Экспериментальное исследование генерации водорода из углеводородов в пластовых условиях (Experimental study of hydrogen generation from hydrocarbons under the reservoir conditions) тема диссертации и автореферата по ВАК РФ 00.00.00, кандидат наук Афанасьев Павел Аркадьевич

• Афанасьев Павел Аркадьевич
• кандидат наук
• 2024

Оглавление диссертации кандидат наук Афанасьев Павел Аркадьевич

Table of Contents

INTRODUCTION

Chapter 1. Technology proposal

Chapter 2. State of the art

2.1 Role of hydrogen in the world

2.2 Traditional hydrogen generation methods

2.3 In situ hydrogen generation methods

2.3.1 Hydrogen generation in oil and bitumen fields

2.3.2 Hydrogen generation in gas fields

2.3.3 Hydrogen generation in coal fields

Chapter 3. Laboratory investigation of in situ hydrogen generation from hydrocarbons under reservoir conditions in autoclave installations

3.1 Laboratory plan for hydrogen generation process investigation

3.2 Target reservoir and samples description

3.3 Catalyst preparation procedure

3.4 SMRs thermodynamic constraints

3.5 Catalytic methane conversion (CMC), static experiments

3.5.1 Samples selection and test design strategy

3.5.2 Methodology

3.5.3 Results

3.5.4 Conclusion

3.6 Catalytic methane conversion (CMC), dynamic experiments

3.6.1 Samples selection and test design strategy

3.6.2 Methodology

3.6.3 Results

3.6.4 Conclusion

3.7 Petroleum coke gasification

3.7.1 Samples selection and test design strategy

3.7.2 Methodology

3.7.3 Results

3.7.4 Conclusion

Chapter 4. Laboratory investigation of in situ hydrogen generation from hydrocarbons under reservoir conditions via combustion tube tests

4.1 In situ hydrogen generation at gas reservoir conditions

4.1.1 Samples selection and test design strategy

4.1.2 Methodology

4.1.3. Results: temperature profiles

4.1.4. Results: oil analysis

4.1.5. Results: gas analysis

4.1.6. Methane conversion rate

4.1.7. Core samples appearance and analysis

4.1.8. Conclusion

4.2 In situ hydrogen generation at heavy oil reservoir conditions

4.2.1 Samples selection and test design strategy

4.2.2 Methodology

4.2.3. Results: temperature profiles

4.2.4. Results: oil analysis

4.2.5. Results: gas analysis

4.2.6. Core samples analysis

4.2.7 Conclusion

Chapter 5. Numerical modeling of in situ hydrogen generation from hydrocarbons under reservoir

conditions

5.1 Model of 1D reactor for kinetics adjustment

5.1.1 Methodology

5.1.2. Results

5.1.3. Conclusion

5.2 Model of medium pressure combustion tube (MPCT)

5.2.1 Methodology

5.2.2 Result

5.2.3 Conclusion

CONCLUSIONS

6.1. Summary

6.2. Conclusions

6.3. Contributions to Knowledge

6.4. Recommendations

List of Symbols, Abbreviations

Bibliography

List of Figures

List of Tables

Appendix A: Core model info for the ISC test

Appendix B: Pyrolytic data for the core samples taken after the ISC test

Введение диссертации (часть автореферата) на тему «Экспериментальное исследование генерации водорода из углеводородов в пластовых условиях (Experimental study of hydrogen generation from hydrocarbons under the reservoir conditions)»

INTRODUCTION Relevance

The increasing demand of humanity for energy leads to an increase in the production and consumption of hydrocarbons, which continue to lead the world's energy resources. However, hydrocarbon resources are limited and non-renewable, and their use is associated with massive amounts of carbon, nitrogen, and sulfur oxides—the main greenhouse gases—being released into the atmosphere. As a result of the annual increase in energy consumption, the amount of greenhouse gas emissions into the atmosphere increases. At the same time, the average global temperature should not rise by more than 2°C this century [1]. Many countries have already announced plans to transition to a low-carbon economy using alternative energy sources soon to reduce greenhouse gas emissions [2]. The energy of the sun, water, and wind, as well as hydrogen energy, are good examples.

