LCA Food 2012 in Saint Malo, France! - Manifestations et colloques ...

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PARALLEL SESSION 6A: TOOLS AND DATABASES 8 th Int. Conference on LCA in the Agri-Food Sector, 1-4 Oct 2012 At the gtg level, other processes with significant energy use and significant byproduct formation are diethanolamine, ethylene, white phosphorus, chlorine, and sodium hydroxide. In this rollup, chlorine and sodium hydroxide are used in quantities similar to their production rates, and so, the impact of allocation choice is minor. The ethylene and diethanol amine gtgs each produce products with similar utility and chemical properties. White phosphorus has a fairly small energy contribution, however, the allocation to lower value products is high. Thus, the phosphorus allocation may be important in the result. The total process energy is 88.1 MJ/kg glyphosate. Process energies are scaled to account for cradle to gate delivery of fuel and again scaled to account for energy generation efficiencies. The total high heat value (HHV) of fuels used ctg is 148 MJ/kg glyphosate. Using this presentation, it is very easy to apply alternative energy production models and update these data as energy supplies change. The process and natural resource energies for glyphosate production are summarized in Fig. 2. In this view, energies for commodity chemicals are shown as ctg values. The energy profile dominated by the glyphosate gtg, which uses 63 MJ of the total 88 MJ of process energy/kg glyphosate. We can learn more about the energy use, potential variability between manufacturers, and potential for improvement by looking more closely at the glyphosate gtg. The full glyphosate gtg report contains a detailed description of the process, a process flow diagram, and Tables detailing mass and energy flows at the unit operation level. This document can be obtained by contacting the article authors. The glyphosate process takes place in a dilute aqueous solution, and about 80% of the energy use in the glyphosate gtg is for evaporation of the water. Based on most of the patent data (US 6,921,84; US 7,799,571; US 5,962,729; US 3,969,398), the water use ratio (kg water/kg PMIDA) was 10:1 to 50:1. In our gtg model, the water use was 36 kg/kg PMIDA. Evaporation of water is an energy intensive process, and this energy can be reduced dramatically by using multi-effect evaporators. These units split the evaporation into multiple stages and utilise the steam from each stage as an energy supply for successive stages. An economic tradeoff between capital cost and operating (energy) costs favours more evaporation steps in larger processes. In the glyphosate model, a single effect evaporator was used. Thus some industrial plants may achieve significantly lower energy use by increasing reactor concentrations and using multiple effect evaporators. Feedstock use of fossil fuels can be seen in Fig. 1. Natural gas is used to make formaldehyde and ammonia, petroleum is used to make ethylene oxide, and coal is used to make metallurgical coke for phosphorus