1. Introduction
Oil and natural gas will still be the main energy sources in the world in the next few decades. Developing unconventional oil and gas reservoirs will guarantee stable oil and gas production. Heavy oil reservoirs have a very unfavorable water–oil mobility ratio, and steam flooding is a favorable means for their efficient development [
1,
2,
3,
4,
5]. However, with the continuous injection of steam, channeling is intensified, influenced by factors such as well spacing, reservoir heterogeneity, crude oil properties, gravity separation, reservoir pressure and temperature, relative permeability, steam quality, mobility ratio, and fluid saturation in the formation [
6,
7]. Control of steam channeling to expand the swept volume is an important guarantee for the heavy oil reservoir to expand the swept volume further and improve oil recovery.
Currently, a common method to solve the problem of gravity overload and the steam channeling of steam flooding is profile control agent-assisted steam flooding. The profile control system is injected into the reservoir with steam to plug the flow channels so that the steam injected into the reservoir will enter the unswept area [
8,
9,
10]. The research proposed by Stanford University [
11] comprehensively considered various chemical additives related to mobility control and considered applying the profile control technology in the steam flooding process an effective method [
12]. The commonly used profile control systems include association polymer [
13], microgel [
14,
15,
16,
17], water-assisted gas flooding [
18,
19], and foam [
20].
Foam as a profile control system [
21,
22] has the mechanism of reducing steam mobility, increasing swept coefficient, and improving oil washing efficiency, which can improve the ultimate oil recovery of the reservoir. Meanwhile, the foam will not permanently block the oil layer because of the good selectivity of its plugging property. In the early 1970s, Needham [
23] and others invented the steam foam flooding technology. Since then, American Shell Oil Company, CLD Group Company, Stanford University Petroleum Research Institute, and Getty Oil Company have conducted in-depth laboratory research on steam foam flooding technology, and conducted field test research in the Midway-Sunset and North Kern Front oilfields, and have achieved initial success [
24]. The U.S. Department of Energy signed cost-sharing research contracts with Petio-Lewis Corporation, CLD, and SUPRI from 1979 to 1980, and entrusted Chemical Oil Recovery Company as the steam foam flooding technology manager from the laboratory to the field [
25,
26,
27,
28,
29]. Surfactant/foam injected into the formation, together with steam, will preferentially enter the formation with steam overburden and channeling and temporarily plug the channeling channels [
23,
30], diverting the steam direction to expand the swept volume [
31,
32]. Borchard [
33], Ettinger et al. [
34], and Schramm et al. [
35] carried out a large number of experimental studies, respectively, and concluded that the use of foam plugging in the steam flooding process is effective.
Although the above laboratory studies have shown that foaming agents can be used as plugging agents for steam flooding, the high price and poor temperature resistance of the foaming system limit its application in the oilfields [
36,
37,
38,
39]. Therefore, the development of a foam system with excellent foamability and high-temperature stability is the key to the study of foam profile control technology [
40]. The injection of a suitable concentration of lignosulfonate solution into the formation can generate a gel and plug the channeling channel. Wang et al. [
41] pointed out that the glue-forming liquid prepared with lignin extracted from paper-making waste liquid as the main material can form a good gel under the conditions of pH > 9 and temperature of 50~150 °C. Therefore, this paper considers the use of cheap modified lignin to improve the temperature resistance and the foam stability of the composite system.
This paper conducts research on the design of high-temperature steam flooding assisted by a profile control system, using modified lignin to improve the temperature resistance and foam performance of the system. Firstly, temperature-resistant modified lignin (CRF) from industrial wastewater was prepared via chain scission and sulfonation reactions, and then its properties were characterized by means of infrared spectroscopy, ultraviolet spectroscopy, and a TGA test. Meanwhile, the high-temperature foaming performance, foam stability, and ability to reduce the surface tension of the solution were evaluated for the foaming agent CX-5. Through the sand pack resistance factor experiment, the optimal formulation of the profile control system (PCS, including CX-5) was optimized. Finally, a single sand pack flooding efficiency experiment, a parallel flooding experiment with three sand-packing tubes, and a large-size core flooding experiment were carried out to clarify the EOR effect of PCS-assist steam flooding. The research contained in this paper can provide an experimental basis and data supporting the optimization of the on-site steam flooding profile control system and the optimal design of the injection parameters.
