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Life-cycle assessment and techno-economic analysis of the utilization of bio-oil components for the production of three chemicals

2018, Green Chemistry

Bio-based chemicals have gained more widespread attention than bio-fuels because of the decline in crude oil prices.

Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2018 1 Electronic Supplementary Information (ESI) 2 Life cycle assessment and techno-economic analysis of the utilization 3 of bio-oil components for the production of three chemicals 4 5 Ji-Lu Zheng a, Ya-Hong Zhu a, Ming-Qiang Zhu a, b*, Guo-Tao Sun b, Run-Cang Sun c 6 7 a Shaanxi 712100, China 8 9 College of Forestry, Northwest A&F University, No. 3 Taicheng Road, Yangling, b Western Scientific Observation and Experiment Station of Development and 10 Utilization of Rural Renewable Energy of Ministry of Agriculture, Northwest A&F 11 University, Yangling 712100, China. 12 13 c Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing, China. 14 15 16 17 18 19 20 *Corresponding authors. Address: Northwest A&F University, 712100, Yangling, 21 China. Tel.: +86-029-87082230; Fax: +86-029-87082216. 22 E-mail address: zmqsx@nwsuaf.edu.cn (M. Q. Zhu). 1 24 Contents 25 1 The procedures of the techno-economic-environmental analysis..............................................3 26 1.1 Methodology for estimation of the total-capital investment..........................................3 27 1.2 Methodology for estimation of the operating cost and direct production cost ..............5 28 1.3 Methodology for estimation of cash flow and IRR .......................................................6 29 1.4 The average delivery distance........................................................................................8 30 2 Investment and production cost .................................................................................................9 31 2.1 The investment...............................................................................................................9 32 2.2 The production cost......................................................................................................10 33 3 Some background data for this LCA study..............................................................................13 34 3.1 LCI data for petrochemical production of phenol - formaldehyde resins (PF)............13 35 3.2 LCI data for petrochemical production of calcium acetate..........................................13 36 3.3 The GWP100a, CED, EI-99 metric for some chemicals and utilities .........................13 2 37 1 The procedures of the techno-economic-environmental analysis 38 1.1 Methodology for estimation of the total-capital investment 39 Table S1 Methodology for total-capital investment for nth plant Item Percent of TDEC Total purchased equipment-delivered (TPEC) Purchased equipment installation 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 cost 100% 39% Instrumentation and controls (installed) 13% Piping (installed) 31% Electrical systems (installed) 10% Buildings (including services) 29% Yard improvements 10% Service facilities (installed) 55% Total installed cost (TIC) 287% Land (if purchase is required) 6% Engineering and supervision 32% Construction expenses 34% Total direct and indirect plant costs (TDIC) 359% Contractor’s fee (CF) 5% of TDIC Contingency (CO) 10% of TDIC Fixed-capital investment (FCI) TDIC+CF+CO Working capital 15% of FCI Total capital investment 475% The total installed equipment cost is part of the total capital investment. The total capital investment for all processes consists of fixed-capital investment for physical equipment and facilities in the plant plus working capital which must be available to pay salaries, keep raw materials and products on hand, and handle other special items requiring a direct cash outlay. This method for estimating the total-capital investment is based on the percentage of delivered-equipment cost. Namely, the determination of the delivered-equipment cost is required firstly. The other items included in the fixedcapital investment are estimated as percentages of the delivered-equipment cost , and the working capital amounts to 15 percent of the fixed-capital investment.1 The items included in the total-capital investment and the corresponding ratio factors based on delivered equipment cost are listed in Table S1. Unit process principles are used to determine the equipment specifications,1, 2 and then the delivered-equipment cost of each piece of the process equipments can be estimated from appropriate manufacturers' bulletins, published cost data, empirical rules1-3 or e-commerce websites (such as Alibaba) as listed in Table S2. 3 56 Table S2 The delivered-equipment cost of each piece of the process equipments Equipments Sub 1 Chopper Biomass Chopping Screen Grinding Hammer Mill Biomass Grinding Screen Belt Press Bale Moving Forklift*4 Concrete Storage Slab Discharge Conveyor Bale Transport Conveyor Bale Unwrapping Conveyor Continuous Spray Rotary Drum Rotary Dryer Biomass Feeding Bin Screw Feeder Pyrolysis Fluid Bed Non-condensible Gas Blower Pyrolysis Vapor Cyclones*2 Bio-oil Condenser*2 Electro-Static Precipitator Condenser Water Pump*3 Ice making machine Condenser Oil Pump Cooling Tower Wash Percolater Solids Combustor Combustor Cyclones Combustion Gas Blower Sub 2 Settling Tank Filter, vacuum rotary drum Vacuum pump Settling Tank Filter, vacuum rotary drum Vacuum pump Mixer Vacuum freeze dryer Mixer Filter, vacuum rotary drum Evaporation crystallizer Settling Tank Specification Deliveredequipment cost 50 kw/ton 60 ton/day 50 kw/ton 60 ton/day 5.5 kw 1.25 ton/h 30 m*29 m*3.5 m 0.75 kw/ton 90 w/ton 5.5 kw 2.2 kw, 2.5 ton/h 2.2 kw Φ1.5*4.3 m 0.75 kw/ton Φ1.2 m*2 m 90 kw 3600 m3 of gas per hour 600 m2 of heat transfer area 30 kw 90 kw 53 /kw, 592 kg of ice per hour 5 kw Φ 8.8m*6.5m 4 m3 Φ0.3 m*0.8 m 3360 m3 of gas per hour 85 kw $44,137 $3,286 $44,137 $3,359 $19,425 $14,021 $87,631 $9,785 $77,845 $29,210 $185,089 $99,519 $6,047 $23,733 $122,099 $31,357 $184,316 $291,722 $42,705 $62,527 $20,000 $6,952 $438,898 $31,459 $35,680 $161,343 $9,084 3 m3 3 kw, 600 kg of filtrate /(m2.h) 10 kw 3 m3 3 kw, 600 kg of filtrate /(m2.h) 10 kw 10 kw, 3m3 130 kw, 1.2 ton water per hour 10 kw, 3 m3 3 kw, 600 kg of filtrate /(m2.h) 1000 kg of acetic ether per 3hour m3 $35,965 $185,089 $28,655 $35,965 $185,089 $28,655 $73,805 $365,261 $73,805 $185,089 $452,879 $35,965 4 Filter, vacuum rotary drum Vacuum pump Sub 3 Mixer*2 Sub 4 Evaporator Mixer Evaporator Mixer*4 Filter, vacuum rotary drum*4 Vacuum pump*4 Evaporator*2 3 kw, 600 kg of filtrate /(m2.h) 10 kw $185,089 $28,655 10 kw, 3 m3 $147,610 600 kg of water per hour 10 kw, 3 m3 600 kg of water per hour 3 kw, 0.8 m3 3 kw, 75 kg of filtrate /(m2.h) 10 kw 50 kg of methanol per hour $349,285 $73,805 $349,285 $104,268 $212,611 $114,620 $190,110 57 1.2 Methodology for estimation of the operating cost and direct production cost 58 Table S3 Variable costs employed in the estimation of the direct production costs 59 (Source: www.alibaba.com and refs). 