Renewable energy is still quite expensive and not widely available because its production is heavily dependent on location, weather conditions, and other factors. However, there are several advantages to using hydrogen as an energy carrier in conjunction with renewable energy sources [3]. Only pure water and energy are released when hydrogen is oxidized. At the same time, it can be considered a sustainable source of energy because hydrogen production is not dependent on environmental conditions and it can be stored for a long time.

According to the international association - Hydrogen Council, with the proper development of hydrogen technologies shortly, hydrogen will firmly establish itself in the market as an energy carrier by 2050. [4]. At a production cost of up to $2.5 per kg, hydrogen can meet up to 8% of global energy demand at a cost of $1.8 per kg—roughly 15%.

Modern hydrogen production technologies, on the other hand, generate significant amounts of greenhouse gases, which are both direct products of chemical transformations and released as a result of energy-intensive technological processes (due to the combustion of hydrocarbons). On a large scale, hydrogen is primarily produced from natural gas via steam reforming, partial oxidation, and autothermal reforming processes. This type of hydrogen is not environmentally friendly because its production emits significant amounts of greenhouse gases into the atmosphere. To produce hydrogen with a zero-carbon footprint, carbon dioxide must be captured and stored, which significantly raises the cost of existing production technologies [4-6].

The synthesis of hydrogen with a negative carbon footprint, whose production cycle is not associated with the formation of greenhouse gases, is possible during water electrolysis using renewable energy. However, the capital costs for implementing the technological scheme are still too high and can

only be justified at a late stage of hydrogen technology introduction (during the transition to a hydrogen economy) and do not allow moving to large-scale hydrogen production under such a scheme now.

Electrolytic methods for producing hydrogen from water or methanol, which uses electricity generated by burning hydrocarbons, are associated with significant energy costs, capital expenditures related to electrolyzers of sufficient capacity, and operating costs for capturing and utilizing carbon oxides. As a result, electrolytic methods are prohibitively expensive for widespread use [5].

Existing production methods are quite expensive and inefficient, so new hydrogen generation processes or a fundamentally new design of existing technologies are required. One of the promising low-carbon hydrogen production methods could be in situ hydrogen generation within hydrocarbon reservoirs followed by selective hydrogen production. Under elevated temperature conditions in the reservoir, underground conversion of hydrocarbons into hydrogen is possible and accelerated in the presence of catalysts. In this case, known thermal steam-air methods for increasing oil production can be used to heat the formation. Carbon, nitrogen, and sulfur oxides formed during chemical transformations can also be left in the reservoir, ensuring their burial. Because hydrogen will be in a gaseous state at reservoir pressure, the transformations leading to its generation will increase the amount of gaseous products. As a result, in situ hydrogen generation can be implemented even in depleted and abandoned hydrocarbon fields.

Furthermore, there is a problem with the deep extraction of hydrocarbons from oil and gas fields, particularly bitumen and heavy oil fields, as well as late-stage development fields. Hydrogen generation from hydrocarbons directly in the pore space of the deposits will contribute to in situ upgrading of the residual hydrocarbon feedstock and increase its mobility. As a result, unconventional hydrocarbon deposits can be developed, and the final hydrocarbon recovery factor can be increased.

For example, approximately half of all developed oil fields in Russia are in the final stages of development [7]. Extraction of oil from such deposits may become economically unprofitable in the near future. At the same time, the residual oil saturation of the rocks remains quite high, accounting for 4060% of the initial saturation. Implementing technologies aimed at increasing the degree of oil recovery in such fields will increase development efficiency and lead to the production of additional quantities of oil.

Furthermore, according to the Russian Federation's Ministry of Energy, approximately 65% of all proven oil reserves in Russia are hard-to-recovery reserves. Aside from fields with poor reservoir properties, difficult-to-recover hydrocarbon reserves include deposits of extra-heavy oil and bitumen, the extraction of which is associated with additional technical difficulties that require additional capital investments and operating costs. Because heavy oil fields present more than half of Russia's proven oil reserves, developing them is a critical strategic goal. However, due to their high viscosity and density,

heavy and extra-heavy oils are difficult to extract. The extraction of natural bitumen, which is immobile at reservoir temperatures, is an even more difficult task.

Thermal methods are the most commonly used for oil recovery from heavy oil and natural bitumen deposits. When the temperature of a hydrocarbon-saturated reservoir rises, the viscosity of the oil decreases, increasing its mobility. However, as the oil cools, its viscosity increases significantly, making pipeline transport difficult (a viscosity in the range of 200-300 cP is required for normal transportation via pipelines). Furthermore, such oil will become more difficult to process in the future. Hydrotreatment, hydrocracking, and isomerization of such oil fractions will necessitate increased quantities of the hydrogen-containing gas.

