Multi-metal supported transition metal oxide catalysts, methods of making and use in the production of renewable fuels

Abstract

The application discloses a multi-metal loaded transition metal oxide catalyst, a preparation method thereof and application thereof in production of renewable fuel, and belongs to the technical field of petroleum refining and sustainable green petroleum chemical industry. A transition metal oxide carrier material with a high specific surface area, weak acidity, a high oxygen defect concentration and a mesoporous structure is prepared, three metals are loaded on the carrier material, and a multi-metal loaded transition metal oxide catalyst is obtained. The catalyst can efficiently perform a deoxidation reaction on bio-crude oil containing oxygen under a methane atmosphere, thereby greatly improving the value of the bio-crude oil, providing a new way for efficient conversion and utilization of the bio-crude oil, and providing a possibility for realizing low carbon emission and achieving carbon neutralization. The application improves the problems in the existing processing technology, such as high energy consumption, high investment cost, complex process route, high water content in products, great corrosion to devices, great environmental protection pressure and the like, and provides a new technical route for preparing high-value low-oxygen-content fuel.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of petroleum refining and sustainable green petroleum chemical technology, and particularly relates to a multi-metal loaded transition metal oxide catalyst, a preparation method thereof and application thereof in the production of renewable fuel. BACKGROUND

[0002] In recent years, with the gradual depletion of fossil fuels, energy crisis has received more and more widespread and sustained attention. The development, production and utilization of renewable resources have gradually become a key issue. At present, bio-derived biomass materials, especially lignocellulosic materials, are a kind of materials with great attraction (R.S. Singh, Bioresour. Technol., 346 (2022), D. Mohan, Energy and Fuels, 20, 848-880, (2006)). The CO2 emitted in the use process of bio-crude is originally captured and converted in the process of photosynthesis to form biomass materials, so the net CO2 emission in the process of consuming bio-derived resources is much lower than that of conventional fossil fuels. At the same time, biomass also includes a variety of naturally available materials widely distributed around the world, so the use of biomass materials locally can greatly reduce the additional costs of development, transportation and storage. In addition, the sulfur content in biomass is generally very low, so the emission of harmful sulfur oxides (SO x ) can be well controlled (E. Alptekin, Renew Energy 33, (2008), 2623-2630). Based on the above advantages, if the biomass can be used in a more effective way, it can play an important role in sustainable energy supply and carbon footprint reduction, and ultimately achieve carbon neutrality in terms of zero carbon emission.

[0003] However, before the biomass materials are utilized, they must be converted and prepared by various pyrolysis-related techniques, which often produce bio-oil rich in oxygen elements. Currently, these pyrolysis bio-oils or plant oils often have problems such as high viscosity, high water content, large acid value (TAN), and serious corrosion to equipment, and thus cannot be directly used as fuel. Therefore, these oxygen-rich bio-oils often need to be hydrotreated and hydrorefined to produce low-oxygen-content gasoline and diesel (CN102199495A, CN105602612A, CN102653691B). Although the hydrotreatment process is efficient, there are still many problems in the bio-oil hydrogenation technology that need to be solved: for example, the cost of producing hydrogen from steam reforming and other processes is high, a large amount of CO2 is emitted during the process, which has a negative impact on the environment, noble metal catalysts are needed, and often their hydrothermal stability is poor, which leads to rapid deactivation during the hydrogenation process, thereby indirectly increasing the cost of renewable gasoline and diesel. Therefore, it is urgent to develop other alternative technical routes to produce renewable high-quality gasoline and diesel. Natural gas is a relatively clean and abundant natural resource, and its main component is methane. Due to the high symmetry structure and high C-H bond energy (425 kJ / mol) of the methane molecule, it has high thermodynamic and kinetic inertness. Therefore, the activation and efficient use of methane are still at a low level, and in real life, natural gas is currently still mainly used for fuel. There are some reports on the synergistic effect between methane and other reactants, and once methane is effectively activated, due to its high hydrogen-to-carbon ratio (4:1), it has the potential to combine carbon into the desired product, making methane an ideal carbon / hydrogen donor. At the same time, methane also helps to disperse metals on the catalyst, helps to maintain the physical and chemical properties of the catalyst material, and reduces coke deposition (H. Xu, Commun. Chem 4, (2021), H. Xu, Fuel, 309, (2022), V. R. Choudhary, Science, 275, (1997), 1286-1288). In fact, there have been some reports on the use of methane to modify heavy oil and light oil, but due to the complexity and diversity of bio-oil, there have been few reports on methane-assisted deoxygenation of real bio-oil.