4-6 Item 60 61 62 63 64 Value Cotton straw $83/metric ton Fertilizer $400/metric ton Transport $0.71/(ton.mile) Sulfuric acid 98 wt.% $300/metric ton Process water $1.0/metric ton Activated carbon $1500/metric ton Calcium hydroxide $110/metric ton Hydrochloric acid 32 wt.% $190/metric ton Ethyl acetate $1200/metric ton Calcium oxide $160/metric ton Methanol $700/metric ton Sodium hydroxide $500/metric ton Phenol $1300/metric ton Formaldehyde 37 wt.% $400/metric ton Cooling water from river $0.15/metric ton Average hourly wage $21/h Electricity $0.061/kwh Steam (6 bar) $20/metric ton Solids disposal cost $22.23/metric ton Waste water disposal cost $1.30/metric ton The operating cost is divided into three classifications as follows: (1) direct production costs, which mainly involve expenditures for raw materials, direct operating labor, supervisory and clerical labor directly connected to the manufacturing operation, utilities, plant maintenance and repairs. Some variable cost parameters, such as the prices of cotton straw, phenol, and utilities, average hourly 5 65 wage and water treatment cost, are listed on the Table S3; (2) fixed charges, 66 essentially include expenses directly associated with depreciation, property taxes, 67 insurance. Some assumptions for the estimation of fixed charges, such as depreciation 68 period, type of depreciation and property tax rate, are listed on the Table S4; (3) 69 70 71 72 73 74 75 76 77 78 79 plant-overhead costs, which are used for medical services, warehouses, safety services, warehouses and so on. The estimation of fixed charges and plant-overhead costs can be based on the method of 'Percentage of total-capital investment'.7 However the estimation of direct production costs is slightly complex. Chemical engineering principles, such as material balance and energy balance, and the methodology proposed by Overcash et.al are used for calculation of the expenditures for raw materials and utilities.8 The method of estimating labor requirements is based on adding up the various principal processing steps on the flow sheet and plant capacity, and the cost for direct supervisory and clerical labor averages about 15 percent of the cost for operating labor.1 The method for estimation of the expenditures for plant maintenance and repairs is the same as that for estimation of fixed charges. Table S4 Assumptions for the estimation of the fixed charges 80 Item Equipment depreciation period Building depreciation period Amortization period Type of depreciation or amortization Property tax rate Insurance rate Value/method 20 years 40 years 5 years Straight-line 2% of FCI 1% of FCI 81 1.3 Methodology for estimation of cash flow and IRR Table S5 Assumptions or parameters for the calculation of IRR 82 Item Value Service life 20 years Construction period 1 years Income tax rate 39% Annual capacity in the first year 30% Annual capacity in the second year 50% Annual capacity in the third year 80% Salvage value at end of service life Levoglucosan Working capital+land+salvage value of buildings 15$/kg Renewable phenol resin 2800$/metric ton Road de-icer 700$/metric ton 83 6 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 The 20-year facility IRR is calculated on the basis of a cash flow sheet in order to perform a profitability evaluation.1 The determination or estimation of the market prices for the three chemicals is important for calculation of IRR. Levoglucosan is advertised for sale at $1500/kg and $20~90/kg on the carbosynth's Web site and the Alibaba Web site, respectively.9, 10 The purity of the levoglucosan sold at the carbosynth's Web site is 3% higher than that of the levoglucosan produced via the process. Moreover, from an economic perspective, mass production will lower the cost. Therefore, the price of the levoglucosan produced via the process is set at $15/kg in this analysis. The phenolic resins from America are priced around $4000/ton (¥25.5/kg) on the Guidechem Web site.11 Considering that about 50wt% of the phenol used in the renewable phenol resin produced via the process is replaced and the phenolic resin is not as good as those phenolic resins based on petrochemical synthesis in quality and performance, the renewable phenol resin was valued at $2800/ton. Food grade calcium acetate is priced at about $1200/ton on the Alibaba Web site.12 The deicer produced via the process is, at best, an industrial grade mixture of calcium salts. Hence the mixture is pegged at $700/ton. Some necessary parameters for the calculation of the cash flow sheet, such as construction period, income tax rate 101 and product prices, are showed in Table S5. 102 Moreover, the cash flow sheet also involves so-called general expenses. The 103 general expenses, including research and development, administrative, distribution, 104 marketing expenses etc, are estimated at about 4% of the operating costs per year.8 105 The cash flow sheet is listed in Table S6. Table S6 The cash flow sheet 106 Yea r 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Annual capacity Cash flow 0 30% 50% 80% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% -$26,240,599 -$12,199,189 $2,381,781 $13,413,186 $15,232,873 $15,232,873 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 7 17 18 19 20 100% 100% 100% 100% $20,350,000 $20,350,000 $20,350,000 $26,701,958 107 1.4 The average delivery distance 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 Since the biorefinery plant is located at the center of a square rural area, where cotton straw is uniformly distributed, the distance traveled by a truck delivering the cotton straw is uncertain and should be a random variable. Therefore, the average transportation distance to this plant, namely the random variable expectation, will be supposed to be the actual distance traveled by trucks delivering all the cotton straw. A formula of computation of the average delivery distance was given by Brown et al, but the deduced method and details of this formula was not provided.13 We give a following deduced method and steps of this formula. 