Sulaimani 220724)

Energy balance is a crucial concept in chemical processes. It plays an essential role in process
equipment as it helps in analyzing how energy is transferred and utilized within the system. By
performing an energy balance, we can ensure that the energy input is equal to the energy output,
which is necessary for efficient operation and preventing energy losses, thus saving costs. When
it comes to the production of formalin, having a good energy balance is crucial for evaluating the
energy efficiency of the equipment and improving the overall process. It allows for a better
understanding of the energy inputs and outputs associated with the equipment and helps to
optimize the process to enhance efficiency. By understanding the energy transfer within the
system, we can achieve better energy performance and improve the overall productivity of the
process. There are three types of thermodynamic systems: open systems, closed systems, and
isolated systems.

1. Closed systems

in closed systems, the energy entering is the same as the energy leaving. No mass transfer
crosses its boundary.

No mass

Energy in Energy out

2. Open systems

In open systems, both heat and mass can cross its boundary. The energy input represents the
different types of energy which are kinetic energy, potential energy, internal energy, and heat.
For the energy outputs, it contains the kinetic energy, potential energy, internal energy, and
output work. But for steady systems the E𝑘𝑗 = 0 because if the linear velocities are all the same,
E𝑝𝑗 = 0 if the heights are the same, and Δ𝐻𝑗= 0 if the specific enthalpies in the inlet and outlet
are the same.
Kinetic energy
Potential energy Kinetic energy
Internal energy Potential energy
Heat Internal energy
 3. Isolated systems
In isolated systems, no mass or energy can cross its boundary.

Product specifications:
Based on the production requirements given, calculations for the daily production of the final product
formalin and hexamine were found to be as follows:

The following BFD shows the production of the formalin 37/3:

water

methanol Vap
Vap Vap Vap Vap
air vaporizer Superheater Reactor WHB Condenser liq
 water Vent gas

absorber

vapor liquid

separator

Heat balance for the formalin process:

This process aims to form formalin 37/3. Based on the BFD diagram above, we can see that the
vaporizer receives a feed of methanol, air, and water. The reaction takes place in the vaporizer,
turning the mixture into vapor. The superheater then heats the vapor, providing only sensible
heat. The vapor exits the superheater at a slightly higher temperature and enters the reactor,
where there is no exchange of heat. The vapor then enters the waste heat boiler, where some heat
is dissipated. Next, the vapor enters the condenser, where it turns into liquid. Finally, the vapor
and liquid mixture goes into the separator and absorber.

Energy balance calculations and process equipment functions (Done by Firdaus al-
Sulaimani 220724 and Shatha Al-Hattali 210205)

Heat balance for the vaporizer:

Inlet:
Methanol, water, air (O2
& N2)
288K

Vaporizer

Outlet:
Methanol, water, air (O2
& N2)
358K
Function: Vaporizers are commonly used in various industries. Their main function is to
facilitate the phase change from liquid or solid to gas, enabling it to be easily utilized by the next
unit of equipment. By adjusting the heat input during the vaporization process, vaporizers can
control and prevent any unwanted reactions. For example, in the production of formalin, the feed
entering the process consists of CH3OH, H2O, O2, and N2. The feed is then transformed into a
vapor phase with a higher temperature than when it entered, changing its phase from liquid to
gas. The vapor leaves the system at 85°C, having successfully undergone the phase change.
CH3OH liquid at 15°C to vapor at 85°C it has sensible and latent heat; H2O enters liquid at 15°C
and leaves as vapor at 85°C (sensible latent heat) and air enters gas at 15°C to gas at 85°C.

Methodology of calculations:
Components including CH3OH at a flow rate of 374.233 kmol/h, O2 at a flow rate of 112.046
kmol/h, N2 at a flow rate of 422.779 kmol/h, and H2O at a flow rate of 224.091 kmol/h are
entering the vaporizer. To determine the total Q for methanol, air, and water, we need to follow a
few steps. Firstly, we need to choose the appropriate routes and calculate the average
temperature of each route. Then, we can find the Cp from references for the average temperature
and finally determine the total Q for each component.

