Methanol Production

Chemical Structure of Methanol

Toxicity of Methanol Methanol is very toxic to humans if ingested and it is also absorbed transdermally(percutaneous absorbtion by the skin) or inhalation as a vapour as it is very volatile. A symptom-free period of 1048 hours is followed by effects such as nausea, blurred vision,headches, vomiting and abdominal pain, mainly caused by the hyperacidity of blood as a result of formic acid production in the bloodstream. Ullmanns Encyclopedia of Industrial Chemistry identifies the Threshold limit value - Time weighted average (TLV-TWA) of exposure to be 200ppm(skin) and lethal dosage for oral ingestion to be between 30-100 ml .Also recommended is protective clothing and air supply via respirators for exposure to methanol for a long period of time when aerial concentration exceeds 0.5 vol%. Lethal effects include irreversible blindness, coma and death. Most Important Industrial Usage The most important industrial usage of methanol is in the chemical syntheses of secondary derivatives such as formaldehyde( as a solvent in paints and varnishes), acetic acid,MTBE(used as an octane enhancer in automotive fuels), methyl methacrylate and other chemicals.Approximately 70% of total methanol production is used to manufacture such industrial chemicals which have applications in chemical products and pharmaceutical industries. Other minor uses of methanol include uses in refrigerant systems,as an absorption agent in gas scrubbers to remove carbon dioxide and as a fuel source for Otto Engines as fuel additives.

Steam Reforming Process

Methanol is made from synthesis gas. Synthesis gas is produced by the catalytic cracking of natural gas in the absence of oxygen, with the addition of water in the form of steam to produce Carbon Monoxide (CO) and Hydrogen gas (H2). Synthesis gas is then used to produce methanol. The mechanism to produce syngas is as follows: CH4 + H2O CO + 3 H2 CO + H2O CO2 + H2 Catalyst: Ni or Pt Catalyst Temperature used is around 850 Pressure used is approximately 3MPa

Synthesis gas is then converted to methanol in the mechanism (low-pressure synthesis) given by the equations: CO+2H2 CH3OH CO2+3H2 CH3OH+H2O Catalyst: Cu-ZnO-Al2O3 Catalyst Temperature used is around 220 -230 Pressure used is approximately 5MPa

Partial Oxidation
Partial Oxidation involves the catalytic cracking of methane in the absence of a catalyst to produce synthesis gas which consists of CO and H2 gases which are then reacted to form methanol with a catalyst. The reaction is exothermic, and energy consumption is lower than in the endothermic reaction of steam reforming. The mechanism for partial oxidation is given by the following equations:

CH4 + 0.5O2 CO+2H2 (Production of Syngas) Temperature used is around 750 -1500 Pressure used is approximately 0.1-9MPa CO + 2H2 CH3OH (Syngas conversion to Methanol)

Net Balanced Equation for Steam Reforming: To produce syngas: CH4+2H2O CO2+4H2 To produce methanol: CO+CO2+5H2 2CH3OH+H2O Overall: CH4 + H2O+ CO+H2 2CH3OH

Net Balanced Equation for Partial Oxidation: Overall: CH4 + 0.5 O2 CO + 2 H2 CH3OH

Task 4)
Fractional Atom Utilisation=

Steam Reforming: 2 CH4 + 3 H2O -> CO + CO2 + 7 H2 CO + CO2 + 7 H2 -> 2 CH3OH + 2 H2 + H2O 2 CH4 2 16.04 32.08 CO CO2 7H2 3 H2O 1 1 7 3 28.07 44.07 2.016 18.02 28.07 44.07 14.11 54.06 Table 1: Weight calculation for steam reforming 2 CH3OH 2 32.05 64.10

mol kg/mol kg

Partial Oxidation: CH4 + O2 -> CO + 2 H2 -> CH3OH CH4 1 16.04 16.04 CO 2 H2 O2 1 2 31.998 28.07 2.016 28.07 4.032 15.999 Table 2: Weight calculation for partial oxidation CH3OH 1 32.05 32.05

mol kg/mol kg

Price, Profit or Loss Steam Reformation 2 CH4 + 3 H2O -> 2 CH3OH + 2 H2 + H2O Hydrogen: $1.62/kg x1000kg/tonne = $1620/tonne Prices Tonne CH4 USD 90.18 H2O USD 1.046 CH3OH USD 440 H2 USD 1620 Table 3: Price of materials per tonne 2 CH4 3 H2O 2 CH3OH mol 2 3 2 kg/mol 16.04 18.02 32.05 kg 32.08 54.06 64.10 ratio 0.5004 0.843 1 Cost(USD$) 90.18 1.046 440 Production 45.13 0.882 440 Price Table 4: Production price for products and reactants 2H2 2 2.016 4.032 0.0629 1620 101.90 H2O 1 18.02 18.02 0.281 1.046 0.294