131 Fig. S1 A square with a side of length 2 132 133 134 135 136 137 138 139 140 141 142 143 144 Firstly, if F is the feedstock delivered annually to the plant, Y is the annual yield of cotton straw and f is the fraction of the acreage around the plant devoted to feedstock production, the square rural area should has a side of length (F/(Y*f))0.5. Suppose that the average distance from a random point in the square to the center of the square is rave if the horizontal and vertical ordinate of the point all follow U (-1, 1). Secondly, a square with a side of length 2 is considered as depicted in Fig. S1. The average distance from a random point in the square to the center of the square (I) can be calculated as following if the horizontal and vertical ordinate of the point all follow U (-1, 1): 1 1 1 1 2 2 x  y dxdy  x 2  y 2 dxdy * *   1 1 0 0 2 2 Let : x  r cos  , y  sin 1 I  1 So :  I   d  4 0 sec 0  8 r dr   d  2 2 4 1 I  ( 2  Ln(1  2 )) csc 0 r 2 dr 145 146 147 148 149 150 151 Finally, the two squares are similar. F Yf r Q ave  I 2 1 F  rave  ( 2  Ln(1  2 )) 6 Yf 152 153 154 155 156 157 A ‘tortuosity factor’ τ is defined as the ratio of actual distance to the straight-line 158 distance from the plant. Therefore, the average delivery distance, which is expressed 159 as rsquare in this following formula, should be: 160 1 F ( 2  Ln(1  2 )) rsquare   161 6 Yf 162 163 In this study, F, Y, f and τ are assumed to be 18000 ton/year, 5 ton/acre per year, 164 60% and 1.5, respectively. Therefore, the average delivery distance is 1.76 miles. 165 2 Investment and production cost 166 2.1 The investment 167 168 169 170 171 172 173 174 175 176 177 178 179 180 $30,000,000 land use $26,240,599 $25,000,000 Working Capital Project contingency Total indirect Cost $20,000,000 Total installed equipment cost $15,000,000 $10,000,000 $5,000,000 $0 Total capital investment 181 182 Fig. S2 Total capital investment of the process 183 184 As showed in Fig. S2, which represents total capital investment as the 185 summation of total installed equipment cost, total indirect cost, project contingency, 9 186 187 188 189 190 191 192 193 194 195 196 197 198 199 200 201 202 203 204 205 206 207 208 209 210 working capital cost, and land use, the total capital investment for the biorefinery process amounts to $26.2 million, while the total installed equipment cost of the whole process is $15.7 million. Such a scale of investment is one order smaller than the investment scale of biofuel plants.5, 14, 15 However, Chemicals have normally higher added value than fuels. And this allows chemical plants can be operated with smaller scale of economies than fuel plants when the two kinds of plants have the same profit margin. Since the biorefinery process consists of four sub-processes, it is important to know the percentage of the total installed equipment cost for each subprocess. Fig. S3 shows the relative weightings (percentage) of the four sub-processes represented in the total installed equipment cost of the whole process. Bio-oil preparation and separation (sub 1), extraction of levoglucosan (sub 2) and preparation of deicer (sub 4) separately contribute 38%, 34% and 25% of the total installed equipment cost, respectively. The really amazing thing about this figure is that production of renewable phenol resin (sub 3) is the smallest (only 3%) contributor to the total installed equipment cost. The reason is that the production of renewable phenol resin requires a minimum number of unit operations or equipments in comparison with other three sub-processes. From an economic point of view, the subprocess 4, the preparation of deicer, seemingly is not feasible or cost-effective because the total installed cost for the sub-process 4 accounts for 25% of the total but the selling price ($700/ton) and the production rate (37kg/h) of the deicer are all comparatively low. On the other hand, it can be expected that the extraction of levoglucosan and the production of renewable phenol resin are all cost-effective because levoglucosan is a high added-value product and the production of renewable phenol resin needs relatively small equipment investment. 211 212 213 214 215 216 217 218 219 220 221 222 223 224 25% 38% 3% Sub 1 Sub 2 Sub 3 Sub 4 34% Fig. S3 The percentage of the total installed equipment cost for each sub-process 225 2.2 The production cost 226 Determination of the necessary capital investment is only one part of a complete 10 227 cost estimate. Another equally important part is the estimation of costs for operating 228 the plant or process. Fig. S4 shows the annual direct production costs for cotton straw 229 to levoglucosan, renewable phenol resin and deicer. Similar to Fig. S3, the direct 230 production cost of the whole process is breakdown to each sub-process area in Fig. S4. 