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CO2 UTILIZATION TO HIGHER VALUE CHEMICALS AND · PDF fileSeparation Ethylene Propylene ......

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CO 2 UTILIZATION TO HIGHER VALUE CHEMICALS AND PRODUCTS 13.12.2017 Lappeenranta University of Technology Francisco Vidal Vázquez Final seminar NCE project
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Page 1: CO2 UTILIZATION TO HIGHER VALUE CHEMICALS AND  · PDF fileSeparation Ethylene Propylene ... Separation Benzene Toluene Xylene + H 2 + BTX ... TECHNOLOGY FOR BUSINESS

CO2 UTILIZATION TO HIGHER VALUE CHEMICALS AND

PRODUCTS

13.12.2017Lappeenranta University of TechnologyFrancisco Vidal Vázquez

Final seminar NCE project

Page 2: CO2 UTILIZATION TO HIGHER VALUE CHEMICALS AND  · PDF fileSeparation Ethylene Propylene ... Separation Benzene Toluene Xylene + H 2 + BTX ... TECHNOLOGY FOR BUSINESS

CONTENTS• Introduction

• Patent landscaping for CO2, H2 and pure O2 utilization

• CO2 to basic chemicals and intermediate products

• CO2 to chemical products

• Conclusions

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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]

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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)

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Patent Landscaping• Number of results per compound:

– H2O2

– Other peroxides– Methanol– Organic acids– Benzene– Other aromatics– Ethers– Olefins– …

• Full report by Pertti Vastamäki

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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)

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CO2 TO BASIC CHEMICALS AND PRODUCT INTERMEDIATES

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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]:

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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

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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

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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]

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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

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CO2 TO CHEMICAL PRODUCTS

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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)

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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

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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

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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]

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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]

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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.

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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]

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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]

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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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References[1] Bayer, “Bayer’s 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. 746–752, 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. 2130–2149, 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. 14–24, May 2014.[7] M. Bender, “Global Aromatics Supply -Today and Tomorrow,” 2013.[8] I. V Asaftei, N. Bilba, and L. M. Birsa, “Aromatization of industrial feedstock mainly with butanes and butenesover HZSM-5 and Zn / HZSM-5 catalysts,” vol. 34, pp. 5–34, 2009.[9] L. M. Lubango and M. S. Scurrell, “Light alkanes aromatization to BTX over Zn-ZSM-5 catalysts: Enhancements in BTX selectivity by means of a second transition metal ion,” Appl. Catal. A Gen., vol. 235, no. 1–2, pp. 265–272, 2002.[10] N. Von Der Assen and A. Bardow, “Life cycle assessment of polyols for polyurethane production using CO 2 as feedstock: insights from an industrial case study,” Green Chem., vol. 16, p. 3272, 2014.[11] “CO as a raw material | Covestro.” [Online]. Available: https://www.co2-dreams.covestro.com/en. [Accessed: 08-Dec-2017].[12] W. K. Teng, G. C. Ngoh, R. Yusoff, and M. K. Aroua, “A review on the performance of glycerol carbonate production via catalytic transesterification: Effects of influencing parameters,” Energy Convers. Manag., vol. 88, pp. 484–497, Dec. 2014.[13] D. Ballivet-Tkatchenko and A. Dibenedetto, “Carbon Dioxide as Chemical Feedstock to Linear and Cyclic Carbonates,” in Carbon Dioxide as Chemical Feedtock, M. Aresta, Ed. Wiley-VCH, 2010, p. 394.[14] “Plexiglas® y sus parientes las lentes de contacto - ADCMurciaADCMurcia.” [Online]. Available: http://murciadivulga.com/2015/02/20/plexiglas-parientes-lentes-de-contacto/. [Accessed: 11-Dec-2017].

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References[15] “A new C2-based production route to MMA - Chemical Engineering.” [Online]. Available: http://www.chemengonline.com/new-c2-based-production-route-mma/?printmode=1. [Accessed: 04-Dec-2017].[16] “Global Polyurethane market to reach 9.6 mln tons by 2015, PU Foams, Thermoplastic Elastomers.” [Online]. Available: http://www.plastemart.com/plastic-technical-articles/Global-Polyurethane-market-to-reach-9-6-mln-tons-by-2015/1674. [Accessed: 08-Dec-2017].[17] M. Klewski, O. Lucyna, S. Micha , and A. Refractories, “Alumina-Magnesia-Carbon Bricks for Steel Ladle,” in Proceedings of the Unified International Technical Conference on Refractories (UNITECR 2013), Hoboken, NJ, USA: John Wiley & Sons, Inc., 2014, pp. 715–718.[18] E. R. Benavidez, E. Brandaleze, Y. S. Lagorio, S. E. Gass, A. Gladys, and T. Martinez, “Thermal and mechanical properties of commercial MgO-C bricks,” Rev. Matéria, vol. 20, no. 3, pp. 571–579, 2015.[19] “KOSMOKRAFT.” [Online]. Available: http://www.kosmokraft.com/product_2_2_3.htm. [Accessed: 30-Nov-2017].[20] I. Romão, M. Slotte, L. M. Gando-Ferreira, and R. Zevenhoven, “CO2 sequestration with magnesium silicates-Exergetic performance assessment,” Chem. Eng. Res. Des., vol. 92, no. 12, pp. 2072–2082, 2014.[21] “Mineral Carbonation International - Orica.” [Online]. Available: http://www.orica.com/About-Us/Innovation---Technology/mineral-carbonation-international#.Wh-q2VVl_DA. [Accessed: 30-Nov-2017].[22] S. A. Walling and J. L. Provis, “Magnesia-Based Cements: A Journey of 150 Years, and Cements for the Future?,” Chem. Rev., vol. 116, pp. 4170–4204, 2016.[23] “Bricks made from sewage - Yorkshire’s latest gift to the world | UK news | The Guardian.” [Online]. Available: https://www.theguardian.com/global/the-northerner/2011/sep/15/yorkshire-water-leeds-university-sewage. [Accessed: 01-Dec-2017].[24] “Bricks made from sewage cut carbon emissions | ZDNet.” [Online]. Available: http://www.zdnet.com/article/bricks-made-from-sewage-cut-carbon-emissions/. [Accessed: 01-Dec-2017].[25] M. Aresta, Ed., Carbon Dioxide as Chemical Feedtock. Wiley-VCH, 2010.


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