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CO2 UTILIZATION TO HIGHER VALUE CHEMICALS AND
PRODUCTS
13.12.2017Lappeenranta University of TechnologyFrancisco Vidal Vázquez
Final seminar NCE project
CONTENTS• Introduction
• Patent landscaping for CO2, H2 and pure O2 utilization
• CO2 to basic chemicals and intermediate products
• CO2 to chemical products
• Conclusions
Introduction• This is not a full review on all the CO2 utilization topics. There is too
many.• Fuels, methanol, synthetic natural gas, FT paraffin products and
syngas are not included because the have been studied before. • The topics were chose based on potential for CO2 utilization and
long-term CO2 “storage”.
Figure borrowed from [1]
Patent landscaping• Patents related with utilization of CO2, H2
and pure O2 in combination.• High number of patents on CO2 utilization.• Main patenting countries.
– Japan– USA– China– Europe:
• Germany• Spain• France
• Institutions with most patents:– Chinese Academy of Science.– Russian Academy of Science– Japan, Ministry of Trade and Industry– China Petroleum and Chemical Corp.– BASF SE.
Patent 3D-landscape
Documents per year: related patents (green) and non-patents (yellow)
Patent Landscaping• Number of results per compound:
– H2O2
– Other peroxides– Methanol– Organic acids– Benzene– Other aromatics– Ethers– Olefins– …
• Full report by Pertti Vastamäki
Products from CO2• Paraffin• Olefins
– Ethylene– Propylene
• Carbonic acids– Formic acid
• Carbonate salts/compounds– Magnesium carbonate silica.
• Alcohols– Polyols
• Polyethercarbonate polyol• Glycerol to Glycerol carbonate
• Esters• Aromatics
– Benzene, Toluene and Xylene (BTX)
• Ethers• Epoxides• Polymers
– Polyurethane– Polymethyl methacrylate (PMMA)
CO2 TO BASIC CHEMICALS AND PRODUCT INTERMEDIATES
CO2 to Carbonic Acids• Formic acid (CH2O2):
• Total production 720,000 tons/year worldwide» Europe:
• 200,000 tons/year: BASF, Germany.• 105,000 tons/year: Eastman, Finland (Oulu)
• Used as preservative, antibacterial, dying textiles…• Traditional production process:
Methanol + CO HCO2CH3
HCO2CH3 + H2O Formic acid + Methanol
• Direct production from CO2 and H2 [2, 3]:
CO2 to Light olefins• Light olefins (alkenes) are short chain hydrocarbons that have at least one
carbon–carbon double bond. Examples:– Ethylene: 150 Mtons/year – Propylene: 100 Mtons/year– Butene and others
• Traditional production process:
Naphtha (gasoline)
C5-C12
750-950°C
Steam crackingLight olefins
Separation
Ethylene
Propylene
Others• Methanol to Olefins (MTO) process [4]:
Methanol400°C
Zeolite Cat.Light olefins
• Fischer-Tropsch to Olefins (FTO) process [5]:
• Bio-ethanol dehydration to olefins (ETO) process [6].
H2 + CO2
300-350°C
Iron Cat.Light olefinsH2 + CO2
rWGSH2 + CO + CO2
CO2 to Aromatics• Benzene, Toluene and Xylene (BTX):
• Worldwide production [7]:– Benzene: 42 Mtons/year.– Toluene: 14 Mtons/year.– Xylenes: 39 Mtons/year.
• Traditional route:• Europe:
– In steam cracking, BTX is generated as side product and then they are separated by distillation.
• US:
Naphtha
C5-C12
500-550°C
Cat. reforming
Others
Separation
Benzene
Toluene
Xylene
+ H2+
BTX
• BTX from CO2 and H2 [5, 8, 9]:
CO2
350°C
FT syn (Fe-cat)+ H2
Light olefins
C2-C6
450°C
Aromatization
(Zeolite)
BTXSep.
Benzene
Toluene
Xylene
CO2 to Polyols• Polyols:
– Hydrocarbons with two or more alcohol groups.– Generally used as artificial sweetener and in polymer chemistry.
• Polyethercarbonate polyol:– Worldwide production of polyether polyols is 8 Mtons/year [10]. – Important compound in synthesis of polymers.– Traditional route:
– New route using CO2 (Covestro, Aachen Uni. and Bayer):
Polyether polyol: Figure borrowed from [11]
Other
Polyethercarbonate polyol
Reaction scheme of commercial process from [11]
CO2 into Glycerol to Glycerol Carbonate• Glycerol:
• Global production of 2 Mtons/year.• Glycerol is a byproduct of bioethanol production.• Low price.