Gross Profit = (Total Production) (Total Reactant) = $542.194 - $46.012 = $496.18/tonne

Partial Oxidation CH4 + O2 -> CH3OH If Air is made up of 79% Nitrogen gas, and 21% oxygen gas by estimation, Oxygen Gas should be free. Prices Tonne CH4 USD 90.18 H2O USD 1.046 CH3OH USD 440 Table 5: Price of materials per tonne CH4 1 16.04 16.04 0.5004 90.18 O2 0.5 31.998 15.999 0.4992 0 CH3OH 1 32.05 32.05 1 440

mol kg/mol kg ratio Cost(USD$)

Production Price 45.13 0 Table 6: Production price for products and reactants

440

Gross Profit = (Total Production) (Total Reactant) = $440 - $45.13 = $394.87/tonne Safety of handling methanol

Both production uses methane to produce the final product which is methanol. As above explained the toxicity, methanol is a highly toxic substance if not handled with extreme care. Methanol can be absorbed by 3 ways, by exposing skin, by inhaling or by swallowing. As for workers who are working on site in production of methanol, if methanol is inhaled continuously, the person will experience dizziness, weakened body, migraine, nauseating, vomiting, blurred vision, or may cause permanent blindness, or death. Thus warning and hazard signs must be posted and to be informed to workers to prevent the consequences. (methanol.org, 2011)

Environmental Consequences

Methanol doesnt affect the environment much, because, methanol is soluble in water and biodegradable, and in addition, it is naturally formed. Methanol as such, are used in the industry such as wastewater management, as methanol not only cleans up water, but also de-nitrify the waste water.

Furthermore, as fuel production is starting to decline, methanol in the other hand, is a cleaner yet, an alternative source of fuel for transportation. It doesnt affect environment much because methanol burns much cleaner than gasoline or other available fuel sources.

Greenhouse gasses are the main issue that has been rising for the past decade. Hence, from the introduction of methanol production, green house gasses has been significantly reduced by 40%. If methanol were to be spilt to waters or rivers, it will biodegrade quickly, thus not affecting both the people and the environment. (methanol.org, 2011)

Summary Factors Profit Steam Reformation $496.18/tonne Partial Oxidation $394.87/tonne

Both having same product which is: methanol Causes: Safety Dizziness weakened body migraine nauseating vomiting blurred vision permanent blindness death Flamable

Prevent consequences by putting up warning and hazard signs to inform workers. Both routes produces methanol Environment Biodegradable Cleaner fuel Reduces greenhouse gasses from production

Table 7: Summary of gross profit, safety and environment consequences of both route

From an overall review and analysis of the methanol production from both steam reformation and partial oxidation, we can conclude that steam reformation will be chosen, as steam reformation has the highest gross profit from production, as it is generally environmental friendly yet giving a good use to the world.

Reference

Mills. B, 2012, About.com Chemistry, Gallery Index: Chemical Structures Starting with the letter M (image), Methanol or Methyl Alcohol Chemical Structure http://chemistry.about.com/od/factsstructures/ig/Chemical-Structures---M/Methanol-orMethyl-Alcohol.-eS7.htm (Accessed 15th March 2012) methanol.org, 2011, Methanol Institute, Applications for Methanol, Applications for Pure Methanol http://www.methanol.org/Methanol-Basics/Methanol-Applications.aspx(Accessed 15th March 2012) methanol.org, July 2011, Methanol facts, Methanol Health Effects http://www.methanol.org/Health-And-Safety/Safety-Resources/Health---Safety/MethanolHealth-Effects.aspx(Accessed 15th March 2012) methanol.org, 2011, Methanol Institute, Environment http://www.methanol.org/Environment.aspx(Accessed 22nd March 2012) methanol.org, 2011, Methanol Institute, Environment, Environmental-Impact http://www.methanol.org/Environment/Environmental-Impact.aspx(Accessed 22nd March 2012) Bullis. K, August 2009, technological review, Energy, Better Gas-to-Methanol Catalyst, An improved catalyst could reduce the cost of making methanol from methane http://www.technologyreview.com/energy/23313/(Accessed 16th March 2012) Periana. R, 2010, Research Focus, Design and Study of Coordination Catalysts for Small Molecule Conversion http://www.scripps.edu/research/faculty/periana(Accessed 16th March 2012) N.A, 2001, PolymerProcessing.com, Polymer, POM http://www.polymerprocessing.com/polymers/POM.html(Accessed 16th March 2012) Quanli. Z, Xutao. Z, Youquan. Deng, November 2004, Journal of Natural Gas Chemistry, Advances in the Partial Oxidation of Methane to Synthesis Gas, Brief thermodynamic analysis of methane partial oxidation, pg. 192

