Amid the global transition toward carbon neutrality, heavy oil-which accounts for more than half of the world's total crude oil reserves-has emerged as a promising feedstock for in-situ hydrogen generation (ISHG), overcoming the longstanding technical and economic bottlenecks of conventional heavy oil extraction and upgrading. In this study, we systematically investigate the three core ISHG mechanisms (pyrolysis, aquathermolysis, and pneumatolysis) through linear-heating pyrolysis (LHP), high-temperature high-pressure reactor (HTPR), and combustion tube (CT) experiments, with a focus on the regulatory effects of temperature, pressure, water content, reaction atmosphere, and catalysts on hydrogen production performance. Key findings show that pyrolysis enables efficient hydrogen production at temperatures above 500 degrees C, with both water injection volume and pressure exhibiting optimal operating ranges. Catalysts effectively alter the product distribution of pyrolysis and regulate the proportion of hydrogen in the gaseous products. Aquathermolysis presents relatively low hydrogen generation efficiency under conventional low-temperature conditions, which can be significantly enhanced by elevated temperatures, and also benefits from the oxidation and mineralization of formation water. Pneumatolysis is subject to a wider range of influencing factors, where the precise regulation of air, nitrogen, and water injection is the key to achieving efficient hydrogen production. The three mechanisms exhibit complementary advantages: pyrolysis delivers high gasification efficiency in the high-temperature stage, aquathermolysis is adaptable to low-temperature reservoir environments, and pneumatolysis realizes sustained hydrogen production via combustion-gasification synergy. This work clarifies the multi-path conversion mechanisms of heavy oil ISHG, identifies the optimal operating parameters for each mechanism, and provides critical experimental support for the development of efficient, low-carbon technologies for heavy oil recovery coupled with in-situ hydrogen production.

The miscibility of flue gas and different types of light oils is investigated through slender-tube miscible displacement experiment at high temperature and high pressure. Under the conditions of high temperature and high pressure, the miscible displacement of flue gas and light oil is possible. At the same temperature, there is a linear relationship between oil displacement efficiency and pressure. At the same pressure, the oil displacement efficiency increases gently and then rapidly to more than 90% to achieve miscible displacement with the increase of temperature. The rapid increase of oil displacement efficiency is closely related to the process that the light components of oil transit in phase state due to distillation with the rise of temperature. Moreover, at the same pressure, the lighter the oil, the lower the minimum miscibility temperature between flue gas and oil, which allows easier miscibility and ultimately better performance of thermal miscible flooding by air injection. The miscibility between flue gas and light oil at high temperature and high pressure is more typically characterized by phase transition at high temperature in supercritical state, and it is different from the contact extraction miscibility of CO2 under conventional high pressure conditions.

