1

CHMT5011A - Oil and Gas Engineering

Projects

Design:
 2

Where do we start?

Design usually starts with an opportunity

Customer need
At this stage the problem is very unclear and ill-defined
At this stage, one would try to define and assess the problem as best as
possible
Major steps in process design

Construction,
Project Preliminary Detailed
Start-up,
Specifications Design Design
Operation
Project specifications Preliminary or conceptual 3

design
 Literature survey
 Collecting data  Come up with a process flowsheet
 Market assessments  Process synthesis and Process analysis
 Feasibility studies  Might require experimental work
 Preliminary economic assessment
Detailed design
 Once the flowsheet has been developed, a
detailed design can be carried out
 Complete mass, energy balance
 Equipment sizing and detailed design
 PFD, PIDs
 Costing
 4
Closer look at conceptual design
Abstract Design Problem

Problem Problem
Formulation Formulation
Objective function
 Is it always economical?
Synthesis
 Other objectives?

Analysis

Evaluation and
Optimization

Refined Description
 5

Defining Process Synthesis

Process Inputs
? Process Outputs

(Known) (Known)

 Given inputs and outputs

 Structure/flowsheet is unknown
 Aim to generate alternative flowsheet
 Limited information; little time
 Traditional approaches 6

Traditional approaches:
 Brainstorming among experienced engineers
 Copy/Adapt a previous design for similar process
Problems with this approach:
 Cannot enumerate the infinite alternatives
 Does not guarantee the optimum (or close) solution
 Does not shed light on global insights and key
 characteristics of the process
 Severely limits groundbreaking and novel ideas
 7

Modern Process synthesis techniques

Newer techniques aim to be

 more systematic
 more general
 more efficient
Three main categories:
 Hierarchical analysis (Douglas, 1988)
 Physical Insights
 Mathematical programming
 8

Aims and objectives

 An introduction to the application of process synthesis concepts to design

problems
 An overview of a methodology that will permit the evaluation and design of
new processes from a very early stage
 Useful for analysing existing processes
 9

Philosophy for Process Synthesis

The decisions we make early on in the laboratory programme and

during the early stages of the design are often the ones that have
the largest impact on the final plant
up to 80% of capex and operational costs fixed
During the experimental program and the early design stages, we
must at all stages keep the plant in mind when we make decisions.
We must consider the implications of our decisions on the final
plant
 10

Philosophy for Process Synthesis

Develop a method for making design decisions systematically

Quick calculations at the required accuracy
Check our decisions against:
Criteria such as economics, feasibility, environment
Decisions made earlier – always able to go back and re-evaluate our earlier
decisions
Initially wish to eliminate bad options rather than find the “best”
option
 11

Analysis of existing processes

 Before changing the operation of an existing unit in a process,

the effect of the change on the entire plant must considered.
 Often the operation of a unit is set to balance factors that are
important in the process
Unless the reasons behind the balance have changed, the operation of the
plant as a whole may be adversely affected by changing the operation of a
single unit
 A Brief Overview of the
Process Synthesis Approach
 13
The Question:

 Consider a process, for example FT synthesis

 We have possible feeds such as natural gas, coal, water, air,

…

 What is the minimum amount of CO2 that the process can

emit?
 What does this minimum depend on?
 Can this minimum be achieved?

 Can we answer this question?

 14

Chemical Engineering and The Microscopic Approach

 Many current approaches look at

equipment and the phenomena
occurring in them

 Use very detailed models

 Try to incorporate all the effects (e.g.

all bubbles, mass transfer coefficients,
detailed flow models,…)

 Not useful for answering the question

about CO2 emissions
 15

The Macroscopic View: A Systems Approach

 An alternative is to view processes

macroscopically

 Do not look at the equipment or

the details

 Only consider the process inputs

and outputs

 This turns out to be a very

powerful approach for answering
the question about CO2 emissions.
 The three major principles in process
16

synthesis
There are three major principles that the are used in this macroscopic
approach.

These are:
 the mass balance constraint
 the energy balance constraint
 an entropy balance constraint:
the change in the entropy of the universe must always be greater than or equal to zero.
 17

Application of these constraints

These concepts are usually used in analysis or design of equipment and flow
sheets.

