A heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production, a preparation method and a viscosity reduction method

Abstract

The present application belongs to the field of catalytic materials and heavy oil exploitation technology, and particularly relates to a heavy oil catalytic system coupled with methanol liquid phase reforming hydrogen production, a preparation method and a viscosity reduction method. A soluble divalent copper salt, a soluble divalent nickel salt and a soluble divalent iron salt are dissolved in water to form a mixed metal salt solution, and the pH is adjusted to 8-12 to obtain a precipitation system; after aging and drying, the system is calcined at 300-700 DEG C to obtain the heavy oil catalytic system coupled with methanol liquid phase reforming hydrogen production. The present application uses the co-precipitation method and calcination to prepare the heavy oil catalytic system coupled with methanol liquid phase reforming hydrogen production, which has the Fe3O4 phase FCC structure, ensures that the multi-metal active interface can be fully exposed, and through the electronic synergistic effect between the strengthened components, has the activities of methanol liquid phase reforming hydrogen production and heavy oil catalytic viscosity reduction, and can in-situ produce active hydrogen species through methanol liquid phase reforming hydrogen production, thereby driving the heavy oil catalytic modification reaction and significantly reducing the viscosity.

Description

Technical Field

[0001] This invention belongs to the field of catalytic materials and heavy oil extraction technology, specifically relating to a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production, its preparation method, and its viscosity reduction method. Background Technology

[0002] Heavy oil, as an important unconventional oil and gas resource, boasts abundant reserves. However, its high viscosity and poor fluidity due to the presence of large amounts of gums and asphaltenes make it difficult to extract and transport using traditional methods. Currently, industrial applications mainly employ thermal recovery technologies such as steam huff and puff and steam drive to reduce heavy oil viscosity. However, these methods rely heavily on temperature; as the temperature decreases, the viscosity of heavy oil tends to rebound rapidly, making long-term stable viscosity reduction difficult. Therefore, altering the molecular structure of heavy oil's heavy components through catalytic cracking to achieve deep upgrading and irreversible viscosity reduction has become an important research direction in the field of heavy oil development.

[0003] In the catalytic reforming of heavy oil, both the catalyst and the hydrogen donor significantly influence the viscosity reduction effect. The catalyst promotes the breaking of C–S, C–N, and C–C bonds in heavy oil, thereby accelerating its recombinant decomposition. The hydrogen donor provides active hydrogen species, stabilizes free radicals generated during cracking, and inhibits condensation reactions, fundamentally improving the viscosity reduction and reforming effect of heavy oil. In reported heavy oil hydroreforming technologies, the relatively expensive tetrahydronaphthalene is typically used as the hydrogen donor. In contrast, methanol has advantages such as wide availability, low price, and convenient storage and transportation, and is considered a potential inexpensive alternative hydrogen source. However, methanol has limited hydrogen supply capacity and poor viscosity reduction effect. Therefore, how to improve the release efficiency of active hydrogen species from methanol and achieve low-cost, high-efficiency hydrogen supply has become a key issue in current research on in-situ catalytic reforming of heavy oil.

[0004] In recent years, methanol liquid-phase reforming for hydrogen production has attracted widespread attention due to its ability to efficiently release hydrogen under mild conditions. This reaction exhibits high compatibility with the hydrothermal catalytic cracking of heavy oil in terms of reaction temperature and pressure, providing a technological basis for their coupling. Through catalytic methanol liquid-phase reforming, in-situ conversion of methanol into active hydrogen species can be achieved, thereby continuously providing active hydrogen species for heavy oil hydrocracking. However, heavy oil is complex in composition and diverse in reaction pathways. It consists of various components such as saturated hydrocarbons, aromatics, gums, and asphaltenes. Among them, gums and asphaltenes have complex molecular structures containing various chemical bonds such as C–C, C–S, C–N, and C–O. The breaking of different chemical bonds requires the participation of different types of active centers. Existing catalyst preparation often adopts core-shell coating or independent phase separation methods, such as CN 118831619 A, a core-shell hydrogenation catalyst and its preparation method. The catalyst includes a core layer and a shell layer, where the core layer is alumina loaded with active metal components and the shell layer is alumina loaded with molybdenum carbide. For the complex reaction system of heavy oil, the active sites are relatively singular and difficult to effectively enter the catalyst channels and contact the active sites. Summary of the Invention

