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Mass Integration CHEN 4470 – Process Design Practice Dr. Mario Richard Eden Department of Chemical Engineering Auburn University Lecture No. 9 – Synthesis of Mass Exchange Networks II February 7, 2013 The Pinch Diagram 1:6 • Amount of Mass Transferred by Rich Streams M R i G i ( y is y it ) , i 1, 2 , ...., N R Mass Exchanged R2 MR2 MR1 R1 y1t y2t y1s y2s y The Pinch Diagram 2:6 • Constructing Rich Composite using Superposition Mass Exchanged MR2 R2 MR1 R1 y1t y2t y1s y2s y The Pinch Diagram 3:6 • Amount of Mass Accepted by Process MSA’s M S j LCj ( x tj x sj ) , j 1, 2, ...., N SP Mass Exchanged S2 MS2 MS1 S1 y x1s x2s y b1 1 m1 y b2 x2 2 m2 x1 x1t x2t The Pinch Diagram 4:6 • Constructing Lean Composite using Superposition Mass Exchanged S2 MS2 MS1 S1 y x1s x2s y b1 1 m1 y b2 x2 2 m2 x1 x1t x2t The Pinch Diagram 5:6 • Constructing the Pinch Diagram – Plot the two composite curves on the same diagram Mass Exchanged Pinch Point Move the lean composite vertically until the entire stream exists above the rich composite. The point closest to the rich composite is the Pinch. Lean Composite Stream Pinch Point Load to be Removed by External MSA’s Excess Capacity of Process MSA’s Integrated Mass Exchange Rich Composite Stream y y b1 1 m1 y b2 x2 2 m2 x1 The Pinch Diagram 6:6 • Decomposing the Synthesis Problem – • Above the Pinch – – • Creates two subregions, i.e. a rich end and a lean end Mass exchange between rich and lean process streams No external MSA’s required Below the Pinch – – Both process and external MSA’s are used If mass is transferred across the pinch, the lean composite moves upward, thus: DON’T TRANSFER MASS ACROSS THE PINCH! Example No. 2 1:17 • Dephenolization of Aqueous Wastes To regeneration & To final recycle finishing S1 S2 S3 S4 Light Gases Waste Gas Oil Deashing and Demetallization Atmospheric R1 Gas Oil Distillation Stripping Steam Waste Lube Oil Deashing and Demetallization R2 R1 Mass Exchange Network S1 Gas Oil R2 Air S5 Vacuum Distillation Lube Oil To phenol condensation S5 Ion Exchange Resin S4 Dewaxing and Deasphalting Activated Carbon S3 Stripping Steam Lube Oil S2 Example No. 2 2:17 • Rich Stream Data Flowrate Gi, kg/s Supply Composition yis Target Composition yit R1 Condensate from first stripper 2 0.050 0.010 R2 Condensate from second stripper 1 0.030 0.006 Stream • Description Candidate MSA’s – – Two process MSA’s Three external MSA’s Example No. 2 3:17 • Process MSA Data Stream • Description Upper Bound on Supply Target Flowrate Composition, Composition, Ljc, kg/s xjs xjt S1 Gas oil 5 0.005 0.015 S2 lube oil 3 0.010 0.030 External MSA’s – – – Absorption using activated carbon (S3) Ion exchange using a polymeric resin (S4) Stripping using air (S5) Example No. 2 4:17 • Equilibrium Data – General equation for transferring phenol to the j’th lean stream y mj xj – m1 2.00 m 1.53 2 , m3 0.02 m 0.09 4 m5 0.04 Minimum allowable composition difference j 0.001 kgkg phenol M SA , i 1, 2, 3, 4, 5 Example No. 2 5:17 • The