FLUE ANDPROCESSGASES Carbon captureandstorageorutilisation(part2)

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EPOS TECHNOLOGY FOCUS Technologies for industrial processes June 2019 About the EPOS Technology Focus Within the scope of the EPOS project, extensive literature and market research reviews were performed in order to identify different technological, organisational, service and management solutions that could be applied to different industrial sites and clusters. The collected information will aid in establishing on-site and/or cross-sectorial industrial symbiosis opportunities; additionally, to enhance overall sustainability, performance and resource efficiency of different process industry sectors. Through the cooperation of project partners, a longlist of different technological options was created. Resource material for this list included: scientific articles, project reports, manufacturer’s documentation and datasheets.

FLUE AND PROCESS

Emission of flue is one of the most desulphurisation, of CO2, significant issues that process industries etc.). This resulted in the establishment must deal with. Flue gas is a result of of several IS options that are now combustion, taking place in ovens, commonly used. furnaces, boilers, etc. The composition Treatment of flue gas and utilisation of the flue gas relates to the type of of the opportunities that are offered source that is burned; mainly consisting by different technological options of water vapour, carbon monoxide, contributes not only to reduced , particulates, emissions and consequently, reduced oxides and sulphur oxides. costs from penalisation fees, but also Flue gas emissions have a significant offers new options for industries to impact on the environment, as generate additional revenue, i.e. from such, there were many incentives re-using or selling products obtained in the last decades from regulatory from flue and process gases (lime,

bodies and national governments CO2, etc.). in order to reduce emissions and The technology market screen identifies enhance sustainability of the critical techniques for the treatment of flue industry sectors. Numerous measures and process gases. The focus is on and environmental standards recovery and abatement of volatile were established. Industries were organic and inorganic compounds; encouraged to invest and develop recovery and abatement of new technologies for emissions particulates; carbon capture, storage reduction and utilise the remaining and utilisation techniques; utilisation of emissions for other activities on industrial waste /methane and monitoring sites (e.g. lime production from the flue gas.

CARBON CAPTURE AND STORAGE OR UTILISATION (PART 2)

Water-gas shift reaction and reverse water-gas shift reaction Sabatier process for methane production Photovoltaic assisted algal carbon conversion bioreactor Anthropogenic chemical carbon cycle

Production of methanol by synthesis of CO2 and hydrogen Artificial photosynthesis

Utilisation of CO2 for urea production

Utilisation of CO2 for production of the polyurethane

CO2 liquefaction methods TECHNOLOGIES FOR CARBON CAPTURE AND STORAGE OR UTILISATION Technology 1: Water-gas shift reaction and reverse water-gas shift reaction

The water-gas shift reaction is a process where water vapour and carbon monoxide react with each other to form CO2 and hydrogen. The chemical reaction that uses the reverse principle is the reverse water-gas shift reaction. In the reverse water-gas shift reaction, hydrogen reacts with CO2 ; the resulting products are carbon monoxide and water. If the reverse water-gas shift reaction is combined with water electrolysis, methane and can be produced from CO2 (Sabatier process). A synthetic gas (methane) can be produced and valorised for other purposes, such as power generation, heat generation, transport, injection into gas networks, etc. 1 2

Figure 1 Water-gas shift reaction 2

Applicability Maturity Project/product reference The water-gas shift reaction is used as Emergent. Water-gas shift (WGS) an intermediate stage for hydrogen operation of pre-combustion

enrichment and the reduction of CO2 capture pilot plant at the CO in synthetic gas. It is also used Buggenum IGCC. in the production of , and methanol. The reverse water-gas shift can

contribute to the reduction of CO2 emissions in various industry sectors. Technology 1: Water-gas shift reaction and reverse water-gas Technology 2: Sabatier process for methane production shift reaction

Sabatier process (or CO2 methanation) is a combination of:

Reverse water-gas shift: CO2 + H2 ↔ CO + H2O

Methanation of carbon monoxide: CO + 3H2 ↔ CH4+ 2H2O

Based on the combination of the two previous chemical reactions, the Sabatier process can be described as:

CO2 + 4H2 ↔ CH4 + 2H2O

The Sabatier process is a reaction, which enables direct transformation of CO2 into

methane and water. CO2 can be obtained from various sources (e.g. industry flue gases), while the required hydrogen can be obtained from the electrolysis of water using renewable energy. The process could be integrated into a “renewable power methane plant”, which could be used as an interface between electrical and gas networks. Other technologies can also be combined, such as an ORC, which can be used to

valorise the waste heat generated in the process of CO2 methanation. Integration of the gas and electrical networks can be achieved since the process is reversible. There are also other options for the utilisation of generated methane (power generation, heat generation, transport, etc.). 3