Inlet [kmol/h]
Compund ---15°C
CH3OH 374.233
O2 112.046
N2 422.779
H2O 224.091

CH3OH heat balance from 15°C (liquid) to 85°C

(vapour):

average temperature=(15+64.7)÷ 2=39.85 ℃

Q from 15°C to 85°C (liquid to liquid, sensible heat):

kJ Figure 1: the follwoing shows the method 1

Cp at 15=79.23 .K ( route 1)
Kmol
kJ
Cp at 64.7 ℃=90.45 .K
Kmol

kJ
Cp at 39.85 ℃ ( ineterpolated )=84.84 .K
Kmol
 kJ
Q= ( 374.233× 84.84 × ( 64.7−15 ) ) ÷ 3600=438.325
s

Q from 64.7°C ( liquid ) to 64.7°C ( vapour) , latent heat:

kJ
Hv at 64.7 ℃=35120
Kmol

kJ
Q= (374.233 × 35120 ) ÷ 3600=3650.851
s

Q from 64.7°C to 85°C (liquid to vapour, latent heat):

average temperature=74.85 ℃

kJ
Cp at 64.7 ℃=141.9 .K
Kmol

kJ
Cp at 85 ℃=52.96 .K
Kmol

kJ
Cp at average temperature=97.43 .K
Kmol

kJ
Q= ( 374.233× 97.43 × ( 85−64.7 ) ) ÷ 3600=205.602
s

kJ
Q total for the CH 3 OH =205.602+3650.851+438.325=4294.779
s

H2O heat balance from 15°C (liquid) to 85°C (vapour):

Q from 15°C to 85°C ( liquid to vapour , latent heat)

kJ
Hv at 15℃=2465.5
kg

kJ
Q= ( 2465.5× 4037.008 ) ÷ 3600=2764.79
s

Q from 15°C to 85°C ( vapour to vapour , sensible heat)

average temperature=50 ℃
 kJ
Cp at 50 ℃=1.87 .K
kg
kJ
Q= ( 4037.008 ÷ 3600 ) × 1.87 × ( 85−15 )=146.825
s

kJ
Q total for the water =146.825+2764.79=2911.614
s

Air heat balance from 15°C (liquid) to 85°C (vapour):

Q from 15°C to 85°C (for O2)

kcal
h eat content at 15 ℃ ( extrapolated )=2
mol

kcal
heat content at 85 ℃ ( interapolated ) =2.494
mol

kJ
Q= ( 2.494−2 ) × 4187 × ( 112.046 ÷3600 )=64.405
s

Q from 15°C to 85°C (for N2)

kJ
Q= ( 2.494−2 ) × 4187 × ( 422.779 ÷3600 )=243.016
s

Q total for the air=64.405+243.016=307.420 kJ /s

kJ
Q total for the vaporizer =307.420+4294.779+ 2911.614=7513.813
s
Heat balance for the superheater:

Inlet:
Methanol, water, air (O2
& N2)
358K

Superheater

Inlet:
Methanol, water, air (O2
& N2)
398K

Function: The main function of a superheater is to heat gas or vapor without causing it to change
phase. This is important in chemical reactions because it increases the thermal energy content of
any substance. Additionally, superheating can improve the efficiency of heat exchangers or
boilers by increasing the temperature and allowing for higher heat transfer rates. By using
superheating, the need for additional energy is reduced, resulting in cost savings, and improved
overall process efficiency. The gas entering the superheater will remain the same without phase
change. It will only get heated up so only sensible heat is required. CH3OH enters as gas at
85°C, and leaves as gas at 125°C(sensible heat), H2O gas at 85°C, and leaves as gas at 125°C,
and lastly the air enters at 85°C, and leaves as gas at 125°C.

Methodology and calculations:

The superheater is receiving components at the following flow rates: 374.233 kmol/h of CH3OH,
112.046 kmol/h of O2, 422.779 kmol/h of N2, and 224.091 kmol/h of H2O. To calculate the total
Q of the superheater, we need to first interpolate the Cp of each component based on the inlet
and outlet temperature. Then, we can calculate the Q for each component and finally add them
up to determine the total Q of the superheater.