http://www.bjb.dicp.ac.cn/jngc/2004/2004-04-191.pdf(Accessed 16th March 2012) N.A. 2011, Material Safety Data Sheet, Hazards Identification, Ingestion http://www.midi-inc.com/pdf/MSDS_Methanol.pdf(Accessed 22nd March 2012) N.A. 1998, Process Flow Diagram, Coogee Energy Pty Ltd (image) http://www.coogeeenergy.com.au/images/methanol/processdiag.jpg(Accessed 22nd March 2012) N.A, N.D, the Energy Lab, Gasifipedia Supporting Technologies, LPMEOH Process (image) http://www.netl.doe.gov/technologies/coalpower/gasification/gasifipedia/5-support/513_meoh-synthesis.html(Accessed 22nd March 2012) N.A, 2012, Methanex, Marketing, Methanol Price, Asia Pacific http://www.methanex.com/products/methanolprice.html(Accessed 22nd March 2012) N.A, 2012, index mundi, Natural Gas Monthly Price, US Dollars per thousand cubic meters of gas http://www.indexmundi.com/commodities/?commodity=natural-gas(Accessed 22nd March 2012) N.A, N.D, the Energy Lab, Hydrogen and Clean fuels, Summary from hydrogen and coal cases http://www.netl.doe.gov/technologies/hydrogen_clean_fuels/systems_studies.html(Access ed 22nd March 2012) N.A, 2007, What is the real cost of water?, Cost of water per tonne, Mains http://ramblingsdc.net/Australia/CostWater.html(Accessed 22nd March 2012) N.A, N.D, Greener Industry, Atom Economy, Yield, Examples http://www.greener-industry.org.uk/pages/atom/1atom_yield.htm(Accessed 21st March 2012)

Steam Reforming
Steam Reforming is where methane or natural gas is used to react with steam, to convert into synthesis gas which consists of CO, CO2, and H2. 2 CH4 + 3 H2O -> CO + CO2 + 7 H2

Then the synthesis gas is then converted to methanol by using a catalyst. The catalyst used is made with carbon, nitrogen and platinum, developed by Roy Periana, directly converts the methane to methanol at low temperatures. Furthermore, the conversion produces less carbon dioxide gas or byproducts. In addition, less energy is used to convert methane to methanol by using the catalyst. CO + CO2 + 7 H2 -> 2 CH3OH + 2 H2 + H2O

Partial Oxidation
Partial oxidation is the chemical process where methane undergoes oxidation to produce carbon monoxide and hydrogen gas, which then the carbon monoxide and hydrogen gas is converted to methanol. A catalyst POM (polyoxymethylene) is used to speeden up the chemical reaction of methane and oxygen. CH4 + O2 -> CO + 2 H2 -> CH3OH

Balanced Equation for both processes. Steam Reforming: 2 CH4 + 3 H2O -> CO + CO2 + 7 H2 CO + CO2 + 7 H2 -> 2 CH3OH + 2 H2 + H2O

Partial Oxidation: CH4 + O2 -> CO + 2 H2 -> CH3OH

Atom Economy Yield

Steam Reforming: 2 CH4 + 3 H2O -> CO + CO2 + 7 H2

CO + CO2 + 7 H2 -> 2 CH3OH + 2 H2 + H2O 2 CH4 2 16.04 32.08 3 H2O 3 18.02 54.06 CO 1 28.07 28.07 CO2 1 44.07 44.07 7H2 7 2.016 14.11 2 CH3OH 2 32.05 64.10

mol kg/mol kg

Partial Oxidation: CH4 + O2 -> CO + 2 H2 -> CH3OH CH4 1 16.04 16.04 O2 31.998 15.999 CO 1 28.07 28.07 2 H2 2 2.016 4.032 CH3OH 1 32.05 32.05

mol kg/mol kg

Price, Profit or Loss 2 CH4 + 3 H2O -> 2 CH3OH + 2 H2 + H2O 2 CH4 2 16.04 32.08 0.5004 3 H2O 3 18.02 54.06 0.843 2 CH3OH 2 32.05 64.10 1 2H2 2 2.016 4.032 0.0629 H2O 1 18.02 18.02 0.281

mol kg/mol kg ratio cost

Will find out the cost tomorrow. But you can find how to solve this question in our 1st lecture given by faye (solution example in blackboard)

http://www.world-wire.com/news/0708080001.html

brunei-methanol.com/products.htm www.ucc.ie/academic/chem/dolchem/html/comp/methanol.html

www.ics.trieste.it/media/139813/df6496.pdf

http://academic.scranton.edu/faculty/cannm1/organicmodule.html