Overall Material Balance for Development of Biodiesel Manufacturing Facility Authors: Abdullah Alzeer, Mary Forde, Kevin Mann, David Matei, and Alexander Otts Comm ho y eZ) Submission Date: Daign Yeo September 11, 2015 Fol 29/20 tals esp ChE 4410— 001: Fall 2015 6P/5D eo. ) Pod No. 9 Yao my naysAtzeer, Forde, Mann, Mate, and Ots Biodiese! Overall Materiat Balance Sept. 11,2015 Pg. 2 1. Executive Summary Biodiesel continues to be a progressing fuel market over the past several decades and is recognized as a viable alternative to petroleum-based diesel fuel. Compared to standard diesel, biodiesel’s environmental impact is significantly less, since the source is from plant or animal oils and not fossil fuel. This report’s purpose is to perform an overall material balance for a commercial biodiesel facility. A reaction schema is developed for an alkaline-catalyzed transesterification reaction, while international biodiese! standards and commercial biodiesel data are presented to complete the balance. A simulation is designed based on one hundred moles per hour triglyceride (TG) feed rate, while a three-to-one molar ratio of methanol-to-triglyceride is used. This ratio is chosen due to the simulation running under steady-state conditions, where a methanol recycle stream, residing internal to the process boundaries, will recycle separated methanol into the reactor. Satisfying the material balance requires water feed greater than one hhundred and twenty five moles per hour (using a one hundred moles per hour TG feed basis). More water is known to be required, but a more accurate amount will not be known until separation units are designed.Atzeer, Forde, Mann, Matei, and Ot Biodiesel Overall Material Balance Sept. 11,2015 Pg.3 2. Introduction Fossil fuels are currently the world’s primary source of energy. However, fossil fuels ate a finite resource, demanding the development of alternative energy sources. Biodiesel production continues to be a growing field for both commercial and personal production. While many commercial processes exist, the most typical is an alkaline-catalyzed transesterification reaction, using methanol to produce the fatty acid methyl ester (FAME), c.g., biodiesel. The feedstock chosen for this material balance is soybean oil, due to its ease of production and low cost (Ash, 2012), Methanol and sodium hydroxide are used “because the transesterification reaction is generally faster, less expensive, and more complete with these materials than with acid catalysts” (Moser, 2009, Pg. 234). ‘An overall material balance is the first step in the design and analysis of a commercial-scale biodiesel facility. Thus, this report only details a process overview, creating the pathway to formulate a more detailed process design in coming months. 3. Project Scope in the current work is mass conservation princ us as a balance using nice data, 1 nd. valuab i by. in e balance using 4, Description of Work 4.1 Design Basis Several methods for producing iced, including! acid!'and /alkaline-catalyzed s and ‘methanol, and sodium hydroxide catalyst. Transesterification consisting a eet ad cna 0 ° ea‘Alzeer, Forde, Mann, Matei, and Ou Biodiesel Overall Material Balance Sept. 11,2015 Pg 4 in Section 4.4. shown in Figure 1. ‘These three reactions do not model the precise reactions occurring, but rather are used to represent the stoichiometry between reactants and products, along with providing relationships between each species reaction rates. ee mene tigre t Riis! ection schemata and sodium bydronde etal transesterification of soybean oil using methanol Creating a basic representation for the process is necessary to aid defining variables. Figure 2 represents the overall schematic outlining the biodiesel facility. VW product streams.Alzeer, Forde, Mann, Matei, and Ot Biodiese! Overall Material Balance Sept 11,2015 Pes 4.2 Degrees of Freedom Analysis ‘A complete