In situ hydrogen generation technology will enable the development of deposits of heavy, superheavy oils and bitumen because it leads to an irreversible increase in reservoir fluid mobility. On the contrary, the heavier feedstock is preferred when implementing the technology because it leads to higher temperatures in the reservoir during the in situ combustion (ISC) process, which is required to achieve high rates of hydrocarbon conversion into hydrogen.

That is, by implementing in situ hydrogen generation using existing thermal methods for enhanced oil recovery (EOR), two acute energy sector problems can be solved at the same time: economically viable low-carbon hydrogen production (an environmentally friendly energy carrier) and the development of unclaimed, and difficult-to-recover hydrocarbon reserves.

But for now, there is no mature technology design for in situ conversion of hydrocarbons to hydrogen without first producing hydrocarbons to the surface and preparing this feedstock. The problem stems from a lack of understanding of the fundamental processes of hydrocarbon to hydrogen conversion in reservoir conditions: at unusually high (comparing with industrial process) pressures, unusually low temperatures, and in the presence of core and natural fluids (formation water, oil and gas). The use of this technology is fraught with uncertainties, including reservoir heterogeneity, selecting the optimal injection air flow rate, heat losses, and complex kinetic reactions leading to chemical and physical hydrocarbon-to-hydrogen transformations. All of these uncertainties, as well as the possibility of efficient hydrogen generation, should be thoroughly investigated and validated through laboratory experiments and numerical simulations at both the laboratory and field scales.

Goal and objectives

The purpose of this work is to reveal regularities of hydrocarbon conversion into hydrogen in reservoir conditions through conducting fundamental experimental and numerical simulation at the lab scale. As part of the research, it is necessary to solve the following tasks:

1) Validate the process of generating hydrogen from natural gas and oil at the reservoir conditions of the target field under thermal stimulation (as a result of steam and/or air injection, followed by in situ combustion).

2) Determine the limits of applicability of the processes of in situ hydrogen generation from hydrocarbons (by estimating the maximum conversion rate of hydrocarbons into hydrogen under specific conditions).

3) Study the effect of the reservoir rock on the processes of hydrocarbon conversion into hydrogen.

4) Develop and optimize the numerical model of the experimental installation of natural gas conversion.

5) Examine the kinetic dependencies of the hydrogen-generation processes from hydrocarbons under various conditions.

6) Propose a further path for the development of technology, and give recommendations regarding the required research.

Factual material

The dissertation is based on the results of experimental studies and numerical simulations carried out by the author separately and as part of an experimental group in the laboratory of the Center for Petroleum Science and Engineering of the Skolkovo Institute of Science and Technology in 2018-2023.

Author's personal contribution

The author created a thermodynamic model of the process of generating hydrogen from methane. The author personally performed and analyzed a series of more than 50 experiments in autoclave units. With the direct participation of the author, two large-scale experiments were carried out in the medium-pressure combustion tube installation, followed by the building of a numerical model of the installation and subsequent simulation.

Research methodology

In this work experimental and numerical modeling were used for the investigation of catalytic hydrocarbon to hydrogen conversion in reservoir conditions. For this aim thermodynamic modeling of the process of steam methane conversion was performed first. Then autoclave and combustion tube experiments were carried out. The majority of the experiments was performed in different autoclave type reactors in static and dynamic modes at high-temperature high-pressure conditions in the presence of reservoir rock samples and nickel-based catalyst. The methodologies of experiments were custom and developed by the author and the research group. Numerical modeling was performed using industrial software for modeling thermal effects on hydrocarbon reservoirs - CMG STARS in two steps by simulating processes in autoclave and combustion tube installations.

Scientific novelty

There is currently no ready for the implementation technology for in situ hydrogen production and knowledge about the conversion of hydrocarbons into hydrogen under reservoir conditions is extremely limited. There was a need to investigate the feasibility of hydrogen generation underground in hydrocarbon fields and the influence of reservoir pressure, temperature, rock, heterogeneity, and other reservoir properties on the hydrogen generation process and hydrogen storage facilities. Thermobaric effects have not been assessed, kinetic dependencies have not been established, and the impact of rock and fluids has not been investigated before. There is currently almost no reliable experimental data on the processes of converting hydrocarbons into hydrogen at pressures and temperatures achievable in hydrocarbon reservoirs.