Pinch Diagram 0.140 Mass Exchanged, kg phenol/s 0.120 0.1224 Excess Capacity of Process MSA’s 0.1040 0.100 0.0184 kg phenol/s Rich Composite Stream 0.060 Pinch Point Load to be 0.040 Removed by External MSA’s y = 0.0168 x1 = 0.0074 x2 = 0.0100 0.1224 – 0.1040 = Lean Composite Stream 0.080 Excess Capacity of Process MSA’s Pinch Point 0.020 0.0124 0.000 0.000 0.010 0.004 0.0055 0.020 0.0168 0.030 0.040 0.050 y 0.009 0.0074 0.014 0.019 0.0024 x1 0.0186 0.0251 0.0317 x2 0.0121 0.0100 External MSA Load 0.0124 kg phenol/s Example No. 2 6:17 • Removing Excess Capacity of Process MSA’s – – Can be eliminated by lowering the flowrate and/or outlet compositions of the process MSA’s. If elected to lower the flowrate of S2 then: new j L Excess t x j x sj new 2 L Excess 0.0184 t 3 2.08 kg/s s x2 x2 0.03 0.01 L L old j old 2 Example No. 2 7:17 • Activated Carbon – – – – Adsorption isotherm is linear up to mass fraction 0.11 Above 0.11 activated carbon becomes saturated Thus x3t is taken at 0.11 Corresponding composition on y-scale: y 0 .0 2 ( 0 .1 1 0 .0 0 1) 0 .0 0 2 2 – – – – Less than supply compositions of R1 and R2 Thus feasible to transfer phenol from both streams to S3 Less than value of tail end of lean composite Hence S3 will not eliminate any phenol that can be removed by the process MSA’s. Example No. 2 8:17 • Activated Carbon (Continued) – Cost of using activated carbon (A) – C 3 0 .0 5 1 .6 0 2 5 1 0 3 x 3t 0 .0 8 0 .0 1 x 3t Amount of activated carbon required to remove 1 kg of phenol can be calculated from a mass balance (B1) 1 k g p h en o l rem o v ed L 3 ( x 3t 0 ) kg activated carbon 1 t (B2) kg phenol x3 Example No. 2 9:17 • Activated Carbon (Continued) – Multiplying equations (A) and (B2) provides the cost of removing 1 kg of phenol from the waste streams using activated carbon 0.08 C t 0.01 x3 r 3 – Substituting x3t = 0.11 kg phenol/kg activated carbon into (A) and (B2) C 3 $ 0 .0 8 1 / k g recircu latin g activ ated carb o n C 3r $ 0 .7 3 7 / k g o f rem o v ed p h en o l Example No. 2 10:17 • Ion Exchange C 6 H 5O H N a O H C 6 H 5O N a H 2O – Regeneration – Cost of using ion exchange (C) – C 4 0 .0 5 3 .8 0 0 .4 6 0 .3 0 x 4t 0 .1 9 0 .1 2 8 x 4t Amount of activated carbon required to remove 1 kg of phenol can be calculated from a mass balance (D1) 1 k g p h en o l rem o v ed L 4 ( x 4 0 ) t kg ion exchange resin 1 t (D2) kg phenol x4 Example No. 2 11:17 • Ion Exchange (Continued) – Multiplying equations (C) and (D2) provides the cost of removing 1 kg of phenol from the waste streams using ion exchange t (E) – – 0.19 C t 0.128 x4 r 4 The higher the value of x4 , the lower the removal cost. So what is the highest possible value of x4t that can be used? No mass should be transferred across the pinch Optimum target composition of S4 is the pinch composition y = 0.0168. Corresponding to: 0.0168 x 0.001 0.186 0.09 t 4 Example No. 2 12:17 • Ion Exchange (Continued) – Substituting x4t = 0.186 kg phenol/kg ion exchange resin into (C) and (E) C 4 $ 0 .2 1 4 / k g recircu latin g resin C 