2. Material and Method
2.1. Materials
Agent: Pure lignin (The molecular weight is 3.2 × 105 Da) is obtained by acid precipitation and purification of low-concentration reed papermaking black liquor from Daqing Haida Paper Co., Ltd. (Daqing, China). Brine is prepared based on the composition of formation water in Daqing Oilfield. It contained 2359.8 ppm Na+ + K+, 4278.2 ppm HCO3−, 1018.6 ppm Cl−, 175.2 ppm CO32−, 110.7 ppm SO42−, 35.4 ppm Ca2+ and 22.1 ppm Mg2+. High temperature resistant foaming agent CX-5 (the molecular weight is 7.4 × 103 Da) is an anionic sulfonate surfactant with an effective concentration of 15%, which is provided by Daqing Petroleum Refinery (Daqing, China); the composite solution prepared by modified lignin (CRF) and CX-5 according to a certain concentration is the profile control system (PCS). Sulfuric acid, hydrochloric acid, ethanol, NaOH, formaldehyde, nonylphenol, sodium sulfite, hydrogen peroxide, etc., were purchased from Shanghai Aladdin Company (Shanghai, China), and were analytically pure.
Crude oil and brine: The deionized water was prepared by the ultra-pure water filter of Chengdu Youpu Company (Chengdu, China). According to the formation water formula, inorganic salt was added to prepare simulated formation water, and its salinity was 8000 mg/L. The crude oil is degassed and dehydrated crude oil from Liaohe Oilfield (Panjin, China), with a viscosity of 63,670 cP at room temperature, and reduced to 10 cP when heated to 200 °C.
Sand packing model: The model is 60 cm long, 2.5 cm in diameter, and filled with 50–220 mesh quartz sand. The permeability can be adjusted by designing the proportion of quartz sand with different mesh numbers, and it can be controlled between 1.0 D–15 D.
Rectangular sand packing model: The model was welded with stainless steel, and its dimensions are as follows: length × width × height = 1200 mm × 40 mm × 120 mm. There is a heating and insulating layer outside the core model; the initial temperature of the core can be set, and experiments can be carried out under thermal insulation conditions. The quartz sand used has 60 mesh, 70~140 mesh, and 270 mesh. The model is divided into the homogeneous model (place the sand packing model vertically, compact it evenly when filling, and try to ensure that the permeability is the same everywhere); and the heterogeneous model (place the sand packing model vertically, place a layer of the screen in the middle of the model, and fill the two sides of the screen with quartz sand of different meshes to form different permeability layers). After filling, the model is placed horizontally, the upper layer has a high permeability and the lower layer has a low permeability, so as to simulate the heterogeneity of the formation.
2.2. Lignin Modification Method
(1) Oxidative chain scission of lignin. A certain amount of lignin was dissolved in NaOH solution with pH = 10 and then reacted with O2 and 20% H2O2 in a 0.3 L autoclave. The reaction pressure was controlled at 0.4 Mpa, the reaction temperature was 70 °C, and the reaction time was 1.5 h. After the reaction, the product was concentrated and dried for analysis. (2) Synthesis of modified lignin surfactant (CRF). A total of 6 g of sodium sulfite and 9 g of formaldehyde were added to the above-purified sample, and 3 g of nonylphenol was weighed and dissolved in an organic solvent, then added to the autoclave, and then heated to 70 °C. After the reaction was completed and cooled to room temperature, the reactant was filtered and the precipitate was collected, vacuum-dried at 50 °C, and finally, the modified lignin solid brown powder was obtained.