These concepts are useful for analysing the process as a system.

i.e. will consider a process without considering the details of the equipment or flow sheet.
Methanol Synthesis 18
 19

What do we see?

A process flowsheet is very complex

Very difficult to understand the process from looking at the flowsheet
We need to extract the essence
We do this by first looking at major inputs and outputs to the overall process
 20

Mass Balance for Synthesis

We are all familiar with the mass balance

Use it to analyse existing processes
Usually only do a mass balance once the flowsheet has been decided on
We propose a back-to-front approach: applying the mass balance
right in the beginning
Do the mass balance without a flowsheet
Use the mass balance to synthesise the flowsheet
 21

Definition of a process

We look at the entire process. We identify:

the outputs i.e. the product(s) that we wish to make
the inputs ie the feed we have available
At this stage we do not consider the details of the utilities and
hence do not regard them as part of the process.
We do however identify the heat and work flows in and out of the process
 22

Approach

The idea at this stage is to try to simplify the analysis in order to get
an overview, “the macroscopic approach”
Ignore small amounts of impurities in the feed
Ignore small amounts of byproducts
Want to get an idea only of the major factors
This will help you to understand what is being attempted and why
 23

The Case Study

We wish to look at the production of methanol

Our raw materials are
 natural gas (methane)
 coal
 water and
 air
 24
A Starting Point

Start with a Mass Balance Analysis

Identify:
Products
Feeds
Possible by products
 25

Feeds and Products

Desired Product: CH3OH

Need C, H and O in feed
Feed Options:
Natural Gas CH4
Coal C
Water H2O
Air N2 79% O2 21 %
Possible By Products:
H2
CO2
H2O
The Overall Process
26

H
CH3OH

What are the possible ratio of feeds?

 27

Methanol as a Product

Desired Product: CH3OH

The product contains C, H and O
Thus we need to feed C, H and O into the process
What feeds could we use?
 28

The Optimal Feed

1C

4H
CH3OH

1O

C + 4H + O => CH3OH
An optimal process will have as few extra inputs
and outputs as possible.
Thus optimally will have feed of 1 C : 4 H : 1 O
 29

The consequence of non-optimal feeds

2C

6H
CH3OH

3O
Waste streams with excess C,H and O

Each additional inlet component will have to be

removed at some stage
Results in a “wastage” of feed materials
This in turn has an environmental impact
 30

Optimising the feed

H
CH3OH

O
Waste streams with excess C,H and O

Thus we need to consider which combinations of the proposed feed

streams can provide C,H and O in the correct proportions.
 The Optimal Feed: 31

Finding Sources of the Atoms

If we start with coal (C); we need to find:
sources of hydrogen and oxygen
If we start with natural gas (CH4); we need to find:
a source of oxygen
The sources that we have available unfortunately need not be such that they
supply the required atoms are in the correct ratio.
The Target and the Consequences of Non Optimal 32

Feeds

The outcome of using feed sources that do not supply atoms in the
correct proportions is that there will be atoms over.
These will give rise to waste products.
We can compare feeds by looking using a target based on the mass
balance
We will consider how many of the atoms that enter the process leave as
useful product
The higher the target, the better the process potentially is.
 33

Analyzing the Process Mass Balances

Using the available feed materials we will write mass balances for the process
These may look like reactions but they are not
For simplicity we will assume coal is pure carbon and natural gas is pure
methane
 34

A Case Study: A Methanol Process with a Coal feed

Feeds Product

Coal, Water Methanol

o o
25 C, 1 atm 25 C, 1 atm

Only look at major inputs and outputs

Not interested at this stage at what happens inside the
box!
 35

The Process Mass Balance for a Methanol Process

with a Coal feed

Feeds Product

Coal, Water Methanol

o o
25 C, 1 atm 25 C, 1 atm

Consider that we produce 1 mole of

methanol, CH3OH
How much feed material do we need?
 36

The Process Mass Balance

Feeds Product

Coal, Water Methanol

o o
25 C, 1 atm 25 C, 1 atm

A mass balance around the process gives:

1 ½ C+ 2 H2O  CH3OH + ½ CO2
We call this the Process Mass Balance
It is not a chemical reaction
It may not even describe any chemical reaction occurring in the
process!
 37