and thorough (d&grees OF freedomil(DF) ff ng Knowing all variables required is the first task and is by the Generalized) uation (4.2.1), GDF=M+M*N+2+N 421) Equation (4.2.2), GDP=747842+8-73 (4.2.2) The total rum uations i deteed by ella th Geral Contntt (GC) wing Equation (4.2.3), wi a |, and n(P-I) represent the number of stream constraints, balances, reaction rate relationships, and equilibrium relationships crossing process boundaries, respectively. Equations (4.2.3) and (4.2.4) complete the GC. GC=M+N +n" ~1) +rank(CCM) (4.2.3) GC=74+8+0%2-1)+5=20 |/ (424) ‘nally, the number of variables specified is determined from the Partieularand Specific Constraints (PSC) shown by Equations (4.2.5) and (4.2.6). PSC = GDF ~ GC 425) 4 PSC = 73-20-53 (42.6) ‘Therefore, the PSC states fifty-three variables (out of the total seventy-three variables) must be defined to uniquely solve the problem and resolve the degrees of freedom to zero. Equation (4.2.7) represents the fundamental degrees of freedom equation, which must equal zero for a completely defined balance. Equation (4.2.8) follows, confirming that the degrees of freedom analysis is satisfied.Alzeer, Forde, Mann, Mate, and Ot Biodiesel Overall Material Balance Sept 11,2015 Pg 6 DF = GDF ~ GC ~PSC 42.7) PSC =73-20-53=0 (4.2.8) Section 4,3 completes the discussion of particular and specific constraints by stating design specifications and the fifty-three specified variables, Reasons are also provided for each assigned value 4.3 Design Specifications ‘As discussed in Section 4.2, fifty-three variables must be specified to solve this material balance uniquely. Variables making up the PSC include flows (F), compositions (C), reaction rates (Nr), temperature (T), pressure (P), and possibly additional constraints (OC). Section 4.3, below, discusses each specification and provides reasons for the particular values chosen, Two specifications include temperature essure, led for the 5 i the Section se two variables must be considered specified for the degrees of freedom formalism to comply. A basis of one hundred moles per hour is chosen for the triglyceride feed (TG). However, neither methanol nor catalyst feeds are specified. Rather, constraints are assigned to compute these two flow rates, Catalyst flow rate is defined as 1.5w1% of methanol stream; constraining the catalyst feed to 1.5wi% stems from Leung and Leung’s work, where this quantity is recommended as the optimum catalyst amount (2010). Equation (4.3.1) depicts the constraint | used in the simulation, where molecular weights are required to convert molar flows into mass flows (since the material balance uses molar flows). 15 FE MW yeon®2neonFs = MW aon nconF G34) Many articles sug While the facility under design wil satisfy this ‘gusratnenarssipfeetpatn aT ETD chosen, This decision is based, primarily, because the model represents a steady-state process, not a dynamic start-up event, Rather, a 3:1 ratio is chosen, since a constant feed at 6:1 ratio of ‘methanol-to-oil would require 50mol% methanol, or more, to leave as waste. Methanol is not intended to leave via product streams intentionally. Instead, methanol should be separated and recycled back into the reaction, allowing only minor quantities to pass through product streams due to imperfect separation. However, the overall material balance does not examine any recycle stream because it will always reside internal to the process boundaries. In summation, methanol is sent into the product stream in a 3:1 molar ratio, while an extra Smol% is added due to minor quantities leaving in product streams; Equation (4.3.2) states this constraint explicitly. osAtveer, Forde, Mann, Matei, and Ot Biodiesel Overall Material Balance Sept.11,2015Pg.7 3.05 x1tG F) = x2Meou Fo (43.2) While a start-up will require more methanol than defined by the ratio from Equation (4.3.2), this report is not concerned with developing