4r $ 1 .1 5 0 / k g o f rem o v ed p h en o l Example No. 2 13:17 • Air Stripping – Based on the cooling duty of the phenol condensation unit, the cost of using air stripping is given as: (F) – The outlet composition should be 50% of the Lower Flammability Limit (LFL) of 5.8 weight%: x 5t 0 .5 0 .0 5 8 0 .0 2 9 Less than supply composition of rich streams and pinch composition. Corresponding y-scale composition Thus thermodynamically feasible! (G) – C 5 $ 0 .0 6 / k g air y m 5 ( x 5t 5 ) 0 .0 4 (0 .0 2 9 0 .0 0 1) 0 .0 0 1 2 Example No. 2 14:17 • Air Stripping (Continued) – Since it is feasible to use air stripping for the phenol removal, the removal cost can be calculated C 5r $ 2 .0 6 9 / k g o f rem o v ed p h en o l • Summary M SA Unit Cost ($/kg M SA) Activated Carbon (S 3 ) 0.081 Ion Exchange Resin (S 4 ) 0.214 Air S tripping (S 5 ) 0.060 Removal Cost ($/kg phenol) 0.737 1.150 2.069 And the winner is Activated Carbon!!! Example No. 2 15:17 • Summary (Continued) – Flowrate of activated carbon MS 3 0.0124 kg/s L3 t 0.1127 kg/s s x3 x3 0.11 0 – Minimum Operating Cost MOC $0.081 kg activated carbon Ahead of design!!! 0.1127 kg activated carbon s s 8760 hr 3600 hr yr MOC $288 10 3 / yr MOC $0.737 kg phenol removed removed 3600 s 8760 hr 0.0124 kg phenol hr yr s MOC $288 10 3 / yr Example No. 2 16:17 • Trading Off Fixed Vs. Operating Cost – – Minimum allowable composition differences can be used to trade off fixed vs. operating cost. When waste streams are mixed, the number of mass exchangers and, consequently, fixed cost decrease. On the other hand, mixing various waste streams normally increases the MOC of the system – Waste stream data for mixing of waste streams Stream Rmixed Description Flowrate Gi , kg/s Mixed R1 and R2 3 Supply Composition (mass fraction) yis 0.0433 Target Composition (mass fraction) yi t 0.0087 Example No. 2 17:17 • Trading Off Fixed Vs. Operating Cost (Continued) – New Pinch Diagram for mixed waste streams 0.140 Mass Exchanged, kg phenol/s 0.120 0.1224 Excess Capacity of Process MSA’s 0.1040 Values Obtained 0.100 Lean Composite Stream 0.080 Pinch location as well as external MSA load is unchanged, i.e. so is the MOC. Rich Composite Stream 0.060 Load to be 0.040 Removed by External MSA’s Pinch Point 0.020 0.0124 0.000 0.000 0.0087 0.004 0.0055 MOC = $288,000/yr 0.020 0.0168 0.030 0.040 0.0433 0.050 y 0.009 0.0074 0.014 0.019 0.0024 x1 0.0186 0.0251 0.0317 x2 0.0121 Screening External MSA’s 1:3 • Questions – – • How do we screen candidate external MSA’s? Is the cost of each MSA ($/kg recirculating MSA) a proper screening criterion? Example - Refinery Hydrogen Removal – – – – Need to remove 10 kg H2/hr from refinery gasses Two candidate MSA’s Absorption on sand (Cost $10-4 /kg sand) Absorption on activated carbon (Cost $1.0 /kg carbon) Screening External MSA’s 2:3 • Example - Refinery Hydrogen Removal (Cont’d) – 1 kg of sand can remove 10-9 kg of H2 L sand MS sand 10 kg/hr 10 t 10 kg sand/hr s 9 x sand x sand 10 0 C o st sa n d 1 0 4 $ / k g sa n d 1 0 1 0 k g sa n d /h r $ 1 0 6 /h r – 1 kg of activated carbon can remove 0.1 kg of H2 Lcarbon MS carbon 10 kg/hr t 100 kg carbon/hr s x carbon x carbon 0.1 0 C o st ca rb o n 1 .0 $ / k g carb o n 1 0 0 k g carb o n /h r $ 1 0 0 /h r Screening External MSA’s 3:3 • Proper Screening Criterion – • Removal cost: $/kg removed of targeted species Conversion to Removal Cost – How to convert from $/kg MSA to $/kg removed? 