production. Using high heat values of 29 MJ/kg for coal, 54 MJ/kg for gas, and 45 MJ/kg for oil, the total feedstock energy is 33,000 MJ/Mt glyphosate. Thus, the cumulative energy demand is 181,000 MJ/Mt glyphosate. Two allocation choices in the glyphosate supply chain are in the ammonia gtg, which produces CO2, and the white phosphorus gtg, which produces slag and fuel gas. We tested the impact of these allocation choices by setting the allocation to ammonia and phosphorus to 1. Thus, no inventories were allocated to CO2, slag, or fuel gases. In that case, the process energy, nre, and cumulative energy demands were 97, 187, and 235 MJ/kg glyphosate. Table 2. Cradle to gate energies for 1000 kg glyphosate. Chemicals Mass By-products Allocation factor Energy with allocation, MJ/1000kg glyphosate Dow- Direct use Trans- Potential Total net kg / 1000 kg glyphosate kg / kg chemical Electricity therm Steam of fuel port* recovery energy glyphosate 1,000 1.00 500 0 7.72E+04 0 440 -1.48E+04 6.33E+04 Oxygen 0.0553 kg Argon; 3.26 kg 641 Nitrogen; 0.231 403 0 0 0 0 -2.88 401 PMIDA 1,422 1.00 25.1 0 2,172 0 626 -745 2,079 DSIDA in 37pct sol 1,186 1.25 kg Ethanol Amine; 0.235 kg Triethanol amine; 0.0141 kg triethanol amine, 85 1.00 340 0 1,570 0 0 -7,323 -5,413 diethanol amine 765 wt pct; 0.400 149 0 3,094 0 337 -1,043 2,536 Ammonia 169 1.18 kg CO2; 3.00E-03 kg Butane; 0.0400 kg Ethane; 7.00E-03 kg LPG condensate; 0.0100 kg 0.459 126 0 738 642 74.5 -606 976 Natural gas 205 Propane; 0.943 0 0 0 698 0 0 698 nitrogen from air 65.1 0.358 kg oxygen from air; 0.736 0 0 0 0 0 0 0 oxygen from air 882 2.79 kg nitrogen from air; 0.264 0 0 0 0 0 0 0 Water for rxn 1,005 1.00 0.809 0 0 0 0 0 0.809 Ethylene oxide 603 0.480 kg C4 stream; 0.0881 kg fuel oil; 0.0484 kg Hydrogen; 0.569 kg CH4; 0.634 kg Propylene; 1.03 kg 1.00 1,169 0 22.5 0 265 -3,426 -1,970 Ethylene 452 pyrolysis gas; 1.55 kg heavy gas oil, from distillation; 0.644 kg kerosene, from distillation; 0.542 kg light gas oil, from distillation; 0.711 kg residum, 0.260 643 0 1,070 5,237 199 -1,280 5,869 489
PARALLEL SESSION 6A: TOOLS AND DATABASES 8 th diethanol amine 765 wt pct; 0.400 149 0 3,094 0 337 -1,043 2,536 Ammonia 169 1.18 kg CO2; 3.00E-03 kg Butane; 0.0400 kg Ethane; 7.00E-03 kg LPG 0.459 126 0 738 642 74.5 -606 976 condensate; 0.0100 kg Natural gas 205 Propane; nitrogen from air 65.1 0.358 kg oxygen from air; 0.943 0.736 0 0 0 0 0 0 698 0 0 Int. Conference 0 698 on LCA in the 0 Agri-Food 0 Sector, 0 1-4 Oct 2012 oxygen from air 882 2.79 kg nitrogen from air; Alloca- 0.264 0 0 0 0 0 0 0 Water for rxn 1,005 tion 1.00 0.809 0 0 0 0 0 0.809 Chemicals Ethylene oxide Mass603 By-products 0.480 kg C4 stream; 0.0881 factor 1.00 Energy 1,169 with allocation, 0 MJ/1000kg 22.5 glyphosate 0 265 -3,426 -1,970 kg fuel oil; 0.0484 kg Dow- Direct use Trans- Potential Total net kg / 1000 kg glyphosate kg Hydrogen; / kg chemical 0.569 kg CH4; Electricity therm Steam of fuel port* recovery energy glyphosate 1,000 0.634 kg Propylene; 1.03 kg 1.00 500 0 7.72E+04 0 440 -1.48E+04 6.33E+04 Ethylene 452 pyrolysis 0.0553 kg gas; Argon; 3.26 kg 0.260 643 0 1,070 5,237 199 -1,280 5,869 Oxygen 641 Nitrogen; 1.55 kg heavy gas oil, from 0.231 403 0 0 0 0 -2.88 401 PMIDA 1,422 distillation; 0.644 kg 1.00 25.1 0 2,172 0 626 -745 2,079 DSIDA in 37pct sol 1,186 kerosene, from distillation; 0.542 1.25 kg kg Ethanol light gas Amine; oil, from 0.235 distillation; kg Triethanol 0.711 kg amine; residum, 1.00 340 0 1,570 0 0 -7,323 -5,413 Naphtha 461 0.0141 from distillation; kg triethanol amine, 85 0.225 110 0 51.7 910 0 0 1,072 diethanol amine 765 wt 0.886 pct; kg Chlorine; 0.0252 0.400 149 0 3,094 0 337 -1,043 2,536 Ammonia Sodium hydroxide 169 854 kg 1.18 Hydrogen; kg CO2; 0.459 0.523 4,045 126 0 2,740 738 6420 74.5 376 -46.3 -606 7,114 976 sodium chloride in brine 3.00E-03 kg Butane; 0.0400 26 wtpct 1,345 kg Ethane; 7.00E-03 kg LPG 1.00 19.2 0 1,212 0 0 0 1,232 Formaldehyde 263 condensate; 0.0100 kg 1.00 202 0 1,459 0 116 -1,176 600 Natural Methanol gas 205 330 Propane; 0.0103 kg Dimethyl ether; 0.943 0.990 4150 0 6940 7,280 698 1450 -6,9350 1,600 698 nitrogen Phosphorus from trichloride air 1,024 65.1 0.358 kg oxygen from air; 0.736 1.00 6.980 0 0 0 4500 0 457 0 oxygen from air 882 2.79 0.0285 kg kg nitrogen Hydrogen; from air; 1.13 0.264 0 0 0 0 0 0 0 Water Chlorine for rxn 1,005 808 kg Sodium hydroxide; 0.464 1.00 0.809 3,826 0 2,5920 0 3550 -43.80 0.809 6,729 Ethylene oxide 603 1.000 kg CO; 1.41 kg Dust; 0.192 0.480 kg Ferrophosphorus; C4 stream; 0.0881 1.00 1,169 0 22.5 0 265 -3,426 -1,970 phosphorus, white 235 kg 8.10 fuel kg oil; Slag; 0.0484 kg Hydrogen; 7.92E-04 kg 0.569 Ammonia; kg CH4; 0.0855 1,172 0 0 0 103 -599 677 0.634 7.25E-03 kg Propylene; kg Ammonium 1.03 kg Ethylene 452 pyrolysis sulfate; 0.0133 gas; kg Benzene; 0.0533 1.55 kg kg heavy coal gas tar from oil, from distillation; coking; 0.0703 0.644 kg kg coke oven 0.260 643 0 1,070 5,237 199 -1,280 5,869 coke, metallurgical 22.1 kerosene, gas; from distillation; 0.873 0.620 0 0.0758 0.120 9.72 0 10.5 coal mass 25.7 0.542 kg light gas oil, from 1.00 5.61 0 0 23.0 11.3 0 39.9 Sulfuric acid 0.115 distillation; 0.711 kg residum, 1.00 8.68E-06 0 0.0829 0 0.0506 -0.0366 0.0970 Naphtha 461 from 0.989 distillation; kg Sulfur dioxide; 0.225 110 0 51.7 910 0 0 1,072 Sulfur trioxide 0.0934 0.506 0.886 kg Sulfuric Chlorine; acid; 0.0252 0.401 0.0474 0 0.0178 0.0523 0.0411 -0.384 -0.226 Sodium Sulfur hydroxide 0.0403 854 kg already Hydrogen; allocated 0.523 0.200 4,0450 0 2,7400 0.1970 0.0177 376 -46.30 7,114 0.215 sodium Phosphate chloride rock in brine 157 1.00 34.0 0 0 4.73 69.0 0 108 26 Silica wtpct 1,345 62.3 1.00 19.20 0 1,2120 0 27.40 0 1,232 27.4 Formaldehyde Total process energy 263 1.00 1.32E+04 202 0 9.46E+04 1,459 1.48E+040 3,604 116 -3.81E+04 -1,176 8.81E+04 600 Methanol Multiplying by pre-combustion factor 330 to 0.0103 account kg for Dimethyl energy ether; 0.990 415 0 694 7,280 145 -6,935 1,600 Phosphorus consumed prior trichloride to point of use. 1,024 1.00 1.45E+04 6.98 0 1.09E+050 1.70E+040 4,325 450 -4.38E+040 1.01E+05 457 Natural resource energy, HHV 0.0285 kg Hydrogen; 1.13 4.54E+04 0 1.36E+05 1.70E+04 4,325 -5.47E+04 1.48E+05 Chlorine Precombustion factors, MJ fuel 808 extracted kg Sodium per hydroxide; MJ delivered (The 0.464 3,826 0 2,592 excess is consumed in delivery) 1.000 kg CO; 1.41 kg Dust; 1.1a 1.15b 1.15b Natural resource energy, MJ HHV 0.192 fuel kg per Ferrophosphorus; MJ energy to process. 