[0005] The purpose of this invention is to provide a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production, as well as its preparation method and viscosity reduction method. The heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production is prepared by co-precipitation and calcination. It possesses an Fe3O4 phase FCC structure, ensuring full exposure of the multi-metal active interface. By enhancing the electronic synergistic effect between components, it combines the activities of methanol liquid-phase reforming for hydrogen production with heavy oil catalytic viscosity reduction. Through methanol liquid-phase reforming for hydrogen production, active hydrogen species can be generated in situ and efficiently, thereby driving the catalytic reforming reaction of heavy oil and significantly reducing its viscosity.

[0006] To achieve the above objectives, the specific technical solution provided by the present invention is as follows: The first objective of this invention is a method for preparing a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production, comprising the following steps: S1. Dissolve soluble divalent copper salt, soluble divalent nickel salt and soluble divalent iron salt in water to form a mixed solution of metal salts. Use co-precipitation to adjust the pH to 8-12 to obtain a precipitation system.

[0007] S2. The precipitate system is aged and dried to obtain a catalyst precursor, which is then calcined at 300℃~700℃ to form a Fe3O4 phase FCC structure, thus obtaining a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production.

[0008] Furthermore, in the mixed metal salt solution, the molar ratio of copper ions, nickel ions, and iron ions is 1–20:1–5:13.

[0009] Furthermore, the total metal ion concentration of the mixed metal salt solution is 0.12 mol / L to 1.2 mol / L.

[0010] Furthermore, the heating rate during calcination is 3℃ / min to 6℃ / min, and the calcination time is 4h to 8h.

[0011] Furthermore, the pH was adjusted to 8-12 by adding NH3·H2O dropwise, and the aging was carried out by stirring at 20℃-70℃ for 30-80 minutes.

[0012] Furthermore, the soluble divalent copper salt is at least one of copper nitrate and copper sulfate, the soluble divalent nickel salt is at least one of nickel nitrate and nickel sulfate, and the soluble divalent ferric salt is at least one of ferrous sulfate, ferric sulfate, or ferric nitrate.

[0013] The second objective of this invention is to provide a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production, wherein the molar ratio of copper, nickel and iron in the copper-based catalytic system is 1-20:1-5:13.

[0014] The third objective of this invention is the above-mentioned heavy oil catalytic viscosity reduction method coupled with methanol liquid-phase reforming for hydrogen production, comprising the following steps: Heavy oil, methanol, and a heavy oil catalytic system are added to a reaction vessel. After being purged with inert gas at least three times, the initial pressure of the system is 0 MPa to 8 MPa. The reaction is carried out at 180°C to 300°C for 6 to 72 hours. The heavy oil catalytic system is the same as described above.

[0015] Furthermore, the amount of methanol added is 0.1 wt.% to 10 wt.% of the heavy oil mass, and the amount of heavy oil catalyst added is 0.1 wt.% to 8 wt.% of the heavy oil mass.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: The preparation method provided by this invention uses a co-precipitation method to prepare Cu 2+ Ni 2+ Fe 2+ Ions co-precipitate to form a catalyst precursor with highly homogeneous composition. Calcination is then used to form a composite eutectic structure, where FeNiOH provides the structural units of layered compounds, and Cu provides active sites for methanol liquid-phase reforming. This results in a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production. The copper-based catalytic system is classified as an Fe3O4 phase FCC structure, avoiding the core-shell coating or independent phase separation phenomena commonly found in existing catalysts. This structural feature ensures that the multi-metal active interface is fully exposed and significantly improves the catalytic cracking efficiency for heavy oil macromolecules by enhancing the electronic synergistic effect between components.

