MB1 Introduction to Mass Balancing

240
www. Chemical Engineering Guy .com Mass Balance: Introduction MB1 Chemical Engineering

Transcript of MB1 Introduction to Mass Balancing

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Mass Balance: Introduction

MB1

Chemical Engineering

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Content

• Section 1

– Theory “Basics of Process/Chemical Engineering”

– System, Process, Unit Operation, Streams, Flows, Variables, Flow Diagrams, MB

• Section 2

– MB basics

– Theory + Problems + Exercises

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Section 1

• Some basic theory in engineering and process engineering

• Easy but Important to understand!

• Learn by hard!

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Theory: Basic Definitions

• Process vs. Chemical Process• Unit Operation• Stream and Flows• Process Variables• Flow Diagram• Block Diagram• System

– Open System– Closed System– Isolated System

• Mass Balance

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Process

• A series of actions or steps taken in order to achieve a particular end.

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Process

• A series of actions or steps taken in order to achieve a particular end.

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Chemical Process

• …chemical process is a method or means of somehow changing one or more chemicals or chemical compounds. It can occur by itself or be caused by an outside force, and involves a chemical reaction of some sort…

From almighty Wikipedia

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Chemical Process Example

Chemical Reaction!

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Types of Diagrams

• Block Diagram

• Flow Diagram

• P&ID Diagram

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Block Diagram

• Simple diagram that “shows at a glance” the process

• Most used for MB solvingShow:• Flows• Unit Operations• Some extra data

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Flow Diagram

• Recommended for “general” information

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P&ID• Pipe and Instrumentation Diagram

• Formal “language” for diagram

• Type of valves• Piping information• Op. Unit detail• Automation units

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Unit Operations

• Basic Process Step in chemical engineering

• Unit operations involve:

– physical change or chemical transformation

• Examples:

– separation, crystallization, evaporation, filtration, polymerization, isomerization, and other reactions

From almighty Wikipedia!

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Unit Operations

• Reactors

• Condensers

• Evaporators

• H-Exchangers

• Crystallizers

• Filters

• Cyclone

• Separators

• Mixers

• Distillation C.

• Absorption Tw.

• Adsorption Tw.

• Pumps

• Compressors

• Storage Tank

Mass operation

Heat operation Momentum operation

Reaction engineering

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Unit Operations

Reactor

Diagram Picture Real-Life Picture

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Unit Operations

Distillation Column

Diagram Picture Real-Life Picture

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Unit Operations

Heat Exchanger

Diagram Picture Real-Life Picture

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Unit Operations

Centrifugal Pump

Diagram Picture Real-Life Picture

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Process Variables

• A process variable, process value or processparameter is the current status of a processunder control.

• Example:

– Temperature of a furnace, process variable.

– Desired temperature is known as the set-point.

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Process Variables

• Typical P.V.:– Pressure

– Volume

– Temperature

– Density

– Height (Level)

– Concentration

– Flow

– % Conversion

TIP: Get to know how these PV are measured in engineering

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Flow (mass, mole, volume)

• Mass flow [kg/s] = mass flow per unit time

• Mole flow [mol/s] = mole flow per unit time

• Volume flow [m3/s] = volume flow per unit time

• How much quantity of (mass/mole/volume) is “flowing” per unit time

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Flow (mass, mole, volume)

• Mass flow examples:– 10 kg/min

– 1 lb/s

– 350 kTon/year

– 3 mg per day

• Mole Flow examples:– 1 mol H2O per min

– 3.02 kmol/h

– 125 lbmol/s

• Volume Flow examples:

– 10 m3/s

– 1 liter per minute

– 4.5 ml/day

– 18,000 gal/year

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Flow Example

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System State

• Steady State

– Typical for continuous processes

• Transient State

– aka unsteady-state/non-steady state

– Typical for batch, semibatch processes

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System State

• Steady State: when all values of all variables in a process do not change in time

Operation of plant: 365 days, 24h

After one year, concentrations, flows and other P.V. Should be the same value

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Transient State

• Transient State: When any of the variables change with time

Example:

10 liters of a mixture is fed to the potAfter 5 hours, the mixture left in the pot is about 2 liters.

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Other Process Classification

• Batch process: Process is being fed once, then time elapses and then the process products are removed.

• Continuous process: Input and Outputs flow/react continuously throughout the duration of the process

• Semibatch process: Combination of Batch-Continuous (charging a reactor)

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Types of Systems

• Open System: inlet/outlet of materials to system

• Closed System: no inlet/outlet of materials

• Isolated System: no inlet/outlet of materials; no inlet/outlet of energy to the system

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Types of Systems

• Open • Closed • Isolated

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Type of Systems

• Isobaric system: Constant Pressure

• Isothermal system: Constant temperature

• Isochoric system: Constant Volume

• Adiabatic system: No heat exchange Q=0

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End of section 1

• Please make sure you understood all material before advancing to the next section

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Section 2

• Now lets actually study Mass Balancing!

• Theory about mass balance

• Exercises about mass balance

– Mastering MB implies lot of exercise

• BE PATIENT!

• Read, re-read, calculate, recalculate!