The lack of knowledge related to these points let to obtain following novel results:

1) The novel process of hydrocarbons to hydrogen conversion in reservoir under thermal methods implementation conditions was validated. The effects of unusually high (comparing with industrial process) pressures, unusually low temperatures, natural reservoir rock and fluids on catalytic methane conversion were investigated.

2) It was revealed that petroleum coke can be actively gasified at low temperatures of 575 °C and pressure 10 atm even without a catalyst with the release of synthetic gas mixture containing hydrogen in the concentration up to 69 vol.%.

3) Experimental test on catalytically enhanced cyclic steam-air stimulation of oil saturated core model of dual porosity was first designed and performed for in situ hydrogen generation and heavy oil upgrading. The assumption on crucial role of core model heterogeneity for hydrogen generation was validated.

4) A kinetic model comprising chemical reactions of thermal cracking, low temperature oxidation (LTO) and high temperature oxidation (HTO) processes, coke gasification, water-gas shift reaction and methanation reactions was developed and validated against experimental data.

Practical value

Studies of the fundamental processes of in situ hydrocarbon-to-hydrogen transformations are of scientific interest because they have the potential to create a fundamentally new low-carbon technology for hydrogen synthesis.

The results obtained can be used in numerical modeling of the development of the target hydrocarbon reservoirs and assessing the technical and economic attractiveness of the pilot project aiming subsurface hydrogen production. In general, results can be used to develop a subsurface hydrogen production technology from hydrocarbon deposits in order to obtain industrial amounts of hydrogen.

Using hydrogen-selective membrane for production or utilization of greenhouse gases this method can be classified as new low carbon way for hydrogen synthesis.

The underground hydrogen generation technology being developed can also ensure the production of upgraded (improved composition) oil from viscous, high-viscosity oils and bitumen deposits while also producing hydrogen-containing gas. Even after being extracted from the reservoir, the produced oil will have lower viscosity and density values, as well as improved mobility, compared to the initial state. As a result, even in late-stage heavy oil fields, the oil recovery factor can be increased. This technology design implies that greenhouse synthetic gases can be separated from hydrogen in a gas separator at the surface and injected back into the target formation or an adjacent formation for disposal. In this case, the re-injection of greenhouse gases, in particular carbon dioxide, also can be considered as an EOR method.

Thus, one portion of the unclaimed or difficult-to-recover hydrocarbon reserves can be converted into a new energy carrier—hydrogen and other can be produced due to the thermal effect on the reservoir and an increase in hydrocarbon mobility. As a result, the hydrocarbon recovery factor from hydrocarbon deposits can be significantly increased.

One more application of the findings of this research attributed with work safety during the implementation of thermal EOR methods, since undesirable amounts of hydrogen can be spontaneously appeared. Predictions for in situ hydrogen generation in hydrocarbon reservoirs can decrease risks related to hydrogen embrittlement of materials and explosive nature of hydrogen, making operations safer. Accidentally formed hydrogen inside the formation can cause serious damage to the production well equipment (casing strings, pumping units, etc.) if unsuitable materials are used [8-12]. It is necessary to consider the presence of hydrogen in the synthetic gases produced during the work and thus to be able to predict its appearance in the reservoir as a result of EOR project implementation.

Statements for the defense

1) The moderate conversions of methane to hydrogen about 14.5% are characteristic even at unusually low (comparing to the industrial steam reforming of methane) temperatures of 550 °C and unusually high pressures above 9 MPa.

2) Active (metal) phase of a nickel-based catalyst can't be formed from a water-soluble nickel nitrate hexahydrate precursor at temperatures below 450 °C and elevated pressures. But starting from this temperature the carbonate minerals and organic matter of the natural core decompose, releasing extra amounts of carbon dioxide and light hydrocarbons, which hinter hydrogen generation process.

3) Thermal and catalytic influence on oil saturated reservoir model in the presence of hydrogen donor within hydrocarbon to hydrogen conversion process is also attributed with oil upgrading. Oil enriched with low boiling fractions which has lower density, viscosity and sulfur content compared with the original one can be obtained.

