MTBE Production. Process Description. Possibility of Changing Process Feed Conditions

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Production You work in a facility that produces about 100,000 tonne/y of methyl tertiary butyl ether (). is an oxygenated fuel additive that is blended with gasoline to promote CO 2 formation over CO formation during combustion. The facility manufactures from methanol and isobutylene. Isobutylene is obtained from a refinery cut, and it also contains 1- butene and 2-butene, both of which do not react with methanol. Process Description The process flow diagram is shown in Figure 1. Methanol and the mixed butylenes feed is pumped and heated to reaction conditions. Both the methanol and the mixed butylenes are made in on-site units, and are sent to this unit at the desired conditions. The reactor operates in the vicinity of 30 bar, to ensure that the reaction occurs in the liquid phase. The reaction is reversible. The feed temperature to the reactor is usually maintained below 90 C to obtain favorable equilibrium behavior. Any side reactions involving 1-butene and 2-butene form small amounts of products with similar fuel blending characteristics, so side reactions are assumed to be unimportant. Other side reactions are minimized by keeping the methanol present in excess. The reactor effluent is distilled, with as the bottom product. Methanol is recovered from the mixed butylenes in a water scrubber, and the methanol is subsequently separated from water so that unreacted methanol can be recycled. Unreacted butylenes are sent back to the refinery for further processing. The product is further purified (not shown), mostly to remove the trace amounts of water. The product stream from Unit 900 must contain at least 94 mol %, with the portion of the stream flowrate at specifications. Tables 1 and 2 contain the stream and utility flows for the process as designed. Table 3 contains an equipment list. Other pertinent information and calculations are contained in the appendix. Possibility of Changing Process Feed Conditions This plant receives the mixed butylenes feed from a neighboring refinery, which has recently changed ownership. The new owners are planning to implement changes based on their proprietary technology. The changes will occur after a regularly scheduled plant shut down (for both plants) within the next six months. The effect on our plant is that they have proposed that the mixed butylenes feed that we receive will contain 23 wt% isobutylene (isobutene), 20 wt% 1- butene, and 57 wt% 2-butene. Our current contract for mixed butylenes expires at the next plant shut down, so we are in the process of negotiating a new contract with the new owners. An additional complication is that is in the process of being phased out as a fuel additive because of ground water contamination from leaky gasoline storage tanks.

V-901 Methanol Feed Vessel P-901 A/B Feed Pump E-901 R-901 Feed Preheater Reactor T-901 E-902 Reboiler E-903 Condenser V-902 Reflux Drum P-902 A/B Reflux Pump T-902 Methanol Absorber P-903 A/B Feed Pump T-903 Methanol Recovery E-904 Methanol Reboiler E-905 Methanol Condenser V-903 Methanol Reflux Drum P-904 A/B Reflux Pump process water FIC E-901 waste butylenes V-901 P-901 A/B lps T-902 methanol butylenes feed R-901 T-901 LIC FIC E-903 cw V-902 P-902 A/B LIC T-903 P-903 A/B E-904 mps LIC FIC E-905 cw V-903 P-904 A/B LIC waste water E-902 hps Figure 1: Unit 900 - Production Facility 2