[0017] The copper-based catalytic system constructed in this invention possesses multiple metal active sites and combines methanol liquid-phase reforming for hydrogen production with heavy oil catalytic viscosity reduction activity. It can efficiently generate active hydrogen species in situ through methanol liquid-phase reforming. This system innovatively utilizes inexpensive methanol to replace traditional expensive organic hydrogen donors such as tetrahydronaphthalene and decahydronaphthalene. With extremely low catalyst (0.1 wt.%–8 wt.%) and methanol (0.1 wt.%–10 wt.%) additions, it significantly enhances the deep coupling of in-situ methanol liquid-phase reforming for hydrogen production and heavy oil catalytic upgrading under initial pressures of 0–8 MPa at 180–300 °C. This results in a substantial increase in extraction efficiency while demonstrating outstanding industrial application value and economic benefits. Attached Figure Description

[0018] Figure 1 The X-ray diffraction patterns are those of the heavy oil catalytic systems for hydrogen production coupled with methanol liquid-phase reforming prepared in Examples 1 to 3 of this invention.

[0019] Figure 2 This is a comparison chart of the viscosity and viscosity reduction rate of the catalytic systems prepared in Examples 1 to 3 and Comparative Examples 1 to 4 of this invention. Figure 2 In the text, a represents Examples 1 to 3, and b represents Comparative Examples 1 to 4.

[0020] Figure 3 The graph shows the viscosity reduction rate of heavy oil under different methanol addition amounts for the catalytic system prepared in Example 1 of this invention. Detailed Implementation

[0021] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific embodiments and accompanying drawings. However, the embodiments described are not intended to limit the present invention.

[0022] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0023] In recent years, methanol liquid-phase reforming for hydrogen production has attracted widespread attention due to its ability to efficiently release hydrogen under mild conditions. This reaction exhibits high compatibility with the hydrothermal catalytic cracking of heavy oil in terms of reaction temperature and pressure, providing a technological basis for their coupling. Through catalytic methanol liquid-phase reforming, in-situ conversion of methanol into active hydrogen species can be achieved, thereby continuously providing active hydrogen species for heavy oil hydrocracking.

[0024] Therefore, developing a multifunctional catalyst system that can simultaneously promote methanol liquid-phase reforming for hydrogen production and heavy oil hydrocracking is of great significance for achieving low-cost, green, and efficient catalytic upgrading of heavy oil.

[0025] Based on this, the present invention provides a method for preparing a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production, comprising the following steps: S1. Dissolve soluble divalent copper salt, soluble divalent nickel salt and soluble divalent iron salt in water to form a mixed solution of metal salts. Use co-precipitation to adjust the pH to 8-12 to obtain a precipitation system.

[0026] In this invention, a co-precipitation method is employed, and the pH is adjusted to alkalinity by adding NH3·H2O dropwise, so that Cu 2+ Ni 2+ Fe 2+ Ions co-precipitate to form a catalyst precursor with highly homogeneous composition. In some preferred embodiments, the total metal ion concentration of the metal salt mixed solution is 0.12 mol / L to 1.2 mol / L, and the molar ratio of copper ions, nickel ions, and iron ions is 1–20:1–5:13. It is understandable that the soluble divalent copper salt is at least one of copper nitrate and copper sulfate, the soluble divalent nickel salt is at least one of nickel nitrate and nickel sulfate, and the soluble divalent ferric salt is at least one of ferrous sulfate, ferric sulfate, or ferric nitrate.

[0027] S2. The precipitate system is aged and dried to obtain a catalyst precursor, which is then calcined at 300℃~700℃ to form a Fe3O4 phase FCC structure, thus obtaining a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production.

[0028] In this invention, aging involves stirring at 20℃ to 70℃ for 30 to 80 minutes to form a composite eutectic structure, followed by calcination at 300℃ to 700℃ for 4 to 8 hours to form a composite metal oxide. FeNiOH provides the structural units of the layered compound, and Cu provides active sites for methanol liquid-phase reforming, resulting in a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production. The copper-based catalytic system is classified as an Fe3O4 phase FCC structure, avoiding the core-shell coating or independent phase separation phenomena commonly found in existing catalysts. This structural feature ensures that the multi-metal active interface is fully exposed and significantly improves the catalytic cracking efficiency for heavy oil macromolecules by enhancing the electronic synergistic effect between components.