Hydrogen is a clean energy because of its high energy density and pollution-free com-bustion. The main ways of hydrogen generation are from coal and methane, as well as hydrogen generation from by-products of chemical plants. It had been reported that heavy oil reservoir in Margaret Lake in Canada produced up to 15 mol% hydrogen indicating that it is feasible to produce hydrogen by in-situ gasification (ISG) from heavy oil reservoir. However, there are relatively few studies on the mechanism and characteristics of hydrogen generation from ISG of heavy oil, the lower limit of hydrogen-production tem-perature, the interaction of produced gas and so on. Previous studies focused on the upgrading of heavy oil rather than hydrogen generation. In order to study the hydrogen generation mechanisms of different samples, The 4 types samples covering heavy oil, light oil, carbon samples were used and the saturate, aromatic, resin and asphaltene (SARA) components was measured by thin layer chromatography and flame ionization detection (TLC-FID). Then, the ramped temperature oxidation (RTO) experiments of 7 Runs of reservoir cores and sand-filling model were designed. The compositions and molar con-tents of produced gas were analyzed combined with gas chromatography (GC), and the lower limit temperature and the advantages of hydrogen generation from heavy oil were analyzed under different air/nitrogen injection rates based on a constant water injection rate. The results showed that the lower limit temperature of hydrogen generation from crude oil was about 500-550 degrees C and that of carbon was 700-750 degrees C. The reservoir core may had catalytic effect, which can promote hydrogen production. The highest hydrogen rate of RTO experiment with reservoir core can reach 55-60mol%, while that of sand-filling experiment was only 5-10mol%. The main chemical reactions for hydrogen generation from crude oil were coke gasification and water-gas shift. Therefore, the hydrogen pro-duction of heavy oil with high hydrocarbon ratio was significantly greater than that of thin oil. It showed the advantages of hydrogen generation from heavy oil. In addition, in order to quantitatively evaluate the efficiency of hydrogen production by gasification, the defi-nition and calculation equation of hydrogen generation efficiency (HGE) were given. The HGE was defined as the ratio of hydrogen production volume and hydrogen consumption volume in a certain period of time (Dt). The Ehg can be used to quantitatively represent HGE, and the calculation of Ehg is the ratio of hydrogen production and twice of oxygen con-sumption in a period of time. The Ehg of Run1 and Run3 were calculated to be 1.47 and 0.15. It indicated that the hydrogen production efficiency of Run1 was about 10 times higher than that of Run3.(c) 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Fire flooding (FF) has been one of the important thermal enhanced-oil-recovery technologies in developing heavy oil reservoir. Many scholars have carried out laboratory studies on the complex oil-displacement mechanism due to the complex physical and chemical reactions for fire flooding. However, almost no one had given an equation expression of gas injection and production during fire-flooding process. Therefore, the FF and flue gas flooding (FGF) experiments of one-dimensional combustion tubes were conducted. The oil-recovery differences of FF and FGF experiments under the same conditions were calculated, and a high linear correlation was found. The results showed that the FF effects were mainly affected by the flue-gas when the gas injection was low, and the combustion-front expansion (CFE) effects made the main contribution when the gas injection was high. The gas injection, water and liquid production were logarithmically treated and compared with the oil production. It was found a strong linear relationship between the two sets of experiments, and the linear relationship was stronger in the FGF experiment. Among all the linear relationships, the logarithm of water production and oil production had the strongest linear relationship. Based on this understanding, the water and oil production were connected from flue gas in FF process, and a novel FF equation was derived and obtained. Finally, the production curves on site of the two typical FF cases and the fitting curves of the FF equation were descripted and compared. The results showed that the novel equation can reflect and forecast the field performance by FF process in developing heavy oil reservoir.

Ketone compounds are oxidation products of crude oil in the in-situ combustion (ISC) process. Revealing the molecular composition of ketones can provide theoretical guidance for understanding the oxidation process of crude oil and valuable clues for studying the combustion state of crude oil in the reservoir. In this study, low-temperature oxidation (LTO) processes were simulated in thermal oxidation experiments to obtain thermally oxidized oil at different temperatures (170 °C, 220 °C, 270 °C, and 320 °C). A combination of chemical derivatization and positive-ion electrospray (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to analyze the molecular composition of different kinds of ketones (fatty ketones, naphthenic ketones, and aromatic ketones) in the oxidized oils at different temperatures. The results showed that the concentration of aliphatic ketones and aliphatic cyclic ketones in the product oils decreased with the increase in temperature, while aromatic ketones increased with the increase in temperature. At the same oxidation temperature, the content of ketones follows this order: fatty ketones < cycloalkanes < aromatic ketones. The concentrations of ketones reached their maximum value at 170 °C and decreased at high temperatures due to over-oxidation. It was also found that nitrogen-containing compounds are more easily oxidized to ketone compounds than their hydrocarbon counterparts in the LTO process.

Ignition design of air injection wells is the crucial factor to a successful in-situ combustion. In this paper, experimental studies were carried out on post steam flooding wells at JIN-91 of Liaohe oilfield for improving ignition success rate. The experiments were conducted by a high temperature-pressure ignition device specifically designed for in-situ combustion, and the effects of various parameters were investigated by factorial experiments. The results showed that the ignition temperature was reduced and the ignition time was shortened due to three factors: heating temperature, reservoir pressure, and clay minerals. When heating temperature exceeded 360 degrees C, experimental pressure was higher than 4.0 MPa, and 10% of montmorillonite clay was added, the crude oil samples could be ignited rapidly. According to the factorial results, the most effective method to shorten ignition time is by increasing heating temperature, the safest method to reduce crude oil spontaneous combustion temperature and to shorten ignition time is by applying clay minerals, and reservoir pressure is the key factor for safety operation during ignition operation. These results will provide experimental theoretical guidance for high efficiency ignition, process optimization, and safe implementation of crude oil reservoir, they also will deliver tech support for the high efficiency operation of in-situ combustion.

