Green is Seen in Fertilizers Municipal Solid Waste Management. Carrie Farberow Kevin Bailey University of Oklahoma May 1, 2007

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Green is Seen in Fertilizers Municipal Solid Waste Management Carrie Farberow Kevin Bailey University of Oklahoma May 1, 007

MSW Overview EPA 005 Facts and Figures U.S. Waste Produced = 45.7 million ton

Municipal Solid Waste Composition is highly variable Poor quality fuel Low heating value High moisture content Difficult to handle and feed to process equipment

Landfilling Waste is deposited and buried Produces leachate Groundwater pollutant Greenhouse gas emissions Methane and CO Costs cities $10 to $70 per ton Reduces nearby land property value 005: Landfill Waste 133.3 million tons

Municipal solid waste has steadily increased throughout the past 45 years. The number of landfills has steadily decreased throughout the past 17 years.

Incineration Waste is completely combusted Minimizes land required by landfills Reduces weight by up to 90% Waste-to-energy Pollutants Greenhouse gases Toxic ash High operation costs 005: Waste combusted with energy recovery 33.4 million tons

Pyrolysis/Gasification Partial combustion Limited (less than stoichiometric) amount of oxygen Thermally self-sustaining Combust a small portion of the feed to generate heat for pyrolytic reactions C C C + + + O H CO O CO CO CO + H H H H = 406MJ / kmol = 131MJ = 173MJ / kmol / kmol

Benefits of Pyrolysis/Gasification Potential to be profitable Produce fuel or chemicals Reduce quantity and improve quality of solid discards Remedy municipal solid waste management problems

Pyrolysis Mass Balance

Pretreatment Processing Shredding to reduce MSW particle size Air/density separator Heavy fraction exits bottom 90% of ferrous removed in magnetic separator 66% of aluminum removed in eddy current aluminum separator Light fraction, mostly organic, exits the top Cyclone removes particulates

Pyrolysis/Gasification Exothermic reactions in oxidative zone High temperature endothermic reactions in the reduction zone In the absence of oxygen Produces two products synthetic gas slag

Synthesis Gas Molar composition Carbon monoxide 40% Hydrogen 4% Carbon dioxide 4% Other gases 1% Typically produced from coal or hydrocarbons Syngas composition can be altered depending on desired end product

Product Options

Product Selection Criteria Profitability based on NPW and IRR Varied MSW capacity Current and Future Market Estimated using information in literature and current journals Total Capital Investment Product Price Operating Cost

Economic Assumptions Total Capital Investment C New = Operating Cost and TCI scaled up using cost indices Product Price Most Current Available Prices Neglected C Old R 0.65 Front End Processing Waste Revenue Taxes, Depreciation, Inflation

Economic Model: Acetic Acid Production Total Capital Investment $130,563,377 Acetic Acid Production 177,94,150 lbs/year 0.00% Inflation 3/7/007 1:53 Tax Rate 0% Acetic Acid Price $0.31/lb 0.00% Inflation Main Display Discount Rate 10% Operating Cost $36,199,558/year 0.00% Inflation Acetic Acid Net Total Yearly Annual Profit 10% Capital Production Price Gross Product After Annual Cumulative Discounted Year Investment (lbs) ($/lb) Revenue Cost Taxes Depreciation Cash Flow Cash Flow Cash Flow 0 $130,563,377 0 $0 $0 $0 $0 -$130,563,377 -$130,563,377 -$130,563,377 007 177,94,150 $0 $54,961,186 $36,199,558 $18,761,68 $0 $18,761,68 -$111,801,749 $17,056,06 008 177,94,150 $0 $54,961,186 $36,199,558 $18,761,68 $0 $18,761,68 -$93,040,10 $15,505,478 009 177,94,150 $0 $54,961,186 $36,199,558 $18,761,68 $0 $18,761,68 -$74,78,49 $14,095,889 010 177,94,150 $0 $54,961,186 $36,199,558 $18,761,68 $0 $18,761,68 -$55,516,864 $1,814,445 011 177,94,150 $0 $54,961,186 $36,199,558 $18,761,68 $0 $18,761,68 -$36,755,35 $11,649,495 01 177,94,150 $0 $54,961,186 $36,199,558 $18,761,68 $0 $18,761,68 -$17,993,607 $10,590,450 013 177,94,150 $0 $54,961,186 $36,199,558 $18,761,68 $0 $18,761,68 $768,01 $9,67,68 014 177,94,150 $0 $54,961,186 $36,199,558 $18,761,68 $0 $18,761,68 $19,59,650 $8,75,438 015 177,94,150 $0 $54,961,186 $36,199,558 $18,761,68 $0 $18,761,68 $38,91,78 $7,956,76 016 177,94,150 $0 $54,961,186 $36,199,558 $18,761,68 $0 $18,761,68 $57,05,907 $7,33,40 S v $0 0 $0 $0 $0 $0 $0 $57,05,907 $0 Total: 1,77,941,497 $549,611,864 $361,995,580 $187,616,84 $0 $57,05,907 $57,05,907 -$15,81,93 Economics Summary Net Present Worth Table: Economics Information: 0% $57,05,907 40% ($85,80,856) Payout Time: 6.96years 5% $14,308,944 50% ($93,690,831) Rate of Return: 7.0% 8% ($4,671,34) 60% ($99,578,390) Return on Investment: 0.44 10% ($15,81,93) 70% ($103,893,999) Disc. Return on Investment: -0.1 15% ($36,403,105) 80% ($107,177,05) 0% ($51,905,774) 90% ($109,751,14) 30% ($7,561,06) 100% ($111,80,071)