The Process Mass Balance

Feeds Product

Coal, Water Methanol

o o
25 C, 1 atm 25 C, 1 atm

The Process Mass Balance is:

1 ½ C+ 2 H2O  CH3OH+ ½ CO2
We see that in order to produce one mole of methanol,
we need
to produce ½ mole CO2
to feed 1 ½ moles C
to feed 2 moles H2O
 38

Comparison of Feedstocks

Will examine both coal and natural gas feed-stocks so as to compare them
In this way we can understand the underlying differences in process targets for the two
feedstocks
Allow us to identify differences in the processes
Will also allow us to identify opportunities
 39

Application:
Write process mass balances for a process that produces methanol from a feed
of:
Methane and water
Methane and oxygen
 40

Possible Process Mass Balances

1. CH4(g)+H2O(l)  CH3OH(l) + H2(g)

2. CH4(g) + ½ O2(g)  CH3OH(l)
3. 1½ C(s)+ 2 H2O(l)  CH3OH(l)+ ½ CO2(g)

Note that these are not reactions but process mass balances
We put in states of materials for later use
The substances in blue would be waste/by-products from the process
 41

Summary of Feed Options in a Table

Remember optimal feed:1 C : 4 H : 1 O

Feed C H O
CH4(g)+H2O(l) 1 6 1
CH4(g) + ½ O2(g) 1 4 1
1½ C(s)+ 2 H20(l) 1½ 4 2
 42

How can we compare these Processes?

2 useful measures of efficiency

Carbon Efficiency
Hydrogen Efficiency
Could use oxygen efficiency but is usually not useful
 43

Carbon Efficiency

This measure considers the overall amount of feed

carbon that exits the process as products:

no of moles C in methanol product

CE 
no of moles C in feed(s) to process

• This can be used as a measure of both the feeds as well as the energy streams used in the process
• A low carbon efficiency indicates either
• the release of either CO or CO2 to the environment
• production of undesired side product
 44

Hydrogen Efficiency

This measure considers the overall amount of

feed hydrogen that exits the process as
products:
no of moles H atoms in methanol product
HE 
no of moles H atoms in feed(s) to process

• A low HE indicates that somewhere in the process we will be required to release H as

either
• H2O or H2 to the environment
• Or production of undesired side product
Comparison of CE and HE for the 45

various feeds for methanol production

Feed CE HE
CH4(g) +H2O(l) 1 0.667
CH4(g) + ½ O2(g) 1 1
1½ C(s) + 2 H2O(l) 0.667 1

• Processes that have poor C and H efficiency result in wastage of feed material
• Also results in more complicated and larger plant as have to deal with these wastes
Consequence for coal based methanol 46

plants

Feed CE HE
CH4(g) +H2O(l) 1 0.667
CH4(g) + ½ O2(g) 1 1
1½ C(s) + 2 H2O(l) 0.667 1

• Notice that the maximum carbon efficiency for a coal based methanol process is 67 %.
• This means that at most only 2 out of every 3 carbon atoms that are gasified end up as methanol!
Consequence for coal based methanol 47

plants

Feed CE HE
CH4(g) +H2O(l) 1 0.667
CH4(g) + ½ O2(g) 1 1
1½ C(s) + 2 H2O(l) 0.667 1

• This also means at best a coal based methanol plant produces 0.7 tons of CO2 per ton of methanol
produced
• Real process could produce considerably more!!
Consequence for coal based methanol 48

plants

Feed CE HE
CH4(g) +H2O(l) 1 0.667
CH4(g) + ½ O2(g) 1 1
1½ C(s) + 2 H2O(l) 0.667 1

• In comparison of natural gas based methanol process can potentially turn all the carbon entering the
process into methanol
• Thus the process potentially produce no CO2
Consequence for coal based methanol 49

plants

Feed CE HE
CH4(g) +H2O(l) 1 0.667
CH4(g) + ½ O2(g) 1 1
1½ C(s) + 2 H2O(l) 0.667 1

• The choice of feed has a tremendous impact on economics, environmental assessments' etc!!
Application 2: Further Feed
50

