Application of composite catalyst in preparation of high-octane gasoline by coupling crude oil and carbon dioxide
By leveraging the synergistic effect of composite catalysts, the problem of coupled conversion between crude oil and carbon dioxide was solved, enabling the efficient production of high-octane gasoline with high yield and good stability, and providing a low-cost green hydrogen production route.
Patent Information
- Application Number
- CN202511548998.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-28
- Publication Date
- 2026-01-23
AI Technical Summary
There are few reports on the direct coupling conversion of crude oil and carbon dioxide in existing technologies, and the large-scale supply of cheap green hydrogen is a challenge for the industrial application of carbon dioxide hydrogenation, making it difficult to efficiently produce high-octane gasoline.
A composite catalyst, including metal-modified molecular sieves and active metals/oxides, is used to promote the formation of aromatics and increase the octane number of gasoline by catalyzing the coupled reaction of crude oil and carbon dioxide and utilizing the synergistic effect of Brønsted acid, Lewis acid and active metals/oxides.
It achieves high yield and high aromatic selectivity of high-octane gasoline, and the catalyst is inexpensive, simple to prepare, and has good cycle stability and economic value.
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Figure CN121372484A_ABST
Abstract
Description
TECHNICAL FIELD
[0002] The application relates to the technical field of high-octane gasoline preparation and carbon dioxide conversion, and particularly relates to application of a composite catalyst in preparation of high-octane gasoline from crude oil and carbon dioxide. BACKGROUND
[0003] Carbon dioxide (CO2) catalytic conversion is an effective path for its large-scale utilization, and through the establishment of a sustainable recycling approach, the influence of the greenhouse effect on human society can be reduced. Although significant progress has been made in the production of green fuels and high-value chemicals from carbon dioxide hydrogenation, the supply of large-scale cheap green hydrogen has always been a great challenge for the industrial application of carbon dioxide hydrogenation. Therefore, the coupling conversion of abundant and cheap low-carbon alkanes (C1-C4) and CO2 to produce synthesis gas, low-carbon olefins and aromatic hydrocarbons has attracted widespread attention from the academic and industrial communities.
[0004] Low-carbon alkanes are mainly derived from natural gas. Compared with natural gas, crude oil rich in carbon and hydrogen resources is a kind of raw material with higher demand. Although direct conversion of crude oil has obvious advantages in reducing energy consumption and CO2 emission, there are few reports on the direct coupling conversion of crude oil and CO2. At present, only researchers have reported the coupling conversion of petroleum derivatives and CO2. SUMMARY
[0005] In view of this, the purpose of the present application is to provide application of a composite catalyst in preparation of high-octane gasoline from crude oil and carbon dioxide, which can realize large-scale preparation of high-octane gasoline through coupling of crude oil and carbon dioxide.
[0006] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions: The present application provides application of a composite catalyst in preparation of high-octane gasoline from crude oil and carbon dioxide, wherein the composite catalyst comprises a metal-modified molecular sieve and an active metal and / or an active metal oxide. The acid content in the metal-modified molecular sieve is greater than or equal to 0.1 mmol / g, and the acid in the metal-modified molecular sieve comprises Brønsted acid and Lewis acid.
[0007] Preferably, the molecular sieve in the metal-modified molecular sieve has a topological structure with a ten-membered ring or a twelve-membered ring. The framework structure of the molecular sieve comprises one or more of Si-O, Si-O-Al, Si-O-Al-P, Si-O-Al-B and Si-O-Al-Ge.
[0008] Preferably, the molecular sieve is one or more of ZSM-5 molecular sieve, Beta molecular sieve and HY molecular sieve.
[0009] Preferably, the modified metal in the metal-modified molecular sieve is one or more of manganese, iron, cobalt, nickel, zinc, gallium, tin, ruthenium, platinum and gold; The metal-modified molecular sieve contains 0.01 to 10% metal by mass.
[0010] Preferably, the active metal is one or more selected from aluminum, titanium, manganese, nickel, iron, copper, cobalt, zinc, gallium, zirconium, molybdenum, silver, rhodium, ruthenium, platinum, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, and cerium.
[0011] Preferably, the active metal in the composite catalyst has a mass percentage content of 0.01~60%.
[0012] Preferably, the active metal oxide is Al2O3, TiO2, ZrO2, or MnO. x FeO x CoO x ZnO, MoO x One or more of MgO, BaO, Y2O3, CeO2 and La2O3.
