A method for separating metalloporphyrin compounds from heavy oil

Abstract

The present disclosure relates to a method for separating metalloporphyrin compounds from heavy oil, wherein the method comprises: loading the heavy oil on water-containing silica gel to obtain a silica gel adsorbent loaded with the heavy oil; packing the silica gel adsorbent into an extraction column, and sequentially eluting the silica gel adsorbent with a set of elution solutions with gradually increasing polarity to obtain eluate containing metalloporphyrin compounds; the water content of the water-containing silica gel is 30-70% by mass; the set of elution solutions with gradually increasing polarity sequentially comprises a first elution solution, a second elution solution, a third elution solution and a fourth elution solution; the first elution solution is an alkane and / or a cycloalkane, the second elution solution is an aromatic hydrocarbon, the third elution solution is a mixture of an aromatic hydrocarbon and a polar organic solvent, and the fourth elution solution is a first polar organic solvent. The method provided by the present disclosure can effectively improve the selectivity and yield of metalloporphyrin compounds, and can realize effective separation and enrichment of metalloporphyrin compounds in heavy oil after a small number of elution treatments.

Description

Technical Field

[0001] This disclosure pertains to the field of heavy oil separation, specifically relating to a method for separating metalloporphyrin compounds from heavy oil. Background Technology

[0002] Most impurities in crude oil are found in residual oil, including 90% nitrogen, 70% sulfur, and 99% metals and solid particles. Among the metals, most iron and calcium exist as organic acid salts, sodium as chlorides, and nickel and vanadium primarily as porphyrins. In terms of metal origin, nickel and vanadium mainly evolved from chlorophyll and heme in ancient organisms, making them important markers of petroleum genesis and the most abundant metals in residual oil. Other metals such as iron, calcium, and sodium mainly originate from transportation impurities and pipeline corrosion during oil extraction or refining, and are present in lower concentrations. Therefore, compared to other metals, porphyrin nickel and porphyrin vanadium have the greatest impact on residual oil processing. Furthermore, other metalloporphyrin compounds have been found in heavy oil, making a detailed analysis of the composition and properties of metalloporphyrin compounds in heavy oil essential for residual oil processing. However, due to the low mass fraction of metalloporphyrin compounds in heavy oil, direct analysis and characterization of these compounds are extremely difficult. Efficient separation and enrichment are necessary to facilitate subsequent analysis and experiments.

[0003] Currently, the main methods for separating metalloporphyrin compounds include solvent extraction, adsorption column chromatography, thin-layer chromatography, solid-phase extraction, and acid extraction. Among these, solid-phase extraction, compared with traditional liquid-liquid extraction, can improve the recovery rate of analytes, effectively separate analytes from interfering substances, and is simple and rapid, making it widely used in petrochemical analysis. However, all of these methods have certain drawbacks, such as the inability to effectively enrich metalloporphyrin compounds, poor selectivity for metalloporphyrins, and low yields. Summary of the Invention

[0004] The purpose of this disclosure is to provide a method for separating metalloporphyrin compounds from heavy oil. The method provided by this invention can effectively improve the selectivity and yield of metalloporphyrin compounds, and can achieve effective separation and enrichment of metalloporphyrin compounds from heavy oil after fewer rinsing treatments.

[0005] To achieve the above objectives, the present invention provides a method for separating metalloporphyrin compounds from heavy oil, wherein the method comprises:

[0006] S1. Load heavy oil onto water-containing silica gel to obtain silica gel adsorbent loaded with heavy oil;

[0007] S2. The silica gel adsorbent is packed into an extraction column, and a series of eluents with gradually increasing polarity are used to elute the silica gel adsorbent in sequence to obtain eluents containing metal porphyrin compounds.

[0008] The water content of the aqueous silica gel is 30-70% by mass;

[0009] The set of rinsing solutions with gradually increasing polarity includes a first rinsing solution, a second rinsing solution, a third rinsing solution, and a fourth rinsing solution; the first rinsing solution is an alkane and / or a cycloalkanes, the second rinsing solution is an aromatic hydrocarbon, the third rinsing solution is a mixture of an aromatic hydrocarbon and a first polar organic solvent, and the fourth rinsing solution is a second polar organic solvent.