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Section 2

• Mass Balance (Principle and Equation)

• MB in Steady, Unsteady and Semibatch

– Diagram Construction

– Scale-up and Basis of Calculation

– Variable-Equation counting (Solve?)

– General Methodology

• MB in Steady state: 1 unit, no reaction

• Recycle + Bypass

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Section 2 (cont.)

• MB with 1 chemical reaction– Chemistry review: Stoichiometry, limiting reactant,

excess reactant, equation balancing, conversion, selectivity, yield and extent of reaction ε.

• MB in Chemical Equilibrium (1 reaction)• MB with 2+ chemical reactions• MB of Atomic and Molecular Species• Purge• MB in Combustion processes

– Excess air, theoretical oxygen, air composition, etc.

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Mass Balance Principle

• Mass can neither be created nor destroyed, only transformed

• Energy-Mass relationship: E=mc2

– Not used in this course; no nuclear reactions!

• We will not analyze ENERGY in this course

– Energy+Mass balances are analyzed in the Energy Balance course

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Mass Balance Principle

System(reactions, mixing, and

other operations may occur here)

Inlet

Inlet

Outlet

Outlet

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Mass Balance Principle

System(reactions, mixing, and

other operations may occur here)

Inlet

Inlet

Outlet

Outlet

MB Analysis

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Mass Balance Principle

System(reactions, mixing, and

other operations may occur here)

Inlet

Inlet

Outlet

Outlet

MB Analysis

Inlet –Outlet + Prod. – Consum. = Accumulation in system

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City example

System(reactions, mixing,

and other operations may

occur here)

Inlet Outlet

MB Analysis Immigration = +50

Emmigration = -3Born = +100Death = -25

What is the “accumulation” in the city?

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City example

System(reactions, mixing,

and other operations may

occur here)

Inlet Outlet

MB Analysis Immigration = +50

Emmigration = -3Born = +100Death = -25

What is the “accumulation” in the city? = 50-3+100-25 = 122

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Reactor Example of A

System(reactions, mixing,

and other operations may

occur here)

Inlet Outlet

MB Analysis MB in system

Inlet of A = 100 kgProduction = 0 kgConsumption = 50 kgOutlet = 25 kg

What is the “accumulation” in the system? = 100+0-50-25 = 25 kg accumulated in system

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The Mass Balance Equation

• General Mass Balance Equation– Inlet – Outlet + Production – Consumption = Accumulation

• It can also be done on a specie:

• Mass balance of species “i” – Inleti – Outleti + Productioni – Consumptionii = Accumulationi

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Types of Mass Balances

• Differential

• Integral

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Differential MB

• Analysis in an “instant” of time

• Use of velocity/rate: g/s or kg/h, barrel/day

• Typical for continuous processes

• TIP: convenient to use time basis (1h, 1 year)

• We WILL use this a lot in the course 80%-90%

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Integral MB

• It occurs between two instants

• We use quantities rather than velocities (kg, ton, lb)

• Time elapsed: Tf-Ti

• Typical for batch processes

• Feed, reaction, discharge; repeat

• We ONLY use this in transient process about 10-20% of the course

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Types of process

• Steady State (Continuous)

• Transient (Batch)

• Transient-Steady (Semi-batch)

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MB: Steady State

• NO accumulation term (no differential equations XD)

• Inlet – Outlet + Production – Consumption = 0

• ExamplesIn-Out +P – C = 0In + P = Out + C

Reactor

Distilation Column

Mixer

20 kg/h

80 kg/h

100 kg/h

100 molTotal

20 mol C80 mol mol A

1 mol A

1 mol B

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MB Steady StateExercise 1

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If you check all MB possibles, you get the same answer and YOU SHOULD

MB Steady StateExercise 1

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MB: Batch

• No Inlet/Outlet, closed system

• Production, Consumption and Accumulation

Feeding Production/reactionDischarge

In-Out + P – C = AccumP – C = Accum.

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MB BatchExercise 1

NOTE: We do not need the MB of Water (WHY??)MB of water proves 1=1 or 0=0 WHY??

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MB: Semibatch

• More complex, include continuous and batch

• Accumulation always is included

• In, Out, P, C may vary

• See next example

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MB SemibatchExample 1

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MB SemibatchExample 1

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MB SemibatchExample 1

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Diagram Flow Construction

• Look for information Organize it and Draw!

• Unit operation are blocks or “box”

• Flows are “arrows”

• No matter size/direction of arrows

F = 100 kg/h

0.5 Water w/w0.2 H2SO4 w/w0.3 NaCl w/w

T= 65ºCP = 1 atm

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Diagram Flow Construction

1. Tag each equipment and arrow

2. Assign variables to unknown data/flow/comp.

3. Avoid excess of variables

– “C” is ½ of the inlet “F” ½·F = C

– E is equal to the flow of the distillate “D” F = D

4. Use same units to avoid error/conversions

F = [] kg/h

60 kmol N2 / min40 kmol O2 / min

Airflow ?

60 kmol N2 / min40 kmol O2 / min

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Diagram Flow Construction Example

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MB Steady State Exercises

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MB Steady State Exercises

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MB Steady State Exercises

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Scale-up & Basis of Calculation

• Review the next Diagrams…

• There is a “Basis of Calculation” for each.

