A catalyst for synthesis of olefin-rich distillate oil and a preparation method and application thereof

Abstract

The application discloses a catalyst for synthesizing gas into olefin-rich fraction oil and a preparation method and application thereof. The catalyst comprises a carrier and ruthenium elements, oxides of first metal elements and oxides of second metal elements supported on the carrier; the first metal elements are selected from alkali metals, and the second metal elements are selected from one or more of Mg, Ca, Sr, Ba, Zn, Cu, Cr, Ce, La, Pr and Sm; the content of the ruthenium elements is 0.5-5 wt% based on the total mass of the ruthenium elements, the oxides of the first metal elements and the oxides of the second metal elements and the carrier, the content of the first alkali metal is 0.01-2 wt%, and the content of the oxides of the second metal elements is 0.01-5 wt%. The catalyst provided by the application has excellent catalytic activity when used for synthesizing gas into olefin-rich fraction oil, has the advantages of high CO conversion rate, low selectivity of by-products (such as CO2) and high olefin selectivity, and the obtained olefin has a high proportion of long-chain olefins. Therefore, the catalyst of the application has wide application prospect and economic value.

Description

Technical Field

[0001] This invention relates to the field of syngas conversion technology, and in particular to a catalyst for producing olefin-rich distillate oil from syngas, its preparation method, and its application. Background Technology

[0002] Traditional Fischer-Tropsch synthesis produces a wide range of products with low target selectivity, and generates a large amount of CO2, resulting in significant carbon resource waste. Meanwhile, the demand for olefins, a core raw material in the chemical industry, is surging, with import dependence on high-end olefins exceeding 50%, necessitating non-petroleum-based alternatives. Developing technology to directly produce high-olefin-content distillate oils from syngas can alter the structure of traditional syngas products, focusing on high-value-added olefins while producing diesel and jet fuel distillates as byproducts. This achieves the dual benefits of "fuel safety net and enhanced chemical efficiency," aligning with the current development needs of the chemical and energy sectors for "diversified raw materials and high-end products."

[0003] However, existing catalytic systems primarily yield saturated alkanes as products, with limited selectivity for olefins. Over the past decade, the direct synthesis of olefins from syngas has attracted significant attention and achieved landmark breakthroughs. Key research pathways include the metal oxide-zeolite bifunctional (OX-ZEO) pathway and the Fischer-Tropsch (FTO) pathway utilizing metal carbides or metals. Notably, metal carbide catalysts in both the OX-ZEO and FTO pathways exhibit high water-gas shift (WGS) activity, generating substantial amounts of carbon dioxide, thus reducing carbon utilization efficiency and olefin yield. Conversely, metal catalysts in the FTO pathway exhibit even lower intrinsic WGS activity. Cobalt-based catalysts modified with co-catalysts have failed to achieve olefin selectivity exceeding 60% when catalyzing syngas, while Ru catalysts, with co-catalyst modification or under specific localized conditions, have demonstrated the potential for syngas-to-olefin production, achieving ultra-high olefin selectivity (~80%).

[0004] However, the high cost of ruthenium poses a significant challenge to its industrial application, and its CO catalytic activity and olefin yield per unit mass remain relatively low. Therefore, reducing ruthenium loading and improving its atom utilization are key to developing more efficient catalysts. However, low ruthenium loading typically leads to smaller metal particle size, resulting in insufficient ruthenium active sites to meet the demands of CO hydrogenation, thus causing a significant decrease in catalytic activity. Furthermore, although alkali metal doping is a key strategy for regulating the reactivity of hydrogen species and inhibiting excessive hydrogenation of olefin products, this modification method is usually accompanied by a decrease in the intrinsic activity of FTO. Therefore, existing alkali metal-promoted low-loaded ruthenium-based catalysts generally suffer from low activity.

[0005] Introducing single atoms (such as iridium, ruthenium, and zirconium) into metal nanoparticles to construct single-atom alloys or to prepare metal-metal oxide interfaces has been proven to be an effective strategy for enhancing the activity of Fischer-Tropsch synthesis of saturated alkanes. For example, by forming a Ru1Zr1-Co alloy interface, the intrinsic activity of cobalt metal catalysts was increased by 4.8 times, and the carbon chain growth capability was increased from 0.46 to 0.78 (Journal of the American Chemical Society, 2023, 145, 7113); the preparation of graphene-confined Ru1Con single-atom alloy catalysts significantly improved the Fischer-Tropsch activity of cobalt metal catalysts by forming a highly stable hexagonal close-packed (HCP) cobalt phase (Applied Catalysis B: Environment and Energy, 2026, 383, 126146); after introducing zirconium oxide into ruthenium nanoparticles to form Ru-Zr-OH active centers, the hydrogen-assisted CO dissociation pathway changed from the HCO intermediate pathway to the COH* intermediate pathway, significantly reducing the energy barrier of the CO dissociation step (Nature Communications, 2024, 15, 5143).

[0006] However, for reactions involving the conversion of syngas to produce high-olefin-rich distillate oils, the products are mainly long-chain α-olefins, with C42 as a byproduct. 5+ With limited hydrocarbon oils available, achieving highly active and selective catalytic synthesis of olefin-rich distillate oils with low Ru loading remains a significant challenge. Summary of the Invention

[0007] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide a catalyst for producing olefin-rich distillate oil from syngas, its preparation method and application, in order to solve the problems in the prior art.

[0008] To achieve the above and other related objectives, the present invention is obtained through the following technical solution.

[0009] A first aspect of the present invention provides a catalyst for producing olefin-rich distillate oil from syngas, the catalyst comprising a support and an oxide of a first metal element and an oxide of a second metal element supported on the support; the first metal element is selected from alkali metals, and the second metal element is selected from one or more of Mg, Ca, Sr, Ba, Zn, Cu, Cr, Ce, La, Pr and Sm.

[0010] Based on the total mass of ruthenium, the oxide of the first metal element, the oxide of the second metal element, and the carrier, the content of ruthenium is 0.5-5 wt%, the content of the first metal element is 0.01-2 wt%, and the content of the oxide of the second metal element is 0.01-5 wt%.

[0011] The catalyst of the present invention forms an interfacial structure between metal Ru and metal oxide, and under the synergistic effect of the oxide of the first metal element and the oxide of the second metal, it catalyzes the synthesis of syngas via the Fytor pathway to directly produce high olefin-rich distillate oil.

[0012] In some embodiments, the content of ruthenium can be 0.5~1.5 wt%, 1~3.5 wt%, 2~5 wt%, or 0.5 wt%, 1 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt%; the content of the first metal element can be 0.01~0.15 wt%, 0.1~1.5 wt%, 1~2 wt%, or 0.01 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%; the content of the oxide of the second metal element can be 0.01~0.15 wt%, 0.1~1.5 wt%, 1~5 wt%, or 0.01 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 2 wt%, 2.4 wt%, 3 wt%. wt%, 3.5wt%, 4wt%, 5wt%.

[0013] In some embodiments, the carrier is formed from columnar particles.

[0014] In some embodiments, the carrier is selected from one or more of SiO2, Al2O3 and TiO2.

[0015] In some embodiments, the diameter of the columnar particles is 1-2 mm. For example, the diameter can be 1-1.5 mm or 1.5-2 mm.

[0016] In some embodiments, the length of the columnar particles is 2 to 6 mm. For example, the length can be 2 mm, 3 mm, 4 mm, 5 mm, or 6 mm.

[0017] In some embodiments, the specific surface area of ​​the oxide support is 100~400 m². 2 / g, with a pore size of 5~30nm.

[0018] In some embodiments, the alkali metal element is selected from one or more of sodium (Na), potassium (K), cesium (Cs), and rubidium (Rb).

[0019] In some embodiments, the alkali metal element is a two-to-two combination of Na, K, Cs and Rb, such as Na and K, Na and Cs, Na and Rb, K and Cs, K and Rb, Cs and Rb; it can also be a three-to-three combination of Na, K, Cs and Rb, such as Na, K and Cs, Na, K and Rb, K, Cs and Rb; or it can be a combination formed by Na, K, Cs and Rb.

[0020] In some embodiments, the oxide of the second metal element is selected from one or more of the oxides of alkaline earth metals, oxides of transition metals, and oxides of lanthanides (excluding Ru).

[0021] In some embodiments, the alkaline earth metal element in the oxide of the alkaline earth metal element is selected from one or more of magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba).

[0022] In some embodiments, the transition metal element in the oxide of the transition metal element is selected from one or more of zinc (Zn), copper (Cu), and chromium (Cr).

[0023] In some embodiments, the lanthanide metal element in the oxide of the lanthanide metal element is selected from one or more of cerium (Ce), lanthanum (La), praseodymium (Pr) and samarium (Sm).

[0024] In some specific embodiments, the oxide of the second metal element is a combination of two of the following: oxides of alkaline earth metals, oxides of transition metals, and oxides of lanthanides. For example, it can be an oxide of alkaline earth metals and an oxide of transition metals, an oxide of transition metals and an oxide of lanthanides, or an oxide of alkaline earth metals and an oxide of lanthanides. Specifically, it can be CaO and Cr2O3, ZnO and CeO2, CaO and Cr2O3, or MgO and CeO2. Alternatively, it can be a combination of all three, specifically BaO, CuO, and CeO2.

[0025] In some embodiments, the catalyst has an average particle size of 2-4 nm.

