Method for graded extraction of organic matters from vacuum residue
By using a fractional extraction method with a composite system of petroleum ether, butane, and furfural-N,N-dimethylformamide, the problems of equipment scaling and high energy consumption in the utilization of vacuum residue were solved, achieving efficient organic matter recovery and making it suitable for large-scale vacuum residue treatment.
Patent Information
- Application Number
- CN202511124251.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-12
- Publication Date
- 2025-11-11
AI Technical Summary
Existing technologies are difficult to utilize vacuum residue efficiently, and there are problems such as equipment scaling and catalyst deactivation. Furthermore, catalytic cracking requires a large amount of energy and has high process requirements.
A fractional extraction method was adopted, using a composite system of petroleum ether, butane, and furfural-N,N-dimethylformamide to extract vacuum residue, recovering saturated hydrocarbons, aromatic hydrocarbons, and gums separately, thus avoiding the cumbersome process of multi-stage extraction.
It achieves efficient fractional extraction of vacuum residue with a total yield of over 99.7%, simplifies the process, reduces energy consumption and equipment requirements, and is suitable for large-scale processing.
Smart Images
Figure CN120919682A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of vacuum residue technology, and more particularly to a method for fractional extraction of organic matter from vacuum residue. Background Technology
[0002] Globally, crude oil resources are trending towards heavier composition, with the proportion of heavy residue in crude oil continuously increasing. The level of heavy oil conversion has become a crucial factor affecting the operating efficiency of refining enterprises, and achieving efficient processing and utilization of heavy oil resources has become key to enhancing their competitiveness. During oilfield extraction, vacuum residue constitutes a significant portion of crude oil. Vacuum residue has the highest boiling point, the largest relative molecular mass, the highest heteroatom content, and the most complex structure. How to rationally and efficiently utilize vacuum residue has become a key concern for every crude oil company.
[0003] Common methods for treating vacuum residue include hydrotreating and catalytic cracking. Hydrotreating suffers from problems such as equipment scaling and catalyst deactivation, making it difficult to achieve breakthroughs in the process. Catalytic cracking requires significant energy and has stringent process requirements. Therefore, providing a method for extracting organic matter from vacuum residue with lower process requirements has become an urgent problem to be solved. Summary of the Invention
[0004] The purpose of this invention is to overcome the deficiencies in the prior art and provide a method for fractional extraction of organic matter from vacuum residue.
[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:
[0006] This invention provides a method for fractional extraction of organic matter from vacuum residue, comprising the following steps:
[0007] (1) The vacuum residue and petroleum ether were mixed and extracted to obtain the extract and primary residue;
[0008] (2) The vacuum residue, primary residue and petroleum ether are mixed and extracted to obtain extract and secondary residue;
[0009] (3) The secondary residue and butane were mixed and extracted to obtain the extract and the tertiary residue;
[0010] (4) Mix some of the tertiary residue with butane and extract to obtain extract and tertiary residue;
[0011] (5) Mix the remaining third-stage residue, fourth-stage residue and composite system for extraction to obtain extract solution and complete extraction.
[0012] Preferably, the mass-to-volume ratio of vacuum residue and petroleum ether in step (1) is 1g:10-15mL.
[0013] Preferably, the extraction temperature in step (1) is 25-30°C and the extraction time is 20-30 min.
[0014] Preferably, the mass-to-volume ratio of vacuum residue, primary residue and petroleum ether in step (2) is 1g:0.5g:20-25mL.
[0015] Preferably, the extraction temperature in step (2) is 60-70°C, the pressure is 3-4 MPa, and the time is 30-60 min.
[0016] Preferably, the mass-to-volume ratio of the secondary residue and butane in step (3) is 1 g: 18-22 mL.
[0017] Preferably, the extraction temperature in step (3) is 30-40°C and the extraction time is 20-30 min.
[0018] Preferably, in step (4), the mass of some of the tertiary residue is 40-50% of the total mass of the tertiary residue;
[0019] In step (4), the mass-to-volume ratio of some of the tertiary residue to butane is 1 g: 55-60 mL;
[0020] In step (4), the extraction temperature is 75-85℃, the pressure is 4.5-5MPa, and the time is 30-40min.