a control strategy for the dynamic conditions at start-up. Equation (4.3.2) is expected to provide acceptable alcohol feeding the overall process. ‘All four feed streams are considered pure, so all but one composition in each stream may be defined. Based on the degrees of freedom formalism, seven out of eight compositions in all four feed streams are specified; this is required because defining all eight variables in a single stream makes that specific stream constraint erroneous. Thus, twenty-eight variables from the feed stream composition are specified, [Component FAME NaOH ilycerol DG MG 0.125% MeOH 0.100%. Compositions in Table 1 are converted into mole fractions via a mole-to-mass fraction conversion before being used in the program. Both glycerol and wastewater streams are assumed to have no ester or oil (TG, DG, and MG). For the glycerol stream, sodium hydroxide and methanol are also defined as zero, since these components are expected to exit through the wastewater stream (excluding minute quantities leaving with the biodiesel). Glycerol and water compositions are defined as 85wi% glycerol and 15wt% water in the glycerol stream. This was chosen based on glycerol data found from Gerpen, stating most biodiesel facilities only purify the glycerol stream up to 80-90%, even though glycerol is ultimately refined to 99.5+% for most practical purposes (2007). Mothes et al. confirmed most biodiesel producers refine glycerol to approximately 85% glycerol and 10%Alzeer, Forde, Mann, Mate, and Orts Biodiesel Overall Material Balance Sept. 11,2015 Pe. water, with salts making up the final 5%, For this balance, the separation scheme has yet to be decided, but the overall balance specifies 15% water composition with 85% glycerol. Thus, seven out of eight compositions are also specified in the glycerol stream. The wastewater stream specifies glycerol’s composition as nil, along with ester and oil, stated previously. Therefore, the simulation solves for water, catalyst, and methanol composition exiting this stream. ‘The water feed is the last variable specified to resolve the degrees of freedom. Since water is used in the separation stage for washing, the exact amount required is unknown. The only requirement for this balance is a water feed large enough to satisfy constraints enforced by water exiting both the biodiesel and glycerol streams. Above this quantity, the material balance converges appropriately. Variables defined under PSC are summarized in Table 2 and tabulated via Equations (4.3.3) and 43.4) Table 2: Variables specified in the Particular and Specific Constraints. Specified Variables ( Temperature (T) a Pressure (P) Q) ‘Two feed flow rates (F) (28) ‘Twenty-eight feed compositions. Seven compositions in four feed streams. (C) oO Seven (out of eight) compositions in biodiesel stream (C) a Seven (out of eight) compositions in glycerol stream (C) 6) Five (out of eight) compositions in wastewater stream (C) Q) Two additional constraints to determine feed rates of methanol and catalyst (OC)_ al PSC P+F+C+0C (43.3) PSC=(1) #(1)+@)+08474745)+2=53 (43.4) ‘The PSC required by the degrees of freedom analysis in Equation (4.2.6) complies with the PSC defined above. Therefore, the problem is completely specified.‘Alzeer, Forde, Mann, Matei, and Ots Biodiesel Overall Material Balance Sept 11,2015 Pg. 9 44° Computer Simulation ‘A model prepared via MathCad simulates this material balance and is found in Appendix A. The program’s layout follows: 1. Reaction schemata to develop independent set of reaction rate relationships Reaction schema defining the chemical reactions occurring Degrees of freedom analysis Specified variables List of unknown variables Solve block with all equations Material balance solution, with molar and mass units Annotations are included in the program file, while the report above describes why certain decisions were made in full detail. 