– This basis is a number assigned to simplify the problem

B flow = T flow

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Scale-up & Basis of CalculationWe could assign 2 kg o of P as “Basis”… solving for B, T you get half eachORWe could assign 1kg to B or T… solving will give you twice P…

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Scale-up & Basis of Calculation

If we wanted 20 kg of P…• Just multiply by 20 the flows• Concentrations stay the same

x10

We could assign 2 kg o of P as “Basis”… solving for B, T you get half eachORWe could assign 1kg to B or T… solving will give you twice P…

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Scale-up & Basis of Calculation

Multiply Units per

time

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Scale-up & Basis of Calculation

By time (x60 min hr)

By mass(x2.2 lb kg)

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Scale-up & Basis of Calculation

• Conclusion all processes are balanced!

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Which Process is Balanced?

• NO, MB don’t match

• Yes

• Impossible to know (reaction?)

• Not enough data!

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Scale-up & Basis of Calculation Exercise 1

• The next process is to be Scaled up from 100 mol/h of Feed (F) to 1250 lbmol/h.

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Scale-up & Basis of Calculation Exercise 1

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MB: Non-reactive systems

• There is no reaction… therefore Production and Consumption = 0

• It is steady state so Accum = 0

In-Out + P – C = AccumIn-Out = 0Inlet = Outlet

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MB: Non-reactive systems

• For N substances… you can ONLY write N equations:

• If you write N+1 equations (1 balance for global system and N balances for substances)

– You will prove 1 = 1 or 0 = 0

3 Equations2 Unknown

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MB: Non-reactive systemsExercise 1

Example 4.3-3

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MB: Non-reactive systemsExercise 1

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MB: Non-reactive systemsExercise 1

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Is it Possible to solve?The problem shown: 10 lbmol of Feed (0.5 of A) enter and then is separated in two streams. D = 5 lbmol and C is not known. D has 20% of A in its composition and 40% of A is in C

All the variables in the problem (known and unknown)

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Is it Possible to solve?

Variables that are explicitly given

Equations from the MB (N=2)

Physical restrictions

Only MATH can STOP you!

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Variable-Equation counting

• Don’t just do problems! Analyze

• Many times you have NO sufficient data to solve the problem

m1

m2

m4

m3

100 kg/h

Impossible to solve for m2, m3, m4

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Variable-Equation counting

• Relating Variable-Equations:

1. MB: global, species … up to N equations

2. Energy Balance: (not included in this course)

3. Problem “text”:

• Product is ½ feed

• 30 kg of A in stream B

• L/B ratio is 0.55

• Final amount of F in C is the same as A

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Variable-Equation counting

4. Physical properties, laws and data

– Density (relates volume to mass, moles)

– Gas laws (ideal gas law, SKR, van der Waals)

– Phases between substances (x, y, P, T) see CH6

5. Physical restriction

– Compound fraction (1 = xa+xb+xc…xz)

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Systems that can be solved

• When unknown variables = independent equations

• The hard part is to find the independent equations

• Try to decrease the # of unknown variables

• Search more!

If #unknown > # independent equations

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Variable-Equation countingExercise

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General MB Problem Solving

1. Draw and label the block diagram

2. Choose a convenient Basis of calculation

3. Tag all variables in Diagram (Flow, conc., T, P)

4. Account all variables & equations (DOF)

5. If solvable, change all volume data to mass/mole

6. When data is given, change all to either m/n

7. Translate all text to equations

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General MB Problem Solving

8. Write Equation of MB (N equations fo N substances). Order from simple to solve to difficult.

9. Do math! Solve for all equations and variables

10. Be sure to scale-up the basis of calculus according to the problem statements

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MB: Non-reactive systemsExercise 1

• A distillation column is being fed with a stream of 45% Benzene and the balance Toluene. The Product “D” flow contains 95% of benzene. An 8% of the fed benzene is being produced in the bottoms “B”.

• If Feed “F” flow is 2000 kg/h, determine:

– A) Flow D

– B) Mass flow of Benzene and Toluene in Bottoms

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MB: Non-reactive systemsExercise 1

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MB: Non-reactive systemsExercise 1

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MB: Non-reactive systemsExercise 1

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MB: Non-reactive systemsExercise 1

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• Conclusion:

– Following the “methodology” helps!

– The difficult part is the assumption of equations

– MB are easy if data is known

MB: Non-reactive systemsExercise 1

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Need more Exercises & Problems?

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• Section: Courses

– Mass Balance Course

• Problems Section

• You will find a problem index there…

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MB in 2 Units

• In chemical processes, its normal to have 2+ Operation Units

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MB in 2 Units

• In chemical processes, its normal to have 2+ Operation Units

Global Balance:Inlet = Sweet gas + Acid gas

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MB in 2 Units

• We could create “ sub-systems” inside the Global System

Subsystems:• Distillation 1• Distillation 2• Reservoir 1• Reservoir 2

Each has a new MB (inlet = outlet)

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MB in 2 Units

• Subsystem = any portion of a chemical process

– Unit Operation

– Two Unit Operation

– 1 Point connecting flows (mixer)

– 1 Point dividing flows (splitter)

• Applying different sub-system we could find more independent equation to solve

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MB in 2 Units

• Many equations may be redundant/dependent

• Example of redundant equations:

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MB in 2 UnitsExercise 1

I labeled them as C1, C2 and P (respectively)

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MB in 2 UnitsExercise 1

WHY P? it’s the most simple mass balance… Recommended ALWAYS to start with the overall mass balance if possible

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MB in 2 UnitsExercise 1

Given P, we would like to calculate other flows (if not possible go directly to compositions!)

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MB in 2 UnitsExercise 1

Given all Flows (calculated) we only need to find all compositions

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MB in 2 UnitsExercise 1

Do Mass Balances in Unit 1, Unit 2… you may get answers from there!

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MB in 2 UnitsExercise 1

• Data Conclusion:– Start doing Overall Mass Balance– Try to get all the flows first– Calculate compositions by doing MB in units

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MB in 2+ Units

• Complexity increases

• MB: Global, unit, group of units

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MB in 2+ UnitsExercise 1

• Calculate all Flows (E1, E2, R, Et, V, B)

• Calculate all compositions

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MB in 2+ UnitsExercise 1

• From the previous problem, it is impossible to calculate all flows

• We need more data– Explicit data (composition values, flow falues)

– Relationship

– Ratios of flows

– % of mass of flows

– Many other data which could be written mathematically

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Need more problems?

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• Section: Courses

– Mass Balance Course

• Problems Section

• You will find a problem index there…

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Recycle + Bypass

Recycle: product stream of a unit being returned to a previous stream/unit

Bypass: a fraction of the feed is diverted around the unit and combined with the output stream

BACKWARDS FORWARD

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Recycle

Identify Recycle

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Recycle

Identify Recycle

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Bypass

Identify Bypass

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Bypass

Identify Bypass

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Why Recycle

• For Chemical reactions to increase conversion(reaction to form product)

• Recover a catalyst ($)

• Dilute a process stream (increasing flow anddecreasing composition)

• Control of process variables (T, P, level, etc)

• Circulation of a working fluid (refrigeration

refrigerant; plant generation steam)

Page 114: MB1 Introduction to Mass Balancing

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Why Bypass

• Increase properties of product by adding raw material (inlet material)

• Operation Unit does not work as desired

• Control Process variables (T,P,level)

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Bypass/Recycle Exercise 1

1) Qw, Pc, Fe, Fc, R/F2) Conclusion if no Recycle

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Bypass/Recycle Exercise 1

• Draw Diagram… Label flows and write all comp.

1) Calculate Qw, Pc, Fe, Fc, R/F

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Bypass/Recycle Exercise 1

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Bypass/Recycle Exercise 1

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Bypass/Recycle Exercise 1

1) Calculate Qw, Pc, Fe, Fc,

2) R/F 5630/4500 = 1.25

If no recycle: you will loss all the crystals in solution!

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• Section: Courses

– Mass Balance Course

• Problems Section

• You will find a problem index there…

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Section 2 Break #1

What we´ve seen

What's left

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MB in Reactive systems

• We've seen so far MB in non-reactive systems:

– MB for 1 unit

– MB for 2 and 2+ unit

– MB with recycle and bypass

• Now we must Balance Problems involving REACTIONS

• We need to cover some theory first

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MB in Reactive systems

• Reaction basics kinetics

• Stoichiometry

• We will use now “Production – Consumption” term

• NO Accumulation in the system (continuous)

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Stoichiometry for MB reactive systems

• Stoichiometry Coefficient

• Stoichiometric Ratio (A/B)

• Balancing Equations

• Limiting reactant

• Excess reactant

• % Conversion

• Extent of reaction ε

Page 125: MB1 Introduction to Mass Balancing

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Stoichiometry Coefficient/Ratio

• Coefficient: “number” applied to a mole in a reaction

– For: C3H8 + 9/2·O2 3CO2 + 3H2O

– Coefficient of Ch3H8 = 1

– Coefficient of O2 = 9/2 or 4.5

– Coefficient of H2O = 3

– Coefficient of CO2 = 3

Page 126: MB1 Introduction to Mass Balancing

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Stoichiometry Coefficient/Ratio

• Ratio: relationship between two species (may be product:product; product:reactant or reactant:reactant)– For: C3H8 + 9/2·O2 3CO2 + 3H2O

– Ratio of A:B

– Ratio of A:C

– Ratio of B:A

– Ratio of C:C

Page 127: MB1 Introduction to Mass Balancing

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Stoichiometry Coefficient/Ratio

• Ratio: relationship between two species (may be product:product; product:reactant or reactant:reactant)– For: C3H8 + 9/2·O2 3CO2 + 3H2O

– Ratio of A:B = 1:9/2 or 0.22 mol A/molB

– Ratio of A:C = 1:3 or 0.33 mol A/ mol C

– Ratio of B:A= 9/2 : 1 or 4.5 mol B / mol A

– Ratio of C:C = 1:1 WHY?

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Stoichiometry: Balancing Equations

• From mass balance concept: mass is not created nor destroyed… Same applies for atoms

• Example: Propane

• C3H8+O2 CO2 +H2O

– Balance C: C3H8 + O2 3CO2 + H2O

– Balance H: C3H8 + O2 3CO2 + 3H2O

– Balance O: C3H8 + 9/2·O2 3CO2 + 3H2O

Page 129: MB1 Introduction to Mass Balancing

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Stoichiometry: Balance Equation

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Stoichiometry: Balance EquationPractice Problems

Balance the next equations to master “Combustion” Equations

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Stoichiometry Limiting Reactant

• If A + B C

• We need 1 mol of A and 1 mol of B to react

• If A is little less than 1 mol.. We wont be able to achieve 1 mol of C, B will not react completely

• A is said to be the limiting reactant (it limits the reaction; B could further react to form C)

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Stoichiometry Excess Reactant

• From A + B C

• B is in “excess” since there is still B able to react but no A

• If A + B + 2F + 2 H C

– There is only one limiting reactant

– There is 3 excess reactants

Page 133: MB1 Introduction to Mass Balancing

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Stoichiometry Limiting/Excess Exercise 1

Page 134: MB1 Introduction to Mass Balancing

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Stoichiometry Limiting/Excess Exercise 2

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Stoichiometry % Conversion

• If A + 2B C

• Not all A reacts…

• % of conversion : amount of reacted A vs feed A…

• XA denotes conversion of A … min = 0; max 1

Page 136: MB1 Introduction to Mass Balancing

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Stoichiometry % ConversionExercise 1

You actually don’t need B,C moles nor P

Page 137: MB1 Introduction to Mass Balancing

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Extent of reaction ε

• If A + B 2C

• This applies always:

• Ni = actual moles of species “i”

• Nio= initial moles of species “i” fed

• ε = extent of reaction

• βi = “reactant/product coefficient of species “i””• - for reactants

• + for products

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Extent of reaction ε

• Then at any moment…

• Ni = Nio + βi·ε

• “Actual moles of I is equal to, Moles fed of I +/- de coefficient of I in the reaction times the extent of reaction”

Hard to get… better go to examples

Page 139: MB1 Introduction to Mass Balancing

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Extent of reaction εExercise 1

Ni = Nio + βi·ε

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Extent of reaction εExercise 1

Substitute!

Given data…

From Equation “Stoichiometric Coefficients”

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Extent of reaction εExercise 2

a) Limiting reactantb) % excess if anyc) How much is left of the excess?d) If Xa = 0.50?

Page 142: MB1 Introduction to Mass Balancing

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Extent of reaction εExercise 2

• Limiting reactant

Ei < Ej … Then “i” limits reaction WHY?A : limiting reactantB : excess reactant

Page 143: MB1 Introduction to Mass Balancing

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Extent of reaction εExercise 2

• How much is left of the excess?

Page 144: MB1 Introduction to Mass Balancing

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Extent of reaction εExercise 2

• % excess if any

Page 145: MB1 Introduction to Mass Balancing

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Extent of reaction εExercise 2

• If Xa = 0.50?

Page 146: MB1 Introduction to Mass Balancing

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Extent of reaction εExercise 3

• The reaction A+B+3/2 C D +3E

• Theres is a 100 mol Feed

Page 147: MB1 Introduction to Mass Balancing

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Extent of reaction εExercise 3

• Change “air” composition to “Oxygen/Nitrogen”

Page 148: MB1 Introduction to Mass Balancing

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Extent of reaction εExercise 3

• We now choose a Basis and calculate all the moles involved in the flows

Page 149: MB1 Introduction to Mass Balancing

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Extent of reaction εExercise 3

• All the stoichiometric values from the equation (BALANCED)

• A+B+3/2 C D +3E

Page 150: MB1 Introduction to Mass Balancing

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Extent of reaction εExercise 3

• Substitute in the generic equation

Ni = Nio + βi·ε

βi= + product- reactant

Page 151: MB1 Introduction to Mass Balancing

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Extent of reaction εExercise 3

• Substitute initial moles (data is given)

Page 152: MB1 Introduction to Mass Balancing

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Extent of reaction εExercise 3

• A) Calculate the limiting reactant.

– Remember Ei < Ej

Page 153: MB1 Introduction to Mass Balancing

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Extent of reaction εExercise 3

• B) Calculate the % excess of the other 2 reactants (by now, you know its O2 and B)

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Extent of reaction εExercise 3

• C) What would be the mole flows if Xa = 30%

Page 155: MB1 Introduction to Mass Balancing

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MB in Chemical Equilibrium

• Chemical Equilibrium: reaction is possible also reversible

• In general, not all reactions are reversible

• If you are nterested in this type of reactions…– Watch:

• Thermodynamics course• Equilibrium Thermodynamics course• @ www.ChemicalEngineeringGuy.com

A + B CC A + B

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MB in Chemical Equilibrium

• We will use Equilibrium constants! @T = constant

• Imagine: CO + H2O <-> CO2 + H2• K eq= [Products]^y/[Reactants]^x = [CO2][H2] / [CO][H2O]

– [X] = typical nomenclature for “molar concentration”

• Lets use another concentration… – yA = mol of A / total moles

• The equilibrium concentration is now:– K eq = (yCO2·yH2)/(yCO2·yH2O)

• @T = 1105 K … K = 1.0

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MB in Chemical Equilibrium

• K eq: Equilibrium constant

• K eq @ T (it is Temperature dependent)

• Want to learn more about chemical equilibirum?