3 Table 1 Stream Tables for Unit 900 Stream No 1 2 3 4 Temp C 25.00 49.84 25.00 45.70 Pres kpa 400.00 400.00 390.00 390.00 Vapor fraction 0.00 0.045 0.00 0.00 Total kg/h 5600.00 16590.16 21875.00 22190.70 Total kmol/h 174.77 427.75 389.88 602.54 Component kmol/h Methanol 174.77 322.15 496.96 i-butene 3.73 155.95 3.73 1-Butene 14.59 46.79 14.59 Trans-2-Butene 74.43 187.14 74.43 11.86 11.86 Water 0.98 0.98 Stream No. 5 6 7 8 Temp C 25.93 26.91 85.00 127.57 Pres kpa 380.00 3000.00 2965.00 2915.00 Vapor fraction 0.00 0.00 0.00 0.00 Total kmol/h 992.42 992.42 992.42 848.70 Total kg/h 44065.70 44065.70 44065.70 44065.70 Component kmol/h Methanol 496.96 496.96 496.96 353.23 i-butene 159.68 159.68 159.68 15.95 1-Butene 61.38 61.38 61.38 61.38 Trans-2-Butene 261.58 261.58 261.58 261.58 11.86 11.860 11.86 155.59 Water 0.97 0.97 0.97 0.97 Stream No. 9 10 11 12 Temp C 178.46 134.37 110.36 30.00 Pres kpa 1925.00 1900.00 500.00 450.00 Vapor fraction 0.00 1.00 1.00 0.00 Total kg/h 12973.05 31272.80 31272.80 21618.00 Total kmol/h 150.40 698.30 698.30 1200.00 Component kmol/h Methanol 7.06 346.17 346.17 i-butene 0.00 15.95 15.95 1-Butene 0.00 61.38 61.38 Trans-2-Butene 0.00 261.58 261.58 142.36 13.22 13.22 Water 0.97 0.00 0.00 1200.00

4 Table 1 (cont d) Stream Tables for Unit 900 Stream No. 13 14 15 16 Temp C 83.49 83.12 70.73 56.27 Pres kpa 110.00 160.00 500.00 500.00 Vapor mole fraction 1.00 0.00 0.00 0.00 Total kg/h 18828.85 34061.93 34061.93 16590.16 Total kmol/h 500.96 1397.34 1397.34 427.75 Component kmol/h Methanol 23.69 322.48 322.48 322.16 i-butene 12.23 3.72 3.72 3.72 1-Butene 46.78 14.60 14.60 14.60 Trans-2-Butene 187.13 74.44 74.44 74.44 1.36 11.86 11.86 11.86 Water 229.76 970.24 970.24 0.97 Stream No. 17 Temp C 155.61 Pres kpa 550.00 Vapor mole fraction 0.00 Total kg/h 17471.77 Total kmol/h 969.60 Component kmol/h Methanol 0.32 i-butene 1-Butene Trans-2-Butene Water 969.27

5 Table 2 Utility Stream Flow Summary for Unit 900 E-901 E-902 E-903 lps hps cw 3572 kg/h 25,828 kg/h 6.31 10 5 kg/h E-904 E-905 mps cw 32,433 kg/h 1.44 10 6 kg/h Table 3 Partial Equipment Summary Heat Exchangers E-901 A = 44.6 m 2 1-2 exchanger, floating head, carbon steel process stream in tubes Q = 7502 MJ/h maximum pressure rating of 35 bar E-902 A = 50.9 m 2 1-2 exchanger, fixed head, carbon steel process stream in shell Q = 43,908 MJ/h maximum pressure rating of 23 bar E-903 A = 92.4 m 2 1-2 exchanger, floating head, carbon steel process stream in shell Q = 26,417 MJ/h maximum pressure rating of 23 bar Reactors and Vessels R-901 carbon steel packed bed, Amberlyst 15 catalyst V = 9.35 m 3 10 m long, 1.1 m diameter maximum pressure rating of 32 bar Pumps P-901 A/B carbon steel power = 220.53 MJ/h (actual) 80% efficient E-904 A = 209 m 2 1-2 exchanger, fixed head, carbon steel process stream in shell Q = 64,542 MJ/h maximum pressure rating of 6.5 bar E-905 A = 1003 m 2 1-2 exchanger, floating head, carbon steel process stream in shell Q = 60,347 MJ/h maximum pressure rating of 6.5 bar V-901 stainless steel V = 11.215 m 3 maximum pressure rating of 5 bar P-903 A/B carbon steel power = 18.65MJ/h (actual) 80% efficient