[0021] Preferably, the composite system in step (5) includes furfural and N,N-dimethylformamide;
[0022] The mass ratio of furfural to N,N-dimethylformamide is 2.5–3.5:1;
[0023] In step (5), the mass-volume ratio of the remaining tertiary residue, quaternary residue and composite system is 1g:1g:40-50mL.
[0024] Preferably, the extraction temperature in step (5) is 80-100°C, the pressure is 4-5 MPa, and the time is 30-40 min.
[0025] This invention provides a method for fractional extraction of organic matter from vacuum residue, comprising the following steps: mixing vacuum residue with petroleum ether for extraction to obtain an extract and primary residue; mixing vacuum residue, primary residue, and petroleum ether for extraction to obtain an extract and secondary residue; mixing secondary residue with butane for extraction to obtain an extract and tertiary residue; mixing a portion of the tertiary residue with butane for extraction to obtain an extract and quaternary residue; and mixing the remaining tertiary and quaternary residues with a composite system for extraction to obtain an extract, thus completing the extraction process. This invention extracts organic matter based on different components in vacuum residue, avoiding the pretreatment required for conventional vacuum residue extraction. First, extraction with petroleum ether recovers saturated hydrocarbon components from the residue. The resulting residue and vacuum residue are then mixed again under high pressure and extracted with petroleum ether. The combined effect of high pressure and high saturated hydrocarbon concentration allows for the complete extraction of saturated hydrocarbons from the residue, avoiding the cumbersome multi-stage extraction process. The obtained secondary residue was extracted with butane to recover aromatic hydrocarbons from vacuum residue. However, the applicant's experiments revealed that using only butane for aromatic hydrocarbon extraction required multiple stages to achieve the desired effect. Therefore, the obtained tertiary residue was extracted in groups to maintain a high level of aromatic hydrocarbon content. Then, a one-step high-temperature and high-pressure extraction was performed using a composite system of furfural and dimethylformamide, which simultaneously recovered aromatic hydrocarbons and gums, achieving complete recovery of vacuum residue. The method provided by this invention is simple, uses pressurized conditions, avoids the cumbersome process of multi-stage extraction with the same reagents, and is suitable for large-scale processing. Attached Figure Description
[0026] Figure 1 This is a flowchart of the fractional extraction of organic matter from vacuum residue in Example 1. Detailed Implementation
[0027] This invention provides a method for fractional extraction of organic matter from vacuum residue, comprising the following steps:
[0028] (1) The vacuum residue and petroleum ether were mixed and extracted to obtain the extract and primary residue;
[0029] (2) The vacuum residue, primary residue and petroleum ether are mixed and extracted to obtain extract and secondary residue;
[0030] (3) The secondary residue and butane were mixed and extracted to obtain the extract and the tertiary residue;
[0031] (4) Mix some of the tertiary residue with butane and extract to obtain extract and tertiary residue;
[0032] (5) Mix the remaining third-stage residue, fourth-stage residue and composite system for extraction to obtain extract solution and complete extraction.
[0033] In this invention, the mass-to-volume ratio of vacuum residue and petroleum ether in step (1) is preferably 1g:10-15mL, more preferably 1g:11-14mL, and even more preferably 1g:12-13mL.
[0034] In this invention, the extraction temperature in step (1) is preferably 25-30°C, more preferably 26-29°C, and even more preferably 27-28°C; the extraction time is preferably 20-30 min, more preferably 22-28 min, and even more preferably 24-26 min.
[0035] In this invention, the mass-to-volume ratio of vacuum residue, primary residue and petroleum ether in step (2) is preferably 1g:0.5g:20-25mL, more preferably 1g:0.5g:21-24mL, and even more preferably 1g:0.5g:22-23mL.
[0036] In this invention, the extraction temperature in step (2) is preferably 60-70°C, more preferably 62-68°C, and even more preferably 64-66°C; the pressure is preferably 3-4 MPa, more preferably 3.2-3.8 MPa, and even more preferably 3.4-3.6 MPa; and the time is preferably 30-60 min, more preferably 35-55 min, and even more preferably 40-50 min.
