Polymer Design: PET Chemical Recycling — Preliminary Process Flow and Data Sets Submission Date: 2-08-2016 Course: ChE 4420 ~ Polymer Production Team Members:The Polymer Design Team Dr. Stretz’s Garage Cookeville, TN 38501 ‘The Super Big Investment Group San Francisco, California February 8th, 2016 Dear Cool Dude, The Chemical Design Team is accepting your invitation for design proposals of innovative, new, and exciting technologies. Our team has recently completed the design of a biodiesel facility and has current interests in the design of a new and environmentally friendly process, providing potential high earnings for SBIG. A poly(ethylene terephthalate) (PET) chemical recycling plant is briefly proposed below. PET is an exceptionally versatile plastic with a wide range of consumer applications including, but not limited to, the textile industry, x-ray films, food packaging, and soft drink bott Approximately 26 million tons are produced per year', and the world consumption of Pi packaging is projected to reach 19.1 million tons by 2012, While additional innovative applications of PET are still being introduced to the marketplace, PET’s non-degradable nature presents an environmental concer and challenge once PET products are discarded as waste. While PET mechanical recycling methods are not uncommon, chemical recycling remains a relatively untapped market because price of petrochemical feedstocks for virgin PET production competes with process costs associated with the PET waste depolymerization®?. Our team proposes to build a full-scale chemical recycling plant to depolymerize waste PET via a methanolysis process to produce dimethyl terephthalate (DMT) and ethylene glycol (EG) ‘monomers. These monomers can be sold to a PET production facility, providing DMT monomer at a high quality (identical to virgin monomers). Attached to this letter is a preliminary process flow diagram accompanied by a succinct description of the process. Additionally, physical property data and a kinetic schema required for mathematical modeling the chemical design is summarized. This new Polymer Production Design Team asks you to carefully consider this preliminary design proposal, as we are excited about an opportunity to design an environmentally friendly, ecological, and innovative process. Your time and consideration is appreciated. We look forward to hearing from you soon. Sincerely, The Polymer Design TeamThe Polymer Design Team Dr. Stretz’s Garage Cookeville, TN 38501 Preliminary Process Flow and Data Set Resources: An Introduction Through detailed research and discussion, a preliminary PET chemical recycling process is presented. In the production of the overall process flow diagram, two specific patents have been helpful in constructing plausible unit operations for PET depolymerization and DMT/EG separation". With respect to the proposed production of pure monomeric compounds on a commercial scale, a preliminary process flow diagram is shown in Appendix A. In terms of initial design plans, the recycled PET will initially be reacted with methanol, using a zine acetate catalyst at a high temperature and pressure, producing DMT and ethylene glycol. ‘After separating solid and liquid phases of the cooled reactor effluent, the crystallized DMT is dried to remove remaining impurities. The liquid stream is put through multiple distillation units to retrieve both methanol and ethylene glycol for recycling and sale, respectively. Beyond the described unit operations, heat exchangers and pumps will be analyzed and implemented as needed. Each of these unit operations will be modeled to judge the economic feasibility of chemically recycling PET. Appendix B details physical property data for compounds in a tabulated format required for the previously specified project scope. This appendix is filled with extended equations and quantitative figures to aid in estimating properties varying with temperature. Having proven that the resources are adequately present to construct analytical models for the specified process, the chemical design team will be thrilled to move forward and produce an opportunity assessment around this system.AowoUoTY Onuy FUYPSI9Y TEO!UON.D pudosoy auasipa)sjog soy wesdeyq MOLY sso90Ig KaouUTaAg 2 aanS arsem, 5 s9po04 mans 5 Poosasheie WBISVIG] MOLY Sssd01g :y xIpusddy , o[ ss200ug KreummTarg pure slag wre BuNOKONY 1.samerodutoy snotsea Ye SOMISODSIA JOY E>1qRL 29S a samproduin snouys y samisuap 05 § aqgp] 205 aumyeioduoy snows SOnIgU9P 205 71 21@B1. 