231 232 $5,000,000 Waste Disposal 233 $4,535,761 $4,500,000 Maintenance 234 $4,191,794 235 $4,000,000 Utilities $3,766,348 236 Labor 237 $3,500,000 $3,199,225 Operating Supplies 238 $3,000,000 Biomass 239 240 $2,500,000 241 $2,000,000 242 243 $1,500,000 244 $1,000,000 245 246 $500,000 247 $0 248 Sub 1 Sub 2 Sub 3 Sub 4 249 250 251 252 253 254 255 256 257 258 259 260 261 262 263 264 265 266 267 268 269 Fig. S4 The annual direct production costs The direct production costs of the four sub-processes vary from around $3.2 million/year to $4.5 million/year, and total up to $15.7 million/year. There is not much difference between the annual direct production cost of sub 4 (preparation of deicer) and the annual direct production cost of sub 2 (extraction of levoglucosan) or sub 3 (production of renewable phenol resin). However, in consideration of the yearly outputs and product prices of the three chemicals, it can be also inferred that sub 4 (preparation of deicer) is not cost-effective. The labor costs of sub 1 (bio-oil preparation and separation), 2 (extraction of levoglucosan) and 4 (preparation of deicer) are the largest contributors to the annual direct production costs of the three sub-processes, respectively. This is because each of the three sub-processes contains quite a number of unit operations or equipments, which require a number of operating labor and a certain amount of direct supervisory and clerical labor for operation. On the basis of the same reason, the maintenance costs of the three sub-processes account for the certain proportion of the annual direct production costs of the three subprocesses. The operating supplies of sub 3 (production of renewable phenol resin) comprise the vast majority of the annual direct production cost of this sub-process because a substantial number of phenol and formaldehyde are used in the sub-process. Direct production cost is only part of operating cost. The operating cost includes all expenses directly connected with the manufacturing operation or the physical equipment of a process plant itself. However, unlike direct production cost, operating 11 270 271 272 273 274 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289 290 291 292 293 294 295 296 297 298 299 300 301 302 303 304 305 306 307 308 309 310 311 312 313 cost is not appropriate for being breakdown to process area because it includes plantoverhead costs, which are reserved for hospital and medical services, safety services, salvage services and warehouse facilities, etc. As shown in Fig. S5, the operating cost of the whole process is around $22.2 million/year. The annual direct production cost, fixed charge and plant-overhead cost of the whole process account for about 71%, 12% and 17% of the operating cost, respectively. These percents are basically similar to other techno-economic analyses of some biorefinery processes via fast paralysis.5, 6 However, the labor cost of the whole process occupies about 29% of the operating cost; In comparison with production of biofuels,5, 6, 15 this percent is remarkably higher. There could be three reasons to explain this. Firstly, production of chemicals usually needs more purification steps or equipments than production of fuels. Secondly, not one chemical but three chemicals are produced in this birefinery process. Finally, mass production of biofuels usually is a continuous process, while the production of the three chemicals contains some batch steps. These reasons could result in more labor requirement in this birefinery process. $25,000,000 $22,245,283 Plant-overhead costs $20,000,000 Fixed Charges Waste Disposal Maintenance $15,000,000 Utilities Labor Operating Supplies $10,000,000 Biomass $5,000,000 $0 Operating cost Fig. S5 The operating cost of the whole process 12 314 315 316 317 3 Some background data for this LCA study 318 3.1 LCI data for petrochemical production of phenol - formaldehyde resins (PF) 319 Wilson et al. has developed an life-cycle inventory of formaldehyde-base resins 320 used in wood composites in terms of resources, emissions, energy and carbon.16 The 321 LCI for the production of PF is shown in Table S7, in which the environmental 322 burdens of the delivery of chemicals to the resin plants are ignored. Table S7 LCI data for conventional PF production route 323 Materials, Energy and Emissions Phenol Methanol Sodium hydroxide Process water Cooling water from river (20℃) Electricity Natural gas Propane Carbon dioxide Carbon monoxide Value 2.44E-01 2.09E-01 6.10E-02 3.34E-01 1.56E-02 Units kg /kgPF kg /kgPF kg /kgPF kg /kgPF kg /kgPF 3.56E-02 8.21E-03 2.93E-06 1.76E-02 3.81E-05 kWh /kgPF Nm3 /kgPF L /kgPF kg /kgPF kg /kgPF 324 3.2 LCI data for petrochemical production of calcium acetate 325 Overcash et al has presented gate-to-gate process energy use for a calcium 326 acetate manufacturing process, in which calcium hydroxide and acetic acid were used 327 as raw materials.17 On the basis of the work of Overcash et al, LCI data for 328 petrochemical production of calcium acetate is shown in Table S8. 329 Table S8 LCI data for petrochemical production of calcium acetate Materials, Energy and Emissions Value Units Calcium hydroxide 4.69E-01 Acetic acid 7.59E-01 kg /kgCalcium acetate kg /kgCalcium acetate Steam (6bar) 1.53E+00 MJ /kgCalcium acetate Electricity 1.05E-03 MJ /kgCalcium acetate Natural gas 9.32E-01 MJ /kgCalcium acetate Carbon dioxide 5.22E-02 kg /kgCalcium acetate 13 330 3.3 The GWP100a, CED, EI-99 metric for some chemicals and utilities 331 Cradle-to-gate LCIA results according to the GWP100a, CED, EI-99 metric for 332 some chemicals and utilities used in this process are listed in Table S9. All the data is 333 mainly based on ecoinvent 2.2 database, and a few of the data is derived from some 334 LCA documents. These LCA documents are listed in the last row in Table S9. 335 Table S9 The GWP100a, CED, EI-99 metric for some chemicals and utilities Substance GWP100a (kgCO2-eq/kg) CEDnon-renewable (MJeq/kg) EI-99 (Points/kg) 1.66E+00 1.20E-01 2.45E-05 2.94E-01 9.90E-01 2.93E+01 2.02E+00 2.79E-04 5.92E+00 5.50E+00 1.66E-01 4.00E-02 1.83E-06 1.76E-02 3.00E-02 8.53E-01 1.75E+01 6.00E-02 3.14E+00 1.10E+00 3.48E+00 4.14E-01 1.31E+00 7.64E-01 9.63E+01 2.14E+01 1.21E+02 1.82E+01 7.30E+00 4.08E+01 3.36E-01 6.00E-01 4.40E-01 6.25E-02 2.80E-02 1.35E-01 1.29E-02 4.90E-01 1.00E-01 1.20E+00 9.87E+00 1.56E+00 6.43E-03 2.00E-02 5.77E-03 0.00E+00 0.00E+00 0.00E+00 2.19E-02 1.34E-02 2.42E-01 6.52E-01 5.00E-04 4.22E-02 Materials Fertilizer a Sulfuric acid (98 wt. %) Process water Activated carbon b Calcium hydroxide Hydrochloric acid (32 wt. %) Ethyl acetate c Sodium hydroxide Phenol Formaldehyde (37 wt.