[0037] In this invention, the mass-to-volume ratio of the secondary residue and butane in step (3) is preferably 1g:18-22mL, more preferably 1g:19-21mL, and even more preferably 1g:19.5-20.5mL.
[0038] In this invention, the extraction temperature in step (3) is preferably 30-40°C, more preferably 32-38°C, and even more preferably 34-36°C; the extraction time is preferably 20-30 min, more preferably 22-28 min, and even more preferably 24-26 min.
[0039] In this invention, the mass of the tertiary residue in step (4) is preferably 40-50% of the total mass of the tertiary residue, more preferably 42-48%, and even more preferably 44-46%.
[0040] In this invention, the mass-to-volume ratio of a portion of the tertiary residue and butane in step (4) is preferably 1g:55-60mL, more preferably 1g:56-59mL, and even more preferably 1g:57-58mL.
[0041] In this invention, the extraction temperature in step (4) is preferably 75-85°C, more preferably 76-84°C, and even more preferably 78-82°C; the pressure is preferably 4.5-5 MPa, more preferably 4.6-4.9 MPa, and even more preferably 4.7-4.8 MPa; and the time is preferably 30-40 min, more preferably 32-38 min, and even more preferably 34-36 min.
[0042] In this invention, the composite system in step (5) contains furfural and N,N-dimethylformamide.
[0043] In this invention, the mass ratio of furfural to N,N-dimethylformamide is preferably 2.5 to 3.5:1, more preferably 2.6 to 3.4:1, and even more preferably 2.8 to 3.2:1.
[0044] In this invention, the mass-to-volume ratio of the remaining tertiary residue, quaternary residue and composite system in step (5) is preferably 1g:1g:40-50mL, more preferably 1g:1g:42-48mL, and even more preferably 1g:1g:44-46mL.
[0045] In this invention, the extraction temperature in step (5) is preferably 80-100°C, more preferably 85-95°C, and even more preferably 88-92°C; the pressure is preferably 4-5 MPa, more preferably 4.2-4.8 MPa, and even more preferably 4.4-4.6 MPa; and the time is preferably 30-40 min, more preferably 32-38 min, and even more preferably 34-36 min.
[0046] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0047] Example 1
[0048] Karamay vacuum residue and petroleum ether were mixed at a ratio of 1 g: 12 mL and extracted at 28 °C for 25 min. The extract (E1) and primary residue were obtained by filtration. Karamay vacuum residue, primary residue, and petroleum ether were mixed at a ratio of 1 g: 0.5 g: 23 mL and extracted at 65 °C and 3.5 MPa for 50 min. The extract (E2) and secondary residue were obtained by filtration. The secondary residue and butane were mixed at a ratio of 1 g: 20 mL and extracted at 35 °C for 25 min. The extract (E3) and tertiary residue were obtained by filtration. 4% of the tertiary residue was extracted. 5% of the component was used as a partial tertiary residue. This partial tertiary residue was mixed with butane at a ratio of 1 g: 55 mL and extracted at 80 °C and 4.5 MPa for 35 min. The residue and extract (E4) were obtained by filtration. Furfural and N,N-dimethylformamide were prepared into a composite system at a mass ratio of 3:1. The remaining tertiary residue, tertiary residue and composite system were mixed at a ratio of 1 g: 1 g: 45 mL and then extracted at 90 °C and 4.5 MPa for 35 min. The extract (E5) was obtained by filtration. No residue remained, thus completing the fractional extraction of organic matter.
[0049] The hierarchical extraction process in this embodiment is as follows: Figure 1 As shown.
[0050] Example 2
[0051] Karamay vacuum residue and petroleum ether were mixed at a ratio of 1 g: 11 mL and extracted at 25 °C for 20 min. The extract (E1) and primary residue were obtained by filtration. Karamay vacuum residue, primary residue, and petroleum ether were mixed at a ratio of 1 g: 0.5 g: 25 mL and extracted at 60 °C and 4 MPa for 40 min. The extract (E2) and secondary residue were obtained by filtration. The secondary residue and butane were mixed at a ratio of 1 g: 18 mL and extracted at 30 °C for 25 min. The extract (E3) and tertiary residue were obtained by filtration. 4% of the tertiary residue was extracted. 0% of the component was used as a partial tertiary residue. The partial tertiary residue was mixed with butane at a ratio of 1g:60mL and extracted at 75℃ and 5MPa for 35min. The residue and extract (E4) were obtained by filtration. Furfural and N,N-dimethylformamide were prepared into a composite system at a mass ratio of 2.8:1. The remaining tertiary residue, tertiary residue and composite system were mixed at a ratio of 1g:1g:50mL and then extracted at 85℃ and 4MPa for 40min. The extract (E5) was obtained by filtration. There was no residue left, and the fractional extraction of organic matter was completed.