4.5 Material Balance The resolved balance usin; i ulated in the following material balance tables. Té molar flowrates, respectively, while Tables amy gjemmeeeensan/ipesiomsmene enaey Durie ‘Table 3: Material Balance for overall Biodiesel Manufacturing Facility (Mole Fractions) ‘Mole Fractions Stream No. Common No.| Components | Name _| Units 1 203 4 5 6 7 1 #20 Water (mol/mol)| 0 0 01,000 0.096 0.474 0.936 2 NaOH NaOH (mol/mol)| 0 0 1,000 00.013 0.000 0.008 3. CsHs(OH); Glycerol (moVmol)] 0 0 0 0 0.003 0.526 0 4 CHOOCR FAME (mol/mol)} 0 0 0 0 0878 0 0 5 CsHsOOCR) TG (molmol)}1000 0 0 OAO 0 6 6 CsH(OH)OCR» DG’ (molimol)| O 0 0 0 wo 0 0” 7 CsHs(OHAOCR) MG, — (mol/mol) | 0 0 0 003) o 0 8 CHhOH MeOH (mol/mol) | 0 00.006 0 0.056 Totals (mol/mol) | 1.000 1.000 1,000 1.000 1.000 1.000 1.000 Process Conditions T NIA °c P NIA atm H NIA korAleer, Forde, Mann, Mate, nd rts Boles! Overall Matra Ralance Sept 1.2015 Pe 10 Table 4: Material Balance for overall Biodiesel Manufacturing Facility (Molar Flow Rates) Molar Flow Rates ‘Stream No, No. | Components |COM™MOM | Units | 1 2 3 4 5 6 7 Name 1 0 Water mols | 0 0 0 200.000 32.530 87.899 79.571 2 NaOH NaOH — molhr | 0 0 5033043370695 3 C3Hs(OH)3 Glycerol mol/hr 0 0 0 0 1.179 97.454 0 4 CHROOCR FAME mol | 0 0 0 0298.84 =o 0 5 GHOOCR) TG —— molhr} 100.000 0 0 0 009 0 0 6 — GsHSOHYOCR»» DG mol/hr| 0 0 0 0 0.149 0 0 7 CsHs(OH){OCR) MG mor | 0 o 0 0 119 0 0 8 CHLOH MeOH mol} 0 305.000 0 = 0.972.744 Totals mol/hr | 100.000 305.000 5.033 200.000 339.669 185.353 85.010 Process Conditions T NIA °c P N/A atm H NA ___ki/hr Table 5: Material Balance for overall Biodiesel Manufacturing Facility (Mass Fractions) Mass Fractions Stream No. No. Components common units} 1 92-3 4S 6 1 0 Water (mim){ 0 0 0 1,000 0,007 0.150 0.858 2 NaOH NaOH (m/m) 0 0 1.000 0 0.002 0 0.017 3. CsH(OH)s Glycerol (mm)} 0 0 0 0 0.001 0.850 0 4 CHOOCR FAME (mim)] 0 0 0 0 098 0 0 5 CsHs(OOCR)s TG (m/m) | 1.000 0 Oo 0 0.001 0 0 6 CsHs(OHOCR =: DG (mm} 0 0 60 0 oor 0 0 7 ~~ CsHs(OH)(OCR) MG (m/m) 0 0 0 0 0.001 0 0 8 CHOH MeOH (mim)| 0 1,000 0 0 0.001 0 0.125 Totals (am) } 1.000 1.000 1.000 1.000 0.997 1.000. 1.000 Process Conditions T NA * P N/A atm H N/A kJ/hrTable 6: Material Balance for overall Biodiesel Manufacturing Facility (Ma Aleeer, Forde, Mann, Mate, and Otts Biodiesel Overall Material Balance Sept. 11,2015 Pg 1 Flow Rates) Mass Flow Rates Stream No. No. Components —— Units} 1 2 3 4 5 6 7 1 20 Water kerf 0 0 03.600 0.586 (1582 1432 2 NaOH NaOH Ach 0 0 0.201 0 0.174 0 0.028 3. CsHs(OH)s Glycerol kh} 0 0 0 0 0,108 8965 0 4 CHj;00CR FAME Aefhr 0 0 0 0 85.011 0 0 5 CsHs(OOCR)s 1G ahr [87240 0 =«000.087 6 CyH(OH)OCR): DG kvhr} 0 0 0 0 0087 0 0 7 C3Hs(OH)2(OCR) MG Ac/hr 0 0 0 0 0.347 0 0 8 CHOW MeOH khr |} 9 13420 000.087 -0—0.209 Totals thr | 87.240 13.420 0.201 3.600 86.486 10.548 1.669 Process Conditions T NIA °c P NIA atm H N/A kJ/br 5. Discussion of Work Defining the material balance with a one hundred mole per hour basis enables scaling much easier. Limits of operation are also explained fairly simply, as well. The only major limit noted is the water feed, where a minimum value of one hundred and twenty five mole per hour is required for the material balance to resolve appropriately. As long as this quantity is present, physically realistic results are plausible, where all mathematical signs on flow rates and compositions are correct. A more precise definition of water quantity will be determined after separation units are designed. 