%) c Calcium oxide d Methanol c Energy e Diesel Electricity e Steam (6 bar) e Cooling water from river (20℃) Waste treatment Waste liquid f Solid waste f 336 337 338 339 340 341 342 a Values based on the work of Hasler et al.18 b Values based on the work of Arena et al.19 c Values based on the work of Amelio et al.20 d Values based on the works of Huijbregts et al. and Alvarez-Gaitan et al.21, 22 e Functional unit for diesel as well as steam is MJ and for electricity kWh f Values based on the works of Rerat et al.23 14 343 Electronic Supplementary Information (ESI) 344 Life cycle assessment and techno-economic analysis of the utilization 345 of bio-oil components for the production of three chemicals 346 Ji-Lu Zheng a, Ya-Hong Zhu a, Ming-Qiang Zhu a*, Guo-Tao Sun a, Run-Cang Sun b 347 a Key Laboratory of Exploitation and Utilization of Economic Plant Resources in 348 Shaanxi Province, Western Scientific Observation and Experiment Station of 349 Development and Utilization of Rural Renewable Energy of Ministry of 350 Agriculture, Northwest A&F University, Yangling 712100, China. 351 352 b Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing, China. 353 354 355 356 357 358 359 *Corresponding authors. Address: Northwest A&F University, 712100, Yangling, 360 China. Tel.: +86-029-87082230; Fax: +86-029-87082216. 361 E-mail address: zmqsx@nwsuaf.edu.cn (M. Q. Zhu). 15 363 Contents 364 1 The procedures of the techno-economic-environmental analysis..............................................2 365 1.1 Methodology for estimation of the total-capital investment..........................................2 366 1.2 Methodology for estimation of the operating cost and direct production cost ..............4 367 1.3 Methodology for estimation of the operating cost and direct production cost ..............5 368 1.4 The average delivery distance........................................................................................6 369 2 Investment and production cost .................................................................................................8 370 2.1 The investment ...............................................................................................................8 371 2.2 The production cost........................................................................................................9 372 3 Some background data for this LCA study..............................................................................11 373 3.1 LCI data for petrochemical production of phenol - formaldehyde resins (PF)...........11 374 3.2 LCI data for petrochemical production of calcium acetate.........................................11 375 3.3 The GWP100a, CED, EI-99 metric for some chemicals and utilities..........................12 16 377 4 The procedures of the techno-economic-environmental analysis 378 4.1 Methodology for estimation of the total-capital investment 379 Table S1 Methodology for total-capital investment for nth plant Item Percent of TDEC Total purchased equipment-delivered (TPEC) Purchased equipment installation 380 381 382 383 384 385 386 387 388 389 390 391 392 393 394 395 cost 100% 39% Instrumentation and controls (installed) 13% Piping (installed) 31% Electrical systems (installed) 10% Buildings (including services) 29% Yard improvements 10% Service facilities (installed) 55% Total installed cost (TIC) 287% Land (if purchase is required) 6% Engineering and supervision 32% Construction expenses 34% Total direct and indirect plant costs (TDIC) 359% Contractor’s fee (CF) 5% of TDIC Contingency (CO) 10% of TDIC Fixed-capital investment (FCI) TDIC+CF+CO Working capital 15% of FCI Total capital investment 475% The total installed equipment cost is part of the total capital investment. The total capital investment for all processes consists of fixed-capital investment for physical equipment and facilities in the plant plus working capital which must be available to pay salaries, keep raw materials and products on hand, and handle other special items requiring a direct cash outlay. This method for estimating the total-capital investment is based on the percentage of delivered-equipment cost. Namely, the determination of the delivered-equipment cost is required firstly. The other items included in the fixedcapital investment are estimated as percentages of the delivered-equipment cost , and the working capital amounts to 15 percent of the fixed-capital investment.1 The items included in the total-capital investment and the corresponding ratio factors based on delivered equipment cost are listed in Table S1. Unit process principles are used to determine the equipment specifications,1, 2 and then the delivered-equipment cost of each piece of the process equipments can be estimated from appropriate manufacturers' bulletins, published cost data, empirical rules1-3 or e-commerce websites (such as Alibaba) as listed in Table S2. 17 396 Table S2 The delivered-equipment cost of each piece of the process equipments Equipments Sub 1 Chopper Biomass Chopping Screen Grinding Hammer Mill Biomass Grinding Screen Belt Press Bale Moving Forklift*4 Concrete Storage Slab Discharge Conveyor Bale Transport Conveyor Bale Unwrapping Conveyor Continuous Spray Rotary Drum Rotary Dryer Biomass Feeding Bin Screw Feeder Pyrolysis Fluid Bed Non-condensible Gas Blower Pyrolysis Vapor Cyclones*2 Bio-oil Condenser*2 Electro-Static Precipitator Condenser Water Pump*3 Ice making machine Condenser Oil Pump Cooling Tower Wash Percolater Solids Combustor Combustor Cyclones Combustion Gas Blower Sub 2 Settling Tank Filter, vacuum rotary drum Vacuum pump Settling Tank Filter, vacuum rotary drum Vacuum pump Mixer Vaccum freeze dryer Mixer Filter, vacuum rotary drum Evaporation crystallizer Settling Tank Specification Deliveredequipment cost 50 kw/ton 60 ton/day 50 kw/ton 60 ton/day 5.5 kw 1.25 ton/h 30 m*29 m*3.5 m 0.75 kw/ton 90 w/ton 5.5 kw 2.2 kw, 2.5 ton/h 2.2 kw Φ1.5*4.3 m 0.75 kw/ton Φ1.2 m*2 m 90 kw 3600 m3 of gas per hour 600 m2 of heat transfer area 30 kw 90 kw 53 /kw, 592 kg of ice per hour 5 kw Φ 8.8m*6.5m 4 m3 Φ0.3 m*0.8 m 3360 m3 of gas per hour 85 kw $44,137 $3,286 $44,137 $3,359 $19,425 $14,021 $87,631 $9,785 $77,845 $29,210 $185,089 $99,519 $6,047 $23,733 $122,099 $31,357 $184,316 $291,722 $42,705 $62,527 $20,000 $6,952 $438,898 $31,459 $35,680 $161,343 $9,084 3 m3 3 kw, 600 kg of filtrate /(m2.h) 10 kw 3 m3 3 kw, 600 kg of filtrate /(m2.h) 10 kw 10 kw, 3m3 130 kw, 1.2 ton water per hour 10 kw, 3 m3 3 kw, 600 kg of filtrate /(m2.h) 1000 kg of acetic ether per 3hour m3 $35,965 $185,089 $28,655 $35,965 $185,089 $28,655 $73,805 $365,261 $73,805 $185,089 $452,879 $35,965 18 Filter, vacuum rotary drum Vacuum pump Sub 3 Mixer*2 Sub 4 Evaporator Mixer Evaporator Mixer*4 Filter, vacuum rotary drum*4 Vacuum pump*4 Evaporator*2 397 398 3 kw, 600 kg of filtrate /(m2.h) 10 kw $185,089 $28,655 10 kw, 3 m3 $147,610 600 kg of water per hour 10 kw, 3 m3 600 kg of water per hour 3 kw, 0.8 m3 3 kw, 75 kg of filtrate /(m2.h) 10 kw 50 kg of methanol per hour $349,285 $73,805 $349,285 $104,268 $212,611 $114,620 $190,110 4.2 Methodology for estimation of the operating cost and direct production cost 399 Table S3 Variable costs employed in the estimation of the direct production costs 400 (Source: www.alibaba.com and refs). 6-8 Item 401 402 403 404 405 Value Cotton straw $83/metric ton Transport $0.71/(ton.mile) Sulfuric acid 98 wt.% $300/metric ton Process water $1.0/metric ton Activated carbon $1500/metric ton Calcium hydroxide $110/metric ton Hydrochloric acid 32 wt.% $190/metric ton Ethyl acetate $1200/metric ton Calcium oxide $160/metric ton Methanol $700/metric ton Sodium hydroxide $500/metric ton Phenol $1300/metric ton Formaldehyde 37 wt.% $400/metric ton Cooling water from river $0.15/metric ton Average hourly wage $21/h Electricity $0.061/kwh Steam (6 bar) $20/metric ton Solids disposal cost $22.23/metric ton Waste water disposal cost $1.30/metric ton The operating cost is divided into three classifications as follows: (1) direct production costs, which mainly involve expenditures for raw materials, direct operating labor, supervisory and clerical labor directly connected to the manufacturing operation, utilities, plant maintenance and repairs. Some variable cost parameters, such as the prices of cotton straw, phenol, and utilities, average hourly 19 406 wage and water treatment cost, are listed on the Table S3; (2) fixed charges, 407 essentially include expenses directly associated with depreciation, property taxes, 408 insurance. Some assumptions for the estimation of fixed charges, such as depreciation 409 period, type of depreciation and property tax rate, are listed on the Table S4; (3) 410 411 412 413 414 415 416 417 418 419 420 plant-overhead costs, which are used for medical services, warehouses, safety services, warehouses and so on. The estimation of fixed charges and plant-overhead costs can be based on the method of 'Percentage of total-capital investment'.4 However the estimation of direct production costs is slightly complex. Chemical engineering principles, such as material balance and energy balance, and the methodology proposed by Overcash et.al are used for calculation of the expenditures for raw materials and utilities.5 The method of estimating labor requirements is based on adding up the various principal processing steps on the flow sheet and plant capacity, and the cost for direct supervisory and clerical labor averages about 15 percent of the cost for operating labor.1 The method for estimation of the expenditures for plant maintenance and repairs is the same as that for estimation of fixed charges. Table S4 Assumptions for the estimation of the fixed charges 421 Item Equipment depreciation period Building depreciation period Amortization period Type of depreciation or amortization Property tax rate Insurance rate Value/method 20 years 40 years 5 years Straight-line 2% of FCI 1% of FCI 422 4.3 Methodology for estimation of the operating cost and direct production cost Table S5 Assumptions or parameters for the calculation of IRR 423 Item Value Service life 20 years Construction period 1 years Income tax rate 39% Annual capacity in the first year 30% Annual capacity in the second year 50% Annual capacity in the third year 80% Salvage value at end of service life Levoglucosan Working capital+land+salvage value of buildings 15$/kg Renewable phenol resin 2800$/metric ton Road de-icer 700$/metric ton 424 20 425 426 427 428 429 430 431 432 433 434 435 436 437 438 439 440 441 The 20-year facility IRR is calculated on the basis of a cash flow sheet in order to perform a profitability evaluation.1 The determination or estimation of the market prices for the three chemicals is important for calculation of IRR. Levoglucosan is advertised for sale at $1500/kg and $20~90/kg on the carbosynth's Web site and the Alibaba Web site, respectively.9, 10 The purity of the levoglucosan sold at the carbosynth's Web site is 3% higher than that of the levoglucosan produced via the process. Moreover, from an economic perspective, mass production will lower the cost. Therefore, the price of the levoglucosan produced via the process is set at $15/kg in this analysis. The phenolic resins from America are priced around $4000/ton (¥25.5/kg) on the Guidechem Web site.11 Considering that about 50wt% of the phenol used in the renewable phenol resin produced via the process is replaced and the phenolic resin is not as good as those phenolic resins based on petrochemical synthesis in quality and performance, the renewable phenol resin was valued at $2800/ton. Food grade calcium acetate is priced at about $1200/ton on the Alibaba Web site.12 The deicer produced via the process is, at best, an industrial grade mixture of calcium salts. Hence the mixture is pegged at $700/ton. Some necessary parameters for the calculation of the cash flow sheet, such as construction period, income tax rate 442 and product prices, are showed in Table S5. 443 Moreover, the cash flow sheet also involves so-called general expenses. The 444 general expenses, including research and development, administrative, distribution, 445 marketing expenses etc, are estimated at about 4% of the operating costs per year.5 446 The cash flow sheet is listed in Table S6. Table S6 The cash flow sheet 447 Yea r 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Annual capacity Cash flow 0 30% 50% 80% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% -$26,240,599 -$12,199,189 $2,381,781 $13,413,186 $15,232,873 $15,232,873 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 $20,350,000 21 17 18 19 20 100% 100% 100% 100% $20,350,000 $20,350,000 $20,350,000 $26,701,958 448 4.4 The average delivery distance 449 450 451 452 453 454 455 456 457 458 459 460 461 462 463 464 465 466 467 468 469 470 471 Since the biorefinery plant is located at the center of a square rural area, where cotton straw is uniformly distributed, the distance traveled by a truck delivering the cotton straw is uncertain and should be a random variable. Therefore, the average transportation distance to this plant, namely the random variable expectation, will be supposed to be the actual distance traveled by trucks delivering all the cotton straw. A formula of computation of the average delivery distance was given by Brown et al, but the deduced method and details of this formula was not provided.13 We give a following deduced method and steps of this formula. 