Sheth Polymer Design: PET Chemical Recycling — Opportunity Assessment and Process Overview Submission Date: 2-15-2016 Course: ChE 4420 — Polymer Production Team Members:PET Recycling: SBIG Proposal and Opportunity Assessment ‘The Super Big Investment Group San Francisco, California February 15th, 2016 Dear Cool Dude, The PET Recycling Design Team seeks to obtain approval from The Super Big Investment Group (SBIG) for a new chemical plant design. The proposal, presented in the following article, is related to chemically recycling poly(ethylene terephthalate) (PET). The proposed plant design focuses solely on the depolymerization process, where PET flakes are converted into its monomers, dimethyl terephthalate (DMT) and ethylene glycol (EG), An opportunity assessment associated with PET recycling is first presented, where a plant capacity seeks to consume an annual amount of 50 million pounds of recycled PET per year. ‘This plant capacity is based on a market report for PET bottle recycling taken over the last decade. The proposed plant capacity of 50 million pounds targets approximately three percent of the annual amount of recycled bottles in the United States. While PET chemical recycling practices are not as common in the United States as European states, the team desires to establish a new venture in the United States open market. In conjunction with the opportunity assessment, the PET Recycling Design Team asks SBIG to examine the prepared process flow sheet, which depicts the proposed method for obtaining ethylene glycol and crystalline DMT products. Numerous patents, literature reviews, and standard design synthesis texts were examined for flow sheet design, as discussed in more detail in the report body. The PET Recycling Design Team hopes the following opportunity assessment and process overview will encourage SBIG to develop interest in the proposed plant design. Sincerely, The PET Recycling Design TeamPET Recycling: SBIG Proposal and al Opportunity Assessment I. Introduction While plastics have improved the quality of life and provided innovative solutions in the consumer goods market, plastics also present an ecological challenge due to their high resistance to degradation. Many plastics ultimately end up in municipal landfills and take up large quantities of space due to their high volume-to-weight ratio.! The amount of plastic entering landfills has continued to increase over time, as shown in Table 1. Table 1: Proportion of Plastic in Municipal Solid Waste? Year % by Weight 1960 0.5 1970 26 1980 5.0 1988 8.0 1990 —|— 98 | 1992 10.6 1994 11.2 1995, 15 1996 123 More recent data from 2013 shows 33 million tons of plastic waste generated, representing 12.8% of total municipal solid waste, showing no decline in the relative amount of plastic waste. A mere 9% of this plastic waste was recycled, leaving 30 million in landfills? Furthermore, when examining the shear magnitude of PET production, one may find that 31% of plastic bottles produced in the United States are made from PET?, At such high capacity, PET recycling has a superb opportunity to significantly reduce the plastic volume entering into ‘municipal landfills. As an attempt to combat the daunting quantity of PET waste, a PET depolymerization plant will serve to break down PET into its monomers. Unlike other recycling methods, the monomers produced via chemical recycling are capable of regenerating high-quality PET via closed-loop recycling. A brief overview related to the feedstocks and products is presented in the following section, while a detailed opportunity assessment follows, examining the viability of PET chemical recycling. Furthermore, the proposed process flow is presented along with a description for all major unit operations. A Gantt chart is presented to show a schedule detailing all major steps required over the upcoming months to complete this plant design, Il. Process and Product Descript Various methods exist to recycle and repurpose PET, including mechanical recycling and incineration. However, both of these methods result in either downgrading PET (mechanical recycling) or complete degradation of PET for energy generation (incineration). Conversely,PET Recycling: SBIG Proposel and Oe : Opportunity Assessment , i chemical reeyeling enables the unique opportunity to break down PET inié its monomers. These monomers may be used later for PET reproduction; however, the focys of this plant is only to generate monomers, allowing another manufacturer to