ORGANIC CHEMICAL
SYNTHESES ON MARS
Robert J. Milligan
4Frontiers
10th Annual International Mars Society
Convention
August 31, 2007
DIFFERENCES
• Mars has no Coal, no Oil, no Biomass.
• The Only Readily Available Source of
Carbon Available on Mars is its CO2
Atmosphere.
• This, Along with Electrolysis of Water to
Provide Hydrogen, Proves to be Entirely
Adequate for Our Needs.
Aug 31, ‘07
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SYNGAS PREPARATION
• Syngas is created by the Incomplete
Burning of Methane.
 It is Comprised of Water, Carbon Monoxide,
Carbon Dioxide, Hydrogen and Unreacted
Methane.
 Water-Gas Shift:
CO + H2O
Aug 31, ‘07
CO2 + H2
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METHANOL SYNTHESIS
• It was Found That Carbon Dioxide and
Hydrogen are the only Constituents in
Syngas to form Methanol.
CO2 + 3H2
Cu
CH3OH + H2O
• The Reaction is Simply a Reduction of
Carbon Dioxide Over a Copper Catalyst.
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METHANOL SYNTHESIS ON
MARS
CH3OH
CO2
Cu, ZnO, 250oC, 50 - 100 bar
H2
electrolysis
Martian
Atmosphere
O2
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+
H2O
other
processes
MTO REACTION
• The Principal Industrial use for Methanol on
Earth is as a Precursor for Polyethylene.
• This Reaction is Called the MTO (Methanol to
Olefins) Reaction.
 Depending on the Zeolite Catalyst Used, a Range of
Olefins can be Built.
 The Catalyst of Choice for our Purposes Prepares C2C4 Alkenes (Ethene, Propene, Butenes) in 90% Yield.
 Most of the Remaining is Carbon Soot. This has to
be Burned Out Periodically to Renew the Catalyst.
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METHANOL TO OLEFIN (MTO)
REACTION
40%
CH3OH
methanol
350-550oC, 1 to 3 bar, gage
CH2=CH2
ethene
40% CH2=CHCH3
propene
MTO-100 Zeolite Catalyst
10%
CH3CH2CH=CH2
1 and 2 -butene
CH3CH=CHCH3
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DISTILLATION
• The Ethene, Propene and the Butenes have to
be Separated From Each Other.
• In Addition Enough 1-Butene has to be
Separated From the Mixed Butenes to Provide
Branching for the Polyethylenes.
 1- Butene Fraction can be Subsequently Passed
Through a Preparative GLC Column to Remove
Traces of Trans 2-Butene.
 The Remainder can be Hydrolyzed to 2-Butanone
and/or Hydrogenated to Butane a Precursor to Maleic
Anhydride. Both are Needed for Polyester Synthesis.
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SCHEMATIC FOR SEPARATING
OLEFINS
ethene
2
propene
butenes
heavies
1.
2.
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1
alkenes
Compressor
Distillation Columns
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MTO
SCHEMATIC FOR ISOLATION OF
1-BUTENE
1-butene
butane
1.
2.
Aug 31, ‘07
H2
heavies
2
1
Compressor
Distillation Columns
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butenes
POLYETHYLENE
• Besides Ethene, Polyethylene Synthesis
Requires 1-Butene, a Zieglar-Natta
Catalyst and is done in an Isobutane
Solvent.
 The Zieglar-Natta Catalyst will be Brought
From Earth.
 The Isobutane will be Prepared From Carbon
Monoxide (CO) and H2 by What is Known as
Isosynthesis.
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ISOSYNTHESIS
(CH3)3CH
(CH3)2C=CH2
CO
ZrO2, > 400oC, 50 - 150 bar
H2
electrolysis
Martian
Atmosphere
or other source
O2
Aug 31, ‘07
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+
H2O
other
processes
SOME COMMENTS ON
ISOSYNTHESIS
• Isosynthesis has Two Drawbacks.
 It Does Not Provide a Clean Yield.
 The Products have to be Distilled and the
Isobutene has to be Hydrogenated.
 The Water-Gas Shift (Above) Works Against
the Reaction.
 It is Found that the CO2 Produced Collects on the
Catalyst Retarding the Reaction.
 An Alternative is Cracking Butane.
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POLYETHYLENE SYNTHESIS
• Continuous Loop Process
 Reactants have to be Free of Water, Alcohols, Carbon
Dioxide and Sulfur Compounds as they Adversely
Affect the Zieglar-Natta Catalyst.