[0026] A second aspect of the present invention provides a method for preparing the catalyst as described above, comprising the following steps:

[0027] 1) The ruthenium-based salt, surfactant, and support undergo a hydrothermal reaction in the first solvent to obtain a ruthenium-based catalyst; the salts corresponding to the first and second metal elements dissolve in the second solvent to form a mixed solution.

[0028] 2) The ruthenium-based catalyst is impregnated in the mixed solution, dried, and calcined to obtain the catalyst.

[0029] The ruthenium-based catalyst of this invention is a ruthenium-based catalyst. Currently, the preparation methods for ruthenium-based catalysts include the traditional impregnation method, which is simple to operate. The traditional impregnation method involves dissolving the salt corresponding to ruthenium in water or an organic solvent, then impregnating the support, followed by drying, calcination, and reduction. The applicant has discovered that the catalyst obtained by using the impregnation method to support ruthenium, an oxide of a first metal element, and an oxide of a second metal element on a support has a wider particle size distribution with a deviation of about 30%, and also a larger particle size, resulting in a lower exposed active surface area. When used for catalytic synthesis gas, the proportion of C1-C4 alkanes is approximately 19.8%, and C... 2+ The selectivity for olefins is approximately 62.6%, C 5+ The selectivity for olefins is approximately 30.9%, C 5+ The selectivity for alkanes is approximately 17.6%, C 2+ Olefins and C 5+ The selectivity for alkanes is approximately 80.2%. However, the ruthenium-based catalyst prepared by hydrothermal reaction has a C1... 2+ olefin selectivity >65%, C 5+ olefin selectivity >40%, C 2+ Olefins and C 5+ Alkane selectivity > 85%.

[0030] In some embodiments, the salt corresponding to the first metal element is selected from one or more of nitrates, sulfates, chlorides, carbonates, and acetates. For example, sodium nitrate, potassium nitrate, cesium nitrate, rubidium nitrate; sodium sulfate, potassium sulfate, cesium sulfate, rubidium sulfate; sodium chloride, potassium chloride, cesium chloride, rubidium chloride; sodium carbonate, potassium carbonate, cesium carbonate, rubidium carbonate; sodium acetate, potassium acetate, cesium acetate, rubidium acetate, etc.

[0031] In some embodiments, the salt corresponding to the second metal element is selected from one or more of nitrates, sulfates, chlorides, carbonates, and acetates. For example, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate; magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate; magnesium chloride, calcium chloride, strontium chloride, barium chloride; magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate; magnesium acetate, calcium acetate, strontium acetate, barium acetate, etc. Alternatively, it can be zinc nitrate, copper nitrate, chromium nitrate; zinc sulfate, copper sulfate, chromium sulfate; zinc chloride, copper chloride, chromium chloride; zinc carbonate, copper carbonate, chromium carbonate; zinc acetate, copper acetate, chromium acetate, etc. For example, it can also be cerium nitrate, lanthanum nitrate, praseodymium nitrate, samarium nitrate; cerium sulfate, lanthanum sulfate, praseodymium sulfate, samarium sulfate; magnesium chloride, lanthanum chloride, praseodymium chloride, samarium chloride; cerium carbonate, lanthanum carbonate, praseodymium carbonate, samarium carbonate; cerium acetate, lanthanum acetate, praseodymium acetate, samarium acetate, etc.

[0032] In some embodiments, the salt corresponding to the ruthenium element is selected from one or more of ruthenium nitrite (Ru(NO)(NO3)3), ruthenium chloride (RuCl3), and ruthenium acetate (Ru2(OAc)4Cl).

[0033] In some embodiments, the surfactant is selected from one or more of polyvinylpyrrolidone (PVP), vinylpyrrolidone (NVP), polyethylene glycol (PEG), chitosan, citric acid, polyvinyl alcohol (PVA), and ethylenediamine.

[0034] In some embodiments, the number-average molecular weight of the polyvinylpyrrolidone is 8000~80000 g / mol. For example, it can be 8000~40000 g / mol or 40000~80000 g / mol.

[0035] In some embodiments, the number-average molecular weight of the polyethylene glycol is 500-2000 g / mol. For example, it can be 500-1000 g / mol or 1000-2000 g / mol.

[0036] In some embodiments, the number-average molecular weight of the polyvinyl alcohol is 5000~80000 g / mol. For example, it can be 5000~10000 g / mol or 10000~80000 g / mol. All number-average components in this invention are obtained using GPC (Geometric Profiling).

[0037] In some embodiments, the mass ratio of ruthenium to surfactant is (1~280):1, or it can be (1~150):1, (120~220):1, (200~280):1, or 1:1, 50:1, 80:1, 100:1, 120:1, 140:1, 160:1, 180:1, 200:1, 220:1, 240:1, 260:1, or 280:1.

[0038] In some embodiments, the first solvent and the second solvent are independently selected from water, N,N-dimethylformamide (DMF), ethylene glycol (EG), and glycerol. Preferably, the first solvent is selected from water, and the second solvent is selected from water.

[0039] In some embodiments, in step 1), the temperature of the hydrothermal reaction is 50~80℃, or it can be 50℃, 52℃, 55℃, 58℃, 60℃, 64℃, 66℃, 68℃, 70℃, 72℃, 76℃, 78℃, or 80℃.

[0040] In some embodiments, in step 1), the hydrothermal reaction time is 1 to 24 h, or it can be 1 h, 4 h, 6 h, 8 h, 12 h, 16 h, 18 h, 20 h, 22 h, or 24 h.

[0041] In some implementations, in step 2), the soaking time is 1-48 h, or it can be 1 h, 4 h, 6 h, 8 h, 12 h, 16 h, 18 h, 20 h, 22 h, 24 h, 26 h, 28 h, 30, 32 h, 36 h, 38 h, 40 h, 44 h, or 48 h.

[0042] In some embodiments, in step 2), the immersion temperature is 20-30°C, or it can be 20°C, 22°C, 25°C, 28°C, or 30°C.

[0043] In some embodiments, in step 2), the calcination temperature is 300~600 ℃, or it can be 300 ℃, 350 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, or 600 ℃.

[0044] In some embodiments, the calcination time in step 2) is 2 to 24 hours, or it can be 2 hours, 4 hours, 6 hours, 8 hours, 12 hours, 16 hours, 18 hours, 20 hours, 22 hours, or 24 hours.

[0045] In some embodiments, the average particle size D of the catalyst 50 The wavelength range is 2.0-4 nm, or 2.9-3.5 nm; the relative standard deviation (RSD) is ≤10%.

[0046] A third aspect of the present invention provides the application of the catalyst described above in the production of olefin-rich distillate oil from catalytic syngas.

[0047] In some embodiments, prior to catalysis, the catalyst is further subjected to a reduction treatment in a reducing atmosphere.

[0048] In some embodiments, the reducing atmosphere comprises H2.

[0049] In some embodiments, the reducing atmosphere further includes a dilution gas selected from one or more of N2, Ar, and He.

[0050] In some specific implementations, the proportion of H2 is 10-100% v / v, based on the total volume of the reducing atmosphere.

[0051] In some embodiments, the temperature of the reduction treatment is 300~600℃, or it can be 300℃, 350℃, 380℃, 400℃, 420℃, 440℃, 460℃, 500℃, 520℃, 540℃, 560℃, 580℃, or 600℃.

[0052] In some embodiments, the reduction process takes 2 to 24 hours, or it can take 2 hours, 4 hours, 6 hours, 8 hours, 12 hours, 16 hours, 18 hours, 20 hours, 22 hours, or 24 hours.

[0053] In some embodiments, the volume hourly space velocity of the reducing atmosphere is 1000~10000 h⁻¹. -1 It can also be 1000h -1 2000 h -1 4000 h -1 6000 h -1 8000 h -1 10000 h -1 .

[0054] In some embodiments, when the catalyst catalyzes the synthesis of olefins from syngas, C 2+ The selectivity of olefins is >65%, such as 68%, 70%, 72%, 75%, 78%, 80%; C 5+ The selectivity of olefins is >40%, such as 42%, 45%, 50%, 55%, 60%, 65%; C 2+ Olefins and C 5+ The sum of selectivity for alkanes exceeds 85%, such as 86%, 88%, 90%, 92%, 95%, and 96%; and the selectivity for CO2 is <3.1%, such as 3.0%, 2.8%, 2.6%, 2.4%, 2.3%, 2.0%, 1.8%, 1.6%, 1.4%, and 1.1%. 2+ Alkenes are alkenes containing two or more carbon atoms, such as alkenes containing 2-7 carbon atoms.

[0055] A fourth aspect of the present invention provides a method for producing olefin-rich distillate oil from syngas, using a catalyst as described above to catalyze the syngas.

[0056] In some embodiments, the synthesis gas comprises H2 and CO, and the molar ratio of H2 to CO is (0.2~3):1.

[0057] In some embodiments, the catalytic temperature is 240~300℃, or it can be 300℃, 350℃, 380℃, 400℃, 420℃, 440℃, 460℃, 500℃, 520℃, 540℃, 560℃, 580℃, or 600℃.

[0058] In some embodiments, the catalytic pressure is 0.1~5 MPa, or it can be 0.1 MPa, 0.5 MPa, 1 MPa, 1.2 MPa, 1.5 MPa, 1.8 MPa, 2 MPa, 2.5 MPa, 3 MPa, 3.5 MPa, 4 MPa, 4.5 MPa, or 5 MPa.

[0059] In some embodiments, the catalytic time is not less than 12 hours, but can also be 16 hours, 18 hours, 20 hours, 22 hours, or 24 hours.