4) The design of the technology of simultaneous production of heavy oil and bitumen and hydrogen-containing gas was developed.

Approbation of the results

The results and main provisions of the work were presented at international and Russian conferences:

1) III International scientific and practical conference "INTEGRATED SCIENTIFIC SUPPORT OF OIL AND GAS ASSETS". Perm, October, 2021.

2) The First International Scientific and Practical Conference "Modern Methods of Enhanced Oil Recovery for Conventional and Unconventional Reservoirs". Russia, Moscow, 2021.

3) SPE Russian Petroleum Technology Conference: SPE Russia and Caspian Student Paper Contest. Russia, Moscow, 2021.

4) Tumen Oil and Gas Forum "TNF". Russia, Tumen, September, 2021.

5) International Forum "Science of the future". Russia, Novosibirsk, August, 2022.

6) SPE Annual Technical Conference and Exhibition (ATCE): International SPE Student Paper Contest. USA, Houston, October, 2022.

7) Gas & Oil Technology Showcase and Conference. UAE, Dubai, March, 2023.

Publications

The results of the work are presented in 11 publications, including 4 papers in scientific journals indexed by Web of Science and Scopus and 1 patent. Here is a list of mentioned publications:

1) Afanasev P., Popov E., Cheremisin A., Berenblum R., Mikitin E., Sorokin E., Borisenko A., Darishchev V., Shchekoldin K., Slavkina O. An experimental study of the possibility of in situ hydrogen generation within gas reservoirs. Energies. 2021. Vol. 14, no. 16. DOI: https://doi.org/10.3390/en14165121

2) Afanasev P., Popov E., Cheremisin A., Berenblum R. On the way to hydrogen-carbon economy. Gas.Oil.Hydrogen. 2021. May; no. 1, pp. 18-23 (RU).

3) Afanasev P., Popov E., Cheremisin A., Berenblum R., Mikitin E., Sorokin E., Borisenko A., Darishchev V., Shchekoldin K., Slavkina O. An investigation of the possibility of in situ hydrogen generation under reservoir conditions of gas fields. Proceedings - III-rd International Scientific and Practical Conference "Integrated Research Support to Oil and Gas Assets: Experience, Innovations, Prospects". 2021. p. 338-346. ISBN 978-5-7934-0999-5 (RU).

4) Afanasev P., Cheremisin A., Popov E. Method for enhanced oil recovery of heavy oil and bitumen deposits, ensuring the production of upgraded oil and hydrogen-containing gas. 2021. Patent RU 2786927 (RU).

5) Afanasev P., Popov E., Cheremisin A. Hydrogen generation potential within hydrocarbon reservoirs. Neftegaz.ru. 2022. April; 4(124):100-105 (RU).

6) Afanasev P., Popov E., Cheremisin A., Berenblum R., Mikitin E. POSSIBILITY OF IN SITU HYDROGEN GENERATION WITHIN GAS RESERVOIRS. Proceedings - 22nd SGEM International Multidisciplinary Scientific GeoConference 2022. 2022. Vol. 22, Issue 4.1. ISBN 978619-7603-44-6. DOI: https://doi.org/10.5593/sgem2022/4.1/s17.19

7) Askarova A., Afanasev P., Popov E., Smirnov A., Cheremisin Al. Application of In Situ Combustion for development of hydrogen generation technology in the reservoir. Proceedings - Thermal EOR International Workshop "Thermal Methods for Enhanced Oil Recovery: Laboratory Testing, Simulation and Oilfields Applications", Baku, Azerbaijan, November 2022.

8) Askarova A., Afanasev P., Popov E., Mikitin E., Darishchev V. Application of oil in situ combustion for the catalytic methane conversion in the porous medium of the gas reservoir. Journal of Petroleum Science and Engineering. 2023. Vol. 220. DOI: https://doi.org/10.1016/j.petrol.2022.111256

9) Afanasev P., Popov E., Cheremisin A., Mikitin E., Darishchev V. In Situ Hydrogen Generation Within Gas Reservoirs. Proceedings - Gas & Oil Technology Showcase and Conference. March 13-15, 2023. DOI: https://doi.org/10.2118/214036-MS

10) Askarova A., Mukhametdinova A., Markovic S., Khayrullina G., Afanasev P., Popov E., Mukhina E. An Overview of Geological CO2 Sequestration in Oil and Gas Reservoirs. Energies. 2023. Vol. 16, Issue 6. DOI: https://doi.org/10.3390/en16062821