6 Table 3 (cont d) Partial Equipment Summary s T-901 carbon steel 97 sieve trays plus reboiler and partial condenser 70% efficient trays feed on tray 27 additional feeds ports on 23 and 30 reflux ratio = 1.62 12 in tray spacing, 2 in weirs column height 30 m diameter = 2.8 m above feed, 4.7 m below feed maximum pressure rating of 23 bar T-902 carbon steel 7.3 m of packing 5 theoretical stages 6.86 kpa/m pressure drop diameter = 2.9 m packing factor 500 maximum pressure rating of 5 bar T-903 carbon steel 42 sieve trays plus reboiler and total condenser 48% efficient trays feed on tray 21 additional feed ports on 16 and 23 reflux ratio = 3.44 24 in tray spacing, 6.8 in weirs column height = 26 m diameter = 2.6 m maximum pressure rating of 6.5 bar

7 Your assignment is first to determine the maximum flowrate of the new feed stream the plant can process and the operating conditions needed for this plant to use the new feed stream and meet the required production rate and specifications without any capital investment. You must also determine whether these are feasible operating conditions. Any change in the cost of manufacture should be documented. Then, you are to determine the cost of any process modifications (capital and operating) needed for our plant to use this new feed to maintain the current production rate and specification of. Cost Saving Strategies Since we are expecting to implement process modifications during the upcoming shut down, please recommend any cost-saving strategies that we can also implement. Economics For all process modifications, use a 15%, before-tax rate of return and a 5-year lifetime. Use an EAOC or an INPV as the measure of profitability. Deliverables Specifically, you are to prepare the following by 9:00 a.m., Monday, November 8, 2004: 1. Determine the maximum flowrate of the new feed stream the plant can process and the operating conditions needed for this plant to use the new feed stream and meet the required production rate and specifications without any capital investment 2. Determine the cost of any process modifications (capital and operating) needed for our plant to use this new feed to maintain the current production rate and specification of 3. Suggest cost-saving measures that you recommend for the plant. All recommendations should be accompanied by an economic analysis that accounts for the savings and cost of implementing the changes. 4. Prepare a written report, conforming to the guidelines, detailing the information in items 1, 2, and 3, above. 5. Include a legible, organized set of calculations justifying your recommendations, including any assumptions made. 6. Attach a signed copy of the attached confidentiality statement.

8 Report Format This report should be brief and should conform to the guidelines. It should be bound in a folder that is not oversized relative to the number of pages in the report. Figures and tables should be included as appropriate. An appendix should be attached that includes items such as the requested calculations. These calculations should be easy to follow. The confidentiality statement should be the very last page of the report. The written report is a very important part of the assignment. Reports that do not conform to the guidelines will receive severe deductions and will have to be rewritten to receive credit. Poorly written and/or organized written reports may also require re-writing. Be sure to follow the format outlined in the guidelines for written reports. Oral Presentation You will be expected to present and defend your results some time between November 11, 2004 and November 18, 2004. Your presentation should be 15-20 minutes, followed by about a 30-minute question and answer period. Make certain that you prepare for this presentation since it is an important part of your assignment. You should bring at least one hard copy of your slides to the presentation and hand it out before beginning the presentation. Other Rules You may not discuss this major with anyone other than the instructors. Discussion, collaboration, or any other interaction with anyone other than the instructors is prohibited. Violators will be subject to the penalties and procedures outlined in the University Procedures for Handling Academic Dishonesty Cases (begins on p. 47 of 2003-05 Undergraduate Catalog). Consulting is available from the instructors. Chemcad consulting, i.e., questions on how to use Chemcad, not how to interpret results, is unlimited and free, but only from the instructors. Each individual may receive five free minutes of consulting from the instructors. After five minutes of consulting, the rate is 2.5 points deducted for 15 minutes or any fraction of 15 minutes, on a cumulative basis. The initial 15-minute period includes the 5 minutes of free consulting. Late Reports Late reports are unacceptable. The following severe penalties will apply: late report on due date before noon: one letter grade (10 points) late report after noon on due date: two letter grades (20 points) late report one day late: three letter grades (30 points) each additional day late: 10 additional points per day

9 Appendix 1 Reaction Kinetics The reactions and reaction kinetics are as follows: CH 3 OH + CH3) 2C = CH 2 ( CH3) 3 ( C O CH 3 (1) Cisobutylene C r = k f kr (2) C C methanol 2 methanol where = 16 85, 400 k f 6.05 10 exp RT = 22 129, 600 k r 1.464 10 exp RT (3) (4) The units of reaction rate, r i, are mol/m 3 h, and the activation energy is in J/mol. These kinetics are only valid when excess methanol is present.