[0052] Example 3
[0053] Karamay vacuum residue and petroleum ether were mixed at a ratio of 1 g: 13 mL and extracted at 30 °C for 25 min. The extract (E1) and primary residue were obtained by filtration. Karamay vacuum residue, primary residue, and petroleum ether were mixed at a ratio of 1 g: 0.5 g: 24 mL and extracted at 68 °C and 3.8 MPa for 30 min. The extract (E2) and secondary residue were obtained by filtration. The secondary residue and butane were mixed at a ratio of 1 g: 22 mL and extracted at 36 °C for 27 min. The extract (E3) and tertiary residue were obtained by filtration. 47% of the tertiary residue was extracted. A certain percentage of the components were used as partial tertiary residue. Partial tertiary residue and butane were mixed at a ratio of 1g:57mL and extracted at 82℃ and 4.6MPa for 30min. The residue and extract (E4) were obtained by filtration. Furfural and N,N-dimethylformamide were prepared into a composite system at a mass ratio of 3.4:1. The ratio of the remaining tertiary residue, tertiary residue and composite system was controlled at 1g:1g:43mL and mixed. The mixture was then extracted at 96℃ and 4.5MPa for 35min and extracted by filtration (E5). No residue was left, thus completing the fractional extraction of organic matter.
[0054] Example 4
[0055] Karamay vacuum residue and petroleum ether were mixed at a ratio of 1 g: 11 mL and extracted at 26 °C for 25 min. The extract (E1) and primary residue were obtained by filtration. Karamay vacuum residue, primary residue, and petroleum ether were mixed at a ratio of 1 g: 0.5 g: 22 mL and extracted at 70 °C and 4 MPa for 45 min. The extract (E2) and secondary residue were obtained by filtration. The secondary residue and butane were mixed at a ratio of 1 g: 19 mL and extracted at 40 °C for 30 min. The extract (E3) and tertiary residue were obtained by filtration. 4% of the tertiary residue was extracted. 4% of the component was used as a partial tertiary residue. This partial tertiary residue was mixed with butane at a ratio of 1 g: 59 mL and extracted at 76 °C and 5 MPa for 35 min. The residue and extract (E4) were obtained by filtration. Furfural and N,N-dimethylformamide were prepared into a composite system at a mass ratio of 2.8:1. The remaining tertiary residue, tertiary residue and composite system were mixed at a ratio of 1 g: 1 g: 46 mL and then extracted at 90 °C and 4 MPa for 30 min. The extract (E5) was obtained by filtration. Residual residue was present, thus completing the fractional extraction of organic matter.
[0056] Example 5
[0057] Karamay vacuum residue and petroleum ether were mixed at a ratio of 1 g: 12 mL and extracted at 28 °C for 30 min. The extract (E1) and primary residue were obtained by filtration. Karamay vacuum residue, primary residue, and petroleum ether were mixed at a ratio of 1 g: 0.5 g: 25 mL and extracted at 70 °C and 3 MPa for 50 min. The extract (E2) and secondary residue were obtained by filtration. The secondary residue and butane were mixed at a ratio of 1 g: 20 mL and extracted at 40 °C for 20 min. The extract (E3) and tertiary residue were obtained by filtration. The tertiary residue was then... 50% of the components were used as partial tertiary residue. Partial tertiary residue and butane were mixed at a ratio of 1g:60mL and extracted at 85℃ and 5MPa for 40min. The residue and extract (E4) were obtained by filtration. Furfural and N,N-dimethylformamide were prepared into a composite system at a mass ratio of 3:1. The ratio of the remaining tertiary residue, tertiary residue and composite system was controlled at 1g:1g:50mL and mixed. The mixture was then extracted at 100℃ and 5MPa for 30min and extracted by filtration (E5). The remaining residue was obtained, thus completing the fractional extraction of organic matter.