[0010] Optionally, the water content of the aqueous silica gel is 40-70% by mass.

[0011] Optionally, the alkane is a C5-C7 alkane; the C5-C7 alkane is n-pentane, n-hexane, or n-heptane; the cycloalkane is a C5-C7 cycloalkane; the C5-C7 cycloalkane is cyclopentane, cyclohexane, or cycloheptane.

[0012] The aromatic hydrocarbon is toluene, p-xylene, o-xylene, or benzene;

[0013] The volume ratio of aromatic hydrocarbon to first polar organic solvent in the third rinsing solution is 1:(1-3), and the first polar organic solvent is methanol, acetonitrile or ethylene glycol;

[0014] The second polar organic solvent is a C3-C4 ketone; the C3-C4 ketone is preferably acetone.

[0015] Optionally, the method further includes: washing the fourth eluted silica gel adsorbent with a third polar organic solvent to obtain a fifth eluent; the third polar organic solvent includes dichloromethane or dichloroethane;

[0016] The second polar organic solvent is more polar than the third polar organic solvent.

[0017] Optionally, the method further includes: drying the silica gel and then mixing it with water to obtain the aqueous silica gel;

[0018] The drying conditions include: a drying temperature of 90–150°C, preferably 100–120°C, and a drying time of 2–4 hours, preferably 2–3 hours.

[0019] Optionally, the method of loading heavy oil onto aqueous silica gel includes: dissolving the heavy oil in an organic solvent and mixing it with the aqueous silica gel, and then removing the organic solvent;

[0020] The mass ratio of the organic solvent to the aqueous silica gel is (1-3):1;

[0021] The organic solvent includes one or more of dichloromethane, dichloroethane, chloroform, benzene, toluene, or xylene.

[0022] Optionally, the mass ratio of the aqueous silica gel to the heavy oil is (15-30):1.

[0023] Optionally, the volume of each eluent is 5 to 20 mL relative to 1 g of the aqueous silica gel.

[0024] Optionally, the content of porphyrin compounds in the heavy oil is 0.1 to 1000 mg / kg; the metalloporphyrin compounds include one or more of nickel porphyrin or vanadium porphyrin.

[0025] Optionally, the heavy oil includes one or more of heavy crude oil, atmospheric residue, vacuum residue, heavy oil gum, or heavy oil asphaltenes.

[0026] Through the above technical solution, this invention loads heavy oil onto hydrous silica gel and then elutes it with an eluent of gradually increasing polarity. This effectively improves the selectivity and yield of metalloporphyrin compounds, achieving effective separation and enrichment of metalloporphyrin compounds in heavy oil. It can obtain highly concentrated metalloporphyrin compounds in a single eluent. Furthermore, the eluent obtained after fewer elutions can be directly used for subsequent analysis and experiments without additional concentration steps. The content of metalloporphyrin compounds in the second eluent can be used as the content of metalloporphyrin compounds in the heavy oil. This reduces the number of elutions while ensuring the accuracy of metalloporphyrin compound content determination in subsequent analyses, achieving rapid and accurate determination of metalloporphyrin compound content in heavy oil. Moreover, the method provided by this invention is simple, convenient, and quick to operate.

[0027] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0028] The following provides a detailed description of specific embodiments of this disclosure. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit this disclosure.

[0029] This disclosure provides a method for separating metalloporphyrin compounds from heavy oil, wherein the method includes:

[0030] S1. Load heavy oil onto water-containing silica gel to obtain silica gel adsorbent loaded with heavy oil;

[0031] S2. The silica gel adsorbent is packed into an extraction column, and a series of eluents with gradually increasing polarity are used to elute the silica gel adsorbent in sequence to obtain eluents containing metal porphyrin compounds.

[0032] The water content of the aqueous silica gel is 30-70% by mass;

[0033] The set of rinsing solutions with gradually increasing polarity includes a first rinsing solution, a second rinsing solution, a third rinsing solution, and a fourth rinsing solution; the first rinsing solution is an alkane and / or a cycloalkanes, the second rinsing solution is an aromatic hydrocarbon, the third rinsing solution is a mixture of an aromatic hydrocarbon and a first polar organic solvent, and the fourth rinsing solution is a second polar organic solvent.