10 Appendix 2 Chemcad Hints If you choose to use Chemcad, here are some hints. Use PSRK for the K-value and SRK for the enthalpy. However, for the absorber (T-902), use ideal vapor pressure for the K-value. If you want to simulate the towers, use TOWR for T-901. Use SCDS for T-902 and T-903. If you want to simulate the reactor, make sure that you set the flag for a liquid-phase reaction.

11 Appendix 3 Calculations and Other Pertinent Information E-901 T 160 85 26.9 Q Q = 7502 MJ/h T lm = 101.3 C process fluid h i = 500 W/m 2 K lps condensing h o = 6000 W/m 2 K U 1/h i + 1/h o = 461.5 W/m 2 K A = 44.6 m 2 Q = m& λ = m& (2100 kj/kg) lps flow in Table 2 E-902 254 T 178.5 Q Q = 43,908 MJ/h T lm = 75.5 C process fluid boiling h o = 5500 W/m 2 K hps condensing h i = 7500 W/m 2 K U 1/h i + 1/h o = 3173 W/m 2 K A = 50.9 m 2 m& hps = Q / λ = Q /( 1700 kj/kg) hps flow in Table 2

12 E-903 134.4 T 40 30 Q Q = 26,417 MJ/h T lm = 99.3 C cw h i = 1000 W/m 2 K condensing organic process stream h o = 4000 W/m 2 K U 800 W/m 2 K A = 92.4 m 2 m& = Q / C T Q /[( 4.184 kj/kgk)( 10K) ] cw p = cw flow in Table 2 E-904 T 187 155.6 Q Q = 64,542 MJ/h T lm = 31.4 C mps condensing h i = 6000 W/m 2 K boiling process stream h o = 5000 W/m 2 K U 1/h i + 1/h o = 2727 W/m 2 K A = 209 m 2 m& mps = Q / λ = Q /( 1990 kj/kg) mps flow in Table 2

13 E-905 56.3 T 40 30 Q Q = 60,347 T lm = 20.9 C cw h i = 1000 W/m 2 K condensing organic process stream h o = 4000 W/m 2 K U 1/h i + 1/h o = 800 W/m 2 K A = 1003 m 2 m& = Q / C T Q /[( 4.184 kj/kgk)( 10K) ] cw p = cw flow in Table 2 R-901 V = 9.35 m 3 V = (πd 2 /4)(L) = 9.35 L = 10 m D = 1.1 m T-901 from Chemcad, 68 ideal trays, plus partial reboiler and partial condenser above feed: L = 45,000 kg/h, G = 75,000 kg/h ρ L = 480 kg/m 3 ρ G = 28 kg/m 3 (L/G)(ρ G /ρ L ) 0.5 = 0.145 from flooding graph for 12 in tray spacing (P. Wankat, Equilibrium Staged Separations, Prentice Hall, 1988, p. 387.) C sb = 0.18 u fl = 0.72 ft/s u act = 0.165 m/s (75% of flooding) if 75% active area A = (G/3600)/[(0.75)(ρ G )(u act )] = 6.01 m 2 D = 2.8 m

