Methanol Methanol production from production from Municipal Solid Municipal Solid Waste (MSW)Waste (MSW)CHE 397CHE 397

Group CharlieGroup Charlie

Priya Chetty, Scott Morgan, Brian Mottel, Daniyal Priya Chetty, Scott Morgan, Brian Mottel, Daniyal Qamar, Sukhjinder SinghQamar, Sukhjinder Singh

Mentor: Dennis O’ BrienMentor: Dennis O’ Brien Dr. Jeffery PerlDr. Jeffery Perl

History History

Natural gas, wood, and coal were Natural gas, wood, and coal were used prior to the use of syngas used prior to the use of syngas

Hydrogenation of CO and COHydrogenation of CO and CO22 at at 300-1000atm and 400 ˚C300-1000atm and 400 ˚C

In 1923 Mittasch and Pier used In 1923 Mittasch and Pier used syngas to synthesize Methanolsyngas to synthesize Methanol

Introduction of catalysts Introduction of catalysts Modern era – Copper based catalysts Modern era – Copper based catalysts

at affordable reaction conditionsat affordable reaction conditions

Objectives Objectives

Eliminate the dependence on natural gasEliminate the dependence on natural gas Significant reduction in total quantity of Significant reduction in total quantity of

waste sent to landfills waste sent to landfills Optimum yield of Methanol from given Optimum yield of Methanol from given

amount of syngas amount of syngas Ensure process is economically profitable Ensure process is economically profitable

while remaining competitive in marketwhile remaining competitive in market Produce sufficient amount to meet Produce sufficient amount to meet

demanddemand

BasisBasis Plasma Gasification of MSW to obtain Plasma Gasification of MSW to obtain

syngassyngas Ideal syngas concentrationIdeal syngas concentration

64 vol% H64 vol% H22

27 vol% CO27 vol% CO 3 vol% CO3 vol% CO22

6 vol% impurities6 vol% impurities SN = SN = [H[H22] - [CO] - [CO22]] = 2.0 = 2.0

        [CO] + [CO2]         [CO] + [CO2] 1 ton MSW = 102 gal Methanol1 ton MSW = 102 gal Methanol Projected 204 million gal Methanol per year Projected 204 million gal Methanol per year

ReactionsReactions CO + 2HCO + 2H22 ↔ CH ↔ CH33OHOH

CO +HCO +H22O ↔ COO ↔ CO22 + H + H22

COCO22 + H + H22O ↔ CHO ↔ CH33OH +3HOH +3H22OO

Exothermic Reactions occur at 50-100 atm over Cu-Exothermic Reactions occur at 50-100 atm over Cu-Zn-Al oxide based catalysts with no SZn-Al oxide based catalysts with no S

Temperature Upper limit 400 C to prevent Methane Temperature Upper limit 400 C to prevent Methane productionproduction

COCO2 2 is needed to activate some catalystsis needed to activate some catalysts

Raw Raw MaterialsMaterials

PressurePressure TemperatureTemperature CatalystCatalyst ReactorReactor Residence Residence TimeTime

(CO, H(CO, H22)*)* 340 atm340 atm 350-400 ° C350-400 ° C ZnO-CrZnO-Cr22OO33 Fluidized Fluidized BedBed

5000 5000 GHSVGHSV

(CO,CO2, (CO,CO2, H2)**H2)**

50-50-100atm100atm

250-300 °C250-300 °C Cu-Zn-Al Cu-Zn-Al

oxidesoxides

Reaction Conditions

*Perry’s Eighth edition

** Perry’s Seventh edition

Basic Flow DiagramBasic Flow Diagram

Methanol Synthesis from MSW Methanol Synthesis from MSW

Competing ProcessesCompeting Processes

Source of MethanolSource of Methanol Natural GasNatural Gas CoalCoal Wood Wood Plasma Gasification of MSWPlasma Gasification of MSW

Pressure/Temperature Pressure/Temperature

Environmental AnalysisEnvironmental Analysis

Based on estimate of 5,000 tons/day Based on estimate of 5,000 tons/day of MSW, process will reduce landfill of MSW, process will reduce landfill waste by 1.825M tons annuallywaste by 1.825M tons annually

Utilizing MSW also results in the Utilizing MSW also results in the capture of heavy metals which capture of heavy metals which prevents water contamination due to prevents water contamination due to run-offrun-off

Neutral process Neutral process

Market OutlookMarket Outlook

MSW tipping fee is $35/tonMSW tipping fee is $35/ton Methanol is currently at $1.35/galMethanol is currently at $1.35/gal In US between mid-August and mid-In US between mid-August and mid-

NovemberNovember Methanol contracts were up 25%Methanol contracts were up 25% Spot Methanol were up 28%Spot Methanol were up 28%

Courtesy of MBET practicum project

Current ProductionCurrent Production

18 Methanol plants in the US, which 18 Methanol plants in the US, which produce 2.6 Billion gallons/yrproduce 2.6 Billion gallons/yr

90 Methanol plants worldwide, 90 Methanol plants worldwide, which produce 11 Billion gallons/yr which produce 11 Billion gallons/yr

Methanol industry generates $12 Methanol industry generates $12 Billion/yr and employs 100k Billion/yr and employs 100k personnel personnel

Future ObjectivesFuture Objectives

Operating conditions and the cost Operating conditions and the cost and maintenance associatedand maintenance associated

Types and cost of equipment neededTypes and cost of equipment needed Type and cost of catalyst(s)Type and cost of catalyst(s) Storage and transportation cost of Storage and transportation cost of

methanolmethanol Production of other chemicals using Production of other chemicals using

methanolmethanol

Questions???Questions???

ReferencesReferences "Fundamentals of Methanol Synthesis - Supermethanol - The GtM "Fundamentals of Methanol Synthesis - Supermethanol - The GtM

Concept." Concept." Home - Supermethanol - The GtM ConceptHome - Supermethanol - The GtM Concept. Web. 23 Jan. 2011. . Web. 23 Jan. 2011. <http://www.supermethanol.eu/index.php?<http://www.supermethanol.eu/index.php?id=21&rid=12&r=methanol_synthesis&PHPSESSID=4fj9m3a9tpl8q1et6id=21&rid=12&r=methanol_synthesis&PHPSESSID=4fj9m3a9tpl8q1et6msktg85o3>. msktg85o3>.

Zoltan, Kish, and Ernie Dueck. "MBET Practicum Project - Waste to Zoltan, Kish, and Ernie Dueck. "MBET Practicum Project - Waste to Methanol Pitch.”24 Apr. 2010. Web. 24 Jan. 2011.Methanol Pitch.”24 Apr. 2010. Web. 24 Jan. 2011.

Perry, Robert H., and Don W. Green. Perry, Robert H., and Don W. Green. Perry's Chemical Engineers' Perry's Chemical Engineers' HandbookHandbook. 7th ed. New York: McGraw-Hill, 1997. Print.. 7th ed. New York: McGraw-Hill, 1997. Print.

Green, Don W.; Perry, Robert H. Green, Don W.; Perry, Robert H. Perry's Chemical Engineers' Handbook.Perry's Chemical Engineers' Handbook. 8th ed. New York: McGraw-Hill, 2008. Print.8th ed. New York: McGraw-Hill, 2008. Print.

"Methanol." "Methanol." Wikipedia, the Free EncyclopediaWikipedia, the Free Encyclopedia. Web. 24 Jan. 2011. . Web. 24 Jan. 2011. <http://en.wikipedia.org/wiki/Methanol>.<http://en.wikipedia.org/wiki/Methanol>.