Sequestration of Carbon Dioxide by Recycling Technology

Increase of carbon dioxide (СО₂) concentration in the atmosphere due to human industrial activity makes significant contribution to global warming: 38 Bln. tons of СО₂ are released in atmosphere per annum, while over 80% of that amount is due to burning fossile fuel. In case no actions will be underatken global atmospheric release of СО₂ may increase 3 times by year 2100 in compare with the 2020 one followed further increase of temperature of the atmosphere and the oceans and inevitable climate change. That is why research and development of СО₂ release reduction technologies - sequestration - is a prominent and urgent need [1].

During 2021 shares of СО2 releases in the global scale have been distributed in a following order [2]: China - 32,9%, USA - 12,9%, EU - 7,3%, India - 7,0%, Russia - 5,1%, Japan - 2,9%. During 2022 [3] СО2 releases due to global power production have increased on 320Мt.

Scheme 1:Synthesis of the novel ZnPc.

By year 2050 European Union is intended completely to ban the energy generation followed СО₂ releases to atmosphere. To accomplish that goal EU has introduced the «carbon tax» (about 100 Euro per ton of СО2). The tax should be paid by industrial companies in accord to their СО₂ releases.

Carbon Capture and Storage - (CCS) - is a process of СО₂ capture, transportation and storage/ burying or final diposal. In a general sense СО2 sequestration includes the following processes:
a) СО2 build-up in biomass of plants, crops, aquaculture and soil humus.
b) СО2 capture and underground storage and burying in the gas/ oil, coal and rock salt reservoirs, or final disposal in the spent rock materials.
c) СО2 recycling to produce valuable chemical products.

СО₂ sequestration technologies are novadays developed by many commercial companies and organizations all over the world, while the technologies are already in use in the countries such as Australia, Great Britain, Island, Netherlands, Norway, Russia, USA etc.

The advantages of СО₂ sequestration in a biomass are relative technological simplicity, input in recovery of green spaces and soils remediation. The drawback - large space area which should be allocated for this purpose, delayed effect in terms of СО2 sequestration when planting perrenials, dependence of СО2 uptake on season and sun activity, and potential negative impact on the environment while using monocultures or gen-modified plants and aquacultures. Thus, in the middle latitudes of Northern hemisphere the maximum uptake of СО2 by plants and crops occurs in May and June, while a limited amount of СО₂ is uptaken just coniferous trees during winter time.

The advantages of СО2 sequestration in underground reservoirs are maturity of technology, availability of existing disposal sites, availability of required gas-transportation and gaspumping infrastructure, relative simplicity of implementaion. The drawbacks are lack of data on safe terms of facility operations, potential simultaneous ingress of large quantities of СО₂ to the environment in case of technogenous accidents or natural disaster and operational expenditures to maintain the facility in a working condition.

The advantages of СО2 recycling technologies are that in addition to reducing СО₂ releases to atmosphere one can produce valuable chemical products. The drawback is that in a general case the technology readiness level still requires additional investments in technology refinment, aprobation, piloting and scalability.

Obviously, the use of any of СО₂ sequestration technologies will increase CAPEX and OPEX of a product manufacturing due to increased power consumption by 20 to 100%. However imposing a «carbon tax» and it consequent further increase will also result in increase of the product cost in a similar or even higher manner for all enterprises with a high «carbon footprint». For that reason one can see a boom of private and governmental investments in R&D of СО₂ sequestration and recycling technologies to do not be late in the race for the «carbon footrpint» reduction.

Thus, Climeworks company captures СО₂ of ambient air since 2022 and pumping it into underground reservoirs with further conversion in a solid rocks. Several companies have made advance payments to Climeworks for future service of СО₂ sequestration. Climeworks has also received over 780M USD on technology further development from wide range of independent investors.

In 2023 U.S. Department of Energy has granted 1.2 Bln. USD to Carbon Engineering Company on creation of additional capacity for СО₂ storage. Two projects of СО₂ capture and storage should be developed in Texas and Louisiana in frame of the grant. СО₂ should be disposed in undeground reservoirs or converted in a useful products.

Mitsubishi Shipbuilding Co. in 2023 has built the first in the world cargo ship to transport liquified СО₂ (LСО₂) [4]. It is also developing tankers to transport both ammonia and liquified СО₂. The tankers can transport ammonia (as a future fuel) to power plants on direct way and return back СО₂ for disposal or recycling.