[0029] It is understood that the calcination heating rate is 3℃ / min to 6℃ / min. In this invention, the calcination heating rate can be any value between 3℃ / min and 6℃ / min, such as 3℃ / min, 4℃ / min, 5℃ / min or 6℃ / min, to calcinate at 300℃ to 700℃ to form a composite metal oxide.

[0030] This invention also provides a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production. In the copper-based catalytic system, the molar ratio of copper, nickel, and iron is 1–20:1–5:13. The copper-based catalytic system constructed in this invention possesses multiple metal active sites, combining methanol liquid-phase reforming for hydrogen production with heavy oil catalytic viscosity reduction activity. Through methanol liquid-phase reforming for hydrogen production, active hydrogen species can be efficiently generated in situ, enhancing the deep coupling between in-situ methanol liquid-phase reforming for hydrogen production and heavy oil catalytic upgrading under initial pressures of 0 MPa–8 MPa. This system innovatively utilizes inexpensive methanol to replace traditional expensive organic hydrogen donors such as tetrahydronaphthalene and decahydronaphthalene. With extremely low catalyst (0.1 wt.%–8 wt.%) and methanol (0.1 wt.%–10 wt.%) addition, it significantly reduces the content of heavy oil heavy components and achieves deep viscosity reduction, greatly improving extraction efficiency while demonstrating excellent industrial application value and economic benefits. In addition, this method is more environmentally friendly and safer while achieving efficient reduction of heavy oil viscosity.

[0031] The following specific examples will provide further explanation.

[0032] Example 1 A method for preparing a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production includes the following steps: S1. Weigh 7.50g of CuSO4·5H2O, 8.34g of FeSO4·7H2O and 3.92g of Ni(NO3)2·6H2O powder using an analytical balance, and then dissolve them in 150mL of deionized water to prepare a mixed metal salt solution with a total metal ion concentration of 0.39mol / L.

[0033] S2. Add ammonia to the mixed metal salt solution to adjust the pH to 10 and obtain a precipitation system.

[0034] S3. The precipitate system was stirred and aged at 30℃ for 60 min, then washed three times with deionized water (10 mL each time) to obtain a washed solid. The obtained solid was dried at 120℃ for 24 h to obtain a catalyst precursor. Finally, the catalyst precursor was calcined at 550℃ for 4 h to obtain a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production, named Cu. 20 Ni9Fe 20 .

[0035] Example 2 A method for preparing a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production includes the following steps: S1. Weigh 3.75g of CuSO4·5H2O, 8.34g of FeSO4·7H2O and 3.92g of Ni(NO3)2·6H2O powder using an analytical balance, and then dissolve them in 150mL of deionized water to prepare a mixed metal salt solution with a total metal ion concentration of 0.39mol / L.

[0036] S2. Add ammonia to the mixed metal salt solution to adjust the pH to 10 and obtain a precipitation system.

[0037] S3. The precipitate system was stirred and aged at 30℃ for 60 min, then washed three times with deionized water (10 mL each time) to obtain a washed solid. The obtained solid was dried at 120℃ for 24 h to obtain a catalyst precursor. Finally, the catalyst precursor was calcined at 550℃ for 4 h to obtain a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production, named Cu. 10 Ni9Fe 20 .

[0038] Example 3 A method for preparing a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production includes the following steps: S1. Weigh 11.25g of CuSO4·5H2O, 8.34g of FeSO4·7H2O and 3.92g of Ni(NO3)2·6H2O powder using an analytical balance, and then dissolve them in 150mL of deionized water to prepare a mixed metal salt solution with a total metal ion concentration of 0.5898mol / L.

[0039] S2. Add ammonia to the mixed metal salt solution to adjust the pH to 10 and obtain a precipitation system.