11) Afanasev P., Smirnov A., Ulyanova A., Popov E., Cheremisin A. Experimental Study of Catalytically Enhanced Cyclic Steam-Air Stimulation for In Situ Hydrogen Generation and Heavy Oil Upgrading. Catalysts. 2023. Vol. 13, 1172. DOI: https://doi.org/10.3390/catal13081172

Заключение диссертации по теме «Другие cпециальности», Афанасьев Павел Аркадьевич

CONCLUSIONS

6.1. Summary

This research consists of fundamental studies with subsequent laboratory investigations, numerical simulation, and validation against experimental data. The main goal of this study was to conduct a comprehensive experimental and numerical modeling of in situ hydrogen generation from hydrocarbons under hydrocarbon reservoir conditions to reveal fundamental regularities.

As a result of the work, the processes of subsurface hydrogen generation from natural gas, heavy oil, and petroleum coke were validated. The limits of applicability of these processes were revealed and the influence of operating parameters (temperature, pressure, type and amount of catalyst, type of core, steam to methane ratio) were investigated. Numerical modeling lets to configure a set of important chemical reactions. The kinetics of the methane to hydrogen-containing gas conversion was further developed and adjusted on experimental data.

The obtained results can be used to develop a low-carbon technology for the in situ hydrogen generation and production from hydrocarbon fields in order to obtain industrial amounts of hydrogen.

6.2. Conclusions

The use of hydrogen as a fuel is a new global trend. The demand for hydrogen will increase as the economy decarbonizes. At the same time, developed economies and technologies are only interested in hydrogen produced using low-carbon methods (without greenhouse gas emissions or with the implementation of procedures for capturing and storing such gases).

In situ hydrogen synthesis has the potential to be a promising low-cost, low-carbon method of producing hydrogen. At the same time, development may involve inefficient and unconventional hydrocarbon deposits. Natural gas, oil, bitumen, and coal can all be converted into hydrogen. Greenhouse gases produced during chemical transformations can be separated and injected back into the developed reservoir or avoided entirely by producing pure hydrogen through a hydrogen-selective filter. The in situ hydrogen generation technology consists in the catalytic steam-air stimulation of the formation followed by the ISC process, which heats the formation and causes the main chemical transformations to occur.

This work presents the findings of experimental studies of hydrocarbon to hydrogen conversion processes under the reservoir conditions, including the presence of reservoir rock material. The findings of experimental and numerical studies are presented, conclusions about the feasibility of the in situ

process in the pore space of hydrocarbon deposits are drawn, and the technology's potential as a method for hydrogen production is evaluated.

Natural gas is the most promising resource for large-scale reservoir hydrogen production. The main processes leading to hydrogen synthesis in gas fields are steam reforming (SMR), cracking, methane partial oxidation (POM), and water-gas shift.

Within the scope of this work, the influence of pressure, temperature, steam/methane ratio, catalyst form and type of porous medium, including the natural reservoir rock, on the CMC process was studied. The CMC process at relatively low temperatures (450-800 °C) and relatively high pressures (up to 21.4 MPa), which represent gas field reservoir conditions under thermal stimulation, was investigated.

The obtained results indicate the possibility of generating hydrogen in situ from natural gas of depleted gas fields. Reservoir temperatures of at least 450 °C are required for this method. It is possible due to the ISC of saturating hydrocarbons (bitumen/oil or even natural gas). The preliminary experimental studies conducted confirm the prospects for catalytic hydrogen generation in situ in natural gas fields. In the presence of an inert core model, the conversion of methane to hydrogen was approximately 14.5% at unusually low (for the process of steam reforming of methane) temperatures of 550 °C and unusually high pressures of 9 MPa. Higher temperatures about 800 °C are required to achieve high methane to hydrogen conversion rates about 79%. The methane to hydrogen conversion rate of about 13.6% was experimentally achieved at 800 °C, in the presence of real gas reservoir rock samples.