2.3. Modified Lignin Properties
The sample was pressed into a film, and its infrared spectrum (wave number 4000–450 cm−1) was measured with a Fourier transform infrared spectrometer (Spectrum 400, Bruker, Billerica, MA, USA, potassium bromide tablet); ethanol was used as a solvent, and an ultraviolet-visible absorption spectrometer (UV-540, Shanghai Metash Instruments Co, Ltd, Shanghai, China) was used to determine the UV spectrum of the sample (wavelength 190–380 nm); the content of carbon, hydrogen, and oxygen elements in the lignin was analyzed with an elemental analyzer (EA-300 series, Keyence, Shanghai, China); a thermogravimetric analyzer (TA Q50, Dupont, Wilmington, DE, USA) was used to perform a thermogravimetric test on the CRF (6.523 mg of the sample was weighed, with high purity N2 used as the carrier gas. The heating rate of the thermogravimeter was 15 °C/min, and the temperature was heated from room temperature to 700 °C).
2.4. Foaming Performance of the Foaming Agent
2.4.1. Determination of Foam Stability by Bubbling Method
Determination of foam stability at room temperature and pressure: Put 20.0 mL of foaming agent solution into the container of the high-temperature and high-pressure foaming device (300 °C, 50 MPa, Huabao, Yangzhou, China), and blow 140.0 mL of N2 at a certain speed. The change in foam height reflects the dynamic balance change in foam formation and collapse, so it is a comprehensive reflection of foam stability and foaming ability. Measure the change in the foam volume with time after the bubbling is stopped, draw the foam decay curve, and obtain the foam half-life t0. In the experiment, a circulating water bath was used to control the temperature of the system.
Determination of high-temperature and high-pressure foam stability: Put 20.0 mL of foaming agent solution into the container of the high-temperature and high-pressure foaming device, adjust the confining pressure of the system with N2, start the incubator to heat up to the predetermined temperature, and inject 140.0 mL at a certain speed after 1 h of N2 at a constant-temperature (condition of temperature and pressure in the container), measure the change in the foam volume with time after the bubbling is stopped, draw the foam decay curve, and obtain the foam half-life t1.
2.4.2. Determination of Surface Tension of Foaming Agents
CX-5 solutions with concentrations of 0.05 wt%, 0.1 wt%, 0.3 wt%, and 0.5 wt% were prepared, and the surface tension was measured by the hanging ring method (CSI-356, Sincerity, Kansas, OK, USA) at 20 °C, and the surface tension was measured by the pendant drop method (Q2000, Hangzhou, China) at high temperature and high pressure, at 200 °C and 300 °C. At the same time, the air was injected into the solution to be tested through a syringe, and the change in the surface tension value within 1000 s was recorded to obtain the dynamic surface tension change curve of CX-5.