472 Fig. S1 A square with a side of length 2 473 474 475 476 477 478 479 480 481 482 483 484 485 Firstly, if F is the feedstock delivered annually to the plant, Y is the annual yield of cotton straw and f is the fraction of the acreage around the plant devoted to feedstock production, the square rural area should has a side of length (F/(Y*f))0.5. Suppose that the average distance from a random point in the square to the center of the square is rave if the horizontal and vertical ordinate of the point all follow U (-1, 1). Secondly, a square with a side of length 2 is considered as depicted in Fig. S1. The average distance from a random point in the square to the center of the square (I) can be calculated as following if the horizontal and vertical ordinate of the point all follow U (-1, 1): 1 1 1 1 2 2 x  y dxdy  x 2  y 2 dxdy * *   1 1 0 0 2 2 Let : x  r cos  , y  sin 1 I  1 So :  I   d  4 0 sec 0  22 r dr  2 d  2 4 1 I  ( 2  Ln(1  2 )) csc 0 r 2 dr 486 487 488 489 490 491 492 Finally, the two squares are similar. F Yf r Q ave  I 2 1 F  rave  ( 2  Ln(1  2 )) 6 Yf 493 494 495 496 497 498 A ‘tortuosity factor’ τ is defined as the ratio of actual distance to the straight-line 499 distance from the plant. Therefore, the average delivery distance, which is expressed 500 as rsquare in this following formula, should be: 501 1 F ( 2  Ln(1  2 )) rsquare   502 6 Yf 503 504 In this study, F, Y, f and τ are assumed to be 18000 ton/year, 5 ton/acre per year, 505 60% and 1.5, respectively. Therefore, the average delivery distance is 1.76 miles. 506 5 Investment and production cost 507 5.1 The investment 508 509 510 511 512 513 514 515 516 517 518 519 520 521 $30,000,000 land use $26,240,599 $25,000,000 Working Capital Project contingency Total indirect Cost $20,000,000 Total installed equipment cost $15,000,000 $10,000,000 $5,000,000 $0 Total capital investment 522 523 Fig. S2 Total capital investment of the process 524 525 As showed in Fig. S2, which represents total capital investment as the 526 summation of total installed equipment cost, total indirect cost, project contingency, 23 527 528 529 530 531 532 533 534 535 536 537 538 539 540 541 542 543 544 545 546 547 548 549 550 551 working capital cost, and land use, the total capital investment for the biorefinery process amounts to $26.2 million, while the total installed equipment cost of the whole process is $15.7 million. Such a scale of investment is one order smaller than the investment scale of biofuel plants.7, 14, 15 However, Chemicals have normally higher added value than fuels. And this allows chemical plants can be operated with smaller scale of economies than fuel plants when the two kinds of plants have the same profit margin. Since the biorefinery process consists of four sub-processes, it is important to know the percentage of the total installed equipment cost for each subprocess. Fig. S3 shows the relative weightings (percentage) of the four sub-processes represented in the total installed equipment cost of the whole process. Bio-oil preparation and separation (sub 1), extraction of levoglucosan (sub 2) and preparation of deicer (sub 4) separately contribute 38%, 34% and 25% of the total installed equipment cost, respectively. The really amazing thing about this figure is that production of renewable phenol resin (sub 3) is the smallest (only 3%) contributor to the total installed equipment cost. The reason is that the production of renewable phenol resin requires a minimum number of unit operations or equipments in comparison with other three sub-processes. From an economic point of view, the subprocess 4, the preparation of deicer, seemingly is not feasible or cost-effective because the total installed cost for the sub-process 4 accounts for 25% of the total but the selling price ($700/ton) and the production rate (37kg/h) of the deicer are all comparatively low. On the other hand, it can be expected that the extraction of levoglucosan and the production of renewable phenol resin are all cost-effective because levoglucosan is a high added-value product and the production of renewable phenol resin needs relatively small equipment investment. 552 553 554 555 556 557 558 559 560 561 562 563 564 565 25% 38% 3% Sub 1 Sub 2 Sub 3 Sub 4 34% Fig. S3 The percentage of the total installed equipment cost for each sub-process 566 5.2 The production cost 567 Determination of the necessary capital investment is only one part of a complete 24 568 cost estimate. Another equally important part is the estimation of costs for operating 569 the plant or process. Fig. S4 shows the annual direct production costs for cotton straw 570 to levoglucosan, renewable phenol resin and deicer. Similar to Fig. S3, the direct 571 production cost of the whole process is breakdown to each sub-process area in Fig. S4. 