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The accounting of all mass in an industrial chemical process is referred to as a mass (or material) balance. ‘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 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? 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. 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? 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. Sequence of operations/steps repeated according to a cycle Batch cycle time Batch size Paul Ashall, 2008 3 steps Add reactants etc Start cycle t=0 reaction Empty reactor Next cycle t, finish cycle 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. 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 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 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 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. F2 F1 F4 F3 Paul Ashall, 2008 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. Streams Operations/equipment sequence Standard symbols Process flow diagram Recycle of unreacted material reactor Fresh feed (reactants, solvents, reagents, catalysts etc) Separation & purification waste product Byproducts/coproducts 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. 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 residue still contains 2% acetone. Calculate the amount of distillate. 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. 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 Mole % is mole fraction multiplied by 100 Benzene is C6H6. The molecular weight is (6x12) + (6x1) = 78 So 1 mole of benzene is 78 grams 1 kmol is 78 kg Paul Ashall, 2008 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. 1. Read the problem and clarify what is to be accomplished. A train is approaching the station at 105 cm/s. A man in one car is walking forward at 30 cm/s relative to the seats. He is eating a foot-long hot dog which is entering his mouth at the rate of 2 cm/s. An ant on the hot dog is running away from the man’s mouth at 1 cm/s. How fast is the ant approaching the station? Paul Ashall, 2008 2. Draw a sketch (flow diagram) 3. Label. Assign symbols to each variable. 4. Put down the known values 5. Select the basis. 6. List the symbols 7. Write down independent equations 8. Count the numbers 9. Solve the equations 10. Check the answer. Paul Ashall, 2008 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 Paul Ashall, 2008 Paul Ashall, 2008 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 residue still contains 2% acetone. Calculate the amount of distillate. wash water/solvent solid feed suspension waste water filtrate 5000 kg DM water F1 Impurity 55 kg Water 2600 kg API 450 kg Water 7300 kg Impurity 50 kg API 2kg Water 300 kg API 448 kg Impurity 5 kg water/evaporated solvent feed product A+B A+B S S+B A – feed solvent; B – solute; S – extracting solvent feed raffinate E1 solvent extract Paul Ashall, 2008 The next step in the synthesis of aspirin in water is to extract the aspirin with chloroform in a batch process. A 195-kg particular batch containing 0.11 kg aspirin/kg water is extracted with 596 kg chloroform. Extraction coefficient is give by y=1.72x where y = kg aspirin/kg chloroform and x = kg aspirin/kg water in raffinate. Calculate amount and composition of extract and raffinate Paul Ashall, 2008 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 exit gas stream feed solvent feed gas stream waste solvent stream Paul Ashall, 2008 A crystallizer 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? Paul Ashall, 2008 T deg cent Solubility gKCl/100 g water 80 51.1 70 48.3 60 45.5 50 42.6 40 40 30 37 20 34 10 31 0 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. Overall balance Unit balances Component balances Paul Ashall, 2008 W2 F1 E C F P3 R4 E – evaporator; C – crystalliser; F – filter unit F1 – fresh feed; W2 – evaporated water; P3 – solid product; R4 – recycle of saturated solution from filter unit Paul Ashall, 2008 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 Paul Ashall, 2008 Stoichiometric quantities Limiting reactant Excess reactant Conversion Yield Selectivity Extent of reaction Paul Ashall, 2008 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 Paul Ashall, 2008 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) Paul Ashall, 2008 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 Paul Ashall, 2008 Paul Ashall, 2008 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 Paul Ashall, 2008 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 Paul Ashall, 2008 Paul Ashall, 2008 Selectivity = (moles product/moles reactant converted) x s.f. x100 OR Selectivity = moles desired product/moles byproduct Paul Ashall, 2008 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) Paul Ashall, 2008 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 Paul Ashall, 2008 P Elementary Principles of Chemical Processes, R. M. Felder and R. W. Rousseau, 3rd edition, John Wiley, 2000 Paul Ashall, 2008