[0013] Preferably, the active metal oxide in the composite catalyst has a mass percentage content of 0.01~60%.
[0014] Preferably, the method of application includes the following steps: When the composite catalyst includes an active metal oxide: The composite catalyst was pre-reduced to obtain a pre-reduced composite catalyst. Under carbon dioxide conditions, the pre-reduced composite catalyst and light crude oil are mixed and catalytically reacted to obtain high-octane gasoline. When the composite catalyst does not contain active metal oxides: Under carbon dioxide conditions, the composite catalyst and light crude oil are mixed and catalytically reacted to obtain high-octane gasoline.
[0015] Preferably, the pre-reduction is carried out in a reducing atmosphere, which is preferably an atmosphere including hydrogen and / or carbon monoxide. The volume concentration of hydrogen and / or carbon monoxide in the reducing atmosphere is 5-100%; The pre-reduction temperature is 200~600℃, and the time is 0.5~5h.
[0016] This invention provides an application of a composite catalyst in the coupling of crude oil and carbon dioxide to produce high-octane gasoline, wherein the composite catalyst comprises a metal-modified molecular sieve and an active metal and / or an active metal oxide. The acid content in the metal-modified molecular sieve is greater than or equal to 0.1 mmol / g, and the acid in the metal-modified molecular sieve includes Brønsted acid and Lewis acid. The composite catalyst involved in the present application mainly includes three active sites, wherein the active sites provided by the Brønsted acid in the molecular sieve, the active sites provided by the Lewis acid, and the active sites provided by the active metal and / or the active metal oxide, the three sites synergize with each other, and overcome the problems of low activity and poor selectivity of single / double sites. Among them, the Brønsted acid catalyzes the cracking, isomerization, dehydrogenation and aromatization process of hydrocarbon molecules in crude oil, while the Lewis acid can accelerate the aromatization reaction, and the metal and / or metal oxide part can catalyze the hydrogen species in the in-situ consumption reaction process of carbon dioxide, and the synergistic effect of the three sites promotes the generation of aromatic hydrocarbons with high C / H ratio. The increase of aromatic hydrocarbon content is beneficial to the increase of the octane number of gasoline, thereby improving the economic value of gasoline, and at the same time, carbon dioxide is converted into CO molecules with higher utilization value. And the catalyst is low in price and simple in preparation method, and in the one-step conversion of crude oil and carbon dioxide to prepare high-octane gasoline, it shows high gasoline yield, and the content of high-octane aromatic hydrocarbons can be more than 30wt%, and the composite catalyst shows good cycle stability. BRIEF DESCRIPTION OF DRAWINGS
[0017] Figure 1 The XRD pattern of Zn / ZSM-5 described in Comparative Example 7 and CuAlO x described in Comparative Example 8; Figure 2 The TEM pattern of Zn / ZSM-5 described in Comparative Example 7 and CuAlO x described in Comparative Example 8; Figure 3 The Py-IR characterization pattern of Zn / ZSM-5 described in Comparative Example 7. DETAILED DESCRIPTION
[0018] The present application provides an application of a composite catalyst in the preparation of high-octane gasoline from crude oil and carbon dioxide, wherein the composite catalyst includes a metal-modified molecular sieve and an active metal and / or an active metal oxide. The acid content in the metal-modified molecular sieve is greater than or equal to 0.1 mmol / g, and the acid in the metal-modified molecular sieve includes Brønsted acid and Lewis acid.
[0019] In the present application, the molecular sieve in the metal-modified molecular sieve is preferably a topological structure with a ten-membered ring or a twelve-membered ring, and more preferably an MFI topological structure. In the present application, the framework structure of the molecular sieve preferably includes one or more of Si-O, Si-O-Al, Si-O-Al-P, Si-O-Al-B and Si-O-Al-Ge.
[0020] In the present application, the molecular sieve is preferably one or more of ZSM-5 molecular sieve, Beta molecular sieve and HY molecular sieve, and more preferably ZSM-5 molecular sieve, Beta molecular sieve or HY molecular sieve.
[0021] The present application does not have any special limitation on the source of the molecular sieve, which can be prepared by a method well known to those skilled in the art.
[0022] In the present application, the metal modification can introduce Lewis acid.