Considerations
Consider the following two processes:
A combined feed of coal and methane to produce methanol
A biomass based methanol process (Biomass Formula: C5H7NO2.15H2O)
Determine the mass balances for these processes and hence the
CE and HE
Compare these processes to the various other mass balances
considered so far
 51
Process Mass Balances: Combined Coal and Methane
Feed

Combined Coal and Methane Based Methanol Process

½ C(s) + ½ CH4(g) + H2O(l)  CH3OH(l)
This is not a unique process mass balance
You may have found a different mass balance.
We will look at how we can scan possible process mass balances later
 52

Process Mass Balances: A Biomass Feed

The Process Mass Balance for a Biomass Based Methanol Process

0.261 C5H7NO2.15H2O(s)  CH3OH(l) + 0.304 CO2(g) + 2.826 H2O(l) + 0.130N2(g)

 53

Summary of Feed Options in a Table

Remember optimal feed:1 C : 4 H : 1 O

Feed C H O
CH4(g)+H2O(l) 1 6 1
CH4(g) + ½ O2(g) 1 4 1
1½ C(s)+ 2 H20(l) 1½ 4 2
½ C(s) + ½ CH4(g) + H2O(l) 1 4 1

0.261 C5H7NO2 .15H2O(s) 1.305 9.657 4.437

Consequence for coal based methanol 54

plants
Feed CE HE
CH4(g) +H2O(l) 1 0.667
CH4(g) + ½ O2(g) 1 1
1½ C(s) + 2 H2O(l) 0.667 1
½ C(s) + ½ CH4(g) + H2O(l) 1 1
0.261 C5H7NO2 .15H2O(s) 0.766 0.414

• Biomass based methanol process have a low carbon efficiency

• Thus biomass process potentially produces CO2 but not as much as coal based methanol processes
Consequence for coal based methanol 55

plants
Feed CE HE
CH4(g) +H2O(l) 1 0.667
CH4(g) + ½ O2(g) 1 1
1½ C(s) + 2 H2O(l) 0.667 1
½ C(s) + ½ CH4(g) + H2O(l) 1 1
0.261 C5H7NO2 .15H2O(s) 0.766 0.414

•A combined coal and methane based methanol process can potentially be 100% efficient from a mass
balance perspective
• Thus this process potentially produce no CO2
 56

Summary

 We can see that the overall process mass balance is very important
 It set the target efficiency of the process
 Real process can at most operate at the target efficiency although most
would operate considerably worse than the target
 The material that does not leave the process as product, becomes a
waste product or by product.
 What is the implications of this on the process?
 57

By-products and Process Complexity

By-products and waste increases the complexity of the process.

We made need extra separation steps
We need to deal with and dispose of wastes
This results in a “wastage” of feed materials
It causes an increase in capital costs of the process:
More feed material must be handled resulting in larger equipment
Additional separation steps needed
 58

By-products and Running Costs

Waste and by products cause an increase in running costs of the process:

More feed material is used which increases running costs
Additional energy will be used in processing the extra feed material
Additional energy is need to effect the extra separation steps required
 59

Implications of Waste Product Formation

Fairly selective process

Process Feeds: Methanol

Natural Gas, Air Process

By-products such as CO2
and H2O
 60

Implications of Waste Product Formation

Less selective process

Process Feeds: Methanol

Natural Gas, Air

Process
and H2O By-products such as CO2

Require more Feedstock

Require a larger process to handle increased flowrates

 61

Example 2

Consider a methanol process

The feed is syngas produced from methane reforming
The reactions occurring are
Synthesis: CO+2H2→CH3OH
Water Gas Shift: CO+H2O→CO2+H2
We will look at a simplified flow sheet
 62
Methanol synthesis flow sheet

Methanol

Synthesis

Reactors
syngas

Methanol

Water
• The ratio of water: methanol in the product is 0.5:1
• Any suggestions to improve efficiency of use of inputs?
 63

Mass balance across synthesis section

½ CO Methanol

2 ½ H2 Synthesis

Reactor
½ CO2
Methanol 1

Water ½
• A mass balance across the process gives:
½ CO + 5/2 H2 + ½CO2 → CH3OH+ ½ H2O

What does this mean for the entire process ?