3.13 1.25 1.25 phosphorus, a. half coal, half white nuclear with no 235 delivery 8.10 kg Slag; 0.0855 1,172 0 0 b. half oil, half natural gas 7.92E-04 kg Ammonia; 7.25E-03 kg Ammonium Table 2 (continued). Cradle-to-gate sulfate; energies 0.0133 kg Benzene; for 1000 kg glyphosate. 0.0533 kg coal tar from 0 1.20 1.00 0 355 1.15b 1.00 103 -43.8 1.15b 1.25 -599 6,729 677 coke, metallurgical coal mass Sulfuric acid coking; 0.0703 kg coke oven Energy use, design basis, abbreviated supply chain. Total 22.1 gas; process energy = 88,100 MJ/1000 0.873 kg. 0.620 Total nre = 148,000 0 0.0758 MJ/kg. 25.7 1.00 5.61 0 0 Process energy Natural resource value of process energy 0.115 1.00 8.68E-06 0 0.0829 100,000 0.989 kg Sulfur dioxide; 0.120 9.72 23.0 11.3 0 0.0506 0 0 -0.0366 10.5 39.9 0.0970 Sulfur trioxide 0.0934 0.506 kg Sulfuric acid; 0.401 0.0474 0 0.0178 0.0523 0.0411 -0.384 -0.226 Sulfur Phosphate rock 80,000 0.0403 already allocated 157 0.200 1.00 0 34.0 0 0 0 0 0.197 0.0177 4.73 69.0 0 0 0.215 108 Silica 62.3 1.00 0 0 0 0 27.4 0 27.4 Total process energy 60,000 1.32E+04 0 9.46E+04 1.48E+04 3,604 -3.81E+04 8.81E+04 Multiplying by pre-combustion factor to account for energy consumed prior to point of use. 40,000 Natural resource energy, HHV Precombustion factors, MJ fuel extracted per MJ delivered (The 1.45E+04 4.54E+04 0 1.09E+05 1.70E+04 0 1.36E+05 1.70E+04 4,325 -4.38E+04 1.01E+05 4,325 -5.47E+04 1.48E+05 excess is consumed in delivery) 20,000 1.1a 1.15b 1.15b 1.20 1.15b 1.15b Natural resource energy, MJ HHV fuel per MJ energy to process. a. half coal, half nuclear with no delivery 3.13 1.25 1.25 1.00 1.00 1.25 b. half oil, half natural gas 0 Energy, MJ per 1000 kg glyphosate -20,000 Figure 2. Cradle-to-gate energy profile for glyphosate production Global warming potentials in particular are typically dominated by energy use. In the glyphosate supply chain, process emissions of CO2 (no other GHG chemicals were formed from this chemical tree) are from the glyphosate gtg (oxidation of organic), ethylene oxide (over oxidation of ethylene), ammonia (coproduct), 490
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Welcome ii Soyez les bienvenus à L
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Programme Overview Room color code:
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General Information 8 th Internatio
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Table of Contents for Sessions TUES
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8 th International Conference on LC
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ORAL SESSIONS 8 th International Co
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KEYNOTE SESSION 8 th Int. Conferenc
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