[0004] The goal of real bio-oil upgrading is to produce fuel substitutes while deoxygenating them, and it is extremely critical to directly remove oxygen atoms without damaging the structural integrity of the raw materials. At the same time, considering that the generation of water in the reaction system will cause equipment corrosion and reduce the stability of the catalyst, and the product still needs to solve the problem of further separation and dehydration, therefore in the design of the catalyst, a technical route that produces as little water as possible and produces CO2 / CO to achieve deoxygenation is needed, thereby further improving the stability and sustainability of the reaction. SUMMARY

[0005] In order to overcome the above-mentioned defects of the prior art, the present application aims to provide a multi-metal loaded transition metal oxide catalyst and a preparation method and application thereof in the production of renewable fuel oil, so as to solve the problems of large hydrogen consumption, high energy consumption, and generation of a certain amount of water, which leads to equipment corrosion and subsequent redundant separation process in the current renewable biofuel oil production process.

[0006] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0007] The present application discloses a multi-metal loaded transition metal oxide catalyst, which is composed of three kinds of metals and a transition metal oxide, and the loading amount of each metal is 0.1% to 5% of the mass of the transition metal oxide; the chemical formula is (M1, M2, M3) / TMO, wherein M1, M2 and M3 are any three metals in Ir, Ga, Ce, Fe, Cu, Zn and Ag, and TMO is mesoporous anatase TiO2, mesoporous rutile TiO2 or titanium silicalite.

[0008] The present application also discloses a preparation method of the above-mentioned multi-metal loaded transition metal oxide catalyst, which comprises the following steps:

[0009] 1) Dissolve a high-molecular template agent in an ethanol solution, adjust the pH value to 1 to 2, stir uniformly, add a transition metal oxide organic precursor, stir into a gel, and then dry, calcine to obtain a transition metal oxide carrier material with a mesoporous structure;

[0010] 2) Load water-soluble salts of three kinds of metals on the transition metal oxide carrier material with a mesoporous structure obtained in step 1) by using an impregnation method, dry, calcine to obtain a multi-metal loaded transition metal oxide catalyst.

[0011] Preferably, in step 1), the high-molecular template agent is a high-molecular pore-forming agent P123; the transition metal oxide organic precursor is n-butyl titanate or isopropyl titanate; and the transition metal oxide carrier material with a mesoporous structure is mesoporous TiO2 with an anatase crystal structure.

[0012] Preferably, in step 1), the drying condition is to dry at room temperature for 24 to 48 hours first, and then dry at 75 to 125 DEG C for 3 to 12 hours; and the calcination condition is to calcine at 350 to 550 DEG C for 3 to 5 hours.

[0013] Preferably, in step 2), the drying condition is to dry at 70 to 150 DEG C for 1 to 24 hours; and the calcination condition is to heat at a heating rate of 1 to 20 DEG C / min to 300 to 700 DEG C, and then calcine in an air or nitrogen atmosphere for 3 to 5 hours.

[0014] Preferably, in step 2), the metal is Ir, Ga, Ce, Fe, Cu, Zn or Ag, the water-soluble salt of the metal is nitrate, sulfate or chloride; and the impregnation method is equal volume impregnation or excess impregnation.

[0015] The application also discloses application of the multi-metal loaded transition metal oxide catalyst in production of renewable fuel through deoxygenation of bio-crude oil.

[0016] Preferably, the mass ratio of the bio-crude oil to the catalyst is (10:1) to (1:10).

[0017] Preferably, the reaction temperature is 300-450 DEG C, the reaction pressure is 0.1-6 MPa, the liquid hourly space velocity is 0.1-5 h-1. -1 .

[0018] Preferably, the reactor is a batch reactor or a small fixed bed reactor.

[0019] Compared with the prior art, the application has the following beneficial effects:

[0020] The application discloses a kind of multi-metal loaded transition metal oxide catalyst, wherein, transition metal oxide specific surface area is large, can be better loaded metal, mesoporous volume is larger, surface oxygen defect is more, material particle morphology is consistent, micro size is uniform, and control in nanometer size.Transition metal oxide as catalyst carrier has abundant high-activity oxygen defects, and therefore can show good C-O bond activation, mesoporous anatase structure TiO2 With abundant mesoporous structure, its oxygen defect concentration is high, therefore has high selectivity deoxidation capacity, help to remove oxygen atom in the molecule of bio crude oil efficiently, and a certain amount of oxygen defects exist in rutile structure TiO2, and titanium-silicon molecular sieve is widely used in oxidation-reduction reaction catalysis, so these two kinds of materials have certain deoxidation capacity, can be used in the reaction of bio crude oil deoxidation.Three kinds of metals in catalyst as active component, three kinds of active metals each has its own characteristics, can improve the comprehensive performance of catalyst, wherein, Ir can activate methane in the oxidation pathway of early stage of reaction, Ga can effectively activate methane by promoting asymmetric methane decomposition and hydrogen transfer reaction, Ce can inhibit the generation of coke, Fe, Cu, Zn and Ag as transition metal, its variable price is rich, and its synergistic combination can effectively activate methane.Meanwhile, the combination of multiple metals can separate the active components from each other, so as to have better dispersion effect and reaction activity.The catalyst has high selectivity deoxidation capacity, can efficiently convert oxygen-containing bio crude oil obtained by pyrolysis and other low-value raw materials into high-value products, such as low-oxygen-content high-quality renewable fuel, bio-diesel and the like, under moderate temperature and pressure.By removing oxygen atom through catalyst, the structure of gas raw material molecule is retained to the greatest extent;Traditional petrochemical fuel is facing the problem of depletion of oil resources, so it is very meaningful to develop renewable fuel from biomass;Currently, hydrogenation treatment process is often used to generate water, which leads to equipment corrosion, and subsequent separation process is needed, while the method of the application generates CO2 and CO and the like, realizes deoxidation while avoiding water generation.