6. Conclusion Biodiesel production has become a topic of interest as of late due to its many advantages and growing desire to eliminate fossil fuel dependency. An alkaline-catalyzed transesterification reaction using methanol and sodium hydroxide to esterify soybean oil triglycerides has been examined, Using a one hundred mole per hour basis for triglyceride, a biodiesel stream at 98wt% purity was accomplished using a 3.05:1 molar ratio of methanol to oil. While this an inadequate amount of alcohol to react with oil alone, steady state conditions should have a recycle stream to supply the reactor with additional methanol, increasing the alcohol amount entering the reactor vessel. A water stream of one hundred and twenty five moles per hour is the lowest quantity capable of satisfying the material balance. However, more water is expected after designing sAlzeer, Forde, Mann, Mati, and Ou Biodiesel Overall Material Balance Sept. 11,2015 Pg 12 7. References Ash, M. (2012, October 10). Soybeans & Oil Crops. Retrieved September 10, 2015. Chang, Ai-Fu, & Lui, Y. (2010). Integrated Process Modeling and Product Design of Biodiesel Manufacturing, American Chemical Society, 49, 1197-1213. Freedman, B., Butterfield, R. & Pryde, Oil. JAOCS, 63, 1375-1380. E. (1986). Transesterification Kinetics of Soybean, Gerpen, J. V. (2007). Improvement of Crop Plants for Industrial End Uses: Biodiesel Production. Dordrecht, The Netherlands: Springer. 281-290. Leung, Dennis ¥.C, & Leung, M. (2010). A Review on Biodiesel Production Using Catalyzed Transesterification. Applied Energy, 87, 1083-1095. Moser, B.R. (2009). Biodiesel Production, Properties, and Feedstocks. In Vitro Cellular & Developmental Biology. Plant, 45 (3), 229-266. Mothes, G., Schnorpfeil, C., Ackermann, J. U. (2007). Production of PHB from Crude Glycerol. Engineering Life Sciences, 7, 475-479.Alzeer, Forde, Mann, Matei, and Otts 8. Variables List Variables Streams rh Fy Bs Fe Ps Ps Py Species Composition xii Species Acronym TG DG MG FAME Gly H20 NaOH MeOH Degrees of Freedom GDF Gc psc M N n P Others R Biodiese] Overall Material Balance Sept 11,2018 Pg. 13 Description Triglyceride Feed Methanol Feed Catalyst (NaOH) Feed Water wash Feed Biodiesel Product Glycerol Byproduet Wastewater Product Species jin stream j Triglyceride Diglyceride Monoglyceride Fatty Acid Methyl Ester Glycerol Water Sodium Hydroxide Catalyst Methanol Generalized Degrees of Freedom General Constraints Particular and Specific Constraints No. of streams ‘No. of species No. of species in equilibrium No. of phases Reaction rate of species iAlzeer, Forde, Mann, Matei, and Otts Biodiesel Overall Material Balance Appendix A: Overall Material Balance for Biodiesel Production 1). Chemical Composition Matrix: Generate chemical composition matrix (CCM) for biodiesel production, consisting of 8 species. Species order is defined via the reaction rate vector (RR), Order of chemical fragments are listed, as well N= 8 Species ‘Species Order: H20 NaOH GLY FAME TG DG MG MeOH Rizo Ran 0100000 Rg 7 0030012 Gly ccm 00013210 REAME, ocr “looo10001 Rig Meo oo10rii0 Rog 10000000 C3H503 Ru R H20 ‘MeOH,Alzeer, Forde, Mann, Matel, and Otts Biodiesel Overall Material Balance 2). Number of Independent Reaction Rate Relationships Determine number of independent reaction rate relationships by taking the CCM's rank. This is further confirmed by taking the row reduced echelon (rref) of the CCM. renk(CCM) -» § independent nxn rate relationships. rref(CCM) -> Sum sulcs oul ounece eule- vires Both the rank of the CCM and rref(CCM) show only 5 rows being linearly independent. Therefore, there will be only five Independent reaction rate relationships defining the biodiesel reaction, 3). Determination of Reaction Rate Relationships: Determine the reaction rate relationships by multiplying the reaction rates (RR) by the row-reduced CCM. Each row will be set equal to zero, defining the appropriate relationships. The reaction rates are written out explicitly in the material balance, 2RMiG Reon +Rgy+— sref(CCM).RR > Rpame + ®McoH‘Aizeer, Forde, Mann, Matei, and Otts Biodiesel Overall Material Balance 4). Determination of Reaction Schemata (Chemical Reactions): Reaction rates are calculated by the following steps: A, Determine number of independent chemical reactions by "N-rank(CCM)’. Ind_Rxn ;= N ~ rank(CCM) > 3. independent chemical reactions B. Calculate the identity (I) based on the number of independent reactions, 100 L:= identity(Ind_Rxn) >| 0 1 0 oon . Extract pivot species from row-reduced CCM. Coef := submatrix(rtef(CCM),0,4,5,7) > Gis e ln D. Transpose matrix containing the pivot species, E. Combine transposed pivot species and the negative identity. m0 Nort ooto2 +10 0 3°35 Gy AugM CoefT, coro o 410 N FAME: eM i= augment(Coett,-1)-»}0 0 2 0 + =| re 14 ootitoo wis 313 MG MeOH,‘Alzeor, Forde, Mann, Matei, and Otts Biodiesel Overall Material Balance F. Multiply the result from step E to the chemical identities, using same order as the reaction rates (RR), By 4g, 218 3 3 2.Gh Te AugMNames 9} = MiG + TG Fame + 2 — eon - 72 3 3 Independent Chemical Reactions: 1). TG + 3MeOH <—> 3FAME +Gly 2), 3DG <—> Gly + 2TG 3). 3MG <> 2Gly + TG‘Alzeer, Forde, Mann, Matel, and Otts Biodiese! Overall Material Balance 5 Degrees of Freedom Analysi N= 8 species M:=7 streams P (0 species in equilibrium (crossing the process boundary) phases GDF:= M+MN+24+N— 73. variables GC= M+N+n-(P~1) + rank(CCM) > 20 equations PSC = GDF - GC 53 variables to specify ‘There are 53 variables that must be specified. The specified variables follow: © @) Temperature and Pressure (these variables are not required for this balance but must be stated due to Degrees of Freedom Analysis (2) One feed flow rate for water and one feed flow for triglycerides. (28) Seven out of the eight compositions in the feed streams, making up 28 compositions for the feed. (19) Nineteen outlet compositions: ‘Seven compositions of the biodiesel stream Seven compositions of the glycerol stream Five compositions in the waste water stream + 2) Thee constraints are used to determine flow rates. These are based on expected annual biodiese! production and stoichiometric amounts. NOTE: If reaction rates for H20 and NaOH are specified as zero, MathCad cannot find a symbolic solution. However, if these variables are included into the solve block, a symbolic solution results. Physical Properties: Data used for mass-to-mole fraction and volumetric-to-molar flow rate conversions. Density (p) of FAME for biodiese! fuel defined by EN 14214 (Range: 0.86 - 0.88 g/cc) (Chang and Lui, 2010) PrAME = 088 om Average molecular weight (MW) (Freedman et al. 1986) wiiggz era meow Ming se Woy vig: st E Mvp 6 pe 285 von «0BAtzeer, Forde, Mann, Matei, and Otts Biodiesel Overall Material 8 Specified Variables Flow Rates: Feed Stream Compositions: r= 100 tygo*® —ypo=® —xdygom algo 1 m ‘mot XINgon= © naon = 011 ‘ XlpaMe=9 fame 0 Spame'= 0 *4rame= Mpg] GRO WyGED — xhygin XIpg=0 xpg=0 xlyg= 0 yc xlMeoH = © 1 8yeoH= 9 “MeoH = ° Outlet Stream Compositions: Waste Water Stream (7): Assume no biodiesel (FAME), oil derivitives, or glycerol pass through the waste water stream. x77g'= 0 XTPAME XIpg = 0 xe = 0 xIMG i= 0 Biodiesel Stream (5): Biodiesel composition specifications are taken from ASTM D8751 and EN 14214 standards (Leung and Leung, 2010}. Specifications are in weight percent (w). Conversions to mole fractions follow in the below equations. WSpAME = 0.98 W5yja0H = 0.002 57g = 0.001 W5cqy= 0000125 W5y199 = 0.00675 WS pg = 0.001 004 W5yfeon = 0.001 WMG‘Alzeer, Forde, Mann, Matel, and Otts Biodiesel Overall Material Balance 7 WSNaOH MW, ‘NaOH xSNa0H = > 12.7692 x 10 Sino | “SwoH | “aly | ™SrAME | “Sta | “Spa, WSMG | _WSMcon + + + MWino MWxon MWoiy MWpame MWrg MWpg MW_Gg MWMeon WSPAME MW, 5 *SEAME —— > 878.1611 x 107 Sino, "Swan | Waly | Same | “Sra | “SG | WSMG | _WSMcOH + + MWipo MWxaor MWe MWrame MWrg MWpg MWéco MWeon xSrg= + 292.7368 x 10 Smo, “Swan, "Saty : ps, SMG | _YSMeoH MWigo MWyaon MWoy MWrame MWrg MWpg MWg MWmeon “S00 MW, ue Spa > 438.8034 x 10 wSiwo | "Syxon | “Soly | “SraMe “5rG | ™SDG | SMG | _YSMeOH. MWi0 MWNaoH May MWrame MWrg MWpg MWvg MWMeoH wma MWg 3 Swag + 32953 x 10 Sino, “Swan “Say | WSrame “Sta | Spa | SMG | YSMeoH MWi0 MWxaon MWoiy MWrame MWg MWpg MWvg MWMeon *SaeoH4 MW, - *SMeoH = ‘MeOH 5.8042 x 10 Sino , “Sao, “Soy , Wrame | “Sra | “Spa, WG | “SMcoH MWpg MWyc MWMeoH 3 MWipo MWxaon MWe MWrame = MWrg Wary MWGiy Soy = > 3.4699 10) wo | "Sao | “Scly | ™SraME , “Sto | “Spa | SMG | _WSMcOHL + + + MWipo MWeon MWoiy MWeame MWrg MWpg MWg MWMeoHAlzeer, Forde, Mann, Matei, and Otts Biodiesel Overall Material Balance Glycerol Stream (6): Glycerol stream composition specifications were determined by crude glycerol compositions taken from various manufactures, where an average weight (wt) of 85 (wt.