Thomas D. Gregory at the Michigan State University Bioeconomy Insitute, 9-14-16

BACK TO THE FUTURE: PLASTICS FROM PLANTS AND CARS THAT RUN ON ELECTRICITY

BACK TO THE FUTURE: PLASTICS FROM PLANTS AND CARS THAT RUN ON ELECTRICITYThomas D. GregoryBorealis Technology Solutions LLCMidland, [email protected]/9-16Borealis Technology Solutions LLC1

The Polymer Industry Didnt Start with HydrocarbonsTDG/9-16Borealis Technology Solutions LLC2Nitrocellulose from cellulose and nitric acid considered to be first man-made plastic (1862)Celluloid (nitrocellulose plasticized with camphor) introduced in 1868

Cellulose acetate from cellulose and acetic anhydride first synthesized in 1865, commercially introduced in 1904

Polystyrene first synthesized in 1839 from resin derived from the Turkish Sweetgum tree

Duroplast (thermosetting resin made from phenol obtained from the East German dye industry reinforced with waste cotton or wool fibers) used in body parts for the Trabant starting in mid-1950s

Distant Past180019002000First commercial synthetic polymer was thermosetting phenol formaldehyde (Bakelite; 1907); formaldehyde obtained from oxidation of methanol produced via destructive distillation of wood

Mankind has used cellulose (poly-D-glucose) for millennia

Electric Vehicles Were Common in the Early 20th CenturyTDG/9-16Borealis Technology Solutions LLC3

http://blackdiamondnow.typepad.com/.a/6a00e5513924e688330147e21ae817970b-pi

http://electricandhybridcars.com/images/uploaded/Fritchle-victoria-phaeton-Ad.jpg

Are we headed back there?

And if so, how do we get there?

TDG/9-16Borealis Technology Solutions LLC4

Part I: Assessing the feasibility of making plastics (and chemicals) from plants: Techhnoeconomic analysis of renewable feedstock-based processesThe use of economic parameters to guide successful R&DTDG/9-16Borealis Technology Solutions LLC5

Hydrocarbons Opened Up New Avenues in the 20th CenturyTDG/9-16Borealis Technology Solutions LLC619002000Synthetic polystyrene first commercial production in 1931 (I.G. Farben)

Polyethylene produced in 1939 (ICI)

PET introduced in 1951 (DuPont)

Polypropylene produced in 1957 (Montecatini)

But Hydrocarbon Price Swings are NotoriousSource: http://www.lankerpack.com/correlation-analysis-of-polyethylene-and-its-upstream/price-comparision-of-el-and-pe//

And sustainability of a petroleum-based economy has come into questionTDG/9-16Borealis Technology Solutions LLC7

This Has Fueled a Renaissance of Interest in Plant-Based Raw MaterialsFermentation of carbohydrates to form alcohol and carboxylic acid monomersCorn Lactic Acid Polylactic acid (NatureWorks)

Chemical processing of biomass to form hydrocarbonsBiomass H2 + CO Alkanes Alkenes Polyalkenes (Gasification/Fischer-Tropsch/Dehydrogenation/Polymerization)Biomass Intermediates Aromatics p-Xylene Terephthalic Acid PET (Virents Aqueous Phase Reforming technology)TDG/9-16Borealis Technology Solutions LLC8

But Will it Play in Peoria?Lots of political support for carbohydrate-based products in the Corn BeltBut experience tells us that few customers will usually pay more for green products

So can we make plant-based chemical products at cost-parity with hydrocarbon-based products? And if so, how?

Technoeconomic analysis is a useful tool to answer this questionTDG/9-16Borealis Technology Solutions LLC9

What is Technoeconomic Analysis?Blending of technical and economic evaluation to determine how a product can be made, what the most economically attractive route is to make it, and if this activity provides a competitive advantage.

It all starts with an opportunityDoes the opportunity have commercial merit?Is the opportunity technically feasible?Does the opportunity have the potential to provide an acceptable economic return?What is the optimum path forward?