State Atomic Energy Corporation «Rosatom» is also working on reduction of a «carbon footprint», including implementation assessment of technological solutions in production of CNG, lowcarbon hydrogen and ammonia as well as in energy production and storage.

PSC «Norilsky Nikel» is implementing R&D for reduction of the «carbon footprint» and transfer to low-carbon paradigme using СО₂ for artificial mineralization of waste rock at the company tailings dump with formation calcites and other minerals.

PSC «Novatek» [5] is going to reduce release of greenhouse gases at oil production on 6% by 2030: from current 12,58 tons of СО₂ per thousand barrels of oil equivalent. They have developed the concept of СО₂ capture and storage in undeground reservoirs. Each of 2 geological reservoirs at the licensed site have potential capacity of 600 Mln. tons of СО₂ [6].

Recycling of СО₂ can be done by reduction with hydrogen and producing various products including soot, methane and other hydrocarbons, methanol, formic acid, urea etc. These processes allow produce valuable chemical products (or precursors) from СО₂ and the products can be used during further production of complex products in industry, agriculture and on transport.

СО₂ can also be recycled with plasma-chemical and radiationchemical processes converting carbon dioxide into various organic compounds, or solids; this allows substantially reduce power comsumption for the process implementation in compare to purely chemical or electro-chemical technologies.

Number of products, which can be produced from СО₂ is quite extensive. In case the recycling technology would be economically justified, СО₂ should be a highly demanded raw material for production of many chemicals such as dimethyl ether, carbon monoxide, etylene, methanol, formic acid etc.

For 165MW fossile power plant annual release of СО₂ is 570 000 tons. To achieve carbon neutrality 1565 tons of СО₂ should be recycled daily. This corresponds to production of 2135 tons of carbamide per day. Power consumption for the production will be about 8% of the power plant capacity.

Commercial success of СО₂ sequestration/recycling technology implementation will depend on the meausures of governmental support. Thus, in EU decarbonisation is supported with governmental funding in the form of subsidies, grants, preferential loans which are provided for the decarbonization projects. Long term subsidies for СО₂ recycling equipment manufacturing and installation will ensure СО₂ increased self-sufficiency, while equipment manufacturers will get opportunity and more important - stimulus to reduce substantially СО₂ atmospheric releases.

Carbon monoxide world market volume in 2022 reached 3,26 Bln. USD and accordingly to forecasts [10] by 2030 will increase up to 4,53 Bln. USD. Carbon monoxide is used in farma and biotech industry, ore mining and processing, chemical industry, metalworking and electronic industry. The factors which support the growth of carbon monoxide market are increased demand on the mass chemical products as well as increased demand on goods in fish and meat packaging sector.

Implementation of the proposed recycling technology of СО₂ sequestration will increase demand on «green» energy production such as: Nuclear, Wind, Solar or Hydro Power Plants. The technology will utilize excess of energy, generated by wind and solar power plants in peak periods.

From the research results it is seen that СО₂ sequestration and reduction of «carbon footprint» can be done as an appropriate combination of radiation-chemical, plasma-chemical and catalytic ways of СО₂ recycling with synthesis of valuable products. Development and scaling of СО₂ recycling technologies will allow:
a) Avoid «carbon tax» burden for enterprises with a high «carbon footprint».
b) Create high-tech industrial production.
c) Benefit of good competitive edge in frame of ESG agenda.

The authors are proposing to implement industrial recycling technology of СО2 sequestration by combining catalytic, plasmachemical and radiation-chemical processes to convert CO2 into carbon monoxide 6 syngas, other substances or solids. The technology allows significantly reduce power consumption for CO2 recycling in compare to just chemical or electro-chemical technologies.

Succes of industrial deployment of CO2 recycling technologies will depend to some extent on the measures of governmental suppport. The best commercial potential has the technology which combines radiation, plasma and catalytic methods of CO2 recycling followed synthesis of valuable chemical products Industrial implementation of the proposed CO2 recycling technology will increase demand on energy produced by «green» and renewable sources cush as: nuclear, wind, solar and hydro power plants.

The authors express their gratitude to State Corporation «Rosatom» for supporting the research in the area of «carbon footprint» reduction.

The authors declare no conflict of interest.

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