– Review Chemistry Classes in “Chemical Equiblirium”

– Review Equilibrium Termodynamics Course

– @ www.ChemicalEngineeringGuy.com

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MB in Chemical EquilibriumExercise 1

• A) Calculate the composition in equilibrium

• B) Calculate the fractional conversion of limiting reactant

Page 159: MB1 Introduction to Mass Balancing

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MB in Chemical EquilibriumExercise 1

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MB in Chemical EquilibriumExercise 1

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MB in Chemical EquilibriumExercise 1

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MB in Chemical EquilibriumExercise 1

• A)

• B) Fractional conversion of CO

– fCO = (1-yco) = 1- 0.333 = 0.667

2/3

Page 163: MB1 Introduction to Mass Balancing

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MB in systems with Multiple Reactions

• Theory

– Yield real vs. theoretical

– Selectivity desired vs. non-desired

– Multiple Reactions 2+ reactions at same place

• Some reactants will react to give our desired product(s)

• Some product/reactant may form side reactions to give non-desired product(s)

• This decreases %Conversion which means -$$

Page 164: MB1 Introduction to Mass Balancing

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MB in systems with Multiple

• Example:

– C2H6 C2H4 + H2 (1)

– C2H6 + H2 2·CH4 (2)

– C2H6+C2H6 C3H6 + CH4 (3)

• We would like to produce C2H4

• CH4, C3H6 are expensive to separate

Page 165: MB1 Introduction to Mass Balancing

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MB in systems with Multiple

• Example:

– C2H6 C2H4 + H2 (1)

– C2H6 + H2 2·CH4 (2)

– C2H6+C2H6 C3H6 + CH4 (3)

• We would like to produce C2H4

• CH4, C3H6 are expensive to separate

• Conclude why is it difficult to produce C2H6 only

Page 166: MB1 Introduction to Mass Balancing

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Yield

• Yield: Describes how our desired reaction performs

• Special attention in “limiting reactant had reacted completely”

• As Yield of A increases, more moles of A are being produced

Page 167: MB1 Introduction to Mass Balancing

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Selectivity

• Selectivity: how the reaction arrange to produce our desired component

• Generally as SA/B= selectivity of A over B

• As SA/B increases, more moles of A are being produced

Page 168: MB1 Introduction to Mass Balancing

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MB in systems with Multiple RXN

• Theory

– Yield real vs. theoretical

– Selectivity desired vs. non-desired

– Multiple Reactions 2+ reactions at same place

• We can use Extent of reaction (ε)

– We need one E.ofR (ε) for every reaction!

– ε1 and ε2 if there are two reactions

– βi1, βj1 ; βi2, βj2

Page 169: MB1 Introduction to Mass Balancing

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MB in systems with Multiple RXNExercise 1

• C4H4 + ½ O2 C2H4O (1)

• C2H4 + 3 O2 2CO2 + 2H2O (2)

• Express all the species with equation:• Ni = Nio + β1i·ε1 +β2i·ε2

Page 170: MB1 Introduction to Mass Balancing

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MB in systems with Multiple RXNExercise 1

• Express all the species with equation:

• Ni = Nio + β1i·ε1 +β2i·ε2

Page 171: MB1 Introduction to Mass Balancing

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Yield+Selectivity in Multiple ReactionsExercise 2

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Yield+Selectivity in Multiple ReactionsExercise 2

• We have ε1 and ε2 (RXN1, RXN2)

• β1i and β2i “i” for every species

Page 173: MB1 Introduction to Mass Balancing

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Yield+Selectivity in Multiple ReactionsExercise 2

• Just substitute values to Equation

– Ni = Nio + β1i·ε1 +β2i·ε2

From the Conversion given in the text… Xe = 50.1%

NR: Non-reacted molesR: Reacted moles

Page 174: MB1 Introduction to Mass Balancing

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Yield+Selectivity in Multiple ReactionsExercise 2

• Calculating moles of C2H6 @ 50.1%

• From the Yield Information Y = 0.471

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Yield+Selectivity in Multiple ReactionsExercise 2

• Finally, substitute and solve equations

Page 176: MB1 Introduction to Mass Balancing

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Yield+Selectivity in Multiple ReactionsExercise 2

• With ε1 and ε2

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• Section: Courses

– Mass Balance Course

• Problems Section

• You will find a problem index there…

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Section 2 - Break

What we´ve seen

What's left

What we´ve seen

Page 179: MB1 Introduction to Mass Balancing

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MB atomic species vs. molecular

• We could either do the mass balance:

– Molecules (H2O, CO2, N2, CH3·OH)

– Atoms (H, C, N, C)

• Some times is more efficient to do atomic species MB

• In Molecular MB: N = molecules

• In Atomic spcies MB: N = atomic species

Page 180: MB1 Introduction to Mass Balancing

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MB atomic species vs. molecular

• Advantage of atoms:– Atoms don’t create nor destroy!

– No production, no consumption

– Inlet = Outlet (Since Accumulation = 0 )

• NOTE: take care in diatomic elements:– HONClBrIF

– H2, O2, N2, Cl2, Br2, I2, F2

– H2 ->Hydrogen gas or even just “Hydrogen”

– H -> Hydrogen Atom

Page 181: MB1 Introduction to Mass Balancing

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MB atomic species vs. molecularExercise 1

Ethane is going to be dehydrated to form ethene. The reactor is fed 100 mol of C2H6.