1 kg of MSA xs (xt – xs) kg of targeted species is removed per kg of the MSA (3.30) C r j xt Cj x tj x sj IMPORTANT!!! No Process MSA’s 1:2 • Screening the External MSA’s If C2r < C1r then eliminate S1 from the problem, as it is thermodynamically and economically inferior to S2 Mass Exchanged If C2r < C3r retain both MSA’s Rich Composite Stream Load to be Removed by S2 Load to be Removed by S3 S1 x 1s S2 x s2 S3 x s3 x t3 x t2 y x 1t y b1 1 m1 y b2 x2 2 m2 x1 x3 THERMODYNAMIC FEASIBILITY y b3 3 m3 No Process MSA’s 2:2 • Constructing the Pinch Diagram Mass Exchanged Pinch Point Rich Composite Stream Lean Composite Stream S1 x 1s S2 x s2 S3 x s3 x t3 x t2 y x 1t y b1 1 m1 y b2 x2 2 m2 x1 x3 y b3 3 m3 Example No. 3 1:4 • Toluene Removal from Wastewater – – – – Flowrate of wastestream: G = 10 kg/s Supply composition of toluene: ys = 500 ppmw Target composition of toluene: yt = 20 ppmw Three external MSA’s • • • Stream Air (S1) for stripping Activated carbon (S2) for adsorption Solvent (S3) for extraction Uppe r bound on flowrate C j L Supply composition Target composition (ppmw) xjs (ppmw) kg/s mj j Cj ppmw $/kg MSA Removal Cost C1r = $0.38/kg xjt S1 0 19,000 0.0084 6,000 7.2x10-3 C2r = $5.53/kg S2 100 20,000 0.0012 15,000 0.11 C3r = $43.90/kg S3 50 2,100 0.0040 10,000 0.09 Example No. 3 2:4 • Screening the MSA’s – S2 and S3 are capable of removing the entire toluene load. S1 has limited removal capability 0.0050 0.0048 Mass Exchanged, kg Toluene/s 0.0040 Rich Stream 0.0030 0.0020 Activated carbon is less expensive than the solvent, thus S2 should be used to remove the remaining load, i.e. 0.0003 kg/s Air is least expensive, thus S1 should be used to remove all the load to its right, i.e. 0.0045 kg/s 0.0010 0.0003 0.000 0 20 50 Carbon 100 0 20,000 100 Air 200 19,000 300 400 500 y, ppmw x1, ppmw x2, ppmw Extractant 50 2100 x3, ppmw Example No. 3 3:4 • Constructing the Pinch Diagram 0.0050 Mass Exchanged, kg Toluene/s 0.0048 0.0040 Air Rich Stream 0.0030 0.0020 Activated Carbon 0.0010 0.0003 0.000 0 20 50 0 100 20,000 100 200 19,000 300 400 500 y, ppmw x1, ppmw x2, ppmw Example No. 3 4:4 • Minimum Operating Cost (MOC) Solution – Flowrate of air: MS1 0.0045 kg/s L1 t 0.237 kg air/s s 6 x1 x1 19, 000 10 0 – Flowrate of activated carbon: MS2 0.0003 kg/s L2 t 0.015 kg carbon/s s 6 x 2 x 2 (20, 000 100) 10 – Assuming 8000 hr/yr: MOC 0.237 kg/s $7.2 10 3 /kg 0.015 kg/s $0.11/kg MOC 0.00335 $/s $96,700/yr Other Business • Michelin Information Session – February 12 – • Meet in McMillan Auditorium during regular lecture time Next Lecture – February 14 – – Graphical mass integration techniques SSLW pp. 297-308