Elements of Technoeconomic AnalysisEvaluation of market opportunityIs there an existing market for the product or is downstream innovation needed?

Evaluation of competitive environmentWhat are the commercial and financial barriers to market entry?

Evaluation of sustainabilityIs the proposed product and/or process route viable long-term?

Evaluation of cost of manufactureCapital costs to build a production plantRaw material costsConversion costs

Evaluation of profitabilityNPV, DCF, etc.TDG/9-16Borealis Technology Solutions LLC11

Critical Cost Factors for Chemical ProductsCapital cost of production plantWhat is the capacity of the proposed plant?How many process steps are in the proposed process?How many reaction steps?What is the total throughput of the plant vs. the net production?Does the process involve extreme temperatures, pressures, or corrosive environments?Alternatively, what will it cost us to have a contract manufacturer make the product?

Raw material costWhat is the unit ratio of primary feedstock, other reactants, and solvents to product?Carbon efficiency of synthetic routeConversion & yieldDownstream recovery & purification lossesFor organic products, what is the net price of carbon obtained from the primary feedstock?


Production Scale is a Critical Issue


For Organic Products, Cost of Carbon is CriticalMaterialPriceWt% CarbonContained Carbon Price, $/KgMarket Price$/KgCrude Oil$50/bbl0.3784 (avg.)0.44Methane (as NG)$3/MSCF0.1574.80.20Ethane$200/MT0.2079.90.25Ethylene (USGC)$500/MT0.5085.60.58Starch$0.15/lb0.3344.40.74#11 Sugar (world)$0.15/lb0.3342.10.78#16 Sugar (U.S.)$0.30/lb0.6642.11.57


Equivalent Carbon Prices


Location, Location, LocationSource: http://sugarreform.org/wp-content/uploads/2011/07/Wholesale-refined-sugar-prices-US-vs-world-1-10-13.png=3y


Are Bio-Based Routes to Polymers Economically Viable?Example: Polyethylene from sugarDow/Crystalsev JV in Brazil

Fermentation: C6H12O6 2 C2H5OH + 2 CO2Dehydration: C2H5OH C2H4 + H20Polymerization: n C2H4 (C2H4)n

Thermodynamics for monomer production are favorable:Glucose Ethanol Ethylene Go = -99.6 kJ/mole


Carbon Yield Isnt Always a Pretty Picture, HoweverProcess RouteTypical Carbon Yield, %Equivalent Carbon Cost, $/Kg Ethane Ethylene840.30Glucose Ethanol Ethylene471.70

Byproducts of ethane dehydrogenation include valuable H2 & hydrocarbonsByproducts of fermentation route include wastewater and CO2Biomass-based processes typically lose a significant amount of carbon as CO2

Carbon efficiency of bio-based feedstocks is typically better for manufacture of oxygenated products than hydrocarbonsTDG/9-16Borealis Technology Solutions LLC18

Are There Better Opportunities for Bio-Based Products?Example: Avantiums process to make polyethylene furanoate (PET replacement)Source: https://www.avantium.com/yxy/yxy-technology/Subject of Avantium/BASF joint venture(https://www.basf.com/en/company/news-and-media/news-releases/2016/03/p-16-153.html)TDG/9-16Borealis Technology Solutions LLC19

19

What are the Relative Costs of PEF and PET?Need to know:What is the target production rate?What would a commercial process look like?What raw materials and how much of them are needed?

From this information, we need to estimate:Capital cost to build the production facilityCost of raw materialsCost to operate the facility, including labor, utilities, waste disposal, maintenance, overhead, taxes, and insurance

Sources of process informationAvantium web siteAvantium patents & published patent applicationsPublications on FDCA & PEF synthesisTDG/9-16Borealis Technology Solutions LLC20

Analysis StrategyPolymerization costs likely similar to PET processKey comparison is cost of manufacture of FDCA vs. terephthalic acidUtilize available information to estimate FDCA cost of manufactureBasis for Analysis:350 kta FDCA + esters capacityFructose is the primary feedstock70% molar yield of MMF/HMF from fructose assumed85% molar yield of FDCA + esters from MMF/HMF assumed (60% overall yield from fructose)95% recycle of solvents and catalysts assumedMethyl levulinate & furfural byproducts credited at $1.00/Kg each