[0060] In some embodiments, the volume hourly space velocity of the synthesis gas is 500 to 10000 h⁻¹. -1 It can also be 500 h -1 800 h -1 1000 h -1 2000 h -1 4000 h -1 6000 h -1 8000 h -1 10000 h -1 .

[0061] Unless otherwise specified in this invention, distillate oil refers to components of gasoline and aviation kerosene. Preferably, it is gasoline.

[0062] Therefore, the catalyst for producing olefin-rich distillate oil from syngas, its preparation method, and its application, as described in this invention, have the following beneficial effects:

[0063] 1) In the catalyst of the present invention, the noble metal Ru exists in the form of nanoparticles, and its content is reduced to less than 5 wt%. The Ru nanoparticles form an interface structure with the oxides of the first metal element and the oxides of the second metal element, generating unique active sites: the Ru nanoparticles provide adsorption and activation sites for the synthesis gas H2 and CO, while the oxides of the first metal element and the oxides of the second metal element act as promoters, not only providing electrons to the Ru active center, weakening the CO bond during adsorption, and strengthening its dissociation and adsorption of CO, but also serving as a fast transfer channel for the dissociation of H by Ru, generating highly active H* (H* represents the active species formed after the dissociation of H2) at the Ru-second metal element oxide interface site, promoting the H-assisted CO dissociation process.

[0064] 2) This invention utilizes a hydrothermal synthesis method to ensure that the dispersion of Ru nanoparticles is not limited by the loading amount (even with a Ru loading as low as 0.5 wt%, they can still be uniformly distributed), and the relative standard deviation (RSD) of the catalyst particle size uniformity is ≤10%. This overcomes the trade-off between activity and selectivity in existing Ru-based catalysts, exhibiting higher catalytic activity in the reaction of syngas composed of H2 and CO into olefins, an important chemical raw material, while simultaneously producing distillate oils rich in olefin components.

[0065] 3) The catalyst of this invention further exhibits high olefin selectivity due to the catalytic effects of the first metal element (alkali metal element) and the second metal element. Specifically, it enables the selective formation of more olefins, especially long-chain olefins (referring to olefins containing 5 or more carbon atoms), and has a higher C... 5+ The selectivity for olefins is >40%. In contrast, existing iron-based catalysts exhibit high selectivity for alkanes but less than 40% selectivity for long-chain olefins. It is well known to those skilled in the art that catalysts with high selectivity for long-chain olefin products have greater application value, as olefins, especially long-chain olefins, have high added value and are widely used in various fields.

[0066] 4) Compared to methods using a single active metal to catalyze the synthesis of olefins from syngas, the catalyst of this invention can obtain highly selective long-chain olefin distillate products during syngas production, effectively reducing separation costs and improving economic efficiency. Simultaneously, this catalyst enables the efficient utilization of the precious metal Ru, significantly reducing catalyst costs. Therefore, the catalyst of this invention combines high selectivity and low cost in the syngas-to-olefins reaction, possessing greater commercial value.

[0067] 5) Traditional catalytic systems (such as carbide systems like iron carbide and cobalt carbide) suffer from high CO2 selectivity (20-50%) in the catalytic synthesis of olefins from syngas, resulting in low carbon atom utilization. The catalyst of this invention exhibits extremely low CO2 selectivity (below 3.1%). This is because a metal oxide-Ru interfacial active structure is formed during the reaction, enabling the high-selectivity production of highly olefin-rich distillate oil while maintaining extremely low CO2 selectivity.

[0068] 6) The catalyst preparation method of this invention is simple, easy to repeat, and can stably obtain products with consistent quality and performance, meeting the needs of large-scale stable industrial production. This effectively solves the problems of complex and poor reproducibility of traditional catalyst preparation methods, ensuring the stability of catalyst quality.

[0069] 7) The catalyst of this invention can still maintain a CO conversion rate of 50-60% after 199 hours of operation; the CO2 selectivity remains below 3.1%; C 2+The selectivity for olefins is maintained between 65-80%, and the selectivity for olefin-containing distillate oils is maintained between 85-96%. This significantly reduces the time, manpower, and material costs incurred due to frequent catalyst changes during continuous large-scale industrial production. Attached Figure Description

[0070] Figure 1 XRD characterization of the catalyst of Example 1 of the present invention.

[0071] Figure 2 This is a STEM-Mapping line scan characterization image of the catalyst in Example 1 of the present invention.

[0072] Figure 3 The TEM image and particle size statistics of the catalyst in Example 1 of the present invention are shown.

[0073] Figure 4 The TEM image and particle size statistics of the catalyst in Comparative Example 5 of the present invention are shown.

[0074] Figure 5 This is a stability test diagram of the catalyst in Example 1 of the present invention during long-term operation.

[0075] Figure 6 XPS characterization of the catalyst in Example 1 of this invention. Detailed Implementation

[0076] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification.

[0077] Before further describing specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terminology used in the embodiments of the present invention is for describing specific embodiments and not for limiting the scope of protection of the present invention. Test methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or as recommended by the respective manufacturers.

[0078] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, apparatus, and materials used in the embodiments, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description of this invention, any prior art methods, apparatus, and materials similar to or equivalent to those described, apparatus, and materials in the embodiments of this invention may be used to implement the present invention.

[0079] In the following embodiments and comparative examples of this application, the saturated adsorption capacity of SiO2 per unit mass is 2 g, and the diameter of its columnar particles is 1.5 mm, the length is 2-5 mm, and the specific surface area is 10-500 m². 2 ·g -1 The pore size is 2~20 nm; the saturated adsorption capacity of Al2O3 per unit mass is 1.2 g, and its columnar particles have a diameter of 2 mm, a length of 3~6 mm, and a specific surface area of ​​5~300 m². 2 ·g -1 The pore size is 2–15 nm; the saturated adsorption capacity of TiO2 per unit mass is 0.6 g, and its columnar particles have a diameter of 1.5 mm, a length of 2–5 mm, and a specific surface area of ​​10–600 m². 2 ·g -1 The pore size is 1~20 nm; the saturated adsorption capacity of ZrO2 per unit mass is 0.5 g, and its columnar particles have a diameter of 1.5 mm, a length of 2~5 mm, and a specific surface area of ​​5~200 m². 2 ·g, with a pore size of 1~10 nm.

[0080] In this application, vernier calipers are used to measure the diameter and length of the columnar particles; mercury porosimetry is used to measure the specific surface area and pore size of the oxide carrier.

[0081] In the following embodiments of this application, the CAS number of ruthenium nitrite is 34513-98-9, and the molecular formula is Ru(NO)(NO3)3 or N4O. 10 Ru.

[0082] Example 1

[0083] This embodiment 1 provides a catalyst for producing olefin-rich distillate oil from syngas and its preparation method.

[0084] Catalyst: Ruthenium (Ru), alkali metal (Na) and metal oxide (CeO2) are supported on SiO2. Based on the total mass of Ruthenium (Ru), alkali metal (Na), metal oxide (CeO2) and support SiO2, the content of Ruthenium (Ru) is 1 wt%, the content of Na is 0.2 wt%, and the content of CeO2 is 0.2 wt%.

[0085] The general formula for the catalyst is 0.2Na-1Ru-0.2CeO2 / SiO2.

[0086] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0087] 1-1) Weigh 0.314 g of the salt corresponding to ruthenium (the salt corresponding to ruthenium, the same below), 18.000 g of surfactant, and 9.860 g of carrier SiO2, dissolve them in 200 g of the first solvent to form a suspension, and then react them in a hydrothermal reactor at 50 °C for 3 h. Afterwards, dry them by vacuum rotary evaporation to obtain the precipitate, which is the ruthenium-based catalyst.

[0088] The salt corresponding to ruthenium is N4O. 10 Ru; the surfactants are PVP and ethylenediamine, with a mass ratio of PVP to ethylenediamine of 8:10; the first solvent is deionized water.

[0089] 1-2) Dissolve 0.074 g of the salt corresponding to the alkali metal element (the salt corresponding to the first metal element, the same below) and 0.062 g of the salt corresponding to the metal oxide (the salt corresponding to the second metal element, the same below) in 15 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst obtained in step 1) and impregnate at room temperature (25°C) for 24 h. Then dry in an oven at 120 °C for 12 h and calcine in air in a muffle furnace at 400 °C for 3 h to obtain the catalyst.

[0090] The salt corresponding to the alkali metal element is NaNO3; the salt corresponding to the metal oxide is Ce(NO3)3·6H2O; and the second solvent is deionized water.

[0091] The method for using this catalyst to catalyze the production of olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0092] 2-1) Reduction treatment

[0093] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0094] The conditions for the reduction treatment were: a pure H2 atmosphere and a reduction space velocity of 6000 h⁻¹. -1 The reduction temperature was 450 °C, the reduction pressure was atmospheric pressure, and the reduction time was 4 h. After the reduction was completed, the reaction was switched to syngas.

[0095] 2-2) Syngas is introduced to carry out the conversion reaction.

[0096] Syngas is introduced into a fixed bed to carry out the conversion reaction.

[0097] The conditions for the conversion reaction are: the syngas is a mixture of H2 and CO, with a molar ratio of H2 to CO of 2:1; and the volume hourly space velocity (VHSV) is 2000 h⁻¹. -1 The reaction temperature was 270 ℃, the reaction pressure was 1.5 MPa, and the reaction time was 48 h.