gproduce PET“ While the proposed plant design does not include PET polymerization, a complete process for PET depolymerization was developed, capable of producing high purity crystalline DMT and liquid EG Furthermore, the exact methods to depolymerize PET were examined. Three well-studied methods include methanolysis, hydrolysis, and glycolysis. After comparing the pros and cons for the previously stated methods, methanolysis was chosen as the desired method. Glycolysis and hydrolysis were not chosen since both methods produce products requiring difficult and expensive separation processes,’ while neutral hydrolysis is also shown to serve as an uneconomical industrial process.’ Details regarding reaction and separation methods for the ‘methanolysis process is presented in section IV. IIL. Opportunity Assessment PET has undoubtedly revolutionized food packaging, where it has been an extfemely common plastic used for soft drink containers over the last several decades. Although thi material is easy to recycle, PET accounts for a significant portion of plastic wrastg-arpreniousy Tous -discuss@i, Both synthetic fibers and soft drink bottles consume a large portion of the PET market, making them highly visible to consumers.° The consumer visibility and increase in PET usage has promoted local governments to encourage increased recycling programs. Figure | shows domestic PET bottle recycle rates based on the total quantity of PET bottles produced.” Years 2004 through 2014 show a notable increase in PET bottle recycling, rising from twenty- two to thirty-one percent.” ° ° oe Gross Recycling Rate (%) « 2 ° 20 2002 2004 2006 2008-2010 2012-2014 «2016 Year Figure 1. PET boitle ‘gross recycling rate over the years 2004 — 20147 ven aye we ag wePET Recycling: SBIG Proposal and 5 ‘Opportunity Assessment When comparing various recycling methods, PET chemical recycling is a Jess common method, in general, as it requires a higher start-up cost than secondary or mechanical recycling methods and is not as prevalent in the United States, as in Europe.’ Of the recycled PET produced globally, only 4% is recycled via chemical methods.* Figure 2, shown below, presents a breakdown of PET bottle consumption in the United States along with the associated the recycle rate. The National Association of PET Container Resources collected data presented in Figure 2, which serves as a guide to define plant capacity. ‘As shown, PET bottle production has steadily increased over the last decade, varying from 4,600 MMibs in 2004 to 5,800 MMibs in 2014.’ Recycle rates of PET bottles, although less than a third of total production, have increased at an even faster rate, ranging from 1000 MMlbs in 2004 to ‘over 1,800 MMlbs in 2014.’ Since chemical recycling is not a common venture in the United States, the proposed plant capacity plans to target 50 MMlbs of recycled PET annually, representing a modest 2.7% of 2014’s recycled PET bottles. This consumes a small portion of the United States PET market and will attempt to show the viability for subsequent domestic ventures. 7000 wTotal U.S bottles collected 6000 Bottles on U.S shelves WINN 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 Years 004 4000 3004 2004 Number of bottles (MMos) 100 Figure 2. Total bottles on U.S. shelves vs. total number of collected bottles? Furthermore, per the recommendation of Seider et al.’ a brief analysis comparing feedstock and product prices was conducted to ensure a profitable venture is even plausible before completing plant design. Using the reaction mechanism in Figure 3, simple stoichiometry helped determine relative DMT, EG, and methanol quantities, based on an average PET molecular weight of 30,000 g/mol (typical food-grade PET molecular weight).'?PET Reeyeling: SBIG Proposal and 6 Opportunity Assessment / \ wre cs Alay Bessie 2n[) + Hobo’ oo nies ‘oH N Jet CI) + (net o_o ort npr irl roy Pt oPon ow Figure 3. Stoichiometric equation for depolymerization via methanolysis, ‘Table 2: Buying and selling prices for PET chemical recycling. Quick calculation to test product viability Compounds Price (S/metric ton) | 8/30 kg PET PET. H 947.97 28.439 * McOH 25.150 0.257 EG "432,98 F 13.949 a, DMT 2,199.4 30.189 ‘ fal Raw 28.696. Bee $/30kg ‘Tptal Produ 44/38 I fom] $/ 30k; Based on the stoichiometry within Figure 3 and commodity chemical prices presented in Table 2, the price of PET, methanol, DMT, and EG were calculated based on a unit quantity of 30 kg of PET; these results are tabulated