572 573 $5,000,000 Waste Disposal 574 $4,535,761 $4,500,000 Maintenance 575 $4,191,794 576 $4,000,000 Utilities $3,766,348 577 Labor 578 $3,500,000 $3,199,225 Operating Supplies 579 $3,000,000 Biomass 580 581 $2,500,000 582 $2,000,000 583 584 $1,500,000 585 $1,000,000 586 587 $500,000 588 $0 589 Sub 1 Sub 2 Sub 3 Sub 4 590 591 592 593 594 595 596 597 598 599 600 601 602 603 604 605 606 607 608 609 610 Fig. S4 The annual direct production costs The direct production costs of the four sub-processes vary from around $3.2 million/year to $4.5 million/year, and total up to $15.7 million/year. There is not much difference between the annual direct production cost of sub 4 (preparation of deicer) and the annual direct production cost of sub 2 (extraction of levoglucosan) or sub 3 (production of renewable phenol resin). However, in consideration of the yearly outputs and product prices of the three chemicals, it can be also inferred that sub 4 (preparation of deicer) is not cost-effective. The labor costs of sub 1 (bio-oil preparation and separation), 2 (extraction of levoglucosan) and 4 (preparation of deicer) are the largest contributors to the annual direct production costs of the three sub-processes, respectively. This is because each of the three sub-processes contains quite a number of unit operations or equipments, which require a number of operating labor and a certain amount of direct supervisory and clerical labor for operation. On the basis of the same reason, the maintenance costs of the three sub-processes account for the certain proportion of the annual direct production costs of the three subprocesses. The operating supplies of sub 3 (production of renewable phenol resin) comprise the vast majority of the annual direct production cost of this sub-process because a substantial number of phenol and formaldehyde are used in the sub-process. Direct production cost is only part of operating cost. The operating cost include all expenses directly connected with the manufacturing operation or the physical equipment of a process plant itself. However, unlike direct production cost, operating 25 611 612 613 614 615 616 617 618 619 620 621 622 623 624 625 626 627 628 629 630 631 632 633 634 635 636 637 638 639 640 641 642 643 644 645 646 647 648 649 650 651 652 653 654 cost is not appropriate for being breakdown to process area because it includes plantoverhead costs, which are reserved for hospital and medical services, safety services, salvage services and warehouse facilities, etc. As shown in Fig. S5, the operating cost of the whole process is around $22.2 million/year. The annual direct production cost, fixed charge and plant-overhead cost of the whole process account for about 71%, 12% and 17% of the operating cost, respectively. These percents are basically similar to other techno-economic analyses of some biorefinery processes via fast paralysis.7, 8 However, the labor cost of the whole process occupies about 29% of the operating cost; In comparison with prodcution of biofuels,7, 8, 15 this percent is remarkably higher. There could be three reasons to explain this. Firstly, production of chemicals usually needs more purification steps or equipments than production of fuels. Secondly, not one chemical but three chemicals are produced in this birefinery process. Finally, mass production of biofuels usually is a continuous process, while the production of the three chemicals contains some batch steps. These reasons could result in more labor requirement in this birefinery process. $25,000,000 $22,245,283 Plant-overhead costs $20,000,000 Fixed Charges Waste Disposal Maintenance $15,000,000 Utilities Labor Operating Supplies $10,000,000 Biomass $5,000,000 $0 Operating cost Fig. S5 The operating cost of the whole process 26 655 656 657 658 6 Some background data for this LCA study 659 6.1 LCI data for petrochemical production of phenol - formaldehyde resins (PF) 660 Wilson et al. has developed an life-cycle inventory of formaldehyde-base resins 661 used in wood composites in terms of resources, emissions, energy and carbon.16 The 662 LCI for the production of PF is shown in Table S7, in which the environmental 663 burdens of the delivery of chemicals to the resin plants are ignored. Table S7 LCI data for conventional PF production route 664 Materials, Energy and Emissions Phenol Methanol Sodium hydroxide Process water Cooling water from river (20℃) Electricity Natural gas Propane Carbon dioxide Carbon monoxide Value 2.44E-01 2.09E-01 6.10E-02 3.34E-01 1.56E-02 Units kg /kgPF kg /kgPF kg /kgPF kg /kgPF kg /kgPF 3.56E-02 8.21E-03 2.93E-06 1.76E-02 3.81E-05 kWh /kgPF Nm3 /kgPF L /kgPF kg /kgPF kg /kgPF 665 6.2 LCI data for petrochemical production of calcium acetate 666 Overcash et al has presented gate-to-gate process energy use for a calcium 667 acetate manufacturing process, in which calcium hydroxide and acetic acid were used 668 as raw materials.17 On the basis of the work of Overcash et al, LCI data for 669 petrochemical production of calcium acetate is shown in Table S8. 670 Table S8 LCI data for petrochemical production of calcium acetate Materials, Energy and Emissions Value Units Calcium hydroxide 4.69E-01 Acetic acid 7.59E-01 kg /kgCalcium acetate kg /kgCalcium acetate Steam (6bar) 1.53E+00 MJ /kgCalcium acetate Electricity 1.05E-03 MJ /kgCalcium acetate Natural gas 9.32E-01 MJ /kgCalcium acetate Carbon dioxide 5.22E-02 kg /kgCalcium acetate 27 671 6.3 The GWP100a, CED, EI-99 metric for some chemicals and utilities 672 Cradle-to-gate LCIA results according to the GWP100a, CED, EI-99 metric for 673 some chemicals and utilities used in this process are listed in Table S9. All the data is 674 mainly based on ecoinvent 2.2 database, and a few of the data is derived from some 675 LCA documents. These LCA documents are listed in the last row in Table S9. 676 Table S9 The GWP100a, CED, EI-99 metric for some chemicals and utilities Substance Materials Sulfuric acid (98 wt. %) Process water Activated carbon a Calcium hydroxide Hydrochloric acid (32 wt. %) Ethyl acetate b Sodium hydroxide Phenol Formaldehyde (37 wt.%) b Calcium oxide c Methanol b Energy d Diesel Electricity d Steam (6 bar) d Cooling water from river (20℃) Waste treatment Waste liquid e Solid waste e 677 678 679 680 681 682 GWP100a (kgCO2-eq/kg) CEDnon-renewable (MJeq/kg) EI-99 (Points/kg) 1.20E-01 2.45E-05 2.94E-01 9.90E-01 2.02E+00 2.79E-04 5.92E+00 5.50E+00 4.00E-02 1.83E-06 1.76E-02 3.00E-02 8.53E-01 1.75E+01 6.00E-02 3.14E+00 1.10E+00 3.48E+00 4.14E-01 1.31E+00 7.64E-01 9.63E+01 2.14E+01 1.21E+02 1.82E+01 7.30E+00 4.08E+01 3.36E-01 6.00E-01 4.40E-01 6.25E-02 2.80E-02 1.35E-01 1.29E-02 4.90E-01 1.00E-01 1.20E+00 9.87E+00 1.56E+00 6.43E-03 2.00E-02 5.77E-03 0.00E+00 0.00E+00 0.00E+00 2.19E-02 1.34E-02 2.42E-01 6.52E-01 5.00E-04 4.22E-02 a Values based on the work of Arena et al.18 b Values based on the work of Amelio et al.19 c Values based on the works of Huijbregts et al. and Alvarez-Gaitan et al.20, 21 d Functional unit for diesel as well as steam is MJ and for electricity kWh e Values based on the works of Rerat et al.22 28 References 1 K. 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