Figure 2 Basic concept of renewable power methane plant 4

Applicability Maturity Project/product reference The Sabatier process could Emergent. Demonstration project MeGa- be used in various industry stoRE. sectors where there is a need

to reduce and valorise CO2 emissions. Technology 3: Photovoltaic assisted algal carbon conversion bioreactor

A novel bioreactor system, incorporating state-of-the-art renewable energy generation (PV), solar capture, light delivery and dispersion, and LED lighting technology. The photovoltaic assisted algal carbon conversion bioreactor is designed to be used alongside point-source carbon emitters. The bioreactor uses light and the CO2 from industrial processes, taking advantage of the natural photosynthesis process, to feed into an algal biomass. This biomass can be further utilised as: 5

Bio- Protein feed Chemicals Bio-based materials

Figure 3 Photovoltaic assisted algal carbon conversion bioreactor 6

Applicability Maturity Project/product reference Photovoltaic assisted algal carbon Emergent. Photovoltaic assisted algal conversion bioreactors can be carbon conversion bioreactor, used to valorise carbon emissions collaborative project of produced by industry sectors; Canada and Israel. generating additional revenues from the production of valuable products. Technology 4: Anthropogenic chemical carbon cycle

The anthropogenic chemical carbon cycle transforms CO2, using a stable catalyst based on the metal ruthenium (Ru), into various products. These can include synthetic hydrocarbons, protein for animal feed and fuels such as methanol and dimethyl ether.

CO2 can be captured from numerous sources, including from natural and industrial processes, human activities and the atmosphere. This can be done using absorption technologies, while the required energy can be obtained from clean energy sources such as wind, solar, water, etc. 7

Figure 4 Anthropogenic chemical carbon cycle 7

Applicability Maturity Project/product reference For the reduction and valorisation Research stage. Anthropogenic chemical of carbon emissions produced by carbon cycle, scientific various industry sectors and other publication. carbon emission sources. New products and revenue streams can be realised. Technology 5: Production of methanol by synthesis of CO2 and hydrogen

This chemical process produces methanol fuel by the synthesis of CO2 obtained from a given source (e.g. industry) and hydrogen, which can be obtained by the electrolysis of water. In order to reduce the overall carbon footprint, electricity, which is required for the process (mainly for the electrolysis) can be obtained from renewable energy sources (e.g. hydro and geothermal). 8

8 Figure 5 Production of methanol by synthesis of CO2 and hydrogen

Applicability Maturity Project/product reference For the reduction and Commercial. Vulcanol solution. valorisation of carbon emissions, produced by various industry sectors and other carbon emission sources. Technology 6: Artificial photosynthesis

CO2 is converted into oxygen and organic materials in the presence of sunlight. Different approaches are under research in the area of artificial photosynthesis.

Photocatalytic water splitting followed by CO2 reduction is believed to be the only true form of artificial photosynthesis. The process of photocatalytic water splitting does not require sunlight; individual protons can be used instead, in order to split the water directly using one catalyser.

A second catalyser is used to reduce the obtained hydrogen using CO2 into methane, methanol or formic acid. 9 10

Figure 6 Artificial photosynthesis 9

Applicability Maturity Project/product reference For the reduction and valorisation Research stage. Panasonic artificial of carbon emissions, produced by photosynthesis system. various industry sectors and other

carbon emission sources. CO2 could be used as a feedstock for the production of valuable resources such as methane, methanol or formic acid. Technology 7: Utilisation of CO2 for urea production

Urea is made from ammonia and CO2 and as it is a nitrogen-rich fertiliser it is important to the agriculture industry. The production of urea requires CO2, which can be obtained from the waste gas streams of different industrial processes. CO2 can be captured using a post-combustion capture method. The captured CO2 can be then introduced into the urea production process. 11 12

11 Figure 7 CO2 for urea production

Applicability Maturity Project/product reference

Captured CO2 can be used as Commercial. CO2 recovery plant for urea a source for urea production, production in Abu Dhabi.

reducing CO2 emissions; furthermore, additional revenue can be generated. The process is especially suitable for the petrochemical industry (production of fertilisers). Technology 8: Utilisation of CO2 for the production of polyurethane

This process uses CO2 , captured from various sources, for the production of polyurethane foam. CO2 is used as an alternative to the polymer materials from fossil fuels (); this technology is based on a catalyst. The quality of the material, produced using CO2 , is at least of the same quality level, compared to the material produced purely out of petroleum. 13