[0023] In the present application, the modified metal in the metal-modified molecular sieve is preferably one or more of manganese, iron, cobalt, nickel, zinc, gallium, tin, ruthenium, platinum and gold; when the modified metal is two or more of the above specific selection, the present application does not have any special limitation on the ratio of the above specific substances, which can be mixed in any ratio. In the present application, the mass percentage of the metal in the metal-modified molecular sieve is preferably 0.01-10%, and more preferably 0.01%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
[0024] In the present application, the preparation method of the metal-modified molecular sieve is preferably impregnation or ion exchange; the present application does not have any special limitation on the process of the impregnation and ion exchange, which can be prepared by a method well known to those skilled in the art.
[0025] In the embodiment of the present application, the preparation process of the metal-modified molecular sieve is to drop the metal precursor solution into the molecular sieve drop by drop for impregnation for 8h, dry at 100℃ overnight, heat to 500℃ at a heating rate of 5℃ / min and calcine for 3h to obtain the metal-modified molecular sieve. The concentration of the metal precursor solution is preferably 0.01-2 mol / L, and more preferably 0.1-1 mol / L; the metal precursor in the metal precursor solution is preferably nitrate and chloride, and more preferably nitrate. Before the impregnation, the present application further preferably includes determining the pore volume of the molecular sieve.
[0026] In the present application, the active metal is one or more of aluminum, titanium, manganese, nickel, iron, copper, cobalt, zinc, gallium, zirconium, molybdenum, silver, rhodium, ruthenium, platinum, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum and cerium; when the active metal is two or more of the above specific selection, the present application does not have any special limitation on the ratio of the above specific substances, which can be mixed in any ratio. In the present application, the mass percentage of the active metal in the composite catalyst is preferably 0.01-60%, and more preferably 0.01%, 10%, 20%, 30%, 40%, 50% or 60%.
[0027] In the present application, the active metal oxide is preferably one or more of Al2O3, TiO2, ZrO2, MnO x , FeO x , CoO x , ZnO, MoO x , MgO, BaO, Y2O3, CeO2, and La2O3. When the active metal oxide is two or more of the above specific choices, the present application does not have any special limitation on the ratio of the above specific substances, and mixing in any ratio can be performed. In the present application, the mass percentage content of the active metal oxide in the composite catalyst is preferably 0.01-60%, more preferably 0.01%, 10%, 20%, 30%, 40%, 50%, or 60%.
[0028] The present application does not have any special limitation on the preparation process of the composite catalyst, and impregnation, ion exchange, ball milling, deposition, or physical mixing methods known to those skilled in the art can be used.
[0029] In the present application, the method for use preferably comprises the following steps: When the composite catalyst comprises an active metal oxide: The composite catalyst is pre-reduced to obtain a pre-reduced composite catalyst; The pre-reduced composite catalyst and light crude oil are mixed and subjected to catalytic reaction under the condition of passing carbon dioxide to obtain high-octane gasoline; When the composite catalyst does not comprise an active metal oxide: The composite catalyst and light crude oil are mixed and subjected to catalytic reaction under the condition of passing carbon dioxide to obtain high-octane gasoline.
[0030] The method for use of the present application is as follows: when the composite catalyst comprises an active metal oxide: The composite catalyst is pre-reduced to obtain a pre-reduced composite catalyst; The pre-reduced composite catalyst and light crude oil are mixed and subjected to catalytic reaction under the condition of passing carbon dioxide to obtain high-octane gasoline.
[0031] The composite catalyst is pre-reduced to obtain a pre-reduced composite catalyst.
[0032] In the present application, the pre-reduction is preferably carried out in a reducing atmosphere, which is preferably an atmosphere comprising hydrogen and / or carbon monoxide; the volume concentration of hydrogen and / or carbon monoxide in the reducing atmosphere is preferably 5-100%, more preferably 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100%; the temperature of the pre-reduction is preferably 200-600°C, more preferably 200°C, 300°C, 400°C, 500°C or 600°C; and the time is preferably 0.5-5h, more preferably 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h.
[0033] After obtaining the pre-reduced composite catalyst, the present application carries out catalytic reaction by mixing the pre-reduced composite catalyst and light crude oil under the condition of passing carbon dioxide, to obtain high-octane gasoline.