In-situ combustion (ISC) or fire flooding (FF) technology had been widely applicated in developing heavy oil reservoirs. Due to the complex physical and chemical processes, it is not easy to guarantee the high oil recovery. For thin layer reservoirs, vertical well mode of FF can achieve good results, but for thick layer reservoirs, the vertical producing degree of FF under vertical well pattern is low. Therefore, it is necessary to deepen the basic understanding of fire flooding under different well patterns and study the influencing factors for thick heavy oil reservoir. Stereoscopic fire flooding (SFF) mode is proposed in this paper, and the one-dimensional combustion tube and differential scanning calorimetry (DSC) experiments were introduced and designed. The heavy oil samples of G block in Liaohe oilfield in China were studied and the oxidation kinetic parameters were obtained by experiments. The applicability of oil samples for fire flooding was tested. The different fire flooding modes was compared and the influencing factors of SFF were analyzed through simulations. The results indicated that the temperature of high temperature oxidation (HTO) was above 450 degrees C. The CO2 content of the produced gas was more than 13% and the apparent HC atomic ratio was 1.28. DSC experiments showed the activation energy of HTO stage was 1.40 x 10(5) J/mol. The results indicated that the heavy oil samples can reach a high temperature combustion state. The SFF mode was simulated by CMG-STARS module based on the experimental results. The simulation results showed that SFF had better performance than FF of only vertical wells in oil recovery. The important factors of SFF, such as gas-injection rate, reservoir thickness, transverse permeability, vertical permeability, crude oil viscosity, formation dip angle and relative position of horizontal wells and the applicable conditions of SFF mode were analyzed and the optimum condition for SFF mode for each influencing factor was analyzed, and the conclusions were obtained.

Petroleum cokes prepared from naphthenic crude oil differ significantly in terms of the oxygen content and hydrogen/carbon (H/C) ratio, which mainly depend on the different coking temperatures. Thermogravimetric-differential scanning calorimetry was applied to study the heat release and combustion weight loss of petroleum cokes prepared at 350 and 500 °C, respectively. The effect of different coke formation temperatures on the combustion properties of the coke formed during air injection in situ combustion (ISC) was also investigated. The results showed that the petroleum coke formed under oxygen exhibited an H/C ratio of 0.895 and an O/C ratio of 0.109 at 350 °C and an H/C ratio of 0.395 and an O/C ratio of 0.054 at 500 °C. As the temperature rises, the hydrogen atoms on the petroleum coke molecules intensify to separate and form water molecules and thus giving off heat. It can be further inferred that under the combustion temperature of air injection ISC, the coke at 350 °C can release more heat in the lower combustion temperature range, and the combustion weight loss is faster; however, the formation temperature continues to rise due to combustion at 500 °C, coke begins to release massive heat, and the combustion weight loss is as high as 97.95%. The combustion residuals of both temperature cokes and the residual solid content of the formation after combustion in porous media are both little, which can be used as fire flooding fuels at different formation temperatures to provide heat energy for oil displacement.