 64
Overall mass balance for methanol process
Methanol Process

Inputs Outputs
Reforming Synthesis

CH4 and O2 CH3OH + r H2O

r/2CO2

An overall balance across the methanol process gives:

(1+r/2) CH4+ (1/2+r) O2→CH3OH + r/2 CO2+ r H2O
Thus from the mass balance, the more water we emit
The more methane and oxygen we consume and
The more CO2 we emit
How can we reduce the CO2 emissions, any suggestions?
Improving the efficiency of the methanol 65

process

H2O
Inputs
Process
CH4 and O2 CH3OH

r/2CO2
We can return (recycle) the water to the process. Thus we go
from:
5/4 CH4+1O2→ CH3OH+¼ CO2 + ½ H2O to:
1CH4 + ½ O2→ CH3OH
Thus per mole of methanol we have reduced:
the amount of CO2 emitted from 1/4 moles to 0
the amount of CH4 used from 5/4 moles to 1
the amount of O2 required from 3/2 moles to ½
Recycling the water reduces the CO2 emissions!!!
 Implementation
66

H2O
Inputs
Process
CH4 and O2 CH3OH

r/2CO2

• Where do we recycle this water to ?

• recycle the water to the synthesis reactor
• recycle water to the reformer
 67
Implementation

CO Methanol

2 H2 Synthesis

Reactors
Methanol 1

Water

• If we recycle the water to the synthesis reactor, then feed to loop must change as the mass balance
becomes:

CO + 2H2 → CH3OH
• Would need to look at implications of this on reformer operation
 68

Application of the mass balance target

 We can look at inputs and outputs of processes and compare the

results with the targets
 Any discrepancies result from inefficiencies
 Can assess if there is a way of avoiding or decreasing these
inefficiencies
 This should be done at an early stage
 Once a flowsheet/process is chosen it often affects the target
irreversibly
 69

Identifying possible mass balances

There are systematic ways of identifying possible process mass

balances, i.e. finding combinations of inputs and associated
outputs.
We will not go further into this in this presentation
Will look at it later
We will rather continue with the next tool in the process synthesis
tool box:
The process energy balance
 Application of the energy balance to a
70

process
Energy balances are usually done on equipment in analysis of an existing flow
sheet.
We wish to do an energy balance on a process before considering the details
of the equipment or flowsheet.
Remember that we have separated process streams from the utilities.
 71

Application of the energy balance to a process

We therefore look at the mass inputs and outputs of the systems

use the energy balance to identify the energy flows associated with the mass flows into or
out of the process.
The energy flows would eventually be provided to the process by the utilities.
 72

The Energy Balance

Inputs at 25 C
o
Process Outputs at 25 C
o

and 1 atm and 1 atm

Energy added or removed Q

Energy Balance 73

(First Law of Thermodynamics)

Energy Balance for a Steady Flow Process
H + u2/2 + gz = Q + ws

H = enthalpy
u = velocity
g = gravitational constant
z = height
q = energy added to system
ws = work added to system
Often Δu≈0 and gΔz can be neglected.
If there is no pumping or compression ws= 0
H = Q
 74

The Energy Balance

The energy balance across a process is:

Energy supplied Q = ∑I,outputHfi,output- ∑I,inputHfi,input

i is the stoichiometric coefficient of component i in the

mass balance description
Hf,i is the enthalpy of formation of component i at 25 C o

and 1 atm in the phase as described in the mass balance

description
Note we have assumed all species enter and leave
as pure components
No heats of mixing
 75

The Energy Balance

We can define ∆Hprocess as:

∆H process = ∑I,outputHfi,output- ∑I,inputHfi,input

Thus the amount of energy that we must supply Q = ∆Hprocess

We can also see that ∆H process = ∆H (To) o

i.e. the energy required by the process is the enthalpy change as

described by the process mass balance.
 76

The energy balance across a process

Energy supplied Q = ∑I,outputHfi,output- ∑I,inputHfi,input=∆Hprocess

The overall quantity of energy supplied or removed from a process is

defined by the mass balance description
It does not depend on the individual reactions occurring in the process,
the flowsheet, the equipment used etc.
 77

The energy balance across a process

The energy balance across a process is:

Q = ∑I,outputHfi,output- ∑I,inputHfi,input=∆Hprocess

If Q < 0, then energy would need to be removed

from the process
If Q > 0, then energy would need to be supplied to
the process
This adds to the running costs of the process as the
energy needs to be supplied by for example burning
methane.
The energy balance as a target
78