%) and ~10 (vat.%) constitutes the crude glycerol. For this uninformed material balance, the stream is specified to contain 85 (wt. %) glycerol and 15 (wt.%) water (Mothes et al. 2007). Specifications are in weight percent (w). Conversions to mole fractions follow in the below equations, 6 Gy = 085 “6xaoH = 0 6PAME w6pg= 0 W6y99 = 0.15 w6neoH = 9 w6rg'= 0 w6yqi= 0 S120 MW; x6y20 = me. = 474.2268 x 109 weno | “aon aly , “rame “ra | “oa, SMG | “Meo MW¥ino MWxaon MWay MWrame MWg MWpg MW_G MWMeon ary MWe ory ot > 525.7732 10" woo, Wxaon , “aly | WSrAME | WOTG | WSDG , W6MG ,_WSMcOH MWino MWxaon May MWrame MWrqg MWpg MWyg MWMcoH WOPAME MWeAME *SPAME =s = 3 70 wé0 | “Oo | “ay | “SraME | “Sra | “SoG | YMG | ME Meort MWino MWyaon MWoly MWpame MWrg MWpg MWva MWmeor 0 w5in0 | Enon | "6ciy “SAME , “Ora | WSDG | WMG | _NSMeOHr MWino MWyaon MWaly MWpame MWrg MWpg MWya MWMcoH pe MW, x6" 78. +0 520 | 6NAOH | MScly | “SraME | WOTG | ™SDG | YEmG | _Y’MeOH MWin0 MWyaoH MWoy MWrame MWrg MWpg MWag MWMecoH omc MWg MG x66 0 6x20 | WSNaOH | wooly + WOPAME, + “ora | “SoG | WMG | _WEMcOH MWino MWnaon = MWaly MWrame MWrg MWpg MWvc MWMeoH‘Alzeer, Forde, Mann, Matei, and Otts Biodiesel Overall Material Balance WOMeOH MWeon 0 *MeOH = WO; WO, w6 w6y wo: w6y wy WO) > io, uo, oy, rae, vere, Moo, ns , MOH MWip0 MWxaoH =MWGly MWeame MWrg MWpg MWaG MWMeou Unknown/Guess Variables Flow Rate Reaction Rats Feod Stam Compoetons: wl wl vat Ripo= 0 a Xlgiy = 0 2Giy= 0 Gly 0 xGIy= 0 tes Moyo a on i ngs oh = 5 hr hr od ox net ml 6 hr hr 7 br hr ol mons 0 : so = Outlet Stream Composition: xSyp9 = 0.1 X6ys0H = 9 X7ypO:= OS X7Meon = 05Alzeer, Forde, Mann, Matei, and Otts Biodiesel Overall Material Balance 10 Initiate the Given - Find Solve Block Balances N=8 S20 * P6*6t0 + P7*7u20) + R20 = 1x10 + Fy2y90 + F328 H20 + Fax ~ *1Na0H * F2%2na0H + F3 NaH * F4*4naoH ~ (P5'*SNaoH + P6%6NaoH * P7*7Naon) * Bnaon *° lary + Fa ay + Fa Bary + Fastaiy~ (Psa + Po Say + Pr*7ay) + Ray =? Fyxlpame + Fy°2pame + F5*SeaME + Pa4pame ~ (P5*Spame + °6%6raMe + Pr*7rame) * RRAME Fyxlgg + Fyx27g + F336 + Fextyg — (P5x576 + Pox67q + P7x77G) + Rtg xlng + F2pg + F336 + Famtyg. Psx8pq + PoX6pg + PyX7pq) + Rog =O Frtlyig +F22MG + F3MG + Fata ~ (Ps*5ua + PeXx6uc + Prx7uq) + Rug #0 1IMeoH * F2%2Meou + Fs'*8eon * Fa4meor~ (Ps*SMeon * P6*SMeon + P7*7Meon) * RMcon Stream Constraints M= xlwp0 + )ysoH + “Gly + *TRAME t *1T¢* *Ipg + XIMG + XIMeoH =! ino + ®naon + Zaly + PRAME + 27a + po + MG + @MeoH =! S120 + SnaoH + Saly * SEAME +376 + Sp¢ + 3G + 3MeoH = xtizo + “4Naon * “aly + ™paME * “4G + *4pG * 4G * “MeOH *5i20 * *SNaOH + Gly + SEAME * *StG + pG * *MG * MeOH 61120 * *SNaOH * “Gly + *SEAME * *rG + *6pG * X6MG * *MeOH Xho + Tyson + *T7oly + 7rame * *77G + X79 + X7MG + *7Mcort Reaction Rate Relationships rank(CCM) = 5 2Ruic + Rpg + 3-Raly + RMcou = 9 Rupo=° Rpame * RMeou = Rnaon =° 2Rpg + BMG * 3-RtG ~ Reon *°Alzeer, Forde, Mann, Matei, and Otts Biodiesel Overall Material Balance " oc_1 oc_2 Equilibrium Constraints n(P-1) =0 Not applicable Other Constraints ‘The stoichiometric ratio for methanol-to-triglycerides is 3:1. Literature states using an excess of methanol at a 6:1 ratio. Since it is expected that methanol will be separated and recycled in the process, at steady-state the methanol feed stream will not require the 6:1 ratio. Therefore, the below constraint states using a 3:1 ratio, and adds 5% extra methanol for any leaving in the glycerol and biodiesel streams. 