Product Comparison 1500 TPD Product Production Price Operating Cost Net Revenue Total Capital Investment Net Present Worth (unit/day) ($/unit) ($/year) ($/year) $ $ Methanol (gal) 39,1 $1.0 $8,973,769 $5,555,679 $84,530,800 ($49,545,577) Acetic Acid (lb) 485,737 $0.31 $36,199,558 $18,761,68 $141,194,77 ($30,53,96) Formaldehyde (lb) 4,909 $0.1 $11,88,176 $6,736,810 $90,784,183 ($51,045,195) Ammonia (ton) 77 $75 $7,04,301 $0,60,95 $107,435,351 $17,016,49 Urea (ton) 489 $3 $9,381,341 $30,437,687 $140,975,657 $4,61,195 Hydrogen (m 3 ) 549,73 $0.08 $4,013,046 $11,877,158 $130,76,86 ($60,701,493) Synthetic Fuel $5,07,041 $11,565,43 $93,765,169 ($,701,754) Diesel (gal) 16,31 $1.98 Naphtha (gal) 8,341 $1.63

Product NPW vs. MSW Capacity $500 Net Present Worth ($MM) $400 $300 $00 $100 $0 ($100) Urea Ammonia Acetic Acid Hydrogen Formaldehyde Synthetic Fuel DME 0 1000 000 3000 4000 5000 6000 7000 Methanol Capacity (tons MSW/day)

Product IRR vs. MSW Capacity

Future Urea Market U.S. fertilizer usage to increase 10-15% in 008 Dependent on Crops Corn 41% of usage U.S. Urea Demand D e m a n d (M M to n s ) 1 10 8 6 4 0 1999 000 001 00 003 004 005 Year

Urea Production Reactions O H CONH NH COONH NH CO NH Synthesis Urea NH N H Synthesis Ammonia H CO O H CO Shift Gas Water 4 3 3 3 + + + + +

Syngas to Ammonia

Ammonia to Urea Ammonia 1.09 x 10 6 moles/unit time From Ammonia Production Unit Ammonia and Carbamate Recycle Carbon Dioxide 3.11 x 10 5 moles/unit time From Ammonia Production Unit P-13 Urea Reactor Decomposition and Recirculation Finishing Evaporation Urea 5.44 x 10 5 moles/unit time Wastewater

Direct Cost Utilities Operating Cost $/ton of Urea steam (10 3-10 4 kpa), m 3 1.84 cooling water, m 3 13.95 Labor, personnel shift ($8/h) 5.7 Supervision 0.86 Catalyst cost.31 Maintenance and Repairs 14.9 Operating Supplies.4 Laboratory Charges 0.86 Fixed Cost Insurance 3.48 Property Taxes 9.95 Overhead 1.90 General Cost Administrative Costs 4.30 Distribution and Marketing Costs 5.4 Total Operating Cost 89.74

Plant Location: New York City Generates about 5,000 TPD waste Contains no landfills, incinerators or resource recovery facilities All MSW is transferred out of the city About 70% is sent to out-of-state landfills Costs up to $70/ton Growing population

Waste Disposal Contracts Waste dropped at transfer station, then transported to landfills or incineration facilities 3 year contracts Option for two 1 year extensions Available TPD from Expiring Contracts Year 000 001 00 003 Available Capacity (TPD) 1700 500 3160 350 Average Standard Deviation Annual Expansion Opportunity 48TPD 599TPD 1800TPD

*Current Urea Demand: 11.6 MMtons/year

Urea Economics

Urea Profitability Sensitivity

Urea Regret Analysis Prices 006 average = $3/ton 000-004 average = $11/ton 006 August Spot Price = $67/ton 005 Urea Market 1.4% (100 TPD) 4.0% (3500 TPD) 6.8% (6000 TPD)