The calculated value of energy supplied Q is a

target and is the minimum amount of energy to
be added an endothermic process
If more energy Q is added, an equivalent
amount of energy Q will need to be rejected

Q Energy rejected
Inputs Process Outputs

Q
Energy added Q+Q
Q
 79

The energy balance as a target

The calculated value of energy supplied Q is a

target and is the minimum amount of energy to
be rejected in an exothermic process
If more energy Q is rejected, an equivalent
amount of energy Q will need to be added

Q Energy supplied
Inputs Process Outputs

Q
Energy rejected Q+Q
Q
 The implication of not operating at the 80

target
Increased running costs due to extra energy
consumption
Increased capital costs due to increased heat
transfer areas
Increased environmental impact due to increased
energy consumption
Q Energy rejected
Inputs Process Outputs Q Energy supplied
Q
Inputs Process Outputs
Energy supplied Q+Q Q
Q
Energy rejected Q+Q Q
 81

Energy balances on processes

Consider the following process mass balance:

CH4(g) + ½ O2(g)  CH3OH(l)

• For the energy balance we need to identify the

phases of the input and output streams
• What are the energy requirements of this process
mass balance?
 82

Process energy requirements

CH4
q CH3OH
O2 (liquid)

25oC, 1 atm 25oC, 1 atm

Mass Balance: CH4(g) + ½ O2(g)  CH3OH(l)

Hf (kJ/mol) -74.85 0 -238.66

Q = ∑i,outputs H o
fi,outputs - ∑i,inputs H o
fi,inputs

=H o
-H
fCH3OH(liquid)
o
fCH4 (gas)

= -163.81kJ/mol
Exothermic - need to remove heat
 83

Example:
Energy balances on processes
Now consider the following process mass balance:
CH4(g)+H2O(l)  CH3OH(l) + H2(g)

What are the energy requirements for this

process mass balance?
 84

Comparison of Energy Requirements

Process Mass Balance Hprocess
(kJ/mol)
1.CH4(g)+H2O(l)  CH3OH(l) + H2(g) 122.03

2. CH4(g) + ½ O2(g)  CH3OH(l) -163.81

Process 1 requires an energy input:

• This increases running costs of process
 85

Comparison of energy requirements

Process Mass Balance Hprocess

(kJ/mol)
1.CH4(g)+H2O(l)  CH3OH(l) + H2(g) 122.03

2. CH4(g) + ½ O2(g)  CH3OH(l) -163.81

The second process looks best as it:

• generates no waste material
• requires no energy input
 86

Looking at options
Process Mass Balance Hprocess
(kJ/mol)
1.CH4(g)+H2O(l)  CH3OH(l) + H2(g) 122.03

2. CH4(g) + ½ O2(g)  CH3OH(l) -163.81

• Consider the first process.

• How could the energy be supplied?
• By burning the H2 with oxygen
• Would this supply sufficient energy
 87

Example: Considering options

Start with
CH4(g)+H2O(l)  CH3OH(l) + H2(g)
Requires 122 kJ/mol of heat to be input
Separate the H2 and burn with oxygen
H2(g)+1/2 O2(g)H2O(l)
This supplies 285 kJ/mol of heat
Use the heat to supply energy to the process. Excess heat can be rejected
 88

Burning H2 to supply heat: heat integration

CH4 CH3OH
Process
H2O H2
H 2O
Combustion
½ O2

Excess energy rejected

Mass integrating process
89

CH4 CH3OH
Process
H2
H2O
Combustion
½ O2

• Note that the water product can be returned to process

• we call this mass integration
• Also notice that the resulting process is now:
• CH4(g) + ½ O2(g)  CH3OH(l)
Mass integrating process
90

CH4 CH3OH
Process
H2
H2O
Combustion
½ O2

Notice how the “apparent reaction” as

described by the mass balance is not the same
as the actual reaction occurring in the process
Mass integrating process
91

CH4 CH3OH
Process
H2
H2O
Combustion
½ O2

• By mass and heat integrating the process we are

able to make an apparently non-feasible chemistry
feasible
• We are also able to achieve the mass and energy
targets by the integration
Mass integrating process
92

CH4 CH3OH
Process
H2
H2O
Combustion
½ O2

Could you improve this process?