[0098] After the reaction was completed, multiple gas chromatographs (Agilent 8860, divided into tail gas, oil phase and wax phase, with different peak times for different products) were used to analyze the types and contents of various components contained in the products, and the conversion rate of CO and the selectivity of the catalyst to the products were calculated accordingly. The specific results are shown in Table 1.

[0099] The specific analysis method is as follows:

[0100] Gas phase products were analyzed using a KCl-modified Al2O3 capillary column (Agilent 19095P-K25 model column) and a flame ionization detector (FID) to identify hydrocarbons with 1 to 7 carbon atoms (C1 to C7).

[0101] Aqueous and liquid oil phase products were collected from the cold trap, and solid wax phase products were collected from the hot trap. Each phase product was analyzed offline using gas chromatography.

[0102] Oil phase products were analyzed by FID using an HP-1 column with N2 as the carrier gas.

[0103] After the wax phase products were dissolved in carbon disulfide (CS2), they were analyzed by FID using an MXT-1 column with N2 as the carrier gas. The mass of C1-C4 alkanes in the aqueous, oil, and wax phase products was summed and divided by the mass of the total product to obtain the C1-C4 alkanes selectivity; other C4 alkanes were analyzed by FID. 2+ Olefins, C 5+ Alkanes are similar.

[0104] The formula for calculating the CO conversion rate is: (Molar concentration of CO in the reactor inlet gas - Molar concentration of CO in the reactor outlet gas) / Molar concentration of CO in the reactor inlet gas. The final data were obtained through analysis.

[0105] XRD (Rigaku Ultima IV, manufactured by Rigaku Corporation), HAADF-STEM-Mapping (JEOL JEM-F200 transmission electron microscope), and HR-TEM particle size distribution of the catalyst are shown in the figures below. Figure 1 , 2 And 3.

[0106] from Figure 1 As can be seen from the X-ray diffraction (XRD) analysis, the catalyst after 48 hours of catalytic synthesis was mainly composed of hexagonal ruthenium phase (☆ in the figure represents hcp-Ru, i.e., hexagonal close-packed metallic ruthenium). No phases of oxides of alkali metals and second metal elements were observed, indicating that the supported oxides of alkali metals and second metal elements did not agglomerate, proving that the dispersion was good.

[0107] from Figure 2 As can be seen, the elemental energy scattering (Mapping) diagrams obtained by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) show that Ce is uniformly dispersed around Ru nanoparticles in the hydrothermal and impregnated catalyst.

[0108] from Figure 3 It can be seen that in the catalyst obtained by hydrothermal synthesis in the preparation method of the present invention, Ru nanoparticles are relatively uniformly distributed on the support, and the relative standard deviation of particle size uniformity is within 10%.

[0109] The catalyst after the reaction was characterized by XPS using a Thermo Scientific KAlpha spectrometer equipped with an Al Kα radiation source (photon energy hv = 1486 eV). The results are shown in [Figure number missing]. Figure 6 .

[0110] from Figure 6 The X-ray photoelectron spectroscopy (XPS) analysis of the Ru 3d energy region indicates that its Ru 3d 5 / 2 The binding energy of Ru is located at 280.8 eV, but shifts to 279.9 eV due to the electron transfer effect between Na and CeO2. Ru mainly exists in the metallic state (Ru...). 0 The Ru nanoparticles existed in the form of +3 and +4 oxidation states, and no obvious characteristic peak of Ru oxidation state (>281.5 eV) was detected, indicating that the Ru nanoparticles did not undergo significant oxidation on the catalyst surface and maintained good metallic characteristics, which is beneficial to their adsorption and activation of CO and H2. Ce existed in the +3 and +4 oxidation states, and Na existed in the +1 oxidation state.

[0111] Example 2

[0112] Example 2 provides a catalyst for producing olefin-rich distillate oil from syngas and its preparation method.

[0113] Catalyst: Ruthenium (Ru), Na (Na), and La2O3 (La2O3) are supported on Al2O3. Based on the total mass of Ruthenium (Ru), Na (Na), La2O3, and Al2O3, the content of Ruthenium (Ru) is 0.5 wt%, the content of Na (Na) is 2 wt%, and the content of La2O3 (La2O3) is 2 wt%.

[0114] The general formula for the catalyst is 2Na-0.5Ru-2La2O3 / Al2O3.

[0115] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0116] 1-1) Weigh 0.103 g of the salt corresponding to ruthenium, 14.000 g of surfactant, and 9.550 g of support Al2O3, dissolve them in 200 g of the first solvent to form a suspension, and then react them in a hydrothermal reactor at 80 °C for 24 h. The precipitate, i.e., the ruthenium-based catalyst, is obtained by vacuum rotary evaporation.

[0117] The salt corresponding to ruthenium is RuCl3; the surfactants are NVP and polyethylene glycol, with a mass ratio of NVP to ethylene glycol of 6:8; and the first solvent is deionized water.

[0118] 1-2) Dissolve 0.508 g of the salt corresponding to the alkali metal element and 0.623 g of the salt corresponding to the metal oxide in 10 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst obtained in step 1) and impregnate at room temperature (25°C) for 24 h. Then dry in an oven at 120 °C for 12 h and calcine in air in a muffle furnace at 600 °C for 24 h to obtain the catalyst.

[0119] The salt corresponding to the alkali metal element is NaCl; the salt corresponding to the metal oxide is La(NO3)3·6H2O; and the second solvent is deionized water.

[0120] The method for using this catalyst to catalyze the production of olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0121] 2-1) Reduction treatment

[0122] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0123] The conditions for the reduction treatment were: a reducing atmosphere of H2 and N2, wherein the volume ratio of H2 was 10%; and a reduction space velocity of 6000 h⁻¹. -1 The reduction temperature was 500 °C, the reduction pressure was atmospheric pressure, and the time was 2 h. After the reduction was completed, the reaction was switched to syngas.

[0124] 2-2) Syngas is introduced into a fixed bed to carry out the conversion reaction. The conditions for the conversion reaction are: the syngas is a mixture of H2 and CO, with a molar ratio of H2 to CO of 3:1; the volume hourly space velocity is 4000 h⁻¹. -1 The reaction temperature was 280 °C, the reaction pressure was 1 MPa, and the reaction time was 48 h.

[0125] After the reaction was completed, the CO conversion rate and the catalyst selectivity for the product were calculated using the same method as in Example 1. The specific results are shown in Table 1.

[0126] Example 3

[0127] This embodiment 3 provides a catalyst for producing olefin-rich distillate oil from syngas and its preparation method.

[0128] Catalysts: Ruthenium (Ru), Na (Na), and PrO (PrO) x (Where x is 1.5 to 2.0, and praseodymium exists in a mixed +3 and +4 valence state) is loaded onto the support TiO2; ruthenium (Ru), alkali metal (Na), and metal oxide (PrO) are also used. x Based on the total mass of TiO2 and its support, the content of ruthenium (Ru) is 3 wt%, the content of alkali metal (Na) is 0.01 wt%, and the content of metal oxide (PrO) is... x The content is 5wt%.

[0129] The general formula for the catalyst is 0.01Na-3Ru-5PrO. x / TiO2.

[0130] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0131] 1-1) Weigh 0.826 g of the salt corresponding to ruthenium, 19.000 g of surfactant, and 9.199 g of support TiO2, dissolve them in 200 g of the first solvent to form a suspension, and then react them in a hydrothermal reactor at 60 °C for 1 h. The precipitate, i.e., the ruthenium-based catalyst, is obtained by vacuum rotary evaporation.

[0132] The salt corresponding to ruthenium is Ru(OAc)3; the surfactants are PVA and chitosan, with a mass ratio of PVA to chitosan of 10:9; and the first solvent is deionized water.

[0133] 1-2) Dissolve 0.004 g of the salt corresponding to the alkali metal element and 1.555 g of the salt corresponding to the metal oxide in 5 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst from step 1) and impregnate at room temperature (25°C) for 24 h. Then dry in an oven at 120 °C for 12 h and calcine in air in a muffle furnace at 300 °C for 2 h to obtain the catalyst.

[0134] The salt corresponding to the alkali metal element is NaOAc; the salt corresponding to the metal oxide is Pr(NO3)3·6H2O; and the second solvent is deionized water.

[0135] The method for using this catalyst to catalyze the production of olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0136] 2-1) Reduction Process

[0137] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0138] The conditions for the reduction treatment were as follows: the reducing atmosphere was a mixture of H2 and He, with H2 accounting for 20% by volume; the reduction space velocity was 6000 h⁻¹. -1 The reduction temperature was 300 °C, the reduction pressure was atmospheric pressure, and the time was 2 h. After the reduction was completed, the reaction was switched to syngas.

[0139] 2-2) Syngas is introduced to carry out the conversion reaction.

[0140] Syngas is introduced into a fixed bed to carry out the conversion reaction.

[0141] The conditions for the conversion reaction are: the syngas is a mixture of H2 and CO, with a molar ratio of H2 to CO of 2:1; and the volume hourly space velocity (VHSV) is 5000 h⁻¹. -1 The reaction temperature was 300 ℃, the reaction pressure was 5 MPa, and the reaction time was 48 h.

[0142] After the reaction was completed, the CO conversion rate and the catalyst selectivity for the product were calculated using the same method as in Example 1. The specific results are shown in Table 1.

[0143] Example 4

[0144] Example 4 provides a catalyst for producing olefin-rich distillate oil from syngas and its preparation method.