Hydrogen was also synthesized during the ISC experiments with the oil-saturated core models. A special technique has been developed for cyclic steam-air stimulation of the reservoir model, followed by ISC, which provides partial conversion of hydrocarbons into hydrogen. The implementation of the process on a reservoir model with non-zero oil saturation leads to the hydrocarbon feedstock upgrading (reduction of viscosity, density, sulfur content). However, only small amounts of hydrogen were detected in the outlet gas mixture at a level of up to 1 vol.%. This can be explained by a non-optimal regime of the steam/air stimulation and secondary interactions. For instance, generated hydrogen could react with hydrocarbons, intensifying processes of hydrocracking and hydroconversion in general. A design of new technology for simultaneous production of oil/bitumen and hydrogen-containing gas was developed based on these results.

As the result of the research some regularities of the hydrocarbon conversion in reservoir conditions were established:

- starting from temperatures of 450 °C, hydrogen generation from methane occurs according to the mechanisms of SMR and methane cracking;

- natural core, which is target reservoir rock samples, negatively affects the process due to the decomposition of carbonate minerals and the release of carbon dioxide, and the decomposition of organic matter and the release of hydrogen sulfide (well-known catalyst poison);

- the negative effect of the natural core is less significant at higher process temperatures, since reducing conditions are created;

- within the considered process liquid hydrocarbons (oil) enter into reactions of aquathermolysis, cracking, hydrocracking and hydroconversion in general, which can be activated by hydrogen formed in situ;

- petroleum coke is one of the main sources of hydrogen when the process is implemented in oil reservoir;

- petroleum coke can be actively gasified with water vapor at a temperature of 575 °C and a pressure of 10 atm, even in the absence of a catalyst. In this case a hydrogen concentration in the gas mixture up to 69 vol.% can be achieved.

As a result of numerical simulation, the adapted kinetic parameters of the main chemical reactions have been identified. The use of this model makes it possible to predict the results of experiments in the CT. The resulting kinetic model can also be used to simulate the application of the underground hydrogen generation technology at the field scale.

To raise the technology readiness level, it is necessary to modify existing industrial hydrocarbon conversion catalysts or select catalysts that are more efficient and less sensitive to catalyst poisons contained in the reservoir rock. It is also required to select a method for delivering the catalyst into the reservoir. Furthermore, the mechanisms of inhibition of secondary and side reactions with hydrogen must be considered, as well as the effect of the core composition on the hydrogen generation process over a wide temperature range and rock mineral composition.

6.3. Contributions to Knowledge

During the shift from a carbon-based economy to a hydrogen-based economy, the processes of in situ hydrogen generation have substantial growth potential. The results demonstrate that in situ hydrogen production can be a viable solution to the problem of commercially low-carbon hydrogen production, while simultaneously ensuring the development of unclaimed hydrocarbon reserves and an increase in the ultimate hydrocarbon recovery factor.

The conducted research made findings in the field of the catalytic conversion of hydrocarbons at the conditions, unusual for the industrial application. The experimental modeling of the fundamental hydrogen generation processes confirms the possibility of in situ hydrogen generation under reservoir conditions (pressure, temperature, fluid saturations, and presence of the rock).

The results obtained made a significant contribution to the development of technology for low-carbon hydrogen production from fossil fuels in Russia as well as to the development of an innovative EOR method with simultaneous hydrogen donor generation. The results of the implementation of the stated set of tasks (experimental studies, numerical modeling, predictive estimates) will have a practical potential for reducing the amount of greenhouse gas emissions into the atmosphere and the cost of their disposal as part of the Russian Federation's strategy for the transition to a carbon neutral economy.

6.4. Recommendations

Additionally, the investigation of various catalysts, as well as the manner of delivery and propagation of the catalyst in the pore media of the reservoir (including the impacts of reducing rock permeability and adsorption), should be conducted. At relevant process temperatures, the impact of core composition on hydrogen generating processes must also be studied in more depth.

Since natural gas fields are the most promising for subsurface hydrogen generation, the ISC of natural gas should be carefully investigated. Combustion of natural gas in a porous medium under high pressure almost was not studied but can create a high-temperature combustion front, which, possibly, lets to accelerate hydrogen formation processes.

To bring more impact the proposed technology should be optimized in terms of the stimulation mode of the reservoir model. This can be done using numerical simulation and verified than experimentally (using a CT). On the next step, numerical modeling of the implementation of the technology at a field scale is expected, followed by feasiability study/detailed economic analysis.

Список литературы диссертационного исследования кандидат наук Афанасьев Павел Аркадьевич, 2024 год

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