Mass integrating process
93

CH4 CH3OH
Process
H2
H2O
Combustion
H2
½ O2

• We do not need to reject heat from the process

• We could burn part of the hydrogen to supply the heat
required and make the process adiabatic
• The remaining hydrogen would then be a product.
Mass integrating process
94

CH4 CH3OH
Process
H2
H2O
Combustion
H2
O2

What is the process mass balance for an adiabatic

process?
 95

Solution:

We could combine:
CH4(g)+H2O(l)  CH3OH(l) + H2(g)
Requires 122 kJ/mol of heat to be input
Separate the H2 and in this case burn only sufficient with oxygen to
provide energy for above reaction
H2+1/2 O2  H2O(l)
This supplies 285 kJ/mol of heat
Thus only combust 0.43 moles of H2 to give 122 kJ/mol heat
 96

Solution Continued:

Thus the overall process mass balance for an

overall adiabatic process becomes:
CH4(g)+0.57H2O(l) + 0.215O2  CH3OH(l) + 0.57H2(g)

CH4 CH3OH
Process
H2
0.57H2O
Combustion
0.57H2
0.215O2
 97
Example: Methanol Processes with Other
Feeds

1. 1½ C(s)+ 2 H2O(l)  CH3OH(l)+ ½ CO2(g)

2. ½ C(s) + ½ CH4(g) + H2O(l)  CH3OH(l)
3. 0.261 C5H7NO2 .15H2O(s)  CH3OH(l) + 0.304 CO2(g) + 2.826 H2O(l) +
0.130N2(g)

Determine the energy requirements for these processes

Thus, determine the CE and HE for these processes
Compare the various processes
Reminder: Carbon and Hydrogen 98

Efficiency for the Process Mass Balance

Feed CE HE
CH4(g) +H2O(l) 1 0.667
CH4(g) + ½ O2(g) 1 1
1½ C(s) + 2 H2O(l) 0.667 1
½ C(s) + ½ CH4(g) + H2O(l) 1 1
0.261 C5H7NO2 .15H2O(s) 0.766 0.414
 99

Energy Requirements

Hprocess
Feed
(kJ/mol) • The marked
CH4(g) +H2O(l) 122.03 processes are
CH4(g) + ½ O2(g) -163.81 endothermic and
1½ C(s) + 2 H2O(l) 136.25 thus heat needs to be
supplied to these
½ C(s) + ½ CH4(g) + H2O(l) 84.60
processes
0.261 C5H7NO2 .15H2O(s) -20.25
 100

Energy Requirements

Hprocess • This energy is

Feed
(kJ/mol) supplied by
CH4(g) +H2O(l) 122.03 combusting the feed
CH4(g) + ½ O2(g) -163.81 • This therefore
1½ C(s) + 2 H2O(l) 136.25 adversely affect the
½ C(s) + ½ CH4(g) + H2O(l) 84.60 Carbon Efficiency
0.261 C5H7NO2 .15H2O(s) -20.25
 101

Energy Requirements: Further Feed

Considerations

Hprocess CE HE
Feed (adiabatic (adiabatic
(kJ/mol) process) process)

CH4(g) +H2O(l) 122.03 0.88 0.61

CH4(g) + ½ O2(g) -163.81 1 1
1½ C(s) + 2 H2O(l) 136.25 0.54 1
½ C(s) + ½ CH4(g) + H2O(l) 84.60 0.91 0.72
0.261 C5H7NO2 .15H2O(s) -20.25 0.77 0.41

Notice that the CE of the marked processes has been

reduced because of the energy demands
 102
Energy Requirements: Further Feed
Considerations

Hprocess CE HE
Feed (adiabatic (adiabatic
(kJ/mol) process) process)

CH4(g) +H2O(l) 122.03 0.88 0.61

CH4(g) + ½ O2(g) -163.81 1 1
1½ C(s) + 2 H2O(l) 136.25 0.54 1
½ C(s) + ½ CH4(g) + H2O(l) 84.60 0.91 0.72
0.261 C5H7NO2 .15H2O(s) -20.25 0.77 0.41