[0034] The inventors of this disclosure have discovered that by using silica gel with a specific water content as a heavy oil adsorbent and then eluting it with a specific set of eluents with gradually increasing polarity, metalloporphyrin compounds in heavy oil can be concentrated in a single eluent, achieving effective separation and enrichment of metalloporphyrin compounds in heavy oil. This allows the eluent obtained after fewer elution processes to be directly used for subsequent analysis and experiments, meeting the requirements of subsequent analysis. Furthermore, this method is simple, convenient, and quick to operate, effectively improving the selectivity and yield of metalloporphyrin compounds.

[0035] In this disclosure, the eluent is added directly from the top of the extraction column, and then flows out of the extraction column naturally from top to bottom under gravity. If the eluent flows out too slowly, appropriate pressure can be applied to the top of the extraction column to accelerate the outflow rate.

[0036] In a preferred embodiment, the aqueous silica gel has a water content of 40-70% by mass. Using aqueous silica gel with a water content within the preferred range as the stationary phase of the extraction column makes the structure of the aqueous silica gel more stable and uniform, which is beneficial to improving the adsorption capacity, enrichment coefficient and selectivity of the aqueous silica gel adsorbent, thereby further improving the selectivity and yield of metalloporphyrin compounds, effectively separating and enriching porphyrin compounds, and obtaining metalloporphyrin compounds with a high degree of concentration in the same eluent.

[0037] In one specific embodiment, the alkane is a C5-C7 alkane; the C5-C7 alkane is n-pentane, n-hexane, or n-heptane, preferably n-hexane; the cycloalkane is a C5-C7 cycloalkane; the C5-C7 cycloalkane is cyclopentane, cyclohexane, or cycloheptane.

[0038] The aromatic hydrocarbon is toluene, p-xylene, o-xylene, or benzene, preferably toluene;

[0039] The volume ratio of aromatic hydrocarbon to first polar organic solvent in the third rinsing solution is 1:(1-3), and the first polar organic solvent is methanol, acetonitrile or ethylene glycol, preferably methanol;

[0040] The second polar organic solvent is a C3-C4 ketone; the C3-C4 ketone is preferably acetone.

[0041] In the above embodiments, using the preferred eluent to elute the silica gel adsorbent loaded with heavy oil is beneficial to improving separation efficiency, making the metalloporphyrin compounds in the heavy oil concentrated in the same eluent component, further improving the concentration of metalloporphyrin compounds, and making the metalloporphyrin compounds more selective and have a higher yield.

[0042] In one specific embodiment, the method further includes: washing the fourth eluted silica gel adsorbent with a third polar organic solvent to obtain a fifth eluent; the third polar organic solvent includes dichloromethane or dichloroethane, preferably dichloromethane.

[0043] The second polar organic solvent is more polar than the third polar organic solvent.

[0044] In a preferred embodiment, the silica gel adsorbent after the fourth elution is stirred, dissolved, and filtered twice using a second polar organic solvent. The filtrates obtained from the two elutions are then mixed to obtain the fifth eluent. In the above embodiment, the silica gel adsorbent after the fourth elution is stirred twice using a second polar organic solvent to ensure that the remaining metalloporphyrin compounds in the heavy oil are fully dissolved.

[0045] In one specific embodiment, the method further includes: drying the silica gel and then mixing it with water to obtain the aqueous silica gel;

[0046] The drying conditions include: a drying temperature of 90–150°C, preferably 100–120°C, and a drying time of 2–4 hours, preferably 2–3 hours.

[0047] In one specific embodiment, silica gel is dried to constant weight and then mixed with water. The silica gel is cooled to room temperature in a desiccator and weighed, recorded as m1. After being reheated for 1 hour, it is taken out, cooled to room temperature in a desiccator, and weighed, recorded as m2. When (m1-m2) / m1 < 5%, the silica gel is considered to have been dried to constant weight.

[0048] In one specific embodiment, the method of loading heavy oil onto aqueous silica gel includes: dissolving the heavy oil in an organic solvent and mixing it with the aqueous silica gel, and then removing the third organic solvent;

[0049] The mass ratio of the organic solvent to the aqueous silica gel is (1-3):1, preferably (1.5-2):1;

[0050] The organic solvent is one or more of dichloromethane, dichloroethane, chloroform, benzene, toluene, or xylene, preferably dichloromethane.

