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CO2 UTILIZATION TO HIGHER VALUE CHEMICALS AND Ethylene Propylene ... Separation Benzene Toluene...

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  • CO2 UTILIZATION TO HIGHER VALUE CHEMICALS AND

    PRODUCTS

    13.12.2017Lappeenranta University of TechnologyFrancisco Vidal Vzquez

    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 Vastamki

  • 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

    carboncarbon double bond. Examples: Ethylene: 150 Mtons/year Propylene: 100 Mtons/year Butene and others

    Traditional production process:

    Naphtha (gasoline)

    C5-C12

    750-950C

    Steam crackingLight olefins

    Separation

    Ethylene

    Propylene

    Others Methanol to Olefins (MTO) process [4]:

    Methanol400C

    Zeolite Cat.Light olefins

    Fischer-Tropsch to Olefins (FTO) process [5]:

    Bio-ethanol dehydration to olefins (ETO) process [6].

    H2 + CO2

    300-350C

    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

    500-550C

    Cat. reforming

    Others

    Separation

    Benzene

    Toluene

    Xylene

    + H2+

    BTX

    BTX from CO2 and H2 [5, 8, 9]:

    CO2350C

    FT syn (Fe-cat)+ H2

    Light olefins

    C2-C6

    450C

    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 UreacarbonylGlycerol 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 (3MgO2SiO22H2O) 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]

    Dont 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/

  • References[1] Bayer, Bayers CO2 projects Use of carbon dioxide for the production of plastics Dream Reactions Dream Production CO2rrect, 2010.[2] S. Moret, P. J. Dyson, and G. Laurenczy, Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media, Nat. Commun., vol. 5, p. 4017, 2014.[3] C. Fink, M. Montandon-Clerc, and G. Laurenczy, Hydrogen Storage in the Carbon Dioxide Formic Acid Cycle, Chim. Int. J. Chem., vol. 69, no. 12, pp. 746752, 2015.[4] P. Tian, Y. Wei, M. Ye, and Z. Liu, Methanol to Olefins (MTO): From Fundamentals to Commercialization.[5] H. M. T. Galvis and K. P. De Jong, Catalysts for Production of Lower Ole fi ns from Synthesis Gas : A Review, ACS Catal., vol. 3, pp. 21302149, 2013.[6] Q. Qian et al., Single-catalyst particle spectroscopy of alcohol-to-olefins conversions: Comparison between SAPO-34 and SSZ-13, Catal. Today, vol. 226, pp. 1424, May 2014.[7] M. Bender, Global Aromatics Supply -Today and Tomorrow, 2013.[8] I. V Asaftei, N. Bilba, and L. M. Birsa, Aromat

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