Steam huff and puff has become one of the most widely used technologies to enhance oil recovery during the early phase in heavy oil reservoirs. However, when the development entered in the later phase gradually, the production performance had characteristics with low oil-to-steam ratio and the oil recovery is generally 20-30%. Predecessors usually study a certain follow-up method for a block, and the well pattern is very regular. For the oilfield in the later phase of steam huff and puff, there was a lack of systematic comparison and evaluation with different follow-up methods under irregular well patterns. In this paper, the heavy oil reservoir in block G of Liaohe oilfield was taken as an example. In view of the complex geological conditions and irregular well pattern, the follow-up developing strategies, steam flooding (SF), steam assisted gravity drainage (SAGD) and fire flooding (FF) were compared and evaluated by numerical simulation. A model with seven components and four reactions (used in FF) was established by using STARS module of CMG software. A variety of combined well patterns with vertical and horizontal wells were designed for comparing the production performance. In total, two cases of SF, three cases of SAGD, and two cases of FF were simulated and the oil recovery were studied. The results indicated that these follow-up development methods can enhance oil recovery in different degrees. The combined well pattern with vertical and horizontal wells had a better production performance than that of only vertical wells. In the study, the performance of FF with the horizontal well was the best (oil recovery was 31.7% in the 20th year; cumulative air oil ratio was 3973 m3/m3; final oil recovery was 54.6%), while the SAGD with one horizontal well was the worst (oil recovery was 15.3% in the 20th year; cumulative steam oil ratio was 17.7 t/m3; final oil recovery was 32.6%). Compared with SAGD and FF, the performance of SF was not the best and far from the worst (oil recovery was 40.3% in the 20th year; cumulative steam oil ratio was 12.7 t/m3; final oil recovery was 40.3%). The results show that when the well pattern conditions are complex, the number of wells is large, and the formation is heterogeneous, the SAGD of the vertical and horizontal well combination is obviously affected by the inter well interference. Meanwhile, SAGD production has certain delay and high water cut. It seems that the production performance of SF is not affected by horizontal wells, and the water cut is high. FF with horizontal wells has obvious production performance and can find more uniform formation temperature rise and stable water cut between 0.5 and 0.7.

Physical modeling, numerical simulation and field case analysis were carried out to find out the subsurface thermal oxidation state, thermal oxidation front characteristics and production dynamic characteristics of high pressure air injection thermal oxidation miscible flooding technology. The lighter the composition and the lower the viscosity of the crude oil, the lower the fuel consumption and the combustion temperature are. The thermal oxidation front of light oil and volatile oil can advance stably, and a medium-temperature thermal oxidation stable displacement state can be formed in the light oil reservoir under high pressure conditions. With strong thermal gasification and distillation, light oil and volatile oil are likely to form a single phase zone of gasification and distillation with thermal flue gas at the high-temperature and high-pressure heat front, finally, an air-injection thermal miscible front. In light oil reservoirs, the development process of high-pressure air-injection thermal miscible flooding can be divided into three stages: boosting pressure stage, low gas-oil ratio and high-efficiency stable production stage and high gas-oil ratio production stage. Approximately 70% of crude oil is produced during the boosting pressure stage and low gas-oil ratio high-efficiency and stable production stage.

In-situ combustion simulation from laboratory to field scale has always been challenging, due to difficulties in deciding the reaction model and Arrhenius kinetics parameters, together with erroneous results observed in simulations when using large-sized grid blocks. We present a workflow of successful simulation of heavy oil in-situ combustion process from laboratory to field scale. We choose the ongoing PetroChina Liaohe D block in-situ combustion project as a case of study. First, we conduct kinetic cell (ramped temperature oxidation) experiments, establish a suitable kinetic reaction model, and perform corresponding history match to obtain Arrhenius kinetics parameters. Second, combustion tube experiments are conducted and history matched to further determine other simulation parameters and to determine the fuel amount per unit reservoir volume. Third, we upscale the Arrhenius kinetics to the upscaled reaction model for field-scale simulations. The upscaled reaction model shows consistent results with different grid sizes. Finally, field-scale simulation forecast is conducted for the D block in-situ combustion process using computationally affordable grid sizes. In conclusion, this work demonstrates the practical workflow for predictive simulation of in-situ combustion from laboratory to field scale for a major project in China.

In-situ combustion simulation from laboratory to fi eld scale has always been challenging, due to di ffi culties in deciding the reaction model and Arrhenius kinetics parameters, together with erroneous results observed in simulations when using large-sized grid blocks. We present a work fl ow of successful simulation of heavy oil in-situ combustion process from laboratory to fi eld scale. We choose the ongoing PetroChina Liaohe D block in-situ combustion project as a case of study. First, we conduct kinetic cell (ramped temperature oxidation) experiments, establish a suitable kinetic reaction model, and perform corresponding history match to obtain Arrhenius kinetics parameters. Second, combustion tube experiments are conducted and history matched to further determine other simulation parameters and to determine the fuel amount per unit reservoir volume. Third, we upscale the Arrhenius kinetics to the upscaled reaction model for fi eld-scale simulations. The upscaled reaction model shows consistent results with di ff erent grid sizes. Finally, fi eld-scale simulation forecast is conducted for the D block in-situ combustion process using computationally a ff ordable grid sizes. In conclusion, this work demonstrates the practical work fl ow for predictive simulation of in-situ combustion from laboratory to fi eld scale for a major project in China. block combustion tube numerical simulation.