The outlet has 40 gmol of H2

A) Calculate n1, n2

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MB atomic species vs. molecularExercise 1

Do atomic Balances on each specie (C,H,O) N = 3

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MB atomic species vs. molecularExercise 1

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MB atomic species vs. molecularExercise 1

MB/Atomic done!

N1, N2 flows

Page 185: MB1 Introduction to Mass Balancing

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MB atomic species vs. molecularExercise 2

• 100 mol of Methane are being burned. There is a 90% conversion of the limiting reactant. Calculate all moles @ outlet

Page 186: MB1 Introduction to Mass Balancing

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MB atomic species vs. molecularExercise 2

Page 187: MB1 Introduction to Mass Balancing

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MB atomic species vs. molecularExercise 2

• Proceed to do Mass Balance of Atomic Species (C, H, and O)

• We could do balance in species C2 and O2 WHY?

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MB atomic species vs. molecularExercise 2

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Conversion: Global vs. Single-Pass

• Global conversion “Xa global” or “Xa process”

• Single-Pass Conversion “Xa in Unit”

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Conversion: Global vs. Single-Pass

• Global:

– Process Inlet

– Process Outlet

• Single-Pass

– Unit Inlet

– Unit Outlet

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Conversion: Global vs. Single-Pass

• It must be specified

• If not, suppose it is Operation Unit conversion

Page 192: MB1 Introduction to Mass Balancing

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Purge

• We are producing non-desired products in the system

• We are recycling some sort of stream with this non-desired product– We need to purge them…

– accum. of substance = 0

Page 193: MB1 Introduction to Mass Balancing

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Purge

• Solve this type of problems as before, no difference (it is actually a “Product” line)

• Purge:Feed ratio is a common data given

Page 194: MB1 Introduction to Mass Balancing

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Purge

Page 195: MB1 Introduction to Mass Balancing

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Purge: Exercise 1

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Purge: Exercise 1

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Purge: Exercise 1

• Make a MB in the Reactor (RKT)

Page 198: MB1 Introduction to Mass Balancing

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Purge: Exercise 1

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Purge: Exercise 1

Page 200: MB1 Introduction to Mass Balancing

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Purge: Exercise 1

• Keep doing math… the MB are almost done

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Purge: Exercise 1

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Purge: Exercise 1

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Purge: Exercise 1

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• Section: Courses

– Mass Balance Course

• Problems Section

• You will find a problem index there…

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MB in Combustion

• Combustion: is a high-temperature exothermic chemical reaction between a fueland an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products

• Why burning? To get heat energy electrical energy electricity!

Page 206: MB1 Introduction to Mass Balancing

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MB in Combustion

• Importance of Combustion– Heat energy (not analyzed in this course)

– Reactants• Fuel

• Oxygen

• Inerts (don’t react)

– Products• CO2

• CO

• H2O

• SO2

• Inerts (just flow out)

Page 207: MB1 Introduction to Mass Balancing

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MB in Combustion

• General idea:

• Fuel + Oxygen CO2 + H2O + Heat

• Ex: CH4 + O2 CO2 + H2O (not balanced)

Page 208: MB1 Introduction to Mass Balancing

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MB in Combustion

• Balancing equation is SUPER important!

• Failing wrong mass balance

• Tips for balancing (order)

– Balance all Carbon atoms

– Balance all Hydrogen Atoms

– Balance all Oxygen Atoms (don’t hesitate to use fractions in moles)

Page 209: MB1 Introduction to Mass Balancing

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MB in Combustion

• Example: Propane

• C3H8+O2 CO2 +H2O

– Balance C: C3H8 + O2 3CO2 + H2O

– Balance H: C3H8 + O2 3CO2 + 3H2O

– Balance O: C3H8 + 9/2·O2 3CO2 + 3H2O

Page 210: MB1 Introduction to Mass Balancing

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Air Composition

• Nitrogen

• Oxygen

• Noble gases (Ar, Kr, Ne, He)

• CO2, Methane, H2, H2O

Page 211: MB1 Introduction to Mass Balancing

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Air Composition (Table)

Source: WikipediaMolecular Weight (average) = 29 g of Air / gmol Air

Page 212: MB1 Introduction to Mass Balancing

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Air Composition

• Why bother balancing 0.97% of other gases?

• In engineering… we can assume air composition as:

– 0.79 N2

– 0.21 O2

• We WILL use this assumption in all Combustion problems!

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N2 – O2 relationship

• 1 mol of air contains:

– 0.21 mol of O2

– 0.79 mol of N2

• Relationship of O2/N2

– 0.79 mol N2 per 0.21 mol O2

– 0.79/0.21 = 3.76 mole of N2 per mol O2

Page 214: MB1 Introduction to Mass Balancing

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Wet vs. Dry Base

• Wet base composition: composition of a flow including Water as a component.

• Dry Base composition: composition of a flow NOT including Water as a component.