[0145] Catalyst: Ruthenium (Ru), Na (Na), and SmO2 (SmO2) are supported on SiO2. Based on the total mass of Ruthenium (Ru), Na (Na), SmO2, and SiO2, the content of Ruthenium (Ru) is 1 wt%, the content of Na (Na) is 0.5 wt%, and the content of SmO2 (SmO2) is 5 wt%.

[0146] The general formula of the catalyst is 0.5Na-1Ru-5SmO2 / SiO2.

[0147] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0148] 1-1) Weigh 0.314 g of the salt corresponding to ruthenium, 14.000 g of surfactant, and 9.350 g of carrier SiO2, dissolve them in 200 g of the first solvent to form a suspension, and then react them in a hydrothermal reactor at 70 °C for 6 h. Afterward, dry the precipitate by vacuum rotary evaporation, which is the ruthenium-based catalyst.

[0149] The salt corresponding to ruthenium is N4O.10 Ru; the surfactants are PEG and citric acid, with a mass ratio of PEG to citric acid of 4:10; the first solvent is deionized water.

[0150] 1-2) Dissolve 0.185 g of the salt corresponding to the alkali metal element and 1.478 g of the salt corresponding to the metal oxide in 15 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst from step 1) and impregnate at room temperature (25 °C) for 24 h. Then dry in an oven at 120 °C for 12 h and calcine in air in a muffle furnace at 500 °C for 5 h to obtain the catalyst.

[0151] The salt corresponding to the alkali metal element is NaNO3; the salt corresponding to the metal oxide is Sm(NO3)3·6H2O; and the second solvent is deionized water.

[0152] The method for using this catalyst to directly produce olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0153] 2-1) Reduction Process

[0154] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0155] The conditions for the reduction treatment were as follows: the reducing atmosphere was a mixture of H2 and Ar, with H2 accounting for 30% by volume; the reduction space velocity was 6000 h⁻¹. -1 The reduction temperature was 500 °C, the reduction pressure was atmospheric pressure, and the time was 2 h. After the reduction was completed, the reaction was switched to syngas.

[0156] 2-2) Syngas is introduced to carry out the conversion reaction.

[0157] Syngas is introduced into a fixed bed to carry out the conversion reaction.

[0158] The conditions for the conversion reaction are: the syngas is a mixture of H2 and CO, with a molar ratio of H2 to CO of 2:1; and the volume hourly space velocity (VHSV) is 1000 h⁻¹. -1 The reaction temperature was 280 ℃, the reaction pressure was 2 MPa, and the reaction time was 48 h.

[0159] After the reaction was completed, the CO conversion rate and the catalyst selectivity for the product were calculated using the same method as in Example 1. The specific results are shown in Table 1.

[0160] Example 5

[0161] Example 5 provides a catalyst for producing olefin-rich distillate oil from syngas and its preparation method.

[0162] Catalyst: Ruthenium (Ru), alkali metal (K), and metal oxide (CeO2) are supported on Al2O3. Based on the total mass of Ruthenium (Ru), alkali metal (K), metal oxide (CeO2), and support Al2O3, the content of Ruthenium (Ru) is 2.5 wt%, the content of K is 1 wt%, and the content of CeO2 is 0.5 wt%.

[0163] The general formula for the catalyst is 1K-2.5Ru-0.5CeO2 / Al2O3.

[0164] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0165] 1-1) Weigh 0.514 g of the salt corresponding to ruthenium, 7.000 g of surfactant, and 9.600 g of support Al2O3, dissolve them in 200 g of the first solvent to form a suspension, and then react them in a hydrothermal reactor at 80 °C for 2 h. Afterward, dry the precipitate by vacuum rotary evaporation, which is the ruthenium-based catalyst.

[0166] The salt corresponding to ruthenium is RuCl3; the surfactant is NVP; and the first solvent is deionized water.

[0167] 1-2) Dissolve 0.191 g of the salt corresponding to the alkali metal element and 0.155 g of the salt corresponding to the metal oxide in 10 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst from step 1) and impregnate at room temperature (25°C) for 24 h. Then dry in an oven at 120 °C for 12 h and calcine in air in a muffle furnace at 350 °C for 3 h to obtain the catalyst.

[0168] The salt corresponding to the alkali metal element is KCl; the salt corresponding to the metal oxide is Ce(NO3)3·6H2O; and the second solvent is deionized water.

[0169] The method for using this catalyst to catalyze the production of olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0170] 2-1) Reduction Process

[0171] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0172] The conditions for the reduction treatment were: a reducing atmosphere of H2 and N2, wherein the volume ratio of H2 was 40%; and a reduction space velocity of 6000 h⁻¹. -1The reduction temperature was 350 °C, the reduction pressure was atmospheric pressure, and the time was 3 h. After the reduction was completed, the reaction was switched to syngas.

[0173] 2-2) Syngas is introduced into a fixed bed to carry out the conversion reaction.

[0174] The conditions for the conversion reaction are: the syngas is a mixture of H2 and CO, with a molar ratio of H2 to CO of 3:1; and the volume hourly space velocity (VHSV) is 10,000 h⁻¹. -1 The reaction temperature was 280 ℃, the reaction pressure was 2.5 MPa, and the reaction time was 48 h.

[0175] After the reaction was completed, the CO conversion rate and the catalyst selectivity for the product were calculated using the same method as in Example 1. The specific results are shown in Table 1.

[0176] Example 6

[0177] Example 6 provides a catalyst for producing olefin-rich distillate oil from syngas and its preparation method.

[0178] Catalyst: Ruthenium (Ru), alkali metal (K), and metal oxide (SrO) are supported on TiO2. Based on the total mass of Ruthenium (Ru), alkali metal (K), metal oxide (SrO), and support TiO2, the content of Ruthenium (Ru) is 5wt%, the content of K is 1.5wt%, and the content of SrO is 3wt%.

[0179] The general formula of the catalyst is 1.5K-5Ru-3SrO / TiO2.

[0180] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0181] 1-1) Weigh 1.569 g of the salt corresponding to ruthenium, 35.000 g of surfactant, and 9.050 g of support Al2O3, dissolve them in 200 g of the first solvent to form a suspension, and then react them in a hydrothermal reactor at 60 °C for 10 h. Afterward, dry the precipitate by vacuum rotary evaporation, which is the ruthenium-based catalyst.

[0182] The salt corresponding to ruthenium is N4O. 10 Ru; the surfactants are PVP and ethylenediamine, with a mass ratio of PVP to ethylenediamine of 20:15; the first solvent is deionized water.

[0183] 1-2) Dissolve 0.287 g of the salt corresponding to the alkali metal element and 1.094 g of the salt corresponding to the metal oxide in 5 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst from step 1) and impregnate at room temperature (25°C) for 24 h. Then dry in an oven at 120 °C for 12 h and calcine in air in a muffle furnace at 550 °C for 16 h to obtain the catalyst.

[0184] The salt corresponding to the alkali metal element is KCl; the salt corresponding to the metal oxide is Sr(NO3)2·6H2O; and the second solvent is deionized water.

[0185] The method for using this catalyst to directly produce olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0186] 2-1) Reduction treatment

[0187] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0188] The conditions for the reduction treatment were: a reducing atmosphere of H2 and N2, wherein the volume ratio of H2 was 70%; and a reduction space velocity of 6000 h⁻¹. -1 The reduction temperature was 600 °C, the reduction pressure was atmospheric pressure, and the reduction time was 5 h. After the reduction was completed, the reaction was switched to syngas.

[0189] 2-2) Syngas is introduced into a fixed bed to carry out the conversion reaction.

[0190] The conditions for the conversion reaction are: the syngas is a mixture of H2 and CO, with a molar ratio of H2 to CO of 2:1; and the volume hourly space velocity (VHSV) is 500 h⁻¹. -1 The reaction temperature was 240 ℃, the reaction pressure was 0.1 MPa, and the reaction time was 48 h.

[0191] After the reaction was completed, the CO conversion rate and the catalyst selectivity for the product were calculated using the same method as in Example 1. The specific results are shown in Table 1.

[0192] Example 7

[0193] Example 7 provides a catalyst for producing olefin-rich distillate oil from syngas and its preparation method.

[0194] Catalysts: Ruthenium (Ru), alkali metal Cs, and metal oxide PrO x Loaded on a SiO2 support; with ruthenium (Ru), alkali metal (Cs), and metal oxide (PrO) xBased on the total mass of SiO2 and its support, the content of ruthenium (Ru) is 1 wt%, the content of alkali metal (Cs) is 0.3 wt%, and the content of metal oxide (PrO) is... x The content is 1 wt%.

[0195] The general formula for the catalyst is 0.3Cs⁻¹Ru⁻¹PrO₂. x / SiO2.

[0196] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0197] 1-1) Weigh 0.275 g of the salt corresponding to ruthenium, 15.000 g of surfactant, and 9.770 g of support Al2O3, dissolve them in 200 g of the first solvent to form a suspension, and then react them in a hydrothermal reactor at 80 °C for 12 h. Afterward, dry the precipitate by vacuum rotary evaporation, which is the ruthenium-based catalyst.

[0198] The salt corresponding to ruthenium is Ru(OAc)3; the surfactants are PEG and chitosan, with a mass ratio of PEG to chitosan of 9:6; and the first solvent is glycerol.

[0199] 1-2) Dissolve 0.038 g of the salt corresponding to the alkali metal element and 0.311 g of the salt corresponding to the metal oxide in 15 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst from step 1) and impregnate at room temperature (25 °C) for 24 h. Then dry in an oven at 120 °C for 12 h and calcine in air in a muffle furnace at 480 °C for 18 h to obtain the catalyst.