Air injection for in situ combustion (ISC) and air injection assisted cyclic steam stimulation (AACSS) techniques have a good application prospective in the development of heavy oils, while the explosion risk in the process of air injection is of great concern and has restricted the application of the technology. So that injection of oxygenreduced air has been proposed to eliminate and control the explosion of oil/gas mixture with air. In this study, low-temperature oxidation experiments of heavy oil samples were conducted using a small batch reactor under the pressure of 5-15 MPa and oxygen content of 5%-15% at 225 degrees C in order to investigate the effect of oxygen content and pressure on the reaction rate and heat release during oxidation of heavy oil with oxygen-reduced air. The variations of temperature and pressure during the oxidation reaction were measured in the experiment, and the explosion phenomena of heavy oils were observed in the air with high oxygen contents (oxygen content more than 15%). The reaction rate and the exothermic heat of the reaction were calculated based on the pressure and temperature curves and using an improved heat loss model. The experimental results showed that reducing the oxygen content (e.g. reduced oxygen less than 10%) in air can effectively prevent the explosion of oil-gas mixtures, and the reaction rate and heat release during heavy oil oxidation are linearly proportional to pressure and oxygen content in the injected air when oil is in excess. The results of this study indicate that the heat generated in oil oxidation, which is important for the ISC and AACSS processes, can be controlled by pressure and oxygen content of the injected air, which can lay a good foundation for the oxygen-reduced air injection technique, especially for its application in deep heavy oil reservoirs, in which injection of oxygen-reduced air at high pressure can offset the effect of low oxygen content on heat release.

火驱驱替特征是火驱的复杂物化过程和油藏地质条件综合作用的结果,是火驱方案设计和跟踪调控的重要基础.利用一维热跟踪补偿燃烧管实验装置,对比分析了不同性质稠油线性火驱的驱替特征,并与烟道气驱驱替特征进行对比.结果表明:原油黏度对火驱产液速率影响较大,黏度较低时火驱初期产液速率较高,大部分原油在中前期采出;黏度较大时,初期产液速率较小,甚至不产液,大部分原油在火驱中后期产出.火驱阶段含水率主要由地层初始含水饱和度(火驱前含水饱和度)决定.当地层初始含水饱和度高于束缚水饱和度时,火驱初期含水率较高,之后逐渐降低并趋于稳定.火驱初期(注气量小于1 PV)的生产动态特征与烟道气驱相近.在持续开发过程中,火驱仍保持稳定的采油速度,而烟道气驱采出程度增幅放缓.火驱开发的原油采出程度与累积注气量呈近似线性的关系,表明要保证火驱开发的效果则需保证相应的注气量.

Ensuring the sustainable propagation of the combustion zone is a prerequisite for in-situ combustion (ISC). The combustion zone propagation processes with different gas injection parameters and reservoir properties were simulated with CMG STARS and a method of determining the propagation state was proposed based on the theoretical analysis of the simulation results. The simulation results of 67 cases with different gas injection parameters and reservoir properties show that there are three states of combustion zone propagation: the sustainable state, the declined state and the extinguished state. The temperature of the combustion zone shows a good correlation with the state of the combustion zone propagation. With increases in the gas injection rate, oxygen concentration, and oil saturation and decrease in the rock permeability, the combustion zone temperature increases and the propagation state changes from the extinguished or declined state to the sustainable state. Analysis of the nondimensionalized energy conservation equation shows that the combustion zone temperature is determined by the two dimensionless numbers HD and CW with the determined core property and domain. A diagram for determining the time-averaged temperature of the combustion zone using the HD and CW numbers was established, with relative deviations within 7%. The combustion zone propagation state under the combination conditions of the gas injection rate, oxygen concentration, oil saturation and reservoir permeability can be judged according to the predicted combustion zone temperature. The proposed method helps optimize the design of gas injection parameters in combustion tube tests and ISC oilfield applications.