Inlet [kmol/h] ---

Compund 85°C
CH3OH 374.233
O2 112.046
N2 422.779
H2O 224.091

Calculate Q for each component.

 kJ
Q CH 3 OH =( 374.233 ÷3600 ) × 1942.768=201.958
s
kJ
Q O2=( 112.046 ÷ 3600 ) ×1189.108=37.010
s

kJ
Q N 2=( 422.779 ÷ 3600 ) ×1168.173=137.189
s

kJ
Q H 2 O= (224.091 ÷ 3600 ) ×1360.775=84.705
s

kJ
Q total for the superheater =201.958+37.010+137.189+84.705=460.861
s

Heat balance for the reactor:

Inlet:
Methanol, water, air (O2
& N2)
398K

Reactor

Outlet:
Methanol, water,
methanal, N2, and H2
358K

Function: Adiabatic reactors are used for both batch and continuous processes. The adiabatic
reactor plays a crucial role in maintaining the heat balance of a chemical reaction. It ensures
accurate temperature control and facilitates reactions without any loss or gain of heat from the
system. This means that the temperature inside the reactor stays constant throughout the reaction.
Moreover, it helps to minimize energy wastage and maximize the utilization of thermal energy,
resulting in higher efficiency.
Methodology and calculations:
The reactor is fed with four components: CH3OH at a flow rate of 374.233 kmol/h, O2 at a flow
rate of 112.046 kmol/h, N2 at a flow rate of 422.779 kmol/h, and H2O at a flow rate of 224.091
kmol/h. To calculate the total Q in the reactor, we need to determine the enthalpy for each
component at two different temperatures, 400K and 800K. We also need to calculate the Q for
each component. The values for partial oxidation and dehydrogenation were obtained from
references. Using a solver, we can determine the Qr value. Finally, we found that Qp is zero.

IN
Compund [kmol/h]
CH3OH 374.233
CH2O 0.000
O2 112.046
N2 422.779
H2O 224.091
H2 0.000

Adiabatic reactor therefore

Qp = Q-Qr=0

This table shows the calculations of the Q for each component:

h at 400K h at 800K △h
Components [kcal/mol] [kcal/mol] [kJ/kmol] Q [kJ/s]
CH3OH 3.85 10.3 27006.150 2807.387
O2 2.792 5.856 12828.968 399.287
N2 2.782 5.669 12087.869 1419.583
H2O 3.194 6.69 14637.752 911.163

total Q of the reactor=2807.387+399.287+ 1419.583+911.163=5537.42 kJ /s

To calculate the Qr using the solver:

QPO: 9591.221
QDH: -3859.163
Qr: 5732.058
 USING SOLVER
Reaction selectivity ratios from reactor 1 (formalin) mass balance
CH3OH through partial oxidation 0.590
CH3OH through dehydrogenation 0.407

Qr 5537.420
Q 5537.420
Qp 0.000

Heat balance for the waste heat boiler:

Inlet:
Methanol, water, N2,
methanal, H2
900K

WHB

Outlet:
Methanol, water, air (O2
& N2)
418K

Function: A waste heat boiler is used to recover and utilize the heat generated as a byproduct in
various industries. These systems have efficient heat exchange mechanisms, which aid in steam
generation and provide environmental benefits. Recovering waste heat is an important step
towards environmental sustainability. It helps to reduce the carbon footprint of industrial
processes by decreasing the consumption of energy and greenhouse gas emissions.
Assumptions:
 Steady-state systems Methanol
vapour
 No accumulation
418K
 All components leave as vapor
 Only sensible heat

Compound IN [kmol/h]
CH3OH 4.491
CH2O 369.742
O2 0.000 Methanol
N2 422.779 vapour
900K
H2O 448.145
H2 145.689

Methodology and calculations:

The waste heat boiler (WHB) is supplied with four components: CH3OH at a flow rate of
374.233 kmol/h, O2 at a flow rate of 112.046 kmol/h, N2 at a flow rate of 422.779 kmol/h, and
H2O at a flow rate of 224.091 kmol/h. To determine the total amount of heat present in the
WHB, you need to calculate the heat content for each component at different temperatures,
specifically 800K and 418K. After that, calculate the enthalpy for each component, and finally,
compute the total heat content of the waste heat boiler.