14 Figure 8 CO2 for the production of polyurethane

Applicability Maturity Project/product reference Polyurethane is used for many Emergent, Covestro plastics production purposes (foam in automotive commercial power plant in Dormagen, Germany. industry mattresses, insulation plant is already in

materials, etc.). Waste CO2 from operation. various industry processes can be used (power generation based on fossil fuels, chemical industry, etc.). Technology 9: CO2 liquefaction methods

These methods liquefy CO2 for further utilisation. The important parameters for the liquefaction process are critical temperature and critical pressure. At or below critical temperature, the gas liquefies if sufficient pressure is applied. The minimum pressure to liquefy the gas at critical temperature is the critical pressure. The critical temperature of CO2 is 31°C and 73,8°C. Three fundamental principles are used:

The Joule-Thomson effect, when a gas is allowed to expand adiabatically from a region of high pressure to a region of extremely low pressure, it is accompanied by cooling (Linde’s method). Compression/ and expansion of a pure component. Expansion turbines or engines, when a gas expands adiabatically against an external pressure (as a piston in an engine), it does some external work. Since work is done by the molecules, at the cost of their kinetic energy, the temperature of the gas falls causing cooling (Claude’s method).

Most processes in cryogenic technology use one or more of the above principles. 15 16

15 Figure 9 CO2 liquefaction

Applicability Maturity Project/product reference

CO2 liquefaction methods are Commercial. - Hitachi’s solution

used to liquefy the CO2 for - GE & Gas solution further utilisation. REFERENCES

1 “Roadmap towards a low-carbon economy in 2050,” CGP Energy & Innovation workgroup.

2 Byron Smith, Murthy Shekhar Shantha, Muruganandam Loganathan, “A Review of the Water Gas Shift Reaction Kinetics,” International Journal of Chemical Reactor Engineering, vol. 8, no. 1, 2010.

3 Peter Lunde, Frank Kester, “Kinetics of carbon dioxide methanation of a ruthenium catalyst”, Journal of the American Chemical Society, 1976.

4 M. Sterner, “Bioenergy and renewable power methane in integrated 100% renewable energy systems,” Kassel University Press, Kassel, 2009.

5 “Photovoltaic assisted algal carbon conversion bioreactor,” [Online].

6 “The Algal Carbon Conversion Project,” [Online].

7 George A. Olah, G. K. Surya Prakash and Alain Goeppert, “Anthropogenic Chemical Carbon Cycle for a Sustainable Future,” Journal of the American Chemical Society, vol. 133, no. 33, p. 12881–12898, 2011.

8 Carbon Recycling International, [Online].

9 “Panasonic Develops Highly Efficient Artificial Photosynthesis System Generating Organic Materials from Carbon Dioxide and Water,” [Online].

10 “CO2 is ready to go as a fuel and chemical feedstock,” [Online].

11 J. C. Copplestone and C. M. Kirk, “Ammonia and urea production,” New Zealand Institute of Chemistry.

12 “CO2 Recovery Plant to Urea production in Abu Dhabi,” [Online].

13 “Polyurethane based on carbon dioxide instead of crude oil,” [Online].

14 “Carbon Dioxide is revolutionizing plastics production,” [Online].

15 W. H. Isalski, “Liquefaction of gases,” [Online].

16 “Conditions of liquefaction of gases: Linde’s Method, Claude’s process,” [Online]. All the EPOS TECHNOLOGY FOCUS Acts could be found on www.spire2030.eu/epos (Section Outcomes/Publications)

  

CREDITS Date June 2019 Authors Podbregar G.; Strmčnik B., Dodig V., Lagler B., Žertek A., Haddad C., Gélix F., Cacho J., Teixiera G., Borrut D., Taupin B., Maqbool A. S., Zwaenepoel B., Kantor I., Robineau J., all names in correct order (2017), G. Van Eetvelde and F. Maréchal and B.J. De Baets (Eds.) Technology market screen. Longlist of technical, engineering, service and management solutions for Industrial Symbiosis. Design CimArk This report is © EPOS. Reproduction is authorised provided the source (EPOS Technology Focus) is acknowledged.

CONTACT

Interested in this work? www.spire2030.eu/epos Please contact us at [email protected] @projectepos

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 679386. This work was supported by the Swiss State Secretariat for Education, Research and Innovation (SERI) under contract number 15.0217. The opinions expressed and arguments employed herein do not necessarily reflect the official views of the Swiss Government.