 Pressure is 40 Bar.
 Temperature is Kept Below 130ºC.
 The Polyethylene is Isolated as Particulate and the
Isobutane is Flashed off to be Collected for a Future
Run.
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ALIPHATIC SYNTHESES FROM
METHANOL
Ag
CH2-CH2
O
oxirane
CH2=CH2
ethene
CO2
cat.
3b.
CO
O O
CH2CH2
CH3OH
cat.
3c.
HOCH2CH2OH + CH3OCOOCH3
dihydroxyethane dimethyl carbonate
To ethylbenzene
To polyethylene
To cumene
H2
CO2 + CO
MTO
CH3OH
methanol
CH3CH=CH2
propene
Cl2
CH2ClCH=CH2
3-chloropropene
LEGEND:
polycarbonate and polyester
polyester
epoxy resin
polyethylene
Aug 31, ‘07
Cl2, H2O
CaO
HOAc
ClCH2CHOHCH2Cl
glycerol dichlorohydrin
As co-reactant for LDPE
H2
CH3CH2CH=CH2
+
CH3CH=CHCH3
1 and 2-butenes
CH3CH2CH2CH3
butane
7/2O2, 400 - 480oC
0.3 - 0.4 Mpa
H2O, H2SO4
Cu D
CH3CH2CHOHCH3
8b.
2-butanol
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CH3CH2COCH3
2-butanone, MEK
CaO
O
O=C
C=O
CH=CH
maleic anhydride
H2S2O8
CH2-CHCH2Cl
O
epichlorohydrin
CH3CH2 CH3
HOOCOOCOOH
CH3 CH2CH3
MEKPO dimer
OTHER SYNTHESES
• In Addition to Polyethylene, We have Devised
Synthesis Routes to:
 Polyester
 Epoxy Resin
 Polycarbonate
• Polycarbonate is Needed for Greenhouse
Windows Once it Became Apparent that Large
Quantities of Useable Silica are not Immediately
Available on Mars.
Aug 31, ‘07
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POLYCARBONATE SYNTHESIS
• The Polycarbonate in Question is Based
on Bisphenol-A.
 This is also the backbone for the epoxy resin
so the synthesis will be shared.
 Preparation goes back to CO2
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BENZENE FROM CO2
9H2
400ºC
6CO2 + 24H2
[6CH4]
Sabatier
Ru, 4bars 12H2O
CO2
700ºC
Mo, Zeolite
METAMARS
15H2
15H2O
+
electrolysis
7.5O2
3H2O
O2
Aug 31, ‘07
H2O
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Benzene
CUMENE
Benzene
+
30 bar, 250oC
Zeolite catalyst
Cumene
(2-Propylbenzene)
CH3CH=CH2
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PHENOL
Phenol
1-10 bar., O2 [Cumene Hydro
Cumene
(2-Phenylpropane) 82 - 90oC,
-peroxide (CHP)]
radical initiator Ca. 30%
60-70oC
H+, H20
+
Acetone
Vacuum distill unreacted cumene
Weak caustic scrub to remove phenol, acids
Aug 31, ‘07
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BISPHENOL - A
Phenol
Ion exchange resin
Excess
+
CH3COCH3
CH3COCH3
Aug 31, ‘07
Bisphenol A
H2O
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OXIRANE (ETHYLENE OXIDE,
EO)
CO2
CH2=CH2
O2, 200-250oC
Ag/Al2O3, 10 to 30 bar
CH2-CH2
O
EO
MTO
Aug 31, ‘07
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1,3-DIOXOLAN-2-ONE (ETHYLENE
CARBONATE, EC)
CO2
+
CH2-CH2
O
100ºC, 50 bar
O-CO-O
EC
3:1 CO2:EO ratio
Aug 31, ‘07
CH2-CH2
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DIMETHYL CARBONATE (DMC)
To polyester
CH2-CH2
HOCH2CH2OH
O-CO-O
1+ bar, 90ºC
excess
TiSiO4 matrix
K2CO3
CH3OH
+
CH3OCO2CH3
DMC
Aug 31, ‘07
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POLY[2,2-PROPANEBIS(4-PHENYL CARBONATE)]
CH3
CH3
-OH + (CH3O)2CO
DMC
HO-
1-3 bar
90ºC
O-
CH3
Bisphenol A
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-OCO
CH3
+ 2CH3OH
n
REFERENCES
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Aug 31, ‘07
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