Regret Analysis NPW Design $11 $3 $67 Average 1 (100 tpd) ($57,374,39) $819,99 $5,93,361-10,10,367 (3500 tpd) ($9,58,310) $160,05,15 $33,43,470 18,033,48 3 (6000 tpd) $86,003,977 $376,975,580 $50,49,74 31,84,100 Regret Design $11 $3 $67 Max 1 (100 tpd) 143,378,369 376,155,651 476,569,381 476,569,381 (3500 tpd) 95,53,87 16,770,455 69,069,7 69,069,7 3 (6000 tpd) 0 0 0 0 Min 0 Optimum Capacity = 6000 TPD MSW

Economic Model: Urea Production 3/7/007 1:44 Total Capital Investment $417,978,064 Urea Production 1,957 tons/day Fixed Capital Investment $355,46,11 Urea Price $3 /ton 0.00% Inflation Working Capital $6,731,95 Municipal Solid Waste 6,000 tons/day MSW Charge $40 /ton Tax Rate 35% Main Display Discount Rate 10% Operating Cost $85 /ton Urea 0.00% Inflation Urea MSW Net Total Yearly Yearly Annual Profit 10% Capital Production Price Take Charge Gross Product After Annual Cumulative Discounted Year Investment (tons) ($/ton) (tons) ($/ton) Revenue Cost Taxes Cash Flow Cash Flow Cash Flow 0 $417,978,064 -$417,978,064 -$417,978,064 -$417,978,064 009 14,73 $3 657,000 $40 $74,06,879 $3,064,136 $35,014,070 $35,014,070 -$38,963,994 $31,830,973 010 48,546 $3 1,314,000 $40 $148,15,758 $39,949,318 $74,044,460 $74,044,460 -$308,919,534 $61,193,769 011 64,818 $3 1,971,000 $40 $,188,414 $55,457,781 $114,591,718 $114,591,718 -$194,37,815 $86,094,454 01 714,43 $3,190,000 $40 $46,876,114 $60,441,455 $17,399,335 $17,399,335 -$66,98,480 $87,015,460 013 714,43 $3,190,000 $40 $46,876,114 $60,441,455 $17,399,335 $17,399,335 $60,470,855 $79,104,964 014 714,43 $3,190,000 $40 $46,876,114 $60,441,455 $17,399,335 $17,399,335 $187,870,190 $71,913,603 015 714,43 $3,190,000 $40 $46,876,114 $60,441,455 $17,399,335 $17,399,335 $315,69,55 $65,376,003 016 714,43 $3,190,000 $40 $46,876,114 $60,441,455 $17,399,335 $17,399,335 $44,668,860 $59,43,730 017 714,43 $3,190,000 $40 $46,876,114 $60,441,455 $17,399,335 $17,399,335 $570,068,195 $54,09,755 018 714,43 $3,190,000 $40 $46,876,114 $60,441,455 $17,399,335 $17,399,335 $697,467,530 $49,117,959 S v $53,86,917 $53,86,917 $0 $34,636,496 $34,636,496 $73,104,06 $1,139,881 Total: 6,85,336 $,5,796,764 $541,561,40 $1,150,08,090 $73,104,06 $73,104,06 $39,71,486 Economics Summary Net Present Worth Table: Economics Information: 0% $73,104,06 40% ($07,514,6) Payout Time: 4.53 years 5% $438,57,96 50% ($56,95,863) Rate of Return: 19.96 % 8% $310,84,67 60% ($89,089,50) Return on Investment: 1.75 10% $39,71,486 70% ($31,193,777) Disc. Return on Investment: 0.57 15% $99,754,4 80% ($39,109,814) 0% ($649,784) 90% ($341,895,34) 30% ($130,651,434) 100% ($351,818,533)

Economic Conclusion Plant Size = 6,000 tons MSW/day TCI = $418,000,000 NPW = $39,000,000 @ 10% discount IRR = 0% Urea Break-even Price = $65/ton

Questions?

Pyrolysis Reactor Vertical shaft reactor Solid waste enters through the top Purified oxygen from air separator fed through the bottom Solid waste dried by upward flowing gases at top of reactor Exiting gas therefore cooled to between 93 C and 315 C Pyrolysis occurs in the middle zone at temperatures above 1500 C Combustion of char in oxidative zone at the bottom of the reactor produces the heat necessary for the pyrolytic reactions Operates between 100 and 00psia

Gas Cleaning Syngas flows through spraying water scrubber Electrostatic precipitator removes particulates and pyrolytic oils These components are recycled back to the reactor Water removed in a shell and tube condenser