[0040] S3. The precipitate system was stirred and aged at 30℃ for 60 min, then washed three times with deionized water (10 mL each time) to obtain a washed solid. The obtained solid was dried at 120℃ for 24 h to obtain a catalyst precursor. Finally, the catalyst precursor was calcined at 550℃ for 4 h to obtain a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production, named Cu. 30 Ni9Fe 20 .

[0041] Comparative Example 1 A method for preparing a metal catalytic system includes the following steps: S1. Weigh 8.34g of FeSO4·7H2O powder using an analytical balance, then dissolve it in 150mL of deionized water to prepare a metal salt solution with an ion concentration of 0.2mol / L.

[0042] S2. Add ammonia to the metal salt solution to adjust the pH to 10, and obtain a precipitation system.

[0043] S3. The precipitate system was stirred and aged at 30℃ for 60 min, and then washed three times with deionized water (10 mL each time) to obtain the washed solid. The obtained solid was dried at 120℃ for 24 h to obtain the catalyst precursor. Finally, the catalyst precursor was calcined at 550℃ for 4 h to obtain a metal catalytic system, named FeO.

[0044] Comparative Example 2 A method for preparing a bimetallic catalytic system includes the following steps: S1. Weigh 8.34g of FeSO4·7H2O and 3.92g of Ni(NO3)2·6H2O powder using an analytical balance, then dissolve them in 150mL of deionized water to prepare a mixed metal salt solution with a total metal ion concentration of 0.2898mol / L.

[0045] S2. Add ammonia to the mixed metal salt solution to adjust the pH to 10 and obtain a precipitation system.

[0046] S3. The precipitate system was stirred and aged at 30℃ for 60 min, then washed three times with deionized water (10 mL each time) to obtain a washed solid. The obtained solid was dried at 120℃ for 24 h to obtain a catalyst precursor. Finally, the catalyst precursor was calcined at 550℃ for 4 h to obtain a bimetallic catalytic system, named Ni9Fe. 20 .

[0047] Comparative Example 3 A method for preparing a bimetallic catalytic system includes the following steps: S1. Weigh 7.50g of CuSO4·5H2O and 3.92g of Ni(NO3)2·6H2O powder using an analytical balance, then dissolve them in 150mL of deionized water to prepare a mixed metal salt solution with a total metal ion concentration of 0.2898mol / L.

[0048] S2. Add ammonia to the mixed metal salt solution to adjust the pH to 10 and obtain a precipitation system.

[0049] S3. The precipitate system was stirred and aged at 30℃ for 60 min, then washed three times with deionized water (10 mL each time) to obtain a washed solid. The obtained solid was dried at 120℃ for 24 h to obtain a catalyst precursor. Finally, the catalyst precursor was calcined at 550℃ for 4 h to obtain a bimetallic catalytic system, named Cu. 20 Ni9.

[0050] Comparative Example 4 A method for preparing a bimetallic catalytic system includes the following steps: S1. Weigh 7.50g of CuSO4·5H2O and 8.34g of FeSO4·7H2O powder using an analytical balance, then dissolve them in 150mL of deionized water to prepare a mixed metal salt solution with a total metal ion concentration of 0.40mol / L.

[0051] S2. Add ammonia to the mixed metal salt solution to adjust the pH to 10 and obtain a precipitation system.

[0052] S3. The precipitate system was stirred and aged at 30℃ for 60 min, then washed three times with deionized water (10 mL each time) to obtain a washed solid. The obtained solid was dried at 120℃ for 24 h to obtain a catalyst precursor. Finally, the catalyst precursor was calcined at 550℃ for 4 h to obtain a bimetallic catalytic system, named Cu. 20 Fe 20 .