2.5. Resistance Factor of Profile Control System
After it is clear that the foaming agent can generate stable foam, it is necessary to evaluate the actual plugging ability of the foam in the core to meet the plugging ability of the steam channeling layer. The plugging performance of the foam is usually evaluated by the resistance factor, calculated during the core flooding experiment. The foaming agent solution and air are injected simultaneously by the ISCO pump (ISCO D, 0.00001–408 mL/min, Teledyne ISCO, Lincoln, NE, USA), and the two are mixed at the inlet of the sand packing pipe. The pressure difference between the inlet and outlet of the core is measured by the pressure sensor, and the resistance factor is calculated. The specific experimental process is as follows:
(1) Design and make sand packing models of artificial quartz sand with different particle sizes to meet the requirements of the specific experimental plan for porosity and permeability. (2) After the sand pack is evacuated, the simulated formation water is saturated, and the porosity is measured. (3) Connect the experimental process according to the experimental flow chart as shown in
Figure 1, and test the leakage at a pressure of 10.0 Mpa. (4) The constant temperature is 24 h, and the core flooding experiment is ready. (5) To determine the basic pressure difference P
0, set the back pressure slightly lower than the saturated vapor pressure at this temperature, turn on the feed water pump to inject water, and turn on the air feed pump (set the displacement of the feed water pump and the air feed pump according to a certain gas–liquid ratio). Then, open the bypass valve to allow the steam and air mixture to pass through the bypass, and then close the bypass valve. When the pressure at the inlet of the sand packing pipe is slightly lower than the saturated vapor pressure at the experimental temperature, open the core inlet valve, and then open the core outlet valve to carry out the flow experiment. When the differential pressure reaches a stable level, record the basic pressure difference at both ends of the core model at this time. (6) To determine the working pressure difference P
1, replace the water with the displacement agent solution, and carry out the experiment according to the same conditions and operating steps as (5). When the pressure difference across the model reaches a steady state, record the working pressure difference across the core model. (7) Calculate the foam resistance factor, that is, the ratio of the working pressure difference to the base pressure difference. (8) Repeat steps (1)–(7) by changing the experimental parameters and conditions. The specific experimental scheme is shown in
Table 1.
2.6. Improved Oil Recovery Effect of Foam Assistant Steam Flooding
2.6.1. Single-Tube Model Experiment
Firstly, the foam-assisted steam flooding efficiency experiment was carried out using a single sand packing model. The experimental flow chart is shown in
Figure 1. The experimental steps are as follows: Step (1)–Step (3) are the same as those in
Section 2.5. (4) Raise the incubator to the set temperature, keep at a constant temperature for 3 h, and use 3 to 5 times the pore volume of crude oil to displace the water in the core at a rate of 0.5 mL/min so that the oil saturation in the core meets the experimental design requirements. (5) For the steam + PCS flooding experiments, set the incubator at 270 °C for 5 h at a constant temperature, make the back pressure slightly lower than the saturated vapor pressure at this temperature, turn on the pump and inject water (or chemicals) and air into the foam generator according to the designed gas–liquid ratio. Then, open the bypass valve to let the injected mixed fluid pass through the bypass, so that the coil is completely filled with the mixed fluid, and then close the bypass valve. When the inlet pressure of the sand pack is slightly lower than the saturated vapor pressure at the experimental temperature, open the inlet valve and outlet valve of the sand pack, and then start the displacement experiment. (6) The amount of oil and water produced is calculated by solvent extraction distillation method. A total of 4 sets of experiments were carried out: (1) steam flooding; (2) steam + surfactant (CRF); (3) steam + CX-5 + air; (4) steam + PCS + air. During the injection process, the total injection speed was controlled to remain unchanged at 6 mL/min. If the air was injected, the gas–liquid ratio was 1:1, and the back pressure was 4.5 MPa.
2.6.2. Three Parallel Sand Packing Model Displacement Experiment
The heterogeneity of the reservoir is simulated by the parallel sand packing tube model, and the effect of the control and flooding system on the channeling phenomenon during steam flooding and the effect of enhancing oil recovery are studied. The experimental steps are the same as those in
Section 2.6.1, only the single sand packing model is replaced with a three-parallel sand packing model. The permeabilities of the three sand packing tubes are set to 1D, 4D, and 10D, respectively, and the model permeability gradient is 10. Four sets of experiments were also carried out: (1) steam flooding; (2) steam + surfactant (CRF); (3) steam + CX-5 + air; (4) steam + PCS + air.
2.6.3. Large-Size Rectangular Sand Filling Mold Displacement Experiment
In order to further study the effect of the PCS in controlling steam overburden, blocking steam channeling channels, and expanding the swept volume of steam flooding, a large-scale sand-filled core insulating air foam steam flooding experiment was carried out. The flow chart of the experimental device and the experimental steps are the same as those in
Section 2.6.1.