Operating Cost Utilities, labor and catalyst costs estimated from data in the Encyclopedia of Chemical Technology Other operating costs estimated from reasonable percentages in Plant Design and Economics for Chemical Engineers Supervision: 15% of labor Maintenance and repairs: 3% of FCI Operating supplies: 15% of maintenance and repairs Laboratory charges: 15% of labor Insurance: 0.7% of FCI Property taxes: % of FCI Overhead: 60% of labor, supervision, and maintenance and repair costs Distribution and marketing: 6% of total operating cost

Carbon Dioxide Process produces 4,305 tons/day Urea synthesis requires 3.5:1 ratio of ammonia to urea in the reactor feed Process uses 80 tons/day carbon dioxide Net carbon dioxide production: 3,485 tons/day Implementation of $5/ton carbon tax would increase operating cost by $45/ton urea CO sequestration estimated at $35/ton would increase operating cost by $6/ton urea Reduces project profitability but does not change project results

Methanol Reactant Ratio : H + CO CH OH 3 3 H + CO CH OH + H O 3 H CO + 3CO = Low Temperatures and High Pressures favor Methanol formation Methanol can be sold as a product or used as an intermediate to produce alternative products 1

Ammonia Reactant Ratio: 3H + N NH H N = Used in fertilizers and refrigeration Reaction occurs at high temperature and pressure 3 3

Synthetic Fuel Reactant Ratio: Fischer-Tropsch synthesis H + CO -CH - + H O H = CO Converts H and CO into straight chain hydrocarbons using metal catalysts Diesel and naphtha

Hydrogen (1) Reactant Ratio: H O CH H + + 4 3 CO ( ) H O + CO H + CO H O CO + CH = Steam reformation (1) is used to convert methane into CO and H 4 Water gas shift reaction () is used to produce additional H Main fuel source for Hydrogen fuel cells 1

Economic Model: Urea Production Total Capital Investment $169,751,84 Urea Production 489 tons/day Fixed Capital Investment $144,74,753 Urea Price $3 /ton 0.00% Inflation Working Capital $5,477,089 Municipal Solid Waste 1500 tons/day MSW Charge $40 /ton Tax Rate 35% Main Display Discount Rate 10% Operating Cost $11 /ton Urea 0.00% Inflation 3/6/007 Urea MSW Net Total Yearly Yearly Annual Profit 10% Capital Production Price Take Charge Gross Product After Annual Cumulative Discounted Year Investment (tons) ($/ton) (tons) ($/ton) Revenue Cost Taxes Cash Flow Cash Flow Cash Flow 0 $169,751,84 -$169,751,84 -$169,751,84 -$169,751,84 009 178,561 $3 547,500 $40 $61,719,08 $0,007,634 $9,637,14 $9,637,14 -$140,114,68 $6,94,9 010 178,561 $3 547,500 $40 $61,719,08 $0,007,634 $9,637,14 $9,637,14 -$110,477,414 $4,493,565 011 178,561 $3 547,500 $40 $61,719,08 $0,007,634 $9,637,14 $9,637,14 -$80,840,199 $,66,878 01 178,561 $3 547,500 $40 $61,719,08 $0,007,634 $9,637,14 $9,637,14 -$51,0,985 $0,4,616 013 178,561 $3 547,500 $40 $61,719,08 $0,007,634 $9,637,14 $9,637,14 -$1,565,771 $18,40,378 014 178,561 $3 547,500 $40 $61,719,08 $0,007,634 $9,637,14 $9,637,14 $8,071,443 $16,79,435 015 178,561 $3 547,500 $40 $61,719,08 $0,007,634 $9,637,14 $9,637,14 $37,708,658 $15,08,577 016 178,561 $3 547,500 $40 $61,719,08 $0,007,634 $9,637,14 $9,637,14 $67,345,87 $13,85,979 017 178,561 $3 547,500 $40 $61,719,08 $0,007,634 $9,637,14 $9,637,14 $96,983,086 $1,569,07 018 178,561 $3 547,500 $40 $61,719,08 $0,007,634 $9,637,14 $9,637,14 $16,60,300 $11,46,49 S v $1,641,13 $1,641,13 $0 $14,066,788 $14,066,788 $140,687,089 $4,930,34 Total: 1,785,607 $638,831,497 $00,076,345 $310,438,931 $140,687,089 $140,687,089 $17,86,333 Economics Summary Net Present Worth Table: Economics Information: 0% $140,687,089 40% ($97,87,957) Payout Time: 5.73 years 5% $67,33,430 50% ($111,34,696) Rate of Return: 1.4 % 8% $35,149,8 60% ($10,75,773) Return on Investment: 0.83 10% $17,86,333 70% ($17,581,935) Disc. Return on Investment: 0.10 15% ($17,985,960) 80% ($13,787,195) 0% ($43,605,48) 90% ($136,863,39) 30% ($77,34,317) 100% ($140,136,70)