14 below feed: L = 244,000 kg/h, G = 231,000 kg/h ρ L = 509 kg/m 3 ρ G = 64 kg/m 3 (L/G)(ρ G /ρ L ) 0.5 = 0.375 from flooding graph for 12 in tray spacing (P. Wankat, Equilibrium Staged Separations, Prentice Hall, 1988, p. 387.) C sb = 0.13 u fl = 0.34 ft/s u act = 0.078 m/s (75% of flooding) if 75% active area A = (G/3600)/[(0.75)(ρ G )(u act )] = 17.1 m 2 D = 4.7 m 70% overall column efficiency (O Connell correlation) 97 trays (so column about 100 ft tall 30 m) P = ρghn 25000 Pa = (520 kg/m 3 )(9.8 m/s 2 )(h weir )(97) h weir = 0.0505 m 2 in T-902 from Chemcad, 5 ideal trays use packed bed: L = 32,000 kg/h, G = 26,500 kg/h ρ L = 760 kg/m 3 ρ G = 2.8 kg/m 3 (L/G)(ρ G /ρ L ) 0.5 = 0.073 packing factor is 500 packing pressure drop is 6.86 kpa/m from flooding (P. Wankat, Equilibrium Staged Separations, Prentice Hall, 1988, p. 421.) G fl = 0.3 lb/ft 2 s = 1.48 kg/m 2 s if 75% of flooding A = (26500 kg/3600 s)/((0.75)(1.48 kg/m 2 s) = 6.63 m 2 D = 2.9 m T-903 from Chemcad, 20 ideal trays, plus partial reboiler and total condenser above feed: L = 55,000 kg/h, G = 71,000 kg/h ρ L = 700 kg/m 3 ρ G = 5.90 kg/m 3 (L/G)(ρ G /ρ L ) 0.5 = 0.071

15 from flooding graph for 24 in tray spacing (P. Wankat, Equilibrium Staged Separations, Prentice Hall, 1988, p. 387.) C sb = 0.35 u fl = 3.80 ft/s u act = 0.87 m/s (75% of flooding) if 75% active area A = (G/3600)/[(0.75)(ρ G )(u act )] = 5.12 m 2 D = 2.6 m use this value below feed: L = 49,000 kg/h, G = 31,000 kg/h ρ L = 910 kg/m 3 ρ G = 2.9 kg/m 3 (L/G)(ρ G /ρ L ) 0.5 = 0.089 from flooding graph for 24 in tray spacing (P. Wankat, Equilibrium Staged Separations, Prentice Hall, 1988, p. 387.) C sb = 0.33 u fl = 5.84 ft/s u act = 1.33 m/s (75% of flooding) if 75% active area A = (G/3600)/[(0.75)(ρ G )(u act )] = 2.98 m 2 D = 2.0 m 48% overall column efficiency (O Connell correlation) 42 trays (so column about 84 ft tall 26 m) P = ρghn 50000 Pa = (700 kg/m 3 )(9.8 m/s 2 )(h weir )(42) h weir = 0.174 m 6.8 in V-901 Use a 10 minute holding time for liquid to P-901 V = (67.29 m 3 /h)(10 min)/(60 min/h) = 11.215 m 3 L/D = 3 V = πd 2 L/4 = πd 3 (L/D)/4 (assuming horizontal bullet of diameter D and length L) D = {(4)(11.215)/[(π)(3)]} 1/3 = 1.68 m L = 5.05 m No calculations are available for following equipment items: P 902 A/B P-904 A/B V-902 V-903

16 P-901 A/B Pump Curve Equation: P ( kpa) = 3000 0.03974v& 2 (m 3 /h) Stream conditions Stream 5: v& = 67.3 m 3 /h, ρ = 655 kg/m 3 Stream 8: ρ = 523 kg/m 3 Pressure drops at design conditions location P (kpa) pump inlet to T-901 inlet 2535 E-901 35 R-901 50 ~25 m head to T-901 inlet 128 frictional losses in pipes 22 control valve 50 Bubble point pressure of Stream 5 at 25.93 C is 2.78 bar At zero flowrate, NPSH A = 3.5 bar NPSH R (kpa) = 30 + 0.011 2 v& (m 3 /h)