Example: Calculate Dry and Wet compoisition of Air if: 1 mol O2, 1 mol N2, 1 mol H2O

0.33 O2; 0.33 N2, 0.33 H2O Wet composition of Air0.5 O2; 0.5 N2; H2O not included Dry composition of Air

View more exercises HERE

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Dry & Wet Base: Exercise 1

Page 216: MB1 Introduction to Mass Balancing

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Dry & Wet Base: Exercise 2

Now go backwards… From Dry basis to mass of Water

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Dry & Wet Base: Exercise 2

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Theoretical Oxygen, Excess Oxygen

• Many times, there is an excess of oxygen to avoid incomplete combustion…

– CH4 + 4·O2 CO2 + 2H2O but may also react:

– CH4 + 3/2·O2 CO + 2H2O

• Using excess:

– CH4 + 5·O2 CO2 + 2H2O (not probably to form CO)

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Theoretical Oxygen

• Oxygen needed to perform a 100% combustion

• For CH4 + 4·O2 CO2 + 2H2O

• Theoretic Oxygen is 4 mol of O2

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Excess Oxygen

• Excess oxygen: oxygen not reacted after a 100% combustion

• CH4 + 5·O2 CO2 + 2H2O

• But we need only 4 mol O2 = 1 mol wont react

• Excess oxygen: 1 mol

Page 221: MB1 Introduction to Mass Balancing

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% of Excess Oxygen

• Express the excess in %

• So a 20% oxygen excess for CH4 would be:

% Excess Oxygen = [Oxygen feed – Oxygen (theoretical)]/[Oxygen (theoretical)]

20%= (Oxygen feed – 4 mol O2)/ (4 mol O2)

0.2·4 = O -4O = 4+0.8 = 4.8 moles of O2

Page 222: MB1 Introduction to Mass Balancing

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Theoretical Air, Excess Air

• Since we use air to get oxygen in the reaction

– We need to calculate air flows from Oxygen

• Theoretical Air: air needed to get the theoretical oxygen contained

• Excess Air: excess air fed to get higher combustion rates

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Page 223: MB1 Introduction to Mass Balancing

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% Excess Air

• Similar to % Excess oxygen:

• Be aware of the NITROGEN content of “air”

• Nitrogen is 3.76x in quantity than O2

• Will definitively change compositions

Page 224: MB1 Introduction to Mass Balancing

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Air & Oxygen excess: Exercise 1

Page 225: MB1 Introduction to Mass Balancing

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Air & Oxygen excess: Exercise 2

Page 226: MB1 Introduction to Mass Balancing

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Air & Oxygen excess: Exercise 2

• NOTE: the definition implies 100% conversion! So there should be no difference

Page 227: MB1 Introduction to Mass Balancing

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Air & Oxygen excess: Exercise 2

Page 228: MB1 Introduction to Mass Balancing

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MB Combustion Tips

• Never forget N2 (inert) in MB equations

• Review CO vs. CO2 balances

• Any side reactions of S or N to SOx or NOx?

• If Oxygen in excess, review Oxygen balance in the outlet stack gas

• Remember the relationship 3.76 mol N2 per mol O2

• Balance equation and double check balance!

Page 229: MB1 Introduction to Mass Balancing

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MB CombustionExercise 1

Page 230: MB1 Introduction to Mass Balancing

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MB CombustionExercise 1

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MB CombustionExercise 1

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MB CombustionExercise 1

• Table of Composition in Outlet (Stack Gas)

Page 233: MB1 Introduction to Mass Balancing

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MB CombustionExercise 1

Page 234: MB1 Introduction to Mass Balancing

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MB CombustionExercise 1

• NOTE: Book is probably wrong

More exercises in problem section!

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Page 235: MB1 Introduction to Mass Balancing

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End of Section 2

• WE are done with Section 2

• You know the basics of MB

– 1,2 or + units

– No Reactive + Reactive systems

– With purge, recycle and bypass

– Combustion

More exercise in problem section!

Page 236: MB1 Introduction to Mass Balancing

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Problems & Exercises

• All pair problems of Elementary Principles in Chemical Processes. Felder, R; Rousseau, R. 3rd edition CH4 are solved in the section of “Solved Problems” in my webpage

• Visit www.ChemicalEngineeringGuy.com

• Remember: practice makes the master

Page 237: MB1 Introduction to Mass Balancing

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End of MB1: Introduction• You should be now able to perform MB of process

• Hopefully:

– You are able to draw a Diagram from a “text” problem

– You are able to apply the methodology of MB

– You are now able to do a DOF analysis

– You can differentiate between: non-reactive MB, reactive MB, 2+ Unit MB, Combustion MB, Purge, Recycle, Bypass…

– You practice a lot of problems!• Theory alone will not help

– This is the basis of chemical engineering! Learn it well!

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MORE INFORMATION

• Get extra information here!

• FB page:

– www.facebook.com/Chemical.Engineering.Guy

• Contact me by e-mail:

[email protected]

• Directly on the WebPage:

– www.ChemicalEngineeringGuy.com/courses

LOGO AQUI

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Bibliography

• Elementary Principles in Chemical Processes. Felder, R; Rousseau, R. 3rd edition.

• Basic Principles and Calculation in Chemical Engineering. Himmelblau, D. 7th edition.

Page 240: MB1 Introduction to Mass Balancing

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