• Glycerol carbonate:• Market still not stablished, but current market price up to 10 times higher
than glycerol [12].• Many applications (polymers, chemicals, pharmaceutical…).• Routes:
– Direct route:
– Indirect route:
Methanol + 2 NH3 Reaction schemes borrowed from [13]
Glycerol Glycerol carbonate
Glycerol Ureacarbonyl
Glycerol carbonate
CO2 TO CHEMICAL PRODUCTS
CO2 into Polymers• List of most used plastics:
1 – PET (Polyethylene Terephthalate)2 – HDPE (High-Density Polyethylene)3 – PVC (Polyvinyl Chloride)4 – LDPE (Low-Density Polyethylene)5 – PP (Polypropylene)6 – PS (Polystyrene)7 – Other (BPA, Polycarbonate)
• List of plastic used in construction:1 – PVC2 – Polyurethane3 – Polycarbonate4 – Polyethylene5 – Vinyl or fiberglass6 – Poly(methyl methacrylate) (Plexiglas)
CO2 to Polymers• Polyethylene (PE) and Polypropylene (PP):
• Total production PE 100 Mtons/year worldwide.• Total production PP 60 Mtons/year worldwide.
• Many different types of PE and PP can be produce with different properties.
• Traditional production process:
Ethylene Cat.
Highly exother.
PE
Propylene Cat.
Highly exother.
PP
Lightolefins
CO2 to Polymers• Poly (methyl methacrylate) PMMA or Plexigas:
• Total production 2 Mtons/year worldwide.• Used mainly for construction, advertising and automotive transport.
• New route recently develop by Evonik:
Figure borrowed from [15]
PMMA
Figure borrowed from [14]
H2 + CO2
rWGS
MTO
CO2 to Polymers• Polyurethane:
• Worldwide production 18 Mtons/year [16]. • Applications mainly in furniture, construction and automotive.• Traditional route (100% fossil carbon):
• New route (10-20% CO2 from emissions, rest fossil):– Commercialized by Covestro [11]
Isocyanate
Polyol
Polyurethane
Figures borrowed from [1]
CO2 into Bricks• Worldwide production of Portland cement is ca. 4000
Mtons/year.• From mineral carbonation:
• Magnesium-carbonate-Silica based bricks.
• Alumina-Magnesium-Carbonate bricks [17]: Steel Ladle (bricks with refractory properties [18])
• From carbon-based waste:• Bricks made out of ash from incinerated sewage with a vegetable oil based binder.
Figure borrowed from [19]
CO2 into Bricks
Figure borrowed from [21]
• From mineral carbonation:• Magnesium-carbonate-Silica based bricks.
– Produced from Serpentine (3MgO·2SiO2·2H2O) and compressed CO2. [20]
– Mineral Carbonization International (Australian start-up for commercialization)– Main issues concerning this route [22]:
» MgO-based cements are generally more costly to produce than Portland cement.» MgO-based cements cannot be used for steel-reinforced concretes for civil engineering applications.» Scarce large-scale sources of Mg.
CO2 into Bricks• From carbon-based waste:
• Bricks made out of ash from incinerated sewage with a vegetable oil based binder.
– Reduccion greenhouse gas emissions by estimates of 160% for blocks and 120% for bricks.» “The innocent-looking blocks combine ash from incinerated sewage with vegetable oil to
make bricks which are classified as carbon-negative because the oil comes from plants which have sucked out CO2 from the atmosphere” – [23]
– Don’t smell.– Encos company (UK) was supposed to commercialize this technology.
» Company created and dissolved 2011-2017.
Figure borrowed from [24]
Summary and conclusions• CO2 utilization has limitless potential for synthesis of chemicals. Plenty of literature
and patents• However, only few examples of actual applications for CO2 utilization in commercial
processes.• The main reason for the limited number of commercial applications is probably the
lack of cost competitive production of basic chemicals from CO2.• For more info on chemistry related to CO2 utilization, CO2 to chemicals the book [25]
is recommended.
Figure borrowed from [1]
NEO-CARBON ENERGY project is one of the Tekes strategic researchopenings and the project is carried out in cooperation with Technical Research
Centre of Finland VTT Ltd, Lappeenranta University of Technology LUT and University of Turku, Finland Futures Research Centre FFRC.
TECHNOLOGY FOR BUSINESS
http://www.neocarbonenergy.fi/
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