[0034] In the present application, the pressure of the carbon dioxide is preferably 0.1-5MPa, more preferably 0.1MPa, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa or 5MPa; and the volume percentage content of the carbon dioxide in the atmosphere in which the catalytic reaction is carried out is preferably 1-100%. In the present application, the temperature of the catalytic reaction is preferably 300-700°C, more preferably 300°C, 310°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C or 700°C; and the time of the catalytic reaction is preferably 6-20h, more preferably 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h.
[0035] The technical solutions in the present application will be described clearly and completely below in combination with the embodiments in the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.
[0036] Comparative Example 1 ZSM-5 (silicon-aluminum ratio 25, from the Catalyst Factory of Nankai University); CuAlO x ; The ZSM-5 and CuAlO x were mixed in a mass ratio of 1:0.625 and ground uniformly using a mortar to obtain a composite catalyst.
[0037] Comparative Example 2 Beta (silicon aluminum ratio of 25), from the catalyst factory of Nankai University; CuAlO x was prepared according to Comparative Example 1; The Beta and CuAlO x were mixed in a mass ratio of 1:0.625 and ground uniformly using a mortar to obtain a composite catalyst.
[0038] Comparative Example 3 HY (silicon aluminum ratio of 25), from the catalyst factory of Nankai University; CuAlO x was prepared according to Comparative Example 1; The HY and CuAlO x were mixed in a mass ratio of 1:0.625 and ground uniformly using a mortar to obtain a composite catalyst.
[0039] Comparative Example 4 ZSM-5 (silicon aluminum ratio of 80), from the catalyst factory of Nankai University; CuAlO x was prepared according to Comparative Example 1; The ZSM-5 and CuAlO x were mixed in a mass ratio of 1:0.625 and ground uniformly using a mortar to obtain a composite catalyst.
[0040] Comparative Example 5 ZSM-5 (silicon aluminum ratio of 130), from the catalyst factory of Nankai University; CuAlO x was prepared according to Comparative Example 1; The ZSM-5 and CuAlO x Mix and grind evenly using a mortar to obtain a composite catalyst.
[0041] Comparative Example 6 ZSM-5 (silicon-aluminum ratio of 300), from the Catalyst Factory of Nankai University; CuAlO x The preparation method of CuAlO The ZSM-5 and CuAlO x Mix and grind evenly using a mortar to obtain a composite catalyst.
[0042] Example 1 ZSM-5 (silicon-aluminum ratio of 130), from the Catalyst Factory of Nankai University; 5 mL of a zinc nitrate aqueous solution with a concentration of 0.18 mol / L was added dropwise into the 3 g of ZSM-5, impregnated for 8 h, dried at 100°C overnight, and finally calcined at a temperature increasing rate of 5°C / min to 500°C for 3 h to obtain a metal-modified molecular sieve (Zn / ZSM-5, the mass percentage content of Zn in the metal-modified molecular sieve was 2%); CuAlO x The preparation method of CuAlO The Zn / ZSM-5 and CuAlO x Mix and grind evenly using a mortar to obtain a composite catalyst.
[0043] Example 2 ZSM-5 (silicon-aluminum ratio of 130), from the Catalyst Factory of Nankai University; 5 mL of a ferric nitrate aqueous solution with a concentration of 0.18 mol / L was added dropwise into the 3 g of ZSM-5, impregnated for 8 h, dried at 100°C overnight, and finally calcined at a temperature increasing rate of 5°C / min to 500°C for 3 h to obtain a metal-modified molecular sieve (Fe / ZSM-5, the mass percentage content of Fe in the metal-modified molecular sieve was 2%); CuAlO x The preparation method of CuAlO The Fe / ZSM-5 and CuAlO x Mix and grind evenly using a mortar to obtain a composite catalyst.
[0044] Example 3 ZSM-5 (silicon-aluminum ratio of 130), from the Catalyst Factory of Nankai University; A 5 mL aqueous solution of cobalt nitrate with a concentration of 0.18 mol / L was dropped into the 3 g ZSM-5, impregnated for 8 h, dried at 100°C overnight, and finally calcined at 500°C for 3 h at a temperature increasing rate of 5°C / min to obtain a metal-modified molecular sieve (Co / ZSM-5, the mass percentage content of Co in the metal-modified molecular sieve was 2%); CuAlO x The preparation method of CuAlO The Co / ZSM-5 and CuAlO x were mixed in a mass ratio of 1:0.625 and uniformly ground using a mortar to obtain a composite catalyst.