[0200] The salt corresponding to the alkali metal element is CsCl; the salt corresponding to the metal oxide is Pr(NO3)3·6H2O; and the second solvent is deionized water.

[0201] The method for using this catalyst to catalyze the production of olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0202] 2-1) Reduction treatment

[0203] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0204] The conditions for the reduction treatment were: reducing atmosphere: H2; reducing space velocity: 6000 h⁻¹ -1 The reduction temperature was 550 °C, the reduction pressure was atmospheric pressure, and the reduction time was 8 h. After the reduction was completed, the reaction was switched to syngas.

[0205] 2-2) Syngas is introduced into a fixed bed to carry out the conversion reaction.

[0206] The conditions for the conversion reaction were: the syngas was a mixture of H2 and CO, with a molar ratio of H2 to CO of 1.5:1; and the volume hourly space velocity (VHSV) was 2000 h⁻¹. -1 The reaction temperature was 260 ℃, the reaction pressure was 1.5 MPa, and the reaction time was 48 h.

[0207] After the reaction was completed, the CO conversion rate and the catalyst selectivity for the product were calculated using the same method as in Example 1. The specific results are shown in Table 1.

[0208] Example 8

[0209] Example 8 provides a catalyst for producing olefin-rich distillate oil from syngas and its preparation method.

[0210] Catalyst: Ruthenium (Ru), Na (Na), and ZnO (ZnO) are supported on Al2O3. Based on the total mass of Ruthenium (Ru), Na (Na), ZnO (ZnO), and Al2O3, the content of Ruthenium (Ru) is 2wt%, the content of Na (Na) is 0.4wt%, and the content of ZnO (ZnO) is 4wt%.

[0211] The general formula for the catalyst is 0.4Na-2Ru-4ZnO / Al2O3.

[0212] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0213] 1-1) Weigh 0.410 g of the salt corresponding to ruthenium, 5.000 g of surfactant, and 9.360 g of support Al2O3, dissolve them in 200 g of the first solvent to prepare a suspension, and then react them in a hydrothermal reactor at 80 °C for 12 h. Afterward, dry the precipitate by vacuum rotary evaporation, which is the ruthenium-based catalyst.

[0214] The salt corresponding to ruthenium is RuCl3; the surfactants are PVA and citric acid, with a mass ratio of PVA to citric acid of 4:1; and the first solvent is deionized water.

[0215] 1-2) Dissolve 0.102 g of the salt corresponding to the alkali metal element and 1.822 g of the salt corresponding to the metal oxide in 10 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst from step 1) and impregnate at room temperature (25 °C) for 24 h. Then dry in an oven at 120 °C for 12 h and calcine in air in a muffle furnace at 420 °C for 14 h to obtain the catalyst.

[0216] The salt corresponding to the alkali metal element is NaCl; the salt corresponding to the metal oxide is Zn(NO3)2·6H2O; and the second solvent is deionized water.

[0217] The method for using this catalyst to catalyze the production of olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0218] 2-1) Reduction treatment

[0219] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0220] The reduction conditions were as follows: the reducing atmosphere was H2 and Ar, with a volume ratio of H2 of 10%; the reduction space velocity was 6000 h⁻¹. -1 The reduction temperature was 520 °C, the reduction pressure was atmospheric pressure, and the reduction time was 14 h. After the reduction was completed, the reaction was switched to syngas.

[0221] 2-2) Syngas is introduced into a fixed bed to carry out the conversion reaction.

[0222] The conditions for the conversion reaction are: the syngas is a mixture of H2 and CO, with a molar ratio of H2 to CO of 1:1; and the volume hourly space velocity (VHSV) is 3000 h⁻¹. -1 The reaction temperature was 270 °C, the reaction pressure was 1.5 MPa, and the reaction time was 48 h.

[0223] After the reaction was completed, the CO conversion rate and the catalyst selectivity for the product were calculated using the same method as in Example 1. The specific results are shown in Table 1.

[0224] Example 9

[0225] Example 9 provides a catalyst for producing olefin-rich distillate oil from syngas and its preparation method.

[0226] Catalyst: Ruthenium (Ru), alkali metals Na and K, and metal oxide La2O3 are supported on SiO2. Based on the total mass of Ruthenium (Ru), alkali metals Na and K, metal oxide La2O3, and support SiO2, the content of Ruthenium (Ru) is 2 wt%, the contents of alkali metals Na and K are 0.5 wt% and 0.5 wt%, respectively, and the content of metal oxide La2O3 is 0.8 wt%.

[0227] The general formula for the catalyst is 0.5Na0.5K-2Ru-0.8La2O3 / SiO2.

[0228] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0229] 1-1) Weigh 0.628 g of the salt corresponding to ruthenium, 53.000 g of surfactant, and 9.620 g of carrier SiO2, dissolve them in 200 g of the first solvent to prepare a suspension, and then react them in a hydrothermal reactor at 80 °C for 12 h. Afterward, dry the precipitate by vacuum rotary evaporation, which is the ruthenium-based catalyst.

[0230] The salt corresponding to ruthenium is N4O. 10 Ru; the surfactants are PVA and ethylenediamine, with a mass ratio of PVA to ethylenediamine of 12:11; the first solvent is deionized water.

[0231] 1-2) Dissolve 0.314 g of the salt corresponding to the alkali metal element and 0.249 g of the salt corresponding to the metal oxide in 15 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst from step 1) and impregnate at room temperature (25°C) for 24 h. Then dry in an oven at 120 °C for 12 h and calcine in air in a muffle furnace at 580 °C for 9 h to obtain the catalyst.

[0232] Among them, the salts corresponding to the alkali metal elements are NaNO3 and KNO3, with a mass ratio of NaNO3 to KNO3 of 0.185:0.129; the metal oxide is La(NO3)3·6H2O; and the second solvent is deionized water.

[0233] The method for using this catalyst to catalyze the production of olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0234] 2-1) Reduction Process

[0235] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0236] The reduction conditions were as follows: the reducing atmosphere was H2 and He, with a volume ratio of H2 of 10%; the reduction space velocity was 6000 h⁻¹. -1 The reduction temperature was 440 °C, the reduction pressure was atmospheric pressure, and the reduction time was 15 h. After the reduction was completed, the reaction was switched to syngas.

[0237] 2-2) Syngas is introduced into a fixed bed to carry out the conversion reaction.

[0238] The conditions for the conversion reaction are: the syngas is a mixture of H2 and CO, with a molar ratio of H2 to CO of 2:1; and the volume hourly space velocity (VHSV) is 6000 h⁻¹. -1 The reaction temperature was 270 ℃, the reaction pressure was 3.5 MPa, and the reaction time was 48 h.

[0239] After the reaction was completed, the CO conversion rate and the catalyst selectivity for the product were calculated using the same method as in Example 1. The specific results are shown in Table 1.

[0240] Example 10

[0241] Example 10 provides a catalyst for producing olefin-rich distillate oil from syngas and a method for preparing the same.

[0242] Catalyst: Ruthenium (Ru), alkali metal Na, and metal oxides ZnO and CeO2 are supported on TiO2. Based on the total mass of Ruthenium (Ru), alkali metal Na, metal oxides ZnO, CeO2, and TiO2, the content of Ruthenium (Ru) is 2 wt%, the content of Na is 0.2 wt%, and the contents of ZnO and CeO2 are 1 wt% and 4 wt%, respectively.

[0243] The general formula of the catalyst is 0.2Na-2Ru-1ZnO-4CeO2 / TiO2.

[0244] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0245] 1-1) Weigh 0.628 g of the salt corresponding to ruthenium, 23.000 g of surfactant, and 9.280 g of support TiO2, dissolve them in 200 g of the first solvent to form a suspension, and then react them in a hydrothermal reactor at 80 °C for 10 h. Afterward, dry the precipitate by vacuum rotary evaporation, which is the ruthenium-based catalyst.

[0246] The salt corresponding to ruthenium is N4O. 10 Ru; the surfactants are PVA and citric acid, with a mass ratio of PVA to citric acid of 12:11; the first solvent is deionized water.

[0247] 1-2) Dissolve 0.074 g of the salt corresponding to the alkali metal element and 1.314 g of the salt corresponding to the metal oxide in 5 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst from step 1) and impregnate at room temperature (25°C) for 24 h. Then dry in an oven at 120 °C for 12 h and calcine in air in a muffle furnace at 380 °C for 18 h to obtain the catalyst.

[0248] The salt corresponding to the alkali metal element is NaNO3; the salts corresponding to the metal oxides are Zn(NO3)2·6H2O and Ce(NO3)3·6H2O, wherein the mass ratio of Zn(NO3)2·6H2O to Ce(NO3)3·6H2O is 0.455:1.240; the second solvent is deionized water.

[0249] The method for using this catalyst to catalyze the production of olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0250] 2-1) Reduction treatment

[0251] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0252] The conditions for the reduction treatment were: reducing atmosphere: H2; reducing space velocity: 6000 h⁻¹ -1 The reduction temperature was 500 °C, the reduction pressure was atmospheric pressure, and the reduction time was 20 h. After the reduction was completed, the reaction was switched to syngas.

[0253] 2-2) Syngas is introduced into a fixed bed to carry out the conversion reaction.