Q total of the WHB=−32.409+ (−1891.704 ) +0+ (−1357.626 ) + (−1743.993 )+¿

Heat balance for the condenser:

 Outlet:
Methanal, water,
hydrogen, nitrogen
Inlet: 333K
Methanol, water, N2,
methanal, H2
418K condenser

Outlet:
Methanol, water,
methanal
333K

Function: The condenser plays a crucial role in maintaining the heat balance. It helps in
removing heat and converting vapors into liquids. As a result, all vapors from the feed stream
exit the system at a lower temperature than the feed since the condenser dissipates the heat. The
condenser maximizes the system's efficiency and optimizes heat transfer within it.

Methodology and calculations:

To calculate the total Q of the condenser, first, we need to calculate the Q1 for all components
(sensible heat) by using the following formula.
Q 1=(ṁ÷ 3 600)× ∆ h
Then at the end find the Q1 total for all components. For Q2 and Q3, latent heat of condensation for H2O
and CH3OH at 60°C. to calculate the total Q2 and Q3 we use the same formula mentioned above.
Lastly, for Q4 latent of the dissolution for CH2O in H2O at 60°C. we get the enthalpy from
references. To calculate the total Q4 we use the same formula mentioned above.

The following table shows the calculation of Q1:

The following table shows the calculations of Q2 and Q3:

To calculate the Q4 :
kJ
Q 4=( 166.384 ÷ 3600 ) ×−15 × 4187=−2902.706
s

Total Q of the condenser:

kJ
Total Q=−2902.706+ (−44.247 ) + (−3023.316 ) + (−1091.81 )=−7062.078
s

Heat balance for the separator and absorber:

Function: the separator is an important unit in any chemical process. Its main function is to
separate water from steam. It helps in stabilizing steam pressure and helps in removing excess
pressure to maintain safe operating conditions within the system.

The function of the Absorber:

It is an equipment or unit used in most of chemical process systems and in various applications.
It is used to remove specific components from the gas or liquid by absorbing them into a solvent.
It is crucial when the purification or separation processes are required and helps in heat
dissipation.
 Heat balance for hexamine process:

Vapor steam

Ammonia gas

evaporator
Formalin
37/3
Hexamine
reactor
cooler
Hexamine
concentrate 60wt%

the BFD illustrates the formation of hexamine concentrate. It is clearly shown that the raw
materials are the formalin 37/3 and the ammonia gas. These raw materials enter into the
hexamine reactor. After the reaction takes place, they will leave the reactor at the same
temperature because the reactor is isothermal. Then it will enter the evaporator releasing vapor
steam. Lastly, it will enter the cooler to dissipate that heat forming hexamine concentrate.

Heat balance for the reactor:

Function: the isothermal reactor plays a huge role in maintaining a constant temperature
throughout the reaction. It helps in improving the quality of the product and it is much faster than
the adiabatic reactors to achieve the desired product.in addition, working with constant pressure
helps in reducing the formation of unwanted byproducts.

Heat balance for the evaporator:

Assumptions:
 All methanol in the vapor
 All formaldehyde in vapor
 All hexamine in concentrate
  All HM in concentrate

Functions: The primary purpose of this equipment or unit is to transform the liquid into vapor by
employing steam within the evaporator. The evaporator's steam generates a significant amount of
heat, which drastically improves the efficiency of the heat transfer process. The equipment works
by heating the liquid and then allowing the steam to separate from it, which creates vapor. This
vapor then collects in a separate chamber, leaving behind any impurities or non-volatile
substances. The vapor can then be condensed back into a liquid form for further processing or
collection. This equipment is commonly used in various industries, including chemical,
pharmaceutical, and food processing.

Vapour

steam
Hexamine reactor evaporator
products

condensate

Concentrate product.
Heat balance in the cooler:

Function: The equipment or unit is designed to effectively dissipate the excess heat generated by
a system while simultaneously regulating the temperature to meet the desired levels. Its
importance cannot be overstated as it plays a critical role in maintaining thermal stability, which
is essential in several industries and applications. The equipment is used in various settings and
performs a range of functions, including facilitating heat transfer, preventing overheating, and
protecting the system from damage. Overall, the equipment's ability to ensure optimal thermal
conditions is vital to the smooth and efficient operation of many systems and processes