[0045] Example 4 ZSM-5 (silicon-aluminum ratio of 130), from the Catalyst Factory of Nankai University; A 5 mL aqueous solution of copper nitrate with a concentration of 0.18 mol / L was dropped into the 3 g ZSM-5, impregnated for 8 h, dried at 100°C overnight, and finally calcined at 500°C for 3 h at a temperature increasing rate of 5°C / min to obtain a metal-modified molecular sieve (Cu / ZSM-5, the mass percentage content of Cu in the metal-modified molecular sieve was 2%); CuAlO x The preparation method of CuAlO The Cu / ZSM-5 and CuAlO x were mixed in a mass ratio of 1:0.625 and uniformly ground using a mortar to obtain a composite catalyst.
[0046] Example 5 ZSM-5 (silicon-aluminum ratio of 130), from the Catalyst Factory of Nankai University; A 5 mL aqueous solution of zinc nitrate with a concentration of 0.36 mol / L was dropped into the 3 g ZSM-5, impregnated for 8 h, dried at 100°C overnight, and finally calcined at 500°C for 3 h at a temperature increasing rate of 5°C / min to obtain a metal-modified molecular sieve (Zn / ZSM-5, the mass percentage content of Zn in the metal-modified molecular sieve was 4%); CuAlO x The preparation method of CuAlO The Zn / ZSM-5 and CuAlO x were mixed in a mass ratio of 1:0.625 and uniformly ground using a mortar to obtain a composite catalyst.
[0047] Example 6 ZSM-5 (silicon-aluminum ratio of 130), from the Catalyst Factory of Nankai University; A 5 mL aqueous solution of zinc nitrate with a concentration of 0.36 mol / L was dropped into the 3 g ZSM-5, impregnated for 8 h, dried at 100°C overnight, and finally calcined at 500°C for 3 h at a temperature increasing rate of 5°C / min to obtain a metal-modified molecular sieve (Zn / ZSM-5, the mass percentage of Zn in the metal-modified molecular sieve was 4%); CuAlO x The preparation method of CuAlO The Zn / ZSM-5 and CuAlO x were mixed in a mass ratio of 1:0.375 and uniformly ground using a mortar to obtain a composite catalyst.
[0048] Example 7 ZSM-5 (silicon-aluminum ratio of 130), from the Catalyst Factory of Nankai University; A 5 mL aqueous solution of zinc nitrate with a concentration of 0.36 mol / L was dropped into the 3 g ZSM-5, impregnated for 8 h, dried at 100°C overnight, and finally calcined at 500°C for 3 h at a temperature increasing rate of 5°C / min to obtain a metal-modified molecular sieve (Zn / ZSM-5, the mass percentage of Zn in the metal-modified molecular sieve was 4%); CuAlO x The preparation method of CuAlO The Zn / ZSM-5 and CuAlO x were mixed in a mass ratio of 1:1 and uniformly ground using a mortar to obtain a composite catalyst.
[0049] Example 8 ZSM-5 (silicon-aluminum ratio of 130), from the Catalyst Factory of Nankai University; A 5 mL aqueous solution of zinc nitrate with a concentration of 0.36 mol / L was dropped into the 3 g ZSM-5, impregnated for 8 h, dried at 100°C overnight, and finally calcined at 500°C for 3 h at a temperature increasing rate of 5°C / min to obtain a metal-modified molecular sieve (Zn / ZSM-5, the mass percentage of Zn in the metal-modified molecular sieve was 4%); CuAlO x The preparation method of CuAlO The Zn / ZSM-5 and CuAlO x were mixed in a mass ratio of 1:1.2 and uniformly ground using a mortar to obtain a composite catalyst.
[0050] Comparative Example 7 ZSM-5 (silicon-aluminum ratio of 130), from the Catalyst Factory of Nankai University; A 5 mL aqueous solution of zinc nitrate with a concentration of 0.36 mol / L was added dropwise to the 3 g of ZSM-5, and after impregnation for 8 h, the mixture was dried at 100 ℃ overnight, and finally calcined at 500 ℃ for 3 h at a temperature increase rate of 5 ℃ / min to obtain a metal-modified molecular sieve (Zn / ZSM-5, the mass percentage of Zn in the metal-modified molecular sieve was 4%).