[0021] The application also discloses a preparation method of the multi-metal loaded transition metal oxide catalyst, a transition metal oxide carrier material with a mesoporous structure prepared by the method, rich mesoporous structure and rich oxygen defects of the transition metal oxide carrier material, which are beneficial to activation and removal of oxygen-containing compounds in the bio-crude oil; and the water-soluble salt of the metal is loaded on the transition metal oxide carrier material with the mesoporous structure by using an impregnation method, and the multi-metal loaded transition metal oxide catalyst is obtained by drying and calcining, wherein the metal dispersion degree of the catalyst is high, the combination of different metals has a good synergistic effect, and the comprehensive performance of the catalyst can be greatly improved. In the design and preparation of the catalyst, the technical route of generating CO2 / CO and realizing deoxidation by generating as little water as possible is adopted, and the reaction stability and sustainability are further improved; under relatively mild reaction conditions, the low-value bio-crude oil with a high oxygen content is efficiently converted into high-value fuel oil with a low oxygen content, and a relatively economical technical route is provided for reducing carbon emission and realizing carbon neutralization.

[0022] Further, the high-molecular template is a high-molecular pore-forming agent P123; the aqueous solution of the high-molecular pore-forming agent P123 can form a good micellar structure, thereby inducing the generation of the mesoporous structure in the carrier material; the organic titanium source is n-butyl titanate or isopropyl titanate; the hydrolysis speed of the two materials can be well controlled, thereby being beneficial to the generation of the mesoporous material; and the transition metal oxide carrier material with the mesoporous structure is mesoporous TiO2 with an anatase crystal structure; the material has a good mesoporous structure and rich oxygen defects.

[0023] Further, the drying condition is that the material is dried at room temperature for 24-48 hours and then dried at 75-125 DEG C for 3-12 hours; under the condition, the organic alcohol molecules can be removed as much as possible.

[0024] Further, the metal is Ir, Ga, Ce, Fe, Cu, Zn or Ag, and the water-soluble salt of the metal is a nitrate, a sulfate or a chloride; the soluble metal salt is selected, and this is beneficial to the generation of the high-dispersion catalyst.

[0025] The application also discloses application of the multi-metal loaded transition metal oxide catalyst in production of renewable fuel oil by deoxidizing bio-crude oil; the bio-crude oil and the catalyst are put into a reactor, reaction gas is introduced, and after the reaction is completed, gaseous products and liquid products are obtained; the conversion of the oxygen-containing bio-crude oil is realized under relatively low operating cost and relatively mild reaction conditions; the oxygen removal rate is 84.7%, the acid value (TAN) of the product oil is reduced from 34.22 mg KOH g -1 to 0.20 mg KOH g -1Meanwhile, the mass percentage of water is controlled at 0.07%; the problems in the existing processing technology, such as high energy consumption, high investment cost, complex process route, high water content in products, great corrosion to the device and great environmental protection pressure, are improved, and a new way is provided for preparing high-value low-oxygen-content fuel oil. The reaction gas is one or more combinations of CH4, N2 and H2; methane in combination with the catalyst prepared in the application can promote the deoxygenation reaction and produce additional CO and CO2, and participate in the chain growth reaction to form more saturated hydrocarbons with higher carbon number. Therefore, the catalyst has good effect on the activation and conversion of the biomolecular crude oil molecules. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 Reaction mechanism diagram of 2-hexyl-decanol. DETAILED DESCRIPTION

[0027] In order to make the personnel in the technical field better understand the application scheme, the technical scheme in the embodiments of the application will be clearly and completely described below in combination with the drawings in the embodiments of the application. Obviously, the described embodiments are only a part of the embodiments of the application, not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor should belong to the protection scope of the application.

[0028] It should be noted that the terms "first", "second" and the like in the specification and claims of the application and the above-mentioned drawings are used to distinguish similar objects, and do not necessarily indicate a specific order or a chronological sequence. It should be understood that the data thus used can be interchanged under appropriate circumstances, so that the embodiments of the application described herein can be implemented in an order other than that illustrated or described herein. In addition, the terms "include" and "have" and any variations thereof are intended to cover non-exclusive inclusion, for example, a process, method, system, product or device including a series of steps or units does not have to be limited to those steps or units clearly listed, but can include other steps or units not clearly listed or inherent to these processes, methods, products or devices.