Notice that the CO2 emissions from a coal based

methanol plant would be the highest
 103

Further Examples
 104

A previous process that we considered:

The overall process mass balance for an overall

adiabatic process is:
CH4(g)+0.57H2O(l) + 0.215O2  CH3OH(l) + 0.57H2(g)

CH4 CH3OH
Process
H2
0.57H2O
Combustion
0.57H2
0.215O2
 Example: Screening alternative 105

products
CH4 CH3OH
Process
H2
0.57H2O
Combustion
0.57H2
0.215O2

• Rather than producing H2, try to utilize the H2

• Consider fuels (-CH2-) that require no O2, only a
carbon source
• What feed is a carbon source – coal!
 106

Combining methanol and fuel production

We could combine:
CH4(g)+H2O(l)  CH3OH(l) + H2(g)
Requires 122 kJ/mol of heat to be input
Separate the H2 and in this case burn only sufficient with oxygen to
provide energy for above reaction
H2+1/2 O2  H2O(l)
This supplies 285 kJ/mol of heat
Use remaining H2 in reaction:
C+H2  -CH2-
This releases 26 kJ/mol of reaction
 107

Combined methanol and fuel production process

This would be described by the process mass balance:

CH4(g)+0.63H2O(l) +0.63C + 0.185O2  CH3OH(l) + 0.63 -CH2-
The process would be overall adiabatic
 108

Combined Process

CH4 CH3OH
Methanol
Process
0.63 H2O H2
H2O
Combustion 0.37 H2 0.63 H2
0.185 O2
Heat to methanol process
0.63 –CH2-
Fuel Production
0.637 C
 109

Example: Improved methanol process –

the energy balance

syngas Methanol
Synthesis
Reactors

Methanol

Water

• The ratio of water: methanol in the product is 0.5:1

• We made suggestions to improve efficiency of use of
inputs - how does this affect the energy balance?
 110
Existing methanol synthesis process

½ CO Methanol
5/2 H2 Synthesis
½ CO2 Reactors
Methanol 1

Water ½

• A mass balance across the process gives:

½CO + 5/2 H2 + ½CO2 → CH3OH + ½H2O
 Overall methanol synthesis process
111

Q
Inputs: Outputs
(1+r/2) CH4 &
Process CH3OH +r H2O
(1/2+r) O2
r/2CO2
The mass overall balance gives:
(1+r/2)CH4+(1/2+r)O2→CH3OH(l)+r/2CO2+rH2O(l)
The overall energy rejected from this process as a function of
r is:

r
Q = -163.85 - 890 kJ/mol
2
 Improving the efficiency of the 112

methanol synthesis process

Q
H2O
Inputs
CH4 and O2
Process CH3OH
¼ CO2
We suggested recycling the water in the process.
Thus we go from:
5/4CH4+1O2→CH3OH+¼ CO2+½ H2O
which rejects -386 kJ/mol methanol to:
1CH4+½ O2→CH3OH
which rejects -163.85 kJ/mol methanol
 Improving the efficiency of the 113

methanol synthesis process

Q
H2O
Inputs
CH4 and O2
Process CH3OH
¼ CO2
Thus recycling the water reduce energy rejected from the
process
This also results in improved utilization of C
Reduced CO2 emissions
 Example: Analysis of a methanol 114

process with increased heat flow

Consider a methanol process described by the
overall mass balance:
¾ CH4 (g)+ 1/4CO2(g) + 1/2H2O(l)  CH3OH(l)
The process overall requires 58.77 kJ/mol
However the heat flowing into the process is
186.9 kJ/mol
Why do we add excess heat to the process?
Inputs Energy rejected 128.16 kJ/mol
¾ CH4+1/4CO2+1/2H2O(l)
Process Output CH3OH(l)

Q
Energy added 186.9kJ/mol
 115

Conclusions

The mass and energy balances are linked

One can more systematically look at the effect of changing the mass balances
on the energy balance
We will not look at this in this presentation
By using appropriate recycles of mass and heat integrations one can change
the process mass and energy balance.
 116

Conclusions

We are able to determine the minimum amount of energy

If a real process inputs or rejects more heat it will potentially make
the process more expensive to run and build
The energy balance tells us about the amount of energy but not
the about the quality of the energy