Module 9001 Mass Balance

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The accounting of all mass in a chemical/pharmaceutical process is referred to as a mass (or material) balance.

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Uses
day to day operation of process for monitoring operating efficiency Making calculations for design and development of a process i.e. quantities required, sizing equipment, number of items of equipment

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Simple example batch mixing process

200 kg of a 40% w/w methanol/water solution is mixed with 100 kg of a 70% w/w methanol/water solution in a batch mixer unit. What is the final quantity and composition?

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continued
Total initial mass = total final mass = 300 kg Initial methanol mass = final methanol mass 80 + 70 = final methanol mass = 150 kg Therefore final composition of batch is (150/300) x 100 = 50 % by wt.

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Exercise
1000 kg of 8% by wt. sodium hydroxide (NaOH) solution is required. 20% sodium hydroxide solution in water and pure water are available. How much of each is required?

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Batch processes
Batch processes operate to a batch cycle and are non-steady state. Materials are added to a vessel in one operation and then process is carried out and batch cycle repeated. Integral balances are carried out on batch processes where balances are carried out on the initial and final states of the system.
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Batch cycle
Sequence of operations/steps repeated according to a cycle Batch cycle time Batch size

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Simple batch reaction cycle

3 steps
Add reactants etc reaction Empty reactor Next cycle

Start cycle t=0

t, finish cycle

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Continuous processes
These processes are continuous in nature and operate in steady state and balances are carried out over a fixed period of time. Materials enter and leave process continuously.

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Law of conservation of mass

When there is no net accumulation or depletion of mass in a system (steady state) then:
Total mass entering system = total mass leaving system or total mass at start = total final mass
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General mass balance equation

Input + generation output consumption = accumulation

Notes: 1. generation and consumption terms refer only to generation of products and consumption of reactants as a result of chemical reaction. If there is no chemical reaction then these terms are zero. 2. Apply to a system 3. Apply to total mass and component mass
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Definitions
System arbritary part or whole of a system Steady state/non-steady state Accumulation/depletion of mass in system Basis for calculation of mass balance (unit of time, batch etc) Component or substance
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Exercise
1000 kg of a 10 % by wt. sodium chloride solution is concentrated to 50 % in a batch evaporator. Calculate the product mass and the mass of water evaporated from the evaporator.

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Mixing of streams
F2 F1 F4

F3

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Example
Calculate E and x
evaporator feed E, composition x%

Fresh feed 1000kg, 15% by wt sodium hydrogen carbonate

Recycle stream 300 kg, 10% satd. soln.

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Flowsheets
Streams Operations/equipment sequence Standard symbols

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Flowsheets
Process flow diagram PID

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Typical simple flowsheet arrangement

Recycle of unreacted material

reactor Fresh feed (reactants, solvents, reagents, catalysts etc)

Separation & purification

product

waste

Byproducts/coproducts

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Exercise
A 1000 kg batch of a pharmaceutical powder containing 5 % by wt water is dried in a double cone drier. After drying 90 % of the water has been removed. Calculate the final batch composition and the weight of water removed.

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Exercise batch distillation

1000 kg of a 20% by wt mixture of acetone in water is separated by multistage batch distillation. The top product (distillate) contains 95% by wt. acetone and the still contains 2% acetone. Calculate the amount of distillate.

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Use of molar quantities

It is often useful to calculate a mass balance using molar quantities of materials and to express composition as mole fractions or mole %. Distillation is an example, where equilibrium data is often expressed in mole fractions.

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Molar units
A mole is the molecular weight of a substance expressed in grams To get the molecular weight of a substance you need its molecular formula and you can then add up the atomic weights of all the atoms in the molecule To convert from moles of a substance to grams multiply by the molecular weight To convert from grams to moles divide by the molecular weight. Mole fraction is moles divided by total moles Paul Ashall, 2008 Mole % is mole fraction multiplied by 100

Molar units
Benzene is C6H6. The molecular weight is (6x12) + (6x1) = 78 So 1 mole of benzene is 78 grams 1 kmol is 78 kg

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Exercise batch distillation

1000 kmol of an equimolar mixture of benzene and toluene is distilled in a multistage batch distillation unit. 90 % of the benzene is in the top product (distillate). The top product has a benzene mole fraction of 0.95. Calculate the quantities of top and bottom products and the composition of the bottom product.
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Mass balance - crystalliser

A crystalliser contains 1000 kg of a saturated solution of potassium chloride at 80 deg cent. It is required to crystallise 100 kg KCl from this solution. To what temperature must the solution be cooled?

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T deg cent

Solubility gKCl/100 g water

80
70 60 50 40

51.1
48.3 45.5 42.6 40

30
20 10

37
34 31
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27.6

At 80 deg cent satd soln contains (51.1/151.1)x100 % KCl i.e. 33.8% by wt So in 1000 kg there is 338 kg KCl & 662 kg water. Crystallising 100 kg out of soln leaves a satd soln containing 238 kg KCl and 662kg water i.e. 238/6.62 g KCl/100g water which is 36 g KCl/100g. So temperature required is approx 27 deg cent from table.
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Mass balance filtration/centrifuge

wash water/solvent
feed suspension solid

waste water

filtrate
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Filtration

5000 kg DM water

F1
Impurity 55 kg Water 2600 kg API 450 kg Water 7300 kg Impurity 50 kg API 2kg
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Water 300 kg API 448 kg Impurity 5 kg

Mass balance - drier

water/evaporated solvent

feed

product

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Mass balance extraction/phase split

A+B

A+B

S+B

A feed solvent; B solute; S extracting solvent

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Example (single stage extraction; immiscible solvents)

feed E1

raffinate

solvent

extract

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F = 195 kg; xf = 0.11 kg API/kgwater S = 596 kg chloroform y = 1.72x, where y is kgAPI/kg chloroform in extract and x is kg API/kg water in raffinate. Total balance 195 + 596 = E + R API balance 19.5 = 175.5x1 + 596y1 19.5 = 175.5x1 + 596.1.72x1 x1 = 0.0162 and y1 = 0.029 R is 175.5 kg water + 2.84 kg API and E is 596 kg chloroform + 17.28 kg API
Note: chloroform and water are essentially immiscible
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Mass balance absorption unit

exit gas stream feed solvent

feed gas stream

waste solvent stream
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Mass balances multiple units

Overall balance Unit balances Component balances

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Multiple units
W2

F1

P3

R4

E evaporator; C crystalliser; F filter unit F1 fresh feed; W2 evaporated P3 solid product; R4 recycle Paulwater; Ashall, 2008 of saturated solution from filter unit

Mass balance procedures

Process description Flowsheet Label Assign algebraic symbols to unknowns (compositions, concentrations, quantities) Select basis Write mass balance equations (overall, total, component, unit) Solve equations for unknowns
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Exercise
A mass balance and tracking of usage of a solvent used in an API production process is required for a Pollution Emission Register (PER). Discuss and outline in general terms how you would do this.

Ref. www.epa.ie
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Definitions
Stoichiometric quantities Limiting reactant Excess reactant Conversion Yield Selectivity Extent of reaction
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Stoichiometry
Refers to quantities of reactants and products in a balanced chemical reaction. aA + bB cC + dD i.e. a moles of A react with b moles of B to give c moles of C and d moles of D. a,b,c,d are stoichiometric quantities

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Reactor mass balances

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Example aspirin synthesis reaction

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Limiting reactant/excess reactant

In practice a reactant may be used in excess of the stoichiometric quantity for various reasons. In this case the other reactant is limiting i.e. it will limit the yield of product(s)

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continued
A reactant is in excess if it is present in a quantity greater than its stoichiometric proportion. % excess = [(moles supplied stoichiometric moles)/stoichiometric moles] x 100

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Example aspirin synthesis

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Conversion
Fractional conversion = amount reactant consumed/amount reactant supplied % conversion = fractional conversion x 100

Note: conversion may apply to single pass reactor conversion or overall process conversion
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Yield
Yield = (moles product/moles limiting reactant supplied) x s.f. x 100
Where s.f. is the stoichiometric factor = stoichiometric moles reactant required per mole product

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Example aspirin synthesis

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Selectivity
Selectivity = (moles product/moles reactant converted) x s.f. x100
OR Selectivity = moles desired product/moles byproduct

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Extent
Extent of reaction = (moles of component leaving reactor moles of component entering reactor)/stoichiometric coefficient of component

Note: the stoichiometric coefficient of a component in a chemical reaction is the no. of moles in the balanced chemical equation ( -ve for reactants and +ve for products)
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Examples
A B i.e. stoichiometric coefficients a = 1; b = 1 100 kmol fresh feed A; 90 % single pass conversion in reactor; unreacted A is separated and recycled and therefore overall process conversion is 100%
R F
reactor
separation
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Discussion - Synthesis of 3,3 dimethylindoline

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Discussion - Aspirin synthesis

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References
Elementary Principles of Chemical Processes, R. M. Felder and R. W. Rousseau, 3rd edition, John Wiley, 2000

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