[0254] The conditions for the conversion reaction are: the syngas is a mixture of H2 and CO, with a molar ratio of H2 to CO of 2:1; and the volume hourly space velocity (VHSV) is 3000 h⁻¹. -1 The reaction temperature was 280 ℃, the reaction pressure was 1.2 MPa, and the reaction time was 48 h.

[0255] After the reaction was completed, the CO conversion rate and the catalyst selectivity for the product were calculated using the same method as in Example 1. The specific results are shown in Table 1.

[0256] Example 11

[0257] This embodiment 11 provides a catalyst for producing olefin-rich distillate oil from syngas and a method for preparing the same.

[0258] Catalyst: Ruthenium (Ru), alkali metal (Rb), and metal oxides (CaO and Cr2O3) are supported on SiO2. Based on the total mass of Ruthenium (Ru), alkali metal (Rb), metal oxides (CaO and Cr2O3), and SiO2, the content of Ruthenium (Ru) is 0.5 wt%, the content of Rb is 1 wt%, and the contents of metal oxides (CaO and Cr2O3) are 0.5 wt% and 3 wt%, respectively.

[0259] The general formula of the catalyst is 1Rb-0.5Ru-0.5CaO-3Cr2O3 / SiO2.

[0260] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0261] 1-1) Weigh 0.103 g of the salt corresponding to ruthenium, 15.000 g of surfactant, and 9.500 g of carrier SiO2, dissolve them in 200 g of the first solvent to prepare a suspension, and then react them in a hydrothermal reactor at 70 °C for 5 h. Afterward, dry the precipitate by vacuum rotary evaporation, which is the ruthenium-based catalyst.

[0262] The salt corresponding to ruthenium is RuCl3; the surfactant is PVP; and the primary solvent is ethylene glycol.

[0263] 1-2) Dissolve 0.173 g of the salt corresponding to the alkali metal element and 1.435 g of the salt corresponding to the metal oxide in 15 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst from step 1) and impregnate at room temperature (25°C) for 24 h. Then dry in an oven at 120 °C for 12 h and calcine in air in a muffle furnace at 400 °C for 12 h to obtain the catalyst.

[0264] The salt corresponding to the alkali metal element is RbNO3; the metal oxides are Ca(NO3)2·4H2O and Cr(NO3)3·4H2O, with a mass ratio of 0.211:1.224; and the second solvent is deionized water.

[0265] The method for using this catalyst to catalyze the production of olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0266] 2-1) Reduction Process

[0267] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0268] The conditions for the reduction treatment were: reducing atmosphere: H2; reducing space velocity: 6000 h⁻¹ -1 The reduction temperature was 490 °C, the reduction pressure was atmospheric pressure, and the reduction time was 18 h. After the reduction was completed, the reaction was switched to syngas.

[0269] 2-2) Syngas is introduced into a fixed bed to carry out the conversion reaction.

[0270] The conditions for the conversion reaction are: the syngas is a mixture of H2 and CO, with a molar ratio of H2 to CO of 2:1; and the volume hourly space velocity (VHSV) is 4000 h⁻¹. -1 The reaction temperature was 270 °C, the reaction pressure was 1.3 MPa, and the reaction time was 48 h.

[0271] After the reaction was completed, the CO conversion rate and the catalyst selectivity for the product were calculated using the same method as in Example 1. The specific results are shown in Table 1.

[0272] Example 12

[0273] This embodiment 12 provides a catalyst for producing olefin-rich distillate oil from syngas and a method for preparing the same.

[0274] Catalyst: Ruthenium (Ru), alkali metal (K), and metal oxides (MgO and CeO2) are supported on TiO2. Based on the total mass of Ruthenium (Ru), alkali metal (K), metal oxides (MgO and CeO2), and support Al2O3, the content of Ruthenium (Ru) is 2 wt%, the content of alkali metal (K) is 0.4 wt%, and the contents of metal oxides (MgO and CeO2) are 1 wt% and 0.2 wt%, respectively.

[0275] The general formula of the catalyst is 0.4K-2Ru-1MgO-0.2CeO2 / Al2O3.

[0276] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0277] 1-1) Weigh 0.411 g of the salt corresponding to ruthenium, 25.000 g of surfactant, and 9.640 g of TiO2 support, dissolve them in 200 g of the first solvent to prepare a suspension, and then react them in a hydrothermal reactor at 60 °C for 15 h. Afterward, dry the precipitate by vacuum rotary evaporation, which is the ruthenium-based catalyst.

[0278] The salt corresponding to ruthenium is RuCl3; the surfactant is NVP; and the primary solvent is DMF.

[0279] 1-2) Dissolve 0.103 g of the salt corresponding to the alkali metal element and 0.686 g of the salt corresponding to the metal oxide in 10 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst from step 1) and impregnate at room temperature (25°C) for 24 h. Then dry in an oven at 120°C for 12 h and calcine in air in a muffle furnace at 420°C for 9 h to obtain the catalyst.

[0280] The salt corresponding to the alkali metal element is KNO3; the salts corresponding to the metal oxides are Mg(NO3)2·6H2O and Ce(NO3)3·6H2O, wherein the mass ratio of Mg(NO3)2·6H2O to Ce(NO3)3·6H2O is 0.636:0.050; the second solvent is deionized water.

[0281] The method for using this catalyst to directly produce olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0282] 2-1) Reduction treatment

[0283] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0284] The reduction conditions were: a reducing atmosphere of 30% H2 / N2; and a reducing space velocity of 6000 h⁻¹. -1 The reduction temperature was 520 °C, the reduction pressure was atmospheric pressure, and the reduction time was 13 h. After the reduction was completed, the reaction was switched to syngas.

[0285] 2-2) Syngas is introduced into a fixed bed to carry out the conversion reaction.

[0286] The conditions for the conversion reaction were: the syngas was a mixture of H2 and CO, with a molar ratio of H2 to CO of 1.8:1; and the volume hourly space velocity (VHSV) was 5000 h⁻¹. -1 The reaction temperature was 260 °C, the reaction pressure was 1.5 MPa, and the reaction time was 48 h.

[0287] After the reaction was completed, the CO conversion rate and the catalyst selectivity for the product were calculated using the same method as in Example 1. The specific results are shown in Table 1.

[0288] Example 13

[0289] This embodiment 13 provides a catalyst for producing olefin-rich distillate oil from syngas and a method for preparing the same.

[0290] Catalyst: Ruthenium (Ru), alkali metal Na, and metal oxides BaO, CuO, and CeO2 are supported on SiO2. Based on the total mass of Ruthenium (Ru), alkali metal Na, metal oxides BaO, CuO, CeO2, and SiO2, the content of Ruthenium (Ru) is 2 wt%, the content of alkali metal Na (Rb) is 0.2 wt%, and the content of metal oxides BaO, CuO, and CeO2 is 0.2 wt%. 、 The CeO2 contents were 2 wt%, 0.4 wt%, and 0.2 wt%, respectively.

[0291] The general formula of the catalyst is 0.2Na-2Ru-2BaO-0.4CuO-0.2CeO2 / SiO2.

[0292] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0293] 1-1) Weigh 0.411 g of the salt corresponding to ruthenium, 20.000 g of surfactant, and 9.520 g of carrier SiO2, dissolve them in 200 g of the first solvent to prepare a suspension, and then react them in a hydrothermal reactor at 70 °C for 14 h. Afterward, dry the precipitate by vacuum rotary evaporation, which is the ruthenium-based catalyst.

[0294] The salt corresponding to ruthenium is RuCl3; the surfactant is PVP; and the first solvent is a mixture of water and ethylene glycol in a volume ratio of 1:1.

[0295] 1-2) Dissolve 0.046 g of the salt corresponding to the alkali metal element and 1.435 g of the salt corresponding to the metal oxide in 15 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst from step 1) and impregnate at room temperature (25°C) for 24 h. Then dry in an oven at 120 °C for 12 h and calcine in air in a muffle furnace at 380 °C for 18 h to obtain the catalyst.

[0296] The salt corresponding to the alkali metal element is Na2CO3; the salts corresponding to the metal oxides are Ba(NO3)2·H2O, CuSO4·5H2O and Ce(NO3)3·6H2O, wherein the mass ratio of Ba(NO3)2·H2O, CuSO4·5H2O and Ce(NO3)3·6H2O is 0.364:0.126:0.050; the second solvent is deionized water.

[0297] The method for using this catalyst to directly produce olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0298] 2-1) Reduction treatment

[0299] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0300] The conditions for the reduction treatment were: reducing atmosphere: H2; reducing space velocity: 6000 h⁻¹ -1 The reduction temperature was 450 °C, the reduction pressure was atmospheric pressure, and the reduction time was 12 h. After the reduction was completed, the reaction was switched to syngas.

[0301] 2-2) Syngas is introduced into a fixed bed to carry out the conversion reaction.

[0302] The conditions for the conversion reaction are: the syngas is a mixture of H2 and CO, with a molar ratio of H2 to CO of 2:1; and the volume hourly space velocity (VHSV) is 3000 h⁻¹. -1 The reaction temperature was 270 °C, the reaction pressure was 1.1 MPa, and the reaction time was 48 h.

[0303] After the reaction was completed, the CO conversion rate and the catalyst selectivity for the product were calculated using the same method as in Example 1. The specific results are shown in Table 1.

[0304] Comparative Example 1

[0305] The difference between Comparative Example 1 and Example 1 is that no metal oxide was added. Everything else is the same as in Example 1.