[0029] The application will be further described in detail below in combination with the drawings:

[0030] A multi-metal loaded transition metal oxide catalyst, which is used to convert oxygen-containing bio-crude molecules into low-oxygen-content high-quality fuel under mild reaction conditions in a reactor system and under certain temperature, pressure and reaction atmosphere; the chemical formula of the catalyst is (M1, M2, M3) / TMO, wherein M1, M2 and M3 are three metals selected from Ir, Ga, Ce, Fe, Cu, Zn and Ag, TMO is a transition metal oxide, and the loading amount of each metal is 0.1% to 5% of the mass of the transition metal oxide based on the carrier material transition metal oxide.

[0031] The application provides a preparation method of a multi-metal loaded transition metal oxide catalyst, which comprises the following steps:

[0032] 1) preparing a transition metal oxide carrier material with mesoporous structure

[0033] 16.0g of a high-molecular pore-forming agent P123 is dissolved in 240g of an ethanol solution, 19.2mL of dilute hydrochloric acid with a concentration of 1mol / L is added, the pH value is adjusted to 1-2, and the solution is stirred uniformly to form a uniform solution; 50mL of an organic titanium source is slowly added to form a gel; the gel is dried at normal temperature for 24-48h, then dried at 75-125℃ for 3-12h, and finally calcined at 350-550℃ for 3-5h to obtain the transition metal oxide carrier material with mesoporous structure;

[0034] 2) preparing a multi-metal loaded transition metal oxide catalyst

[0035] The metal is loaded on the carrier material by using an equal-volume impregnation method or an excess-impregnation method; water-soluble salts of three preferred active metal substances or a combination of the above substances are dissolved in water, and the loading amount of each metal in the carrier is 0.1% to 5% by weight; the mixture is dried at 70-150℃ for 1-24h, and then calcined at 300-700℃ at a temperature increasing rate of 1-20℃ / min in an air or nitrogen atmosphere for 3-5h to obtain the final multi-metal loaded transition metal oxide catalyst.

[0036] The application further improves the transition metal oxide carrier material to be mesoporous TiO2 with an anatase crystal structure.

[0037] The application further improves the preparation method of the mesoporous anatase TiO2 material, that is, a high-molecular pore-forming agent P123 is dissolved in a certain amount of ethanol, a certain amount of 1mol / L dilute hydrochloric acid is added, the mixture is stirred for 1h to form a uniform solution, a certain amount of an organic titanium source is slowly added to form a gel, the gel is dried at normal temperature for 24-48h, then dried at 75-125℃ for 3-12h, and finally calcined at 350-550℃ for 3-5h to obtain the mesoporous TiO2.

[0038] The further improvement of the present application is that the organic titanium source is selected from n-butyl titanate or isopropyl titanate.

[0039] The further improvement of the present application is that in step 2), the water-soluble salt of three active metal substances selected from Ir, Ga, Ce, Fe, Cu, Zn or Ag is selected.

[0040] The further improvement of the present application is that the water-soluble salt is nitrate, sulfate or chloride.

[0041] The present application researches and finds that under the action of a specific multi-metal supported catalyst, oxygen-containing bio-crude oil and other raw materials can be efficiently converted into low-oxygen-content fuel oil such as renewable gasoline and diesel oil, and only a small amount of coke is produced.

[0042] The present application provides an application of a prepared multi-metal supported transition metal oxide catalyst in the production of renewable fuel oil from bio-crude oil.

[0043] Catalyst application: the catalyst is used together with oxygen-containing bio-crude oil and the like in a reactor under a reaction atmosphere. The product distribution of gas products, liquid products and coke is studied, and in particular the oxygen content of the liquid products.

[0044] The further improvement of the present application is that the bio-crude oil used is a high-oxygen-content bio-oil obtained by pyrolysis of various biomasses or a model compound (such as 2-hexyl decanol).

[0045] The reaction atmosphere is a mixed gas of one or more of N2, CH4 and H2, and the reaction temperature is 300-450 DEG C and the reaction pressure is 0.1-6 MPa.

[0046] The mass ratio of the reaction raw material bio-crude oil to the catalyst is (10:1)-(1:10), the liquid hourly space velocity is 0.1-5 h -1

[0047] The further improvement of the present application is that the reactor system used is one or a combination of the following: a small fixed-bed reactor or a batch reactor (Parr reactor).

[0048] Reference Figure 1 is a reaction mechanism diagram of 2-hexyl-decanol; as can be seen from the figure, under the optimized conditions of the present application, the oxygen-containing groups can be efficiently removed to produce CO2 and CO, and at the same time the molecular structure can be well maintained. The present application provides a new way for preparing high-quality low-oxygen renewable gasoline and diesel oil.

[0049] Various embodiments of the present application include but are not limited to the synthesis of a weakly acidic, three-metal, mesoporous structure developed catalyst, which converts oxygen-containing bio-crude oil into low-oxygen-content high-quality fuel oil. ​

[0050] The transition metal oxide support with abundant mesoporous structure in the present application includes one or more of the following: mesoporous anatase TiO2, mesoporous rutile TiO2, titanium silicalite TS-1, porous Al2O3 or porous SiO2, etc. In the present application, the use of loading including but not limited to Ir, Ga, Ce, Fe, Cu, Zn or Ag can greatly improve the reaction performance of the catalyst, and the mass percentage of each metal loading is 0.1% to 5%.

[0051] Example 1

[0052] A multi-metal loaded transition metal oxide catalyst, specifically including the following steps:

[0053] The 1% Ir-1% Ga-5% Ce / TiO2-A catalyst was prepared in the following manner:

[0054] First, prepare anatase TiO2 with mesoporous structure; take 16.0g P123 and add it to 240g ethanol, add 19.2mL of 1mol / L dilute hydrochloric acid, stir for 1h to form a uniform solution; add 48mL of isopropyl titanate dropwise and continue stirring until a gel is formed, dry at room temperature for 48h, then transfer to an oven at 110°C for 6h, then calcine at 450°C for 4h to obtain a light yellow solid material, labeled as mesoporous TiO2-A.

[0055] Secondly, dissolve 0.3999g Ga(NO3)3·9H2O and 2.171g Ce(NO3)3·6H2O metal salts in 20mL deionized water to form a metal precursor solution, impregnate the TiO2-A support with an equal volume of the metal precursor solution to achieve a Ga metal loading of 1% and a Ce metal loading of 5%; then dry the impregnated solid at 110°C and calcine in static air at 550°C for 4h to obtain the 1% Ga-5% Ce / TiO2-A catalyst; again, dissolve 0.1503g IrCl3 in 10mL deionized water to obtain an IrCl3 solution, pour the IrCl3 solution into a beaker containing the 1% Ga-5% Ce / TiO2-A catalyst, add urea to adjust the pH to 9.0, keep the solution at 80°C for 10h until it is dry, and calcine in static air at 550°C for 4h to prepare the 1% Ir-1% Ga-5% Ce / TiO2-A catalyst.

[0056] Biocracking oil (PTJ) provided by Forge Hydrocarbons Company was used as the reaction raw material to carry out biocrude deoxygenation experiments on a 20 liter / day small fixed bed reactor. The catalyst filling amount was 5.4mL, the biocrude liquid flow rate was 0.09mL / min, and the liquid hourly space velocity was 1h-1 The reaction temperature was 400°C, the reaction atmosphere was 3.0 MPa CH4, the CH4 flow rate was 100 sccm, the reaction time was 3 h, the gaseous product and the liquid product oil were collected, the spent catalyst was collected after the reaction, and the raw material conversion rate, the gas yield, the liquid yield, and the oxygen element content in the liquid product were measured, and the results are listed in Table 1. As can be seen from Table 1, the liquid yield can reach 94.7%, and the deoxygenation rate can reach 84.7%.

[0057] Referring to Figure 1 A reaction mechanism diagram of 2-hexyl-decanol; as can be seen from the diagram, under the optimized conditions of the present application, the biomass oil molecules are removed of oxygen atoms under the reuse of the catalyst to generate high-quality fuel oil, while byproducts CO2 and CO are generated, and the molecular structure integrity can be well maintained.

[0058] Example 2

[0059] A multi-metal loaded transition metal oxide catalyst, specifically comprising the following steps:

[0060] A 1%Ir-1%Ga-5%Ce / TiO2-A catalyst with a mass percentage was prepared in the following manner:

[0061] First, prepare anatase TiO2 with a mesoporous structure; take 16.0 g of P123 and add it to 240 g of ethanol, add 19.2 mL of dilute hydrochloric acid with a concentration of 1 mol / L, stir for 1 h to form a uniform solution; add 48 mL of isopropyl titanate dropwise and continue to stir until a gel is formed, dry at room temperature for 24 h, then transfer to an oven and dry at 75°C for 12 h, then calcine at 350°C for 5 h to obtain a light yellow solid material, marked as mesoporous TiO2-A.

[0062] Secondly, dissolve 0.3999 g of Ga(NO3)3·9H2O and 2.171 g of Ce(NO3)3·6H2O metal salt in 20 mL of deionized water to form a metal precursor solution, and immerse the TiO2-A carrier with the same volume of the metal precursor solution to achieve a Ga metal loading of 1% and a Ce metal loading of 5%; then dry the immersed solid at 70°C for 24 h and calcine in static air at 300°C for 5 h to obtain a 1%Ga-5%Ce / TiO2-A catalyst; again, dissolve 0.1503 g of IrCl3 in 10 mL of deionized water to obtain an IrCl3 solution, pour the IrCl3 solution into a beaker containing the 1%Ga-5%Ce / TiO2-A catalyst, add urea to adjust the pH value to 9.0, and keep the solution at 80°C for 10 h until it is dry and calcine in nitrogen at 550°C for 4 h to prepare a 1%Ir-1%Ga-5%Ce / TiO2-A catalyst with a mass percentage.

[0063] The bio-cracking oil (PTJ) provided by Forge Hydrocarbons was used as the reaction raw material to carry out the bio-cracking oil deoxygenation experiment on a 300 mL Parr high-pressure reactor. The weight ratio of bio-cracking oil and catalyst was 1:1, and both were 20 g. The reaction temperature was 400°C, and the stirring reaction was continued at this temperature for 1 h. The reaction atmosphere was 3.0 MPa CH4, and the reaction time was 3 h. The gas product and liquid product oil were collected. After the reaction was completed, the spent catalyst was collected. The raw material conversion rate, gas yield, liquid yield, and oxygen element content in the liquid product were measured, and some key indicators are listed in Table 1. As can be seen from Table 1, the liquid yield can reach 92.9%, and the deoxygenation rate can reach 82.1%.

[0064] Example 3

[0065] A multi-metal loaded transition metal oxide catalyst, specifically comprising the following steps:

[0066] The 0.1% Ir-1% Ga-5% Zn / TS-1 catalyst was prepared in the following manner:

[0067] First, directly use commercial titanium silicalite (TS-1) as a catalyst carrier;

[0068] Second, dissolve 0.3999 g Ga(NO3)3·9H2O and 2.171 g Ce(NO3)3·6H2O metal salts in 20 mL deionized water to form a metal precursor solution, and immerse the TS-1 carrier with the same volume of the metal precursor solution to achieve a Ga metal loading of 1% and a Zn metal loading of 5%; then dry the immersed solid at 150°C for 1 h and calcine it in nitrogen at 500°C for 5 h to obtain a 1% Ga-5% Zn / TS-1 catalyst; third, dissolve 0.1503 IrCl3 in 10 mL deionized water to obtain an IrCl3 solution, pour the IrCl3 solution into a beaker containing the above catalyst, add urea to adjust the pH value to 9.0, and keep the solution at 80°C for 5 h. After collecting the solid by filtration, dry it at 110°C and calcine it in static air at 550°C for 4 h to prepare a 0.1% Ir-1% Ga-5% Zn / TS-1 catalyst.

[0069] 2-hexyl-decanol (2H1DOL) was selected as a representative oxygen-containing model compound and directly used as a reaction raw material to carry out bio-cracking oil deoxygenation experiments on a 20 liter / day small fixed-bed reactor. The catalyst filling amount was 5.4 mL, the liquid flow rate was 0.009 mL / min, the liquid hourly space velocity was 0.1 h -1, the reaction temperature was 450°C, the reaction atmosphere was 6.0 Mpa of CH4, the CH4 flow rate was 100 sccm, the reaction time was 3 h, the gaseous product and liquid product oil were collected, and the spent catalyst was collected after the reaction was completed. The raw material conversion rate, gas yield, liquid yield, and oxygen element content in the liquid product were measured and are listed in Table 1. As can be seen from Table 1, the liquid yield can reach 95.1%, and the deoxygenation rate can reach 77.5%.

[0070] Example 4

[0071] A 1%Ir-1%Ga-5%Ce / TiO2-A catalyst was prepared in the following manner:

[0072] First, a mesoporous anatase TiO2 was prepared; 16.0 g of P123 was added to 240 g of ethanol, 19.2 mL of 1 mol / L concentrated hydrochloric acid was added, and stirring was performed for 1 h to form a uniform solution; 48 mL of isopropyl titanate was added dropwise and stirring was continued until a gel was formed, the gel was dried at room temperature for 36 h, then transferred to an oven and dried at 125°C for 3 h, and then calcined at 550°C for 3 h to obtain a light yellow solid material, which was labeled as mesoporous TiO2-A.

[0073] Second, 0.3999 g of Ga(NO3)3·9H2O and 2.171 g of Ce(NO3)3·6H2O were dissolved in 20 mL of deionized water to form a metal precursor solution, and the catalyst was prepared by an excess impregnation method using the metal precursor solution to achieve a Ga metal loading of 1% and a Ce metal loading of 5%. Subsequently, the impregnated solid was dried at 150°C for 1 h and calcined in static air at 700°C for 3 h to obtain a 1%Ga-5%Ce / TiO2-A catalyst; again, 0.15 g of IrCl3 was dissolved in 5 mL of deionized water to obtain an IrCl3 solution, the IrCl3 solution was poured into a beaker containing the 1%Ga-5%Ce / TiO2-A catalyst, urea was added to adjust the pH value to 9.0, the solution was maintained at 80°C for 10 h, the solid was collected after filtration, dried at 110°C, and calcined in static air at 550°C for 4 h to prepare a 1%Ir-1%Ga-5%Ce / TiO2-A catalyst.

[0074] Biocracking oil (PTJ) provided by Forge Hydrocarbons was used as a reaction raw material to carry out a biocracking oil deoxygenation experiment on a 20 liter / day small fixed bed reactor. The catalyst filling amount was 5.4 mL, the liquid flow rate was 0.09 mL / min, the liquid hourly space velocity was 1 h -1The reaction temperature was 400°C, the reaction atmosphere was 3.0 MPa of H2or 3.0 MPa of N2, the gas flow rate was 100 sccm, the reaction time was 3 h, the gaseous product and the liquid product oil were collected, and the spent catalyst was collected after the reaction. The raw material conversion rate, the gas yield, the liquid yield, the oxygen element content in the liquid product, and the like were measured, and some key indicators are listed in Table 1. As can be seen from Table 1, the deoxygenation rate is the highest under the hydrogen atmosphere, and the deoxygenation rate is lower under the nitrogen atmosphere.

[0075] Example 5

[0076] Experiments under different reaction conditions were carried out using the catalyst 1%Ir-1%Ga-5%Ce / TiO2-A prepared in Example 1.

[0077] 2-hexyl-decanol (2H1DOL) was selected as a representative oxygen-containing model compound and directly used as a raw material for the bio-crude deoxygenation experiment on a 20 L / day small fixed-bed reactor. The catalyst filling amount was 5.4 mL, the liquid flow rate was 0.09 mL / min, the liquid hourly space velocity was 1.0 or 5.0 h -1 The reaction temperature was 420°C, the reaction atmosphere was 3.0 MPa of CH4, 3.0 MPa of H2or 3.0 MPa of N2, the gas flow rate was 100 sccm, the reaction time was 3 h, the gaseous product and the liquid product oil were collected, and the spent catalyst was collected after the reaction. The raw material conversion rate, the gas yield, the liquid yield, the oxygen element content in the liquid product, and the like were measured, and some key indicators are listed in Table 1. As can be seen from Table 1, if the liquid hourly space velocity and the reaction atmosphere are changed, the liquid yield and the deoxygenation rate can change accordingly. For example, under the CH4atmosphere, the liquid yield can reach 94.1%, and the deoxygenation rate can reach 85.2%. Under the N2atmosphere, the liquid yield can be as high as 98.2%, but the deoxygenation rate is only 71.4%. Under the H2atmosphere, both the liquid yield and the deoxygenation rate are high, which are 95.6% and 98.3%, respectively.

[0078] Example 6

[0079] A multi-metal supported transition metal oxide catalyst, specifically comprising the following steps:

[0080] A 0.1%Ag-5%Fe-2.5%Zn / TiO2-R catalyst with a mass percentage of 0.1%Ag-5%Fe-2.5%Zn / TiO2-R was prepared in the following manner;

[0081] First, TiO2with a rutile structure was directly used as a catalyst carrier;

[0082] Secondly, metal salts of Fe(NO3)3-9H2O, ZnSO4and AgNO3were dissolved in deionized water to form a metal precursor solution, the rutile carrier was impregnated with the metal precursor solution in equal volume, dried at 70°C, and calcined at 700°C in static air for 5h to prepare the mass percentage of 0.1%Ag-5%Fe-2.5%Zn / TiO2-R catalyst.

[0083] The bio-cracking oil (PTJ) provided by Forge Hydrocarbons Company was used as the reaction raw material to carry out the bio-cracking oil deoxidation experiment on a 300mL Parr high-pressure reactor. The weight ratio of the raw oil and the catalyst was 10:1, the raw oil was 10g, the catalyst was 1g, the reaction temperature was 450°C, and the reaction was continuously stirred at this temperature for 1h, the reaction atmosphere was 0.1MPa of CH4, the reaction time was 3h, the gas product and the liquid product oil were collected, the spent catalyst was collected after the reaction, the raw material conversion rate, the gas yield, the liquid yield, the oxygen element content in the liquid product, and other results were measured, and part of the key indicators were listed in Table 1. As can be seen from Table 1, the liquid yield can reach 74.1%, and the deoxidation rate can reach 15.3%, because the reaction conditions have too high temperature and pressure, and the carrier and active metal of the catalyst are not good.

[0084] Example 7

[0085] The mass percentage of 0.1%Ag-5%Fe-2.5%Cu / TiO2-R catalyst was prepared in the following way;

[0086] Firstly, TiO2with a rutile structure was directly used as a catalyst carrier;

[0087] Secondly, metal salts of Fe(NO3)3-9H2O, CuSO4and AgNO3were dissolved in deionized water to form a metal precursor solution, the rutile carrier was impregnated with the metal precursor solution in equal volume, dried at 70°C, and calcined at 700°C in static air for 5h to prepare the mass percentage of 0.1%Ag-5%Fe-2.5%Cu / TiO2-R catalyst.

[0088] The bio-cracking oil (PTJ) provided by Forge Hydrocarbons Company was used as the reaction raw material to carry out the deoxygenation experiment of the bio-cracking oil on a 300 mL Parr high-pressure reactor. The weight ratio of the raw oil and the catalyst was 1:10, the raw oil was 5 g, the catalyst was 50 g, the reaction temperature was 300 DEG C, the reaction was continuously stirred at this temperature for 1 h, the reaction atmosphere was 6.0 MPa of CH4, the reaction time was 3 h, the gas product and the liquid product oil were collected, the spent catalyst was collected after the reaction, the raw material conversion rate, the gas yield, the liquid yield, the oxygen element content in the liquid product and the like were measured, and part of the key indicators were listed in Table 1. As shown in Table 1, the liquid yield can reach 87.0%, and the deoxygenation rate can reach 5.3%. It is proved again that the catalyst has poor performance, which is also related to the too low reaction temperature.

[0089] Table 1. Performance evaluation of the catalyst prepared in the application, reaction conditions and results

[0090]

[0091]

[0092] Referring to Table 1 for the performance evaluation of the catalyst prepared in the application, the reaction conditions and the results, it can be seen from the table that when the mesoporous anatase TiO2 is used as the carrier, the catalyst with 1% Ir, 1% Ga and 5% Ce can have the best performance. Under the optimized reaction conditions, the deoxygenation rate of the real bio-cracking oil under the methane reaction atmosphere can be as high as 84.7%, and the deoxygenation rate under the nitrogen atmosphere is lower. Although the deoxygenation rate under the hydrogen atmosphere is higher, the hydrogen cost is higher, and the product contains a large amount of water.

[0093] The above content only illustrates the technical idea of the application, and cannot limit the protection scope of the application. Any modification made according to the technical idea of the application on the basis of the technical scheme falls within the protection scope of the claims of the application.

Claims

1. Use of a multi-metal loaded transition metal oxide catalyst in the production of renewable fuels from bio-crude deoxygenation, characterized in that, The bio-crude oil and the transition metal oxide catalyst are put into a reactor, a reaction gas is introduced, and after the reaction, a gas product and a liquid product are obtained; the reaction gas is one or more combinations of CH4, N2 and H2; The mass ratio of the bio-crude oil to the multi-metal loaded transition metal oxide catalyst is (10:1) to (1:10); The multi-metal loaded transition metal oxide catalyst is composed of three metals and a transition metal oxide, and the loading amount of each metal is 0.1% to 5% of the mass of the transition metal oxide; the chemical formula is (M1, M2, M3) / TMO, wherein M1, M2 and M3 are Ir, Ga and Ce, and TMO is mesoporous anatase TiO2; The preparation method of the multi-metal loaded transition metal oxide catalyst comprises the following steps: 1) Dissolve a high-molecular template agent in an ethanol solution, adjust the pH value to 1 to 2, stir uniformly, add a transition metal oxide organic precursor, stir into a gel, dry, and calcine to obtain a transition metal oxide carrier material with a mesoporous structure; 2) Load water-soluble salts of three metals on the transition metal oxide carrier material with a mesoporous structure obtained in step 1) by an impregnation method, dry, and calcine to obtain a multi-metal loaded transition metal oxide catalyst; In step 1), the high-molecular template agent is a high-molecular pore-forming agent P123; the transition metal oxide organic precursor is isopropyl titanate; and the transition metal oxide carrier material with a mesoporous structure is mesoporous TiO2 with an anatase crystal structure; In step 1), the drying condition is to first dry at room temperature for 48 h and then dry at 110°C for 6 h; and the calcining condition is to calcine at 450°C for 4 h; In step 2), the drying condition is to dry at 110°C for 1 to 24 h; and the calcining condition is to heat at a heating rate of 1 to 20°C / min to 550°C, and calcine in an air atmosphere for 4 h; In step 2), the metals are Ir, Ga and Ce, the water-soluble salts of the metals are nitrate or chloride; and the impregnation method is an equal-volume impregnation method or an excess impregnation method.

2. Use of the multi-metal supported transition metal oxide catalyst according to claim 1 for the deoxygenation of bio-crude oil to produce renewable fuels, characterized in that, The reaction temperature is 300-450°C, the reaction pressure is 0.1-6 MPa, and the liquid hourly space velocity is 0.1-5 h -1 .

3. Use of the multi-metal supported transition metal oxide catalyst according to claim 1 for the deoxygenation of bio-crude oil to produce renewable fuels, characterized in that, The reactor is a batch reactor or a small fixed-bed reactor.

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