[0053] The structure of the heavy oil catalytic systems for hydrogen production coupled with methanol liquid-phase reforming prepared in Examples 1 to 3 was tested. Figure 1 The X-ray diffraction patterns are those of the heavy oil catalytic systems for hydrogen production coupled with methanol liquid-phase reforming prepared in Examples 1 to 3 of this invention. Figure 1 As shown, characteristic diffraction peaks are observed at 2θ = ~19°, ~30°, ~57°, and ~63°, which are highly consistent with the standard card Fe3O4 (PDF#98-000-0294). With increasing Cu content, the diffraction peak positions did not shift significantly and no impurity peaks were observed, indicating that Cu atoms entered the face-centered cubic (FCC) lattice to form a stable Fe3O4 phase.

[0054] The heavy oil catalytic systems prepared in Examples 1-3 and Comparative Examples 1-4 were used in methanol liquid-phase in-situ reforming for hydrogen production and heavy oil catalytic upgrading and viscosity reduction, including the following steps: 100g of heavy oil was weighed and placed in a high-pressure reactor. 1wt.% of a powdered catalytic system and 1wt.% of methanol (based on the weight of the heavy oil) were added. These catalytic systems were prepared in Examples 1-3 and Comparative Examples 1-4, respectively. After sealing the reactor, nitrogen gas was introduced to purge the air from the reactor three times. The temperature was then programmed to 250℃ and reacted for 24 hours. After the reaction, the mixture was allowed to cool naturally to room temperature, the air was vented, and the reaction product was transferred to a beaker to obtain heavy oil treated with catalytic hydrothermal pyrolysis. The viscosity change of the treated heavy oil was measured using a viscometer, and its viscosity reduction rate was calculated.

[0055] Meanwhile, a blank control was set up without adding a catalyst, and its reaction conditions were kept consistent with those of the examples.

[0056] Figure 2This is a comparison chart of the viscosity and viscosity reduction rate of the catalytic systems prepared in Examples 1 to 3 and Comparative Examples 1 to 4 of this invention. Figure 2 In the text, a represents Examples 1 to 3, and b represents Comparative Examples 1 to 4. Figure 2 As shown, under the same reaction conditions, the blank control group could only reduce the viscosity of heavy oil from approximately 7000 mPa·s to approximately 5957 mPa·s, with a viscosity reduction rate of approximately 16%, indicating that the viscosity reduction effect of simple thermal action is limited. FeO and Ni9Fe were used... 20 Cu 20 Ni9 and Cu 20 Fe 20 After treatment with the catalytic system, the viscosity of heavy oil decreased to 2518 mPa·s, 2243 mPa·s, 2705 mPa·s, and 2185 mPa·s, respectively, with viscosity reduction rates of 64.49%, 68.37%, 61.85%, and 69.19%. In contrast, the catalytic systems of Examples 1 to 3 all exhibited significant catalytic upgrading effects, with heavy oil viscosity decreasing to the range of 1500 mPa·s to 2000 mPa·s, and corresponding viscosity reduction rates exceeding 70%. Among them, Example 1 showed the best performance, with a viscosity reduction rate as high as 78.65%. The results indicate that there is a significant synergistic catalytic effect among the multi-metal components, which can effectively promote the cracking and conversion of macromolecular components in heavy oil. The catalytic system provided by this invention has excellent catalytic activity and efficient viscosity reduction performance in the hydrothermal cracking and upgrading of heavy oil.

[0057] Table 1 shows the changes in the content of the four components of heavy oil before and after the reaction in the catalytic system of Example 1 of the present invention. As shown in Table 1, the Cu prepared in Example 1 20 Ni9Fe 20 After the catalytic system was upgraded, the heavy oil showed a clear trend towards becoming lighter: the mass fractions of saturated and aromatic components increased significantly by 15.59% and 12.19%, respectively, while the gum content decreased by 20.74% and the asphaltenes content decreased by 6.05%, demonstrating that the catalyst has excellent recombination and decomposition activity.