[0051] Comparative Example 8 A mixture of copper nitrate trihydrate and aluminum nitrate nonahydrate was prepared in a molar ratio of 2:1, and then dissolved in deionized water to obtain a mixed solution; a mixed solution of sodium hydroxide and sodium carbonate (both with a concentration of 1 mol / L) was added dropwise to the mixed solution, and the pH was maintained at 9 during the dropwise addition; after the dropwise addition was completed, the mixture was stirred at room temperature for 2 h, and then placed in an oil bath at 75 ℃ overnight; the obtained solid was washed with deionized water until the pH was 7, and then dried at 100 ℃ for 10 h; the dried solid was transferred to a muffle furnace and calcined at 600 ℃ for 6 h at a temperature increase rate of 5 ℃ / min; finally, the calcined product was reduced in a hydrogen atmosphere at a rate of 5 mL / min at 300 ℃ for 1 h to obtain CuAlO x .
[0052] Test Example Figure 1 The XRD patterns of the Zn / ZSM-5 of Comparative Example 7 and the CuAlO x of Comparative Example 8 are shown in FIG. 1. Figure 1 As can be seen from FIG. 1, the Zn / ZSM-5 of Comparative Example 7 exhibits a typical MFI topology, and no peaks of metal oxides are observed, indicating that the metal is uniformly dispersed on the support; in the CuAlO x of Comparative Example 8, obvious diffraction peaks of CuO can be observed, indicating that Cu is mainly dispersed on the surface of the active metal oxide in the form of CuO. Figure 2 The TEM images of the Zn / ZSM-5 of Comparative Example 7 and the CuAlO x of Comparative Example 8 are shown in FIG. 2. Figure 2 As can be seen from FIG. 2, in the Zn / ZSM-5 of Comparative Example 7, the molecular sieve particles are uniformly dispersed, and from the elemental mapping, it can be seen that Zn is uniformly distributed without obvious aggregation; in the CuAlO x of Comparative Example 8, CuO particles are uniformly dispersed on the surface of the alumina. Figure 3 The Py-IR characterization pattern of the Zn / ZSM-5 of Comparative Example 7 is shown in FIG. 3. Figure 3 As can be seen from FIG. 3, both Brønsted acid and Lewis acid exist in the Zn / ZSM-5 of Comparative Example 7, which are derived from Si-OH-Al and Zn 2+The content of Brønsted acid was 0.54 mmol / g and the content of Lewis acid was 2.21 mmol / g, which were quantitatively calculated according to the number of acid sites.
[0053] Examples 1-15 and Comparative Examples 1-9 A certain amount of catalyst (the amount of catalyst is shown in Table 2, and the catalyst is a catalyst after reduction, and the reduction process is reduction at 300 DEG C for 1 h under H2 atmosphere) and 10 g of light crude oil (the crude oil is Karamay light crude oil, and the composition is shown in Table 1) were added into a high-pressure reactor, 0.5-2 MPa of carbon dioxide gas (the specific pressure of carbon dioxide gas in each example is shown in Table 2) was filled, and the temperature was raised to 310-350 DEG C for 6-20 h (the specific temperature and time in each example are shown in Table 2); after the reaction was completed, the gas and liquid products were collected, and the components of the gas and liquid products were analyzed by Agilent GC-8860 and Agilent GC-7890A respectively, the product composition was analyzed by correction factor method, the content of each component in the product was obtained, and the conversion rate and selectivity were calculated (specifically shown in Table 2); Table 1 Composition of Karamay light crude oil
[0054] Table 2 Reaction condition parameters and conversion rate and selectivity of Examples 1-15 and Comparative Examples 1-9
[0055] It can be seen from Table 2 that the composite catalysts involved in the present application have high catalytic activity and aromatic hydrocarbon selectivity (high octane number) in the gasoline prepared by catalyzing the coupling conversion of crude oil and carbon dioxide; Comparative Example 1 is the reaction activity under nitrogen atmosphere, and it can be found that the composite catalysts involved in the present application have higher gasoline yield and aromatic hydrocarbon selectivity under carbon dioxide atmosphere, and since the aromatic hydrocarbon component has high octane number, it proves the excellent performance of the coupling conversion strategy of crude oil and carbon dioxide in preparing high-octane gasoline. The catalysts described in Comparative Examples 7 and 8 used in Comparative Examples 2 and 3 have low gasoline yield and aromatic hydrocarbon content in the coupling conversion of crude oil and carbon dioxide, and do not have the excellent performance described in the present application.