[0051] In this disclosure, the method for removing organic solvents is to take advantage of the volatile nature of organic solvents by means of standing or vacuum drying. To accelerate the evaporation of organic solvents, appropriate heating can be used. There is no particular limitation on the heating temperature, but for safety reasons, the heating temperature is below 80°C.

[0052] In one specific embodiment, the mass ratio of the aqueous silica gel to the heavy oil is (15-30):1, preferably (15-20):1.

[0053] In one specific embodiment, the volume of each eluent is 5 to 20 mL, preferably 5 to 10 mL, relative to 1 g of the aqueous silica gel.

[0054] In one specific embodiment, the content of porphyrin compounds in the heavy oil is 0.1 to 1000 mg / kg; the metalloporphyrin compounds include one or more of nickel porphyrin or vanadium porphyrin.

[0055] In one specific embodiment, the heavy oil includes one or more of heavy crude oil, atmospheric residue, vacuum residue, heavy oil gum, or heavy oil asphalt.

[0056] The present invention will be further illustrated by the following examples, but the invention is not limited thereto. All reagents used in the examples are commercially available chemically pure reagents.

[0057] Example 1

[0058] a. Weigh 20g of silica gel (purchased from Qingdao Ocean Chemical Plant), heat it in an oven at 105℃ for 2 hours until constant weight, place it in a desiccator and cool it naturally to room temperature, add 10g of deionized water, mix thoroughly and pour it into a plastic bottle, tighten the cap and let it stand overnight to obtain hydrated silica gel.

[0059] b. Dissolve 0.1898g of heavy oil asphalt (Maoming residue oil, prepared according to NB / SH / T0509-2010 four components of petroleum asphalt) in 5mL of dichloromethane, add 3g of the aqueous silica gel prepared in step a, stir thoroughly and mix well, let stand until the dichloromethane completely evaporates, pack the silica gel adsorbent loaded with heavy oil asphalt into the extraction column, and add 20mL of n-hexane, 20mL of toluene, 20mL of a mixture of toluene and methanol (volume ratio of toluene to methanol is 1:3) and 20mL of acetone from the top in sequence to obtain four eluents F1-F4.

[0060] c. Pour the silica gel adsorbent after the fourth elution from the extraction column, mix it with 10 mL of dichloromethane, stir thoroughly, and filter. Mix the filter paper and filter residue again with 10 mL of dichloromethane, stir thoroughly, and filter. Combine the two filtrates to obtain the fifth eluent F5. The nickel and vanadium contents of the heavy oil asphaltene and each eluent component F1-F5 were determined, and the results are shown in Table 1.

[0061] Example 2

[0062] The method of Example 1 was used, with the only difference being that in step a, 20g of deionized water was added; and in step b, the mass of heavy oil asphalt was 0.1600g. The nickel and vanadium contents of the heavy oil asphalt and each eluent component F1-F5 were determined, and the results are shown in Table 2.

[0063] Comparative Example 1

[0064] The method of Example 1 was used, with the only difference being that 2g of deionized water was added in step a; and the mass of heavy oil asphaltene was 0.1639g in step b. The nickel and vanadium contents of the heavy oil asphaltene and each eluent component F1-F5 were determined, and the results are shown in Table 3.

[0065] Comparative Example 2

[0066] The method of Example 1 was used, with the only difference being that 6g of deionized water was added in step a, and the mass of heavy oil asphalt was 0.1828g in step b. The nickel and vanadium contents of the heavy oil asphalt and each eluent component F1-F5 were determined, and the results are shown in Table 4.

[0067] Comparative Example 3

[0068] The method of Example 1 was used, except that in step b, the mass of heavy oil was 0.3695 g, and the eluents were 20 mL of a mixed solution of n-heptane and toluene (volume ratio 3:1), 20 mL of a mixed solution of n-heptane and toluene (volume ratio 1:1), 20 mL of toluene, 20 mL of a mixed solution of toluene and methanol (volume ratio 3:1), and 20 mL of a mixed solution of toluene and methanol (volume ratio 1:3). The nickel and vanadium contents in the asphaltenes of the heavy oil and the various eluent components F1-F5 were determined, and the results are shown in Table 5.