针对多层油藏火驱开发过程面临的点火初期井筒内发生燃烧和储层纵向有效动用程度低、油藏动态跟踪和调控难度大等问题,结合室内实验数据、矿场试验数据,运用油藏工程分析方法,明确了火驱的本质特征是高温氧化反应,保证高温氧化的最关键参数是不同阶段注气强度,火驱开发是一种末次采油方式.将上述研究成果应用于多层油藏火驱开发方案设计中,结果表明:多层油藏火驱开发方案应细分开发层系,开发目的层的总厚度应小于30 m,含油层段厚度应小于20 m;开发程序可采用自下而上、逐层上返,通过层间接替实现长期稳产.研究内容对多层油藏火驱开发提高采收率和降低工程风险具有重要意义.

•The influence of steam on the heavy oil coking is studied.•Steam shows little effect under atmospheric pressure.•Coke yield of heavy oil is reduced by steam in an oxidizing atmosphere under 4 MPa.•Steam accelerates coke oxidation as well as inhibits the coke precursor formation.

The oil oxidation characteristics of the whole temperature regions from 30 °C to 600 °C during oil reservoir air injection were revealed by experiments. The whole oil oxidation temperature regions were divided into four different parts: dissolving and inflation region, low temperature oxidation region, medium temperature oxidation region and high temperature oxidation region. The reaction mechanisms of different regions were explained. Based on the oil oxidation characteristics and filed tests results, light oil reservoirs air injection development methods were divided into two types: oxygen-reducing air flooding and air flooding; heavy oil reservoirs air injection in-situ combustion development methods were divided into two types: medium temperature in-situ combustion and high temperature in-situ combustion. When the reservoir temperature is lower than 120 °C, oxygen-reducing air flooding should be used for light oil reservoir development. When the reservoir temperature is higher than 120 °C, air flooding method should be used for light oil reservoir development. For a normal heavy oil reservoir, when the combustion front temperature is lower than 400 °C, the development method is medium temperature in-situ combustion. For a heavy oil reservoir with high oil resin and asphalting contents, when the combustion front temperature is higher than 450 °C, the development method at this condition is high temperature in-situ combustion. Ten years field tests of air injection carried out by PetroChina proved that air has advantages in technical, economical and gas source aspects compared with other gas agents for oilfield gas injection development. Air injection development can be used in low/super-low permeability light oil reservoirs, medium and high permeability light oil reservoirs and heavy oil reservoirs. Air is a very promising gas flooding agent.

Coke formation during the process of in-situ combustion is affected by clay minerals, among which montmorillonite shows the most significant effect. A fixed-bed reactor was used to conduct the thermal conversion experiments of heavy oil and model compounds to reveal the mechanism of montmorillonite affecting the coke formation. Under the inert atmosphere, in the presence of montmorillonite, the temperature at which aromatic C-C groups of coke appeared decreased from 500 degrees C to 450 degrees C and polymers were formed when toluene was heated, indicating that montmorillonite catalyzed aromatization and polymerization, respectively. The increase in the supporter surface area promoted the formation of coke from pyrolysis by shortening the induction of coking. Under the oxidizing atmosphere, in the presence of montmorillonite, the initial temperature of O-2 consumed by heavy oil decreased from 270 degrees C to 250 degrees C, indicating that montmorillonite catalyzed oxygenadding reaction. The temperature of COx released by acetaldehyde and acetic acid decreased, and the release amounts increased, indicating that montmorillonite catalyzed decarbonylation and decarboxylation. Polymers were formed when acetaldehyde, acetic acid, ethanol, and acetone were heated, indicating that montmorillonite catalyzed polycondensation. When the oil mass fraction in the sample was within 18%, further increase in the supporter surface area did not affect the formation of coke from oxidation. The catalysis of montmorillonite was the main mechanism affecting coke formation during the thermal conversion of heavy oil under the inert and oxidizing atmospheres.