[0056] Repeated use performance: the catalyst after the reaction of Example 8 was centrifuged, washed with 50 mL of ether for 3 times, dried at 100 DEG C for 2 h, calcined at 500 DEG C in a muffle furnace under air condition for 3 h, and then reduced at 300 DEG C under hydrogen atmosphere for 1 h to obtain a regenerated catalyst; the regenerated catalyst was repeatedly used according to the conditions shown in Table 3, and the data are shown in Table 3: Table 3 Recycling performance of catalyst used in application example 8
[0057] As shown in Table 3, the composite catalyst involved in the present application shows good reusability, and the activity remains basically unchanged after 3 cycles.
[0058] As can be seen from the above, the composite catalyst involved in the present application can obtain gasoline product with high yield, high aromatic content and high octane value, and the carbon dioxide atmosphere can promote the generation of high-octane component aromatic hydrocarbons; at the same time, the composite catalyst involved in the present application has good catalytic performance, simple preparation method, high stability, low cost and reusability, and provides a new production path for one-step conversion of crude oil and carbon dioxide to prepare high-octane gasoline.
[0059] The above description is only the preferred embodiments of the present application, and does not limit the present application in any form. It should be noted that for ordinary skilled persons in the art, some improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.
Claims
1. Use of a composite catalyst in the preparation of high-octane gasoline from crude oil and carbon dioxide, characterized in that, The composite catalyst comprises a metal-modified molecular sieve and an active metal and / or an active metal oxide; The acid content in the metal-modified molecular sieve is ≥0.1 mmol / g, and the acid in the metal-modified molecular sieve comprises Brønsted acid and Lewis acid.
2. Use according to claim 1, wherein The molecular sieve in the metal-modified molecular sieve has a topology structure with a ten-membered ring or a twelve-membered ring. The framework structure of the molecular sieve comprises one or more of Si-O, Si-O-Al, Si-O-Al-P, Si-O-Al-B and Si-O-Al-Ge.
3. Use according to claim 2, wherein the compound is ###0002### The molecular sieve is one or more of ZSM-5 molecular sieve, Beta molecular sieve and HY molecular sieve.
4. The use according to claim 3, wherein the compound is ###0002### The modified metal in the metal-modified molecular sieve is one or more of manganese, iron, cobalt, nickel, zinc, gallium, tin, ruthenium, platinum and gold. The mass percentage of the metal in the metal-modified molecular sieve is 0.01-10%.
5. The use according to claim 1, wherein The active metal is one or more of aluminum, titanium, manganese, nickel, iron, copper, cobalt, zinc, gallium, zirconium, molybdenum, silver, rhodium, ruthenium, platinum, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum and cerium.
6. Use according to claim 5, wherein The mass percentage of the active metal in the composite catalyst is 0.01-60%.
7. The use according to claim 1, wherein The active metal oxides are one or more of AI2O3, TiO2, ZrO2, MnO x , FeO x , CoO x , ZnO, MoO x , MgO, BaO, Y2O3, CeO2and La2O3.
8. Use according to claim 7, wherein the compound is ###0002### The mass percentage of the active metal oxide in the composite catalyst is 0.01-60%.
9. Use according to any one of claims 1 to 8, wherein The method for the application comprises the following steps: When the composite catalyst comprises an active metal oxide: The composite catalyst is pre-reduced to obtain a pre-reduced composite catalyst; The pre-reduced composite catalyst and light crude oil are mixed and subjected to catalytic reaction under the condition of passing carbon dioxide to obtain high-octane gasoline; When the composite catalyst does not comprise an active metal oxide: The composite catalyst and light crude oil are mixed and subjected to catalytic reaction under the condition of passing carbon dioxide to obtain high-octane gasoline.
10. The use according to claim 9, wherein the compound is ###0002### The pre-reduction is performed in a reducing atmosphere, and the reducing atmosphere is preferably an atmosphere comprising hydrogen and / or carbon monoxide; The volume concentration of hydrogen and / or carbon monoxide in the reducing atmosphere is 5-100%; The temperature of the pre-reduction is 200-600°C, and the time is 0.5-5 h.