[0069] Test case

[0070] The mass fractions of nickel and vanadium in the heavy oil asphaltene and eluent components F1-F5 of Examples 1-2 and Comparative Examples 1-3 were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). The specific test methods are as follows:

[0071] Weigh a certain mass of the sample to be tested and mix it with 9 times its mass of xylene to form the test sample.

[0072] Commercially available organometallic standard solutions (purchased from Conostan, USA) were diluted with xylene to prepare working curve solutions with nickel and vanadium contents of 0.05 mg / kg, 0.10 mg / kg, 0.2 mg / kg, 0.5 mg / kg, and 1.0 mg / kg, respectively. Xylene was used as the zero point of the working curve.

[0073] An inductively coupled plasma atomic emission spectrometer (ARCOS, manufactured by SPECTRO, Germany) was used. The specific operating parameters of the inductively coupled plasma atomic emission spectrometer were: RF power 1.5 kW, plasma argon flow rate 20 L / min, auxiliary argon flow rate 1.5 L / min, nebulized argon flow rate 0.7 L / min, oxygen flow rate 0.03 L / min, and peristaltic pump speed 15 RPM. Wavelengths of 231.604 nm and 309.311 nm were selected as the spectral lines for nickel and vanadium elemental measurements.

[0074] Before injection, input the sample mass, volume, and other information. Under the above equipment parameters, measure the working curve solution and the sample solution in sequence. The instrument compares the emission intensity of the solution (the difference between the intensity of the sample solution and the intensity of the blank sample solution) with the intensity of the working curve and calculates the result directly to obtain the content of nickel and vanadium in the sample. The results of Examples 1-2 and Comparative Examples 1-3 are shown in Tables 1-5.

[0075] Table 1

[0076]

[0077] Table 2

[0078]

[0079] Table 3

[0080]

[0081] Table 4

[0082]

[0083] Table 5

[0084]

[0085] As can be seen from Tables 1 and 2, the method of this disclosure effectively improves the selectivity and yield of metalloporphyrin compounds. In Example 1, approximately 89% of the nickel and 92% of the vanadium were concentrated in eluent F2, and the yields of nickel and vanadium obtained according to the yield calculation formula were 84% and 91%, respectively. In Example 2, approximately 96% of the nickel and 93% of the vanadium were concentrated in eluent F2, and the yields of nickel and vanadium obtained according to the yield calculation formula were 81% and 97%, respectively. These results demonstrate that this disclosure effectively improves the selectivity and yield of metalloporphyrin compounds in heavy oil. This method achieves efficient separation and enrichment, enabling the acquisition of highly concentrated metalloporphyrin compounds in a single eluent. Furthermore, the eluent obtained after fewer elution cycles can be directly used for subsequent analysis and experiments without additional concentration steps. The content of metalloporphyrin compounds in the second eluent can be used as the concentration of metalloporphyrin compounds in heavy oil. This reduces the number of elution cycles while ensuring the accuracy of metalloporphyrin compound determination in subsequent analyses, achieving rapid and accurate determination of metalloporphyrin compound content in heavy oil.

[0086] As shown in Tables 3 and 4, when the added deionized water mass is 9% of the total mass of the aqueous silica gel, nickel and vanadium are mainly distributed in eluents F2 and F3. Only about 42% of the nickel and vanadium are concentrated in eluent F2. According to the yield calculation formula, the yields of nickel and vanadium are 48% and 57%, respectively. Compared with Example 1, the selectivity and yield of nickel and vanadium in Comparative Example 1 are significantly reduced. When the added deionized water mass is 23% of the total mass of the aqueous silica gel, nickel is mainly distributed in eluent F2, and vanadium is mainly... The nickel and vanadium molecules were distributed in eluents F2 and F3, respectively. Only about 64% of the nickel and about 62% of the vanadium were concentrated in eluent F2. According to the yield calculation formula, the yields of nickel and vanadium were 47% and 57%, respectively. Compared with Example 1, the water content of the aqueous silica gel was reduced, which made the interaction force between the metalloporphyrin molecules and the silica gel stronger. The weaker polarity of the eluent made it difficult to elute the metalloporphyrin molecules from the silica gel. The metalloporphyrin distribution shifted to the more polar eluent, resulting in a significant decrease in the selectivity and yield of nickel and vanadium.