[0058] The extraction yields of the extracts from Examples 1 to 5 are shown in Table 1.
[0059] Table 1 Extraction Yield
[0060] Yield (%) Example 1 Example 2 Example 3 Example 4 Example 5 E1 71.4 72.6 71.8 75.7 76.3 E2 81.7 82.5 80.6 81.1 82.3 E3 6.4 7.3 5.1 7.6 6.2 E4 4.7 3.6 3.4 4.2 3.4 E5 7.2 6.6 10.9 6.8 7.9
[0061] As shown in Table 1, the method provided by this invention achieves complete fractional extraction of vacuum residue. Using E2 as the starting yield, the total yield of the extract (E2+E3+E4+E5) in Examples 1, 2, and 3 reached 100%, the total yield of the extract (E2+E3+E4+E5) in Example 4 was 99.7%, and the total yield of the extract (E2+E3+E4+E5) in Example 5 was 99.8%. The results of these examples demonstrate that using the method provided by this invention to directly extract vacuum residue without any pretreatment achieves a total extraction yield of over 99.7%, with low cost and outstanding performance, facilitating the fractional extraction and utilization of large quantities of vacuum residue by refining enterprises.
[0062] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for fractional extraction of organic matter from vacuum residue, characterized in that, Includes the following steps: (1) The vacuum residue and petroleum ether were mixed and extracted to obtain the extract and primary residue; (2) The vacuum residue, primary residue and petroleum ether are mixed and extracted to obtain extract and secondary residue; (3) The secondary residue and butane were mixed and extracted to obtain the extract and the tertiary residue; (4) Mix some of the tertiary residue with butane and extract to obtain extract and tertiary residue; (5) Mix the remaining third-stage residue, fourth-stage residue and composite system for extraction to obtain extract solution and complete extraction.
2. The method for fractional extraction of organic matter from vacuum residue as described in claim 1, characterized in that, The mass-to-volume ratio of vacuum residue and petroleum ether in step (1) is 1g:10-15mL.
3. The method for fractional extraction of organic matter from vacuum residue as described in claim 2, characterized in that, The extraction temperature in step (1) is 25-30℃ and the extraction time is 20-30 min.
4. The method for fractional extraction of organic matter from vacuum residue as described in claim 3, characterized in that, The mass-volume ratio of vacuum residue, primary residue and petroleum ether in step (2) is 1g:0.5g:20-25mL.
5. The method for fractional extraction of organic matter from vacuum residue as described in claim 4, characterized in that, The extraction temperature in step (2) is 60-70℃, the pressure is 3-4MPa, and the time is 30-60min.
6. The method for fractional extraction of organic matter from vacuum residue as described in claim 5, characterized in that, The mass-to-volume ratio of the secondary residue and butane in step (3) is 1 g: 18-22 mL.
7. The method for fractional extraction of organic matter from vacuum residue as described in claim 6, characterized in that, The extraction temperature in step (3) is 30-40℃ and the extraction time is 20-30 min.
8. The method for fractional extraction of organic matter from vacuum residue as described in claim 7, characterized in that, In step (4), the mass of some of the tertiary residues is 40-50% of the total mass of the tertiary residues; In step (4), the mass-to-volume ratio of some of the tertiary residue to butane is 1 g: 55-60 mL; In step (4), the extraction temperature is 75-85℃, the pressure is 4.5-5MPa, and the time is 30-40min.
9. The method for fractional extraction of organic matter from vacuum residue as described in claim 8, characterized in that, The composite system in step (5) contains furfural and N,N-dimethylformamide; The mass ratio of furfural to N,N-dimethylformamide is 2.5–3.5:1; In step (5), the mass-volume ratio of the remaining tertiary residue, quaternary residue and composite system is 1g:1g:40-50mL.
10. The method for fractional extraction of organic matter from vacuum residue as described in claim 9, characterized in that, The extraction temperature in step (5) is 80-100℃, the pressure is 4-5MPa, and the time is 30-40min.