[0058] Table 1. Changes in the content of the four components of heavy oil before and after the catalytic system reaction. Before the reaction 7.43 12.16 63.54 16.87 After the reaction 22.02 24.35 42.80 10.82 To further illustrate the effect of the catalytic system prepared in this invention, taking Example 1 as an example, 100g of Karamay heavy oil was added to a high-temperature and high-pressure reactor, and Cu prepared in Example 1 was added at 1wt.% of the heavy oil mass. 20 Ni9Fe 20The catalytic system was subjected to at least three purgings of high-purity nitrogen in the reactor to achieve an initial pressure of 3 MPa. The reaction was carried out at 250°C for 24 hours, with methanol additions controlled at 1 wt.%, 3 wt.%, and 5 wt.% of the heavy oil mass to investigate the effect of methanol dosage on the viscosity-reducing effect of heavy oil.

[0059] Figure 3 This is a graph showing the viscosity reduction rate of heavy oil under different methanol addition amounts for the catalytic system prepared in Example 1 of this invention. Figure 3 As shown, methanol acts as both a physical dispersant and a hydrogen donor in the reaction system: as a polar small molecule, it weakens the interaction between asphaltenes and gum molecules, while simultaneously acting as a hydrogen donor to inhibit condensation reactions, thereby improving the viscosity reduction effect. With the methanol addition increasing from 1 wt.% to 3 wt.%, the viscosity reduction rate increased from 78.65% to 82.95%; however, when the methanol addition further increased to 5 wt.%, the increase in viscosity reduction rate decreased.

[0060] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, it is intended to include any modifications and variations that fall within the scope of the claims and their equivalents.

Claims

1. A method for preparing a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production, characterized in that, Includes the following steps: Soluble divalent copper salt, soluble divalent nickel salt, and soluble divalent iron salt are dissolved in water to form a mixed solution of metal salts. The pH is adjusted to 8-12 by co-precipitation to obtain a precipitation system. The precipitate system was aged and dried to obtain a catalyst precursor, which was then calcined at 300℃~700℃ to form a Fe3O4 phase FCC structure, thus obtaining a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production.

2. The method for preparing a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production according to claim 1, characterized in that, In a mixed solution of metal salts, the molar ratio of copper ions, nickel ions, and iron ions is 1–20:1–5:

13.

3. The method for preparing the heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production according to claim 1, characterized in that, The total metal ion concentration of the mixed metal salt solution is 0.12 mol / L to 1.2 mol / L.

4. The method for preparing the heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production according to claim 1, characterized in that, The heating rate for calcination is 3℃ / min to 6℃ / min, and the calcination time is 4h to 8h.

5. The method for preparing a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production according to claim 1, characterized in that, The pH was adjusted to 8-12 by adding NH3·H2O dropwise. The aging process was carried out by stirring at 20℃-70℃ for 30-80 minutes.

6. The method for preparing a heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production according to claim 1, characterized in that, The soluble divalent copper salt is at least one of copper nitrate and copper sulfate, the soluble divalent nickel salt is at least one of nickel nitrate and nickel sulfate, and the soluble divalent ferric salt is at least one of ferrous sulfate, ferric sulfate, or ferric nitrate.

7. A heavy oil catalytic system coupled with methanol liquid-phase reforming for hydrogen production, characterized in that, The copper-based catalytic system is prepared by the preparation method described in any one of claims 1 to 6, wherein the molar ratio of copper, nickel, and iron is 1 to 20: 1 to 5:

13.

8. A method for catalytic viscosity reduction of heavy oil coupled with methanol liquid-phase reforming for hydrogen production, characterized in that, Includes the following steps: Heavy oil, methanol, and a heavy oil catalytic system are added to a reaction vessel. After being purged with an inert gas at least three times, the initial pressure of the system is 0 MPa to 8 MPa. The reaction is carried out at 180°C to 300°C for 6 to 72 hours. The heavy oil catalytic system is the heavy oil catalytic system described in claim 7.

9. The heavy oil catalytic viscosity reduction method coupled with methanol liquid-phase reforming for hydrogen production according to claim 8, characterized in that, The amount of methanol added is 0.1 wt.% to 10 wt.% of the heavy oil mass, and the amount of heavy oil catalyst added is 0.1 wt.% to 8 wt.% of the heavy oil mass.

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