in Table 2. The comparison of feedstocks and products, based on the 30 kg PET basis shows PET depolymerization has the potential to be a viable process, where a modest margin exists between feedstock costs and product sales. It is pertinent to realize that no operating or production costs are considered in Table 2; rather, this calculation is completed as a quick assurance that a profitable margin may exist. A more informed economic report will be provided in the second quarter of this year, following plant design. IV. Product Production Strategy Great discussion-has-beerr devoted into the poteiitialflow sheet-design forthe PET-chemical recycting fuclity. Figure 4 provides a general process flowsheet from the reduction of amorphous PET flakes to produce purified DMT and ethylene glycol BG. “The Flow sheet digeussion begins with the methanolysis reactor. The premise of this reactor requires placing PET powder, methanol, and a zinc acetate catalyst into a CSTR at 130 to 140°C and increased pressure of 10.3 atm to depolymerize the PET feedstock.'* Due to PET melting at 250°C, the reaction occurs heterogeneously, and particle size plays an important role. Along with Goje and Mishra’s kinetic mode! for the methanolysis depolymerization, particle size andPET Reeyeling: SBIG Proposal and 7 Opportunity Assessment product yield were compared, where a particle size less than 127.5 micrometers provided acceptable yields." Since particle size plays an important, role, additional unit operations are alps precediag | the CSTR to form PET powder SAH AES itical limit. Based on a patent for ‘continuous depolymerization, PET flakes will be melted down and extruded into a thin band. Subsequent cooling will be required following extrusion to solidify PET.'* Following cooling, PET will enter into a mechanical grinder, reducing its size to 2 micrometers, well below the critical limit proposed by Goje and Mishra.'’ This provides the appropriate PET size such that mass transfer limitations do not occur. Immediately following the reaction resides a hydroclone. The purpose of this unit is to separate solid particles from a liquid phase through a vortex.'” Since the depolymerization will not go to completion, some residual PET particulates will be recycled to the reactor. Following the hydroclone, multiple separation operations are required. Various separation and unit operation texts, such as Harriot et al, and Seader and Henley, were examined to define the most appropriate separation processes.'*!7 Due to the crystalline nature of the DMT. product, the remainder of the separation scheme is largely focused on providing high purity crystalline structures. Multiple patents confirmed crystallization as a viable method to separate DMT from the reactor effluent.'*'? The crystallizer is chosen since DMT in the reactor effluent (130°C) is completely soluble in the methanol-EG mixture but becomes completely insoluble at 12°C.'8 Following crystallization and subsequent filtration, DMT cake will enter a solid/liquid extractor cascade (leaching) as it is washed with methanol 2-4 times, removing much of the ethylene glycol, Following this cascade, residual methanol will he remaved from DMT hy using, an evaporator as the last unit operation, as recommended by Harriot et al.!” All methanol and ethylene glycol removed from the DMT purification stream will be transferred into a distillation column to separate and purify methanol and ethylene glycol. Methanol should be obtained at a high enough purity to recycle back into the methanolysis reactor and the solid-liquid extraction cascade. Ethylene glycol and DMT will be in acceptable condition for the commodity chemical market,‘worezuawixjodsp Jd Jo Wondvad sts > 2c ee erardiod % = & a or -sen- iz et ven 9-2-0 91 -a04-62 91-aeJ-2z 91-494-64 91 -094-30 91-9240 ot-uer- 52 oy saoy- 9 -6¥-40 ‘eyeidwog shea |e (sheq) uoneang r r r 1" juouissassy Awunsoddo pue yesodorg Oras “Buyohooy LadZ ueg “ueys nuep wee, SurjaKoey 144 Jo Idi2o%g “gs ams SESEES sssE be SECESEE Buluieway sheglt v2 e-+-vondeoowe oeeern Q 2 = 2 ma ues ore sam Beet eB 2 F FGBvssse oe 2 8 8B Fee BBB RRRRaEE eo 23 8 FRrrresererrr Tee aE ses 3 sees 3338 33 5 BB BS Ba ° 8 aaar ae wg ata . a juauissassy Aynmuoddy pue pesodorg nas ‘Sumpamooy LadQ] GB PET Recycling: SBIG Proposal and B Opportunity Assessment gout References fj»), Ingham, A. (2006). Improving Markets for Waste Plastics. In Improving recycling markets. 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