3.05x1 76°F} = 2yeou Literature states using an alkaline catalyst between 0.5-2.0 (wt%) compared to the methanol feed stream. However, Leugn et. al. found that a 1.5 (wt%) NaOH catalyst produced optimum conditions (Leung and Leung, 2010) Ls Too MW Meon*@Meou 2 = MWnaor*3NaoH FsAlzeer, Forde, Mann, Matei, and Otts Material Balance Output: Rro R DG Ber Final Rua Ryeou ‘lay Xay Say ayy x50 *6Na0H Tino XTNOH XT MeOH, Compositions: Biodiesel Overall Material Balance 30s 50325 339.6692 1853529 85,0103 0 0 98,6322 298.2883 99.9006 oo Flows; Reaction Rates: 149,048 x 10 . mol oof 1s met Rage 80 298.2843 : ° Bac 1750325 Baou= %> 0 ° ol 5 Bae, 73376602 Rayo, 986822 0 so eee 81053529 Ra age ay sans 95.7688 x 10 3 br ol 0 Bare 2,7 50108 Bt Rygsn #, + 999006 3 9360148 x 10 Boose %p > 149048 x 10 8.1779 x 10 3 - = 8,9 14193 55,8073 x 107 > Amas= 1) ‘Bateous 4p 72982883 3 -3 Muna % yy > 9360148 x 10 Bhaayi= 2139 AS s= 9 yy > 95-7688 x 107 Bay 247° argo 25 70 ahaa" 816° 3 Mawatn: Pay 7 81779 « 10 Meteoun’= ®y, 7 55.8073 « 10 R mol hr mol mol molAlzeer, Forde, Mann, Matel, and Ots Biodiesel Overall Material Balance 13 Mole Fractions: Species Order: This page contains vectors listing each stream's mole fractions. 20 NaOH FAME Ts be MG cy MeOH xo 20 xin0 x4yn0 o 0 0 1 XlNa0H *2Na0H *SNaOH (20H 1 ° Dy ° 3 : 4 ° XIFAME 0 *2F AME. 0 *SFAME. 0 *4FAME 0 xIT¢ I 216 ° Sta ° “ta 0 xls > xz > ae > Ms > xIpg _|7]o 2p5 0 Bpq |” fo xing || o o o ° ° IMG MG SMG IMG ° ° ° ° xlgiy o 2qry 1 Soy 0 x4gly 0 XIMeOH, 2MeOH, 2S MeOH , 4 MeOH, -3 S 95.7688 x 10) se 3 “m0 3 “70 936.0148 x 107? x 12.7692 x 10 474.2268 x 107 x NOH x6 Xn, *SPAME. 878.1611 x 10> Neon 7 Nott 8.1779 « 10"? bin ‘ XOPAME 7 XTRAME ° 5 STG 292.7368 x 10" x6rg, 0 xI9g er) 5 > —6 x6 > xT= > ° DG] | 438.8034% 10 x66 ° X16 0 x ma 3.2953 10> x6MG ° x7MG 0 Fe are) ° Gly 3.4699 x 10"? x6Giy 525.7732. 10 Tay ove ° 7 MeOH) LS cag? X6y4eoH eon) \S88073 10Aizeer, Forde, Mann, Matei, and Otts Molar Flows: ‘This page contains the molar flow rates of each species for all seven streams in a vector. Biodiesel Overall Material Balance Below the seven vectors lies the total molar flow rates for each stream, Fy Byx2> 32.5297 43373 298.2843 99.4337 x 10 5x5 > P6, 149.048 x 107 L193 L786 1ons PS, Molar Flows: Total Flow Rates Flgr'= Solty > 100 Pages Fon 7305 Bar Dy 50325 Pigr= SPA + 200 mol hr mol be mol mol br 87,8993 P)q i= Pyx? > 97.4536 0 PSar = SoPSq > 339.6692 Pogr i= PG 1853529 Prep SoPy > 850103 14 Species Order: H20 NaOH FAME 1S DG 200 MG Gly MeOH 79.5109 695.2028 x 107 0 ° ° ° ° 4.7442 mol mol hr mol heAtzeer, Forde, Mann, Matei, and Otts Biodiesel Overall Material Balance 6 Mass Flows: Species Order: H20 This page contains the mass flow rates of each species for all seven streams in a vector. NaOH Below the seven vectors lies the total mass flow rates for each stream FAME TS ° 0 ° os MG ° 0 2013 oy ° 0 0 MeOH 3 ° 87.24% 10 . ° Figg FM 9] POT | a= } ; ° ° ° 0 ° 0 san 108 ° 0 arn 10 36% 10° 585.5351» 1.5822 10° 5 i919 ° 0 85.011 « 10° 0 ° ° PSn4 := (PS, mw; >| 867459 pg > ° ° 86.7459 ° 346.9838 ° o _ 8.9657 x 10° ° 86.7459, 0 1.4323 x 10" 27.8081 ° P= (mamw)>| —° ° ° Mass Flows: Total Flow Rates 0 38 Flyer = Fly > 87.24% 10° iggy = SPS g > 86.4857 « 10 susan) Maar SP Sbsger= SP B68 1 fer DoF 19425 10° Pogge = SP 10:8079% 10 hr Byers BM 9 2013 Pry_n= SPT > 1.688 We n= Fy 96% 10 E‘Alzeer, Forde, Mann, Matei, and Otts Biodiesel Overall Material Balance Mass Fractions: This page contains the mass fractions of each species for all seven streams in a vector. 0 0 ° 1 o ° _ FM jo 0 Pur | 0 ° ° ° ° ° 1 0 6.7703 x 10 2.006 x 10° 3 982.9488 x 10 5 2M 1.003 x 107 6. 2M 7M Par 1.003% 107 Pour Phar 4012x103 1.2538 « 10 ° 1.003 x 107? 16 H20 NaOH FAME 1S 1 Ds MG o ey 0 MeOH ° o o ° 0 858.2522 10" 16.6632 x 107 0 0 ° o o 125.0845 x 107