205 - xcossz_| eeere | OHEsaatOPHYD SWeIpAYLL O1IOW PLAT Novi +1 - orst | Is'612_ | OFHZeUZIO NAD arwspkyiq areiaay ou, WZ eI = zc 00EL aera SOM HED, arepeynydozay ([AupoAXOmpAY-Z) SIL JaHa a 7 7 lost| 09 aprKoUoW UOQeD 09 UL - 7 lor 209 eprxord woqse) | zoo or : 1 S9EL zo'sz N UoBOIN | aN 6 ot 1 S8L, 9ZSO'bY OTHE opcyopreeoy vv. 8 1 £4000 s801_| z1'901 soo'HD Took ovayctparc Dad L oc oot | szstorst OH IEA OvH 9 = * rove HO'HO, jourqpoyy HOW s ot ust Loz “OHO, Jook]p auaycya oF ¥ : o6zt_| Zor "OSHS aprender, Kunoung 52 Blos) uwa_| ae 1 78901000 | _ 91 06ZL zrer_ | 08H orepeunydes, you (pmbr) twa_| ee 2 zest | ergor +0989 proy omeuydazo, Vd z = oct St zoL “OHSD) (erepernydasay auapAipo)AJog Grew) Lad ot - Ocel 81-261 “CO8H"'D) Grepenydaroy ouaysqa)sjog | (snoydsour) Lad | 4 1 E Parsal si zol “OSH"'D) (exeqeypydasoy auayAtpo)K}od SED Lad et (s-0d) (uy | (roucy Sy sn fi) 80981, Ba, jn | Comin | siege | sms won punoduy womeongay | ew wyuq Apsadorg jearsdyg sopadg 28] 9140], 9G BV SulpAdY Lad :@ xIpueddy mol ssooorg KsmuruHalg pure siag wEC BUNPKODY La(o/s) subg pur siajaumsng Asoede 194] 305 p 2]gR, 995 dura, snoue, ye sontoede3 89} [ld UTUIEAD Of pu E SAIN ADs 3 weSk : z > = : VI tL - oe LEC : - - 362 se'6991- VZ a - 6LE oe = = = = ISHE a - 7 : et = 862 a €SO1T- 09 in : 1 S61 - ut - 360, «x 1S'€68 zoo = sso Sele oc 80P162, = 860 0 uN ¥ i 861 6860 2 50°68 a 862 961" vv : LU SIS - 1 907. 862 SSC pga 2 rd vee at = 360 oc £8 1bC- Ot - - Lee at z 867, or 99°80 HOOW > nto | sroer : 1 90FE, 867 SS oa = oi SUEIb ST'19S sc? 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0D (PP) (eye | Guay | Surv uojsuay wap afaads | aanssarg | dusoasiy | Aysoosy, | dnsuaq | Ausuog | waxy Oo aonfang pinbry aodo, adn, sodo4 pinbyT sodoy pinbyy | juamy | aummiodmay oly ssoo0ug Aseunusjarg par si9g wie BuyoKooy Lad o¢ SPMpBIadway, snouwA ye EEG Apadorg eorskyg [UCIT 25 140,PET Recycling Data Sets and Preliminary 10 Process Flow Methanolysis Reaction Kinetics “” /o ° \ Lol, ore rO4,) . ke Recyios PET vetnanat Figure 2: Mechanism for Transesterification Reaction Between Methanol and PET “ Rate of Appearance of Carboxymethyl Groups: aC, C00cHs | 1 = K+ CexCueou — K' * Ceoocn,Con o ‘Table 6: Definition of Terms for Methanolysis Reaction Ca ‘Concentration of Ester Linkages Con | Concentration of Ethylene Glycol Ccoocus_| Concentration of Methyl Esters Ceon _| Concentration of Methanol k Rate Constant for Methanolysis Reaction kK Rate Constant for Condensation Reaction Table 7: Methanolysis Reactis ata Summary *” | G K TO | (g PET/mol- | (g PETmol- | (Equilibrium | 4G (mo | AH i ; (/mol) min) min) Constant) 120 | 0.000676 0.01971 0.0343, 11000 -38600 130 | 0.000899 0.03596 0.0250 12300 -60600 140_| 0.001392 0.08000 0.0174 13900 -60900 Table 8: Arrhenius Constants for Forward Reaction (k) * Frequency Factor (A) 107.1 | g PET/mol-min | Activation Energy (Ea) 95.31__| kJ/molPET Recycling Data Sets and Preliminary Process Flow Table 9: PET Processing Properties * Processing Properties Metric Melt Temperature 275 - 295 °C Mold Temperature | __10.0-30.0°C___ Drying Temperature 150 - 160°C Dry Time 4-6 hour ‘Temperatures * Table 10: PET Specific Heats for Various Temp 0) Cp (/kg*K) 80 [_ 1300_ 100 1400 200 1900 280 2100 Various Temperatures *° Table 11: PET Dynamic Viscosity for Temp (°C) Vise (cP) 145.8 0.772 1513 0.725 156.9 0.682 | ene 0.642 168.0 0.605 1336 0.572 179.1 0.541 184.7 0.512 190.2 0.485 195.8 0.461 201.3 0.438 206.9 0.417 212.4 0397 218.0 0.378 223.6 0.361 229.1 0.345 234.7 033PET Recycling Data Sets and Preliminary Process Flow ‘Apparent Heat Capacity [KKK mal) 5 PET melt crystallized ° ® quastisothermal (60 8/1.0K) — standard DSC = (10 K/min) computed ace (ve =44%) ——— ° 3 2 Tg mettheat capacity - ‘crystal heat capacty 350400450 500-550 Temperature (K) ° Capaci 3 Plois depicting PET (crystallized and amorphous) Heat ies for Various Temperatures * quasi-jsothermal (60 8/1.0 K) ‘9 1nbaby amorphous FET, 40% crystaine 450) baby sermery tnine, 64% crystane Sp UKK mon) 350 400 ~~ 480 —~S~C«OSSC«O Temperature (K) Figures 4 Plots depicting PET (crystallized and amorphous) Specific Heats for Various Temperatures * 12PET Recycling Data Sets and Preliminary Process Flow Table 12: Ethylene Glycol Physical Property Data at Various Temperatures Temp | Density Dynamic Specific Heat CO _|_(kg/m3)_| Viscosity (Pa-sec) | _ (/kg-K) “178 1160 031 2260.87 44 1145 0.048 2352.9816 26.7 | 1125.48 0.014 2470.212 48.9 | 1101.62 0.007 2562.3216 Tl 1075.8 0.0038 2679.552 93.3 | 1046.06 0.0014 2763.288, 115.6 [1013.65 0.0018 284.7052 137.8 987 0.0014 2972.628 Table 13: Diethylene Glycol Density at Various Temperatures °° Temp (°C) | Density (kg/m*) 0 [ 1131.8 3 1128.3. 10 11248 15 1121.2 20 117.7 25 Ta 30. 1110.6 33 1107.1 60 1065 B0) 22) (3) [6] a) (12) PET Recycling Data Sets and Preliminary 4 Process Flow’ References Karayannidis GP, Achilias DS. 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