[0087] As can be seen from Table 5, the types of eluents used in Comparative Example 3 are not within the scope of this disclosure. Although the first and second eluents have a certain degree of polarity, their polarity is too weak to remove the non-polar components first, which strengthens the interaction between the metalloporphyrin molecules and the silica gel. The metalloporphyrin molecules transfer to the more polar components, resulting in nickel and vanadium being mainly distributed in eluents F3 and F4. Among them, only about 54% of the nickel and about 55% of the vanadium are concentrated in eluent F4. According to the yield calculation formula, the yields of nickel and vanadium are 81% and 90%, respectively. Compared with Example 1, the yields of nickel and vanadium are similar, but the selectivity is significantly reduced.

[0088] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0089] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0090] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A method for separating metalloporphyrin compounds from heavy oil, wherein, The method includes: S1. Load heavy oil onto water-containing silica gel to obtain silica gel adsorbent loaded with heavy oil; S2. The silica gel adsorbent is packed into an extraction column, and a series of eluents with gradually increasing polarity are used to elute the silica gel adsorbent in sequence to obtain eluents containing metal porphyrin compounds. The water content of the aqueous silica gel is 40-70% by mass. The set of eluents with gradually increasing polarity includes a first eluent, a second eluent, a third eluent, and a fourth eluent; the first eluent is an alkane and / or a cycloalkanes, the second eluent is an aromatic hydrocarbon, the third eluent is a mixture of an aromatic hydrocarbon and a first polar organic solvent, and the fourth eluent is a second polar organic solvent. The volume ratio of aromatic hydrocarbon to first polar organic solvent in the third rinsing solution is 1:(1~3), and the first polar organic solvent is methanol, acetonitrile or ethylene glycol; the second polar organic solvent is a C3 to C4 ketone.

2. The method according to claim 1, wherein, The alkane is a C5-C7 alkane; the C5-C7 alkane is n-pentane, n-hexane, or n-heptane; the cycloalkanes are C5-C7 cycloalkanes; the C5-C7 cycloalkanes are cyclopentane, cyclohexane, or cycloheptane. The aromatic hydrocarbon is toluene, p-xylene, o-xylene, or benzene; The C3-C4 ketone is acetone.

3. The method according to claim 1, wherein, The method further includes: washing the fourth eluted silica gel adsorbent with a third polar organic solvent to obtain a fifth eluent; the third polar organic solvent includes dichloromethane or dichloroethane; The second polar organic solvent is more polar than the third polar organic solvent.

4. The method according to claim 1, wherein, The method further includes: drying the silica gel and then mixing it with water to obtain the aqueous silica gel; The drying conditions include: a drying temperature of 90~150℃ and a drying time of 2~4h.

5. The method according to claim 4, wherein, The drying conditions include: a drying temperature of 100~120℃ and a drying time of 2~3 hours.

6. The method according to claim 1, wherein, A method for loading heavy oil onto aqueous silica gel includes: dissolving the heavy oil in an organic solvent, mixing it with the aqueous silica gel, and then removing the organic solvent; The mass ratio of the organic solvent to the aqueous silica gel is (1~3):1; The organic solvent includes one or more of dichloromethane, dichloroethane, chloroform, benzene, toluene, or xylene.

7. The method according to claim 1, wherein, The mass ratio of the aqueous silica gel to the heavy oil is (15~30):

1.

8. The method according to claim 1, wherein, The volume of each eluent is 5 to 20 mL relative to 1 g of the aqueous silica gel.

9. The method according to claim 6, wherein, The content of porphyrin compounds in the heavy oil is 0.1~1000 mg / kg; the metalloporphyrin compounds include one or more of nickel porphyrin or vanadium porphyrin.

10. The method according to claim 1, wherein, The heavy oil includes one or more of the following: heavy crude oil, atmospheric residue, vacuum residue, heavy oil gum, or heavy oil asphaltenes.

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