Avantium FDCA Process Block Flow DiagramHMF/MMF Synthesis, Reference US 2013/0324708 A1


Avantium FDCA Process Block Flow DiagramFDCA from MMF/HMF, Reference US 8,865,921 B2 & related

TDG/9-16Borealis Technology Solutions LLC23MMF/HMFHOAcWaterBatch ReactorAirNaBrCo(OAc)2Mn(OAc)2Catalyst PrepSeparationSeparationSeparationMeOHAq. HOAc/catalystFDCA/estersPurificationAir/CO2

How do we Estimate the Capital Cost of a Conceptual Plant?Complexity factor (step counting) methodsCorrelation between number of major operating steps, plant capacity, and operating conditions and capital cost

Factored cost estimatesSpecify major equipment (type, size, material of construction) and multiply cost by factors representing installation, construction, engineering, etc.Capital cost is typically ~6X purchased cost of major equipment

Process simulation-based capital cost estimatesExample: Aspen process simulation and cost estimation softwareTDG/9-16Borealis Technology Solutions LLC24

FDCA Process Capital Cost EstimationWhat do you do when you have little information to go on?Example methodology: Complexity factor cost estimation method of Bridgewater as modified by G.J. Petley G. J. Petley, A method for Estimating the Capital Cost of Chemical Process Plants Fuzzy Matching, Ph.D. thesis, Loughborough University, U.K., 1997.

ISBL Capital Cost (2016 $US) = 5010 * N * (Q/s)0.586

Where N = number of major process steps Q = production capacity, MTA s = wt. ratio of reactor product:total feedFactors used:Number of major process steps: 5 for MMF/HMF synthesis, 6 for MMF/HMF conversion to FDCA/estersProduction rate, throughput & yields as per analysis bases

Results:Total ISBL capital = $305MM ($0.87/Kg FDCA+esters/yr)Total fixed capital = $460MMTDG/9-16Borealis Technology Solutions LLC25

Raw Material CostsRaw material requirements are estimated based on Avantium patent literature

ComponentMoles/mole Fructose feedKg/Kg FDCA+estersPrice, $/KgTotal Cost, $/Kg FDCA+estersFructose1.01.921.001.92Methanol1.40.60.380.23H2SO4Neg.0Furfural0.030.031.00(0.03)Methyl levulinate0.10.151.00(0.15)HOAc0.30.20.550.11Catalyst0.0051$11.39/mole0.034Total Raw Material Cost2.11


Operating CostsLabor4 operators/shift + 2 for MMF/HMF @ $75,000 each6 operators/shift + 3 for FDCA/esters @ $75,000 each4 salary total for both operations @ $120,000 eachNet yearly cost = $3.9MM = $0.01/Kg FDCA+esters

Utilities & waste treatmentEstimated as 4% of unit direct fixed capital (ISBL capital)$0.035/Kg FDCA+esters

Total operating costs = $0.045/Kg


Other Fixed CostsTypically estimated as percentages of direct fixed capital for early stage cost estimates:Cost Element% Unit direct fixed capital$/Kg FDCA+estersOverhead40.035Maintenance60.052Taxes & insurance20.017Depreciation10% ISBL + 5% OSBL0.109Total fixed costs0.21


FDCA Cost of Manufacture SummaryNote that these numbers have wide error bars

Cost Item$/Kg FDCA+estersRaw materials2.11Operating costs0.05Fixed costs0.21Total cost of manufacture2.37

TDG/9-16Borealis Technology Solutions LLC29Compare to long-term price of purified terephthalic acid of

Thomas D. Gregory at the Michigan State University Bioeconomy Insitute, 9-14-16

Engineering

Transcript of Thomas D. Gregory at the Michigan State University Bioeconomy Insitute, 9-14-16