[0306] Catalyst: Ruthenium (Ru) and Na are supported on SiO2; based on the total mass of Ruthenium (Ru), Na, and SiO2, the content of Ruthenium (Ru) is 2 wt% and the content of Na is 0.2 wt%.

[0307] The general formula for the catalyst is 0.2Na-2Ru / SiO2.

[0308] The catalyst obtained in Comparative Example 1 was then used to catalyze the synthesis of olefins from syngas according to the same steps as in Example 1, and the results are shown in Table 1.

[0309] Comparative Example 2

[0310] The difference between Comparative Example 2 and Example 1 is that no alkali metal element was added. Everything else is the same as in Example 1.

[0311] Catalyst: Ruthenium (Ru) and CeO2 metal oxide are supported on SiO2 support; based on the total mass of Ruthenium, CeO2 metal oxide and SiO2 support, the content of Ruthenium (Ru) is 2wt% and the content of CeO2 metal oxide is 0.2wt%.

[0312] The general formula for the catalyst is 2Ru-0.2CeO2 / SiO2.

[0313] The catalyst obtained in Comparative Example 2 was then used to catalyze the synthesis of olefins from syngas according to the exact same steps as in Example 1. The results are shown in Table 1.

[0314] Comparative Example 3

[0315] The difference between Comparative Example 3 and Example 1 is that the content of the metal oxide CeO2 is 15 wt%. All other aspects are the same as in Example 1.

[0316] Catalyst: Ruthenium (Ru), Na (Na), and CeO2 (CeO2) are supported on SiO2. Based on the total mass of Ruthenium (Ru), Na (Na), CeO2 (CeO2), and SiO2 (CeO2), the content of Ruthenium (Ru) is 1 wt%, the content of Na (Na) is 0.2 wt%, and the content of CeO2 (CeO2) is 15 wt%.

[0317] The general formula of the catalyst is 0.2Na-1Ru-15CeO2 / SiO2.

[0318] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0319] 1-1) Weigh 0.314 g of the salt corresponding to ruthenium, 18.000 g of surfactant, and 8.280 g of carrier SiO2, dissolve them in 200 mL of the first solvent to prepare a suspension, and then react them in a hydrothermal reactor at 50 °C for 3 h. Afterward, dry the precipitate by vacuum rotary evaporation, which is the ruthenium-based catalyst.

[0320] The salt corresponding to ruthenium is N4O. 10 Ru; the surfactants are PVP and ethylenediamine, with a mass ratio of PVP to ethylenediamine of 8:10; the first solvent is deionized water.

[0321] 1-2) Dissolve 0.074 g of the salt corresponding to the alkali metal element and 4.650 g of the salt corresponding to the metal oxide in 15 g of the second solvent to form a mixed solution. Then add all the ruthenium-based catalyst obtained in step 1) and impregnate at room temperature (25°C) for 24 h. Then dry in an oven at 120 °C for 12 h and calcine in air in a muffle furnace at 400 °C for 3 h to obtain the catalyst.

[0322] The salt corresponding to the alkali metal element is NaNO3; the salt corresponding to the metal oxide is Ce(NO3)3·6H2O; and the second solvent is deionized water.

[0323] The method for using this catalyst to catalyze the production of olefin-rich distillate oil from syngas is carried out in a fixed bed and includes the following steps:

[0324] 2-1) Reduction treatment

[0325] The catalyst obtained in steps 1-2) is pressed into tablets and sieved to obtain 1 g of catalyst with a particle size of 40-60 mesh. It is then mixed with 4 g of quartz sand and packed into a fixed bed; then reduction treatment is carried out.

[0326] The conditions for the reduction treatment were: a pure H2 atmosphere and a reduction space velocity of 6000 h⁻¹. -1 The reduction temperature was 450 °C, the reduction pressure was atmospheric pressure, and the reduction time was 4 h. After the reduction was completed, the reaction was switched to syngas.

[0327] 2-2) Syngas is introduced to carry out the conversion reaction.

[0328] Syngas is introduced into a fixed bed to carry out the conversion reaction.

[0329] The conditions for the conversion reaction are: the syngas is a mixture of H2 and CO, with a molar ratio of H2 to CO of 2:1; and the volume hourly space velocity (VHSV) is 2000 h⁻¹. -1 The reaction temperature was 270 ℃, the reaction pressure was 1.5 MPa, and the reaction time was 48 h.

[0330] After the reaction was completed, the product analysis method was as shown in Example 1, and the conversion rate of CO and the selectivity of the catalyst to the product were calculated accordingly. The specific results are shown in Table 1.

[0331] Comparative Example 4

[0332] The difference between Comparative Example 4 and Example 5 is that ZrO2 is used as the carrier. All other aspects are the same as in Example 1.

[0333] Catalyst: Ruthenium (Ru), Na (Na), and CeO2 (CeO2) are supported on ZrO2. Based on the total mass of Ruthenium (Ru), Na (Na), CeO2 (CeO2), and ZrO2 (CeO2), the content of Ruthenium (Ru) is 1 wt%, the content of Na (Na) is 0.2 wt%, and the content of CeO2 (CeO2) is 15 wt%.

[0334] The general formula for the catalyst is 1K-2.5Ru-0.5CeO2 / ZrO2.

[0335] The catalyst obtained in Comparative Example 4 was then used to catalyze the synthesis of olefins from syngas according to the same steps as in Example 1, and the results are shown in Table 1.

[0336] Comparative Example 5

[0337] The difference between Comparative Example 5 and Example 2 is that the catalyst was synthesized using an impregnation method. The preparation process is as follows:

[0338] Catalyst: Ruthenium (Ru), alkali metal (K), and metal oxide (CeO2) are supported on Al2O3. Based on the total mass of Ruthenium (Ru), alkali metal (K), metal oxide (CeO2), and support Al2O3, the content of Ruthenium (Ru) is 2.5 wt%, the content of K is 1 wt%, and the content of CeO2 is 0.5 wt%.

[0339] The general formula for the catalyst is 1K-2.5Ru-0.5CeO2 / Al2O3 (impregnation method).

[0340] A method for preparing a catalyst for producing olefin-rich distillate oil from syngas includes the following steps:

[0341] Weigh 0.514 g of the salt corresponding to ruthenium, 7.000 g of surfactant, 9.600 g of Al2O3 support, 0.191 g of the salt corresponding to alkali metal, and 0.155 g of the salt corresponding to metal oxide, and dissolve them in a mixture of 200 g of the first solvent and 10 g of the second solvent. Impregnate at room temperature (25 °C) for 24 h, then dry in an oven at 120 °C for 12 h, and finally calcine in air in a muffle furnace at 350 °C for 3 h to obtain the catalyst.

[0342] The salt corresponding to ruthenium is RuCl3; the surfactant is NVP; and the first solvent is deionized water. The salt corresponding to alkali metal is KCl; the salt corresponding to metal oxide is Ce(NO3)3·6H2O; and the second solvent is deionized water.

[0343] The catalyst obtained in Comparative Example 5 was then used to catalyze the synthesis of olefins from syngas according to the exact same steps as in Example 1. The results are shown in Table 1.

[0344] Table 1

[0345]

[0346] C 5+ Alkanes can be used as oil products; therefore, distillate oils rich in olefins mainly refer to C464-C ... 2+ Olefins and C 5+ A mixture of alkanes, with alkenes being the predominant component.

[0347] As can be seen from Table 1, the catalyst of the present invention exhibits high activity and high olefin selectivity (C1) in the syngas reforming reaction. 2+ olefin selectivity >65%, C 5+ olefin selectivity > 40%, C 2+ Olefins and C 5+ It exhibits a total alkane selectivity of over 85% and low carbon dioxide selectivity (CO2 selectivity < 3.1%).

[0348] Compared to Comparative Example 1 without the addition of metal oxides, the CO conversion rate in Example 1 increased from 22.1% to 56.1%, while the selectivity for CO2 decreased from 4.5% to 2.3%. 2+ The selectivity for olefins increased from 60.1% to 75.2%, C 5+ The selectivity for olefins increased from 35.3% to 52.3% (an increase of 48.2%), C 2+ Olefins and C 5+ The selectivity for alkanes increased from 77.6% to 93.4%.

[0349] Compared to Comparative Example 2 without the addition of alkali metals, the CO conversion rate in Example 1 decreased from 74.2% to 56.1%, while the selectivity for CO2 increased from 2.1% to 2.3%. 2+ The selectivity for olefins increased from 8.9% to 75.2%, C 5+ The selectivity for olefins increased from 3.6% to 52.3% (an increase of 1352.8%), C 2+ Olefins and C 5+ The selectivity for alkanes improved from 89.1% to 93.4%. This is likely because the addition of alkali metals effectively increased the electron density of the active sites, significantly inhibiting the hydrogenation process of intermediate species and improving the selectivity for C. 2+ Olefins, C 5+ It exhibits selectivity for olefins, but also inhibits CO conversion.

[0350] Compared to Example 1, in Comparative Example 3, the metal oxide exceeded 5 wt%, resulting in a decrease in CO conversion from 56.1% to 12.2%; the selectivity for CO2 increased from 2.3% to 2.8%, and C 2+ The selectivity for olefins decreased from 75.2% to 25.6%, C 5+ The selectivity for olefins increased from 21.5% to 52.3% (an increase of 143.3%), C 2+ Olefins and C 5+ The selectivity for alkanes decreased from 93.4% to 57.6%. This is likely because the presence of excess CeO2 covers the active sites of Ru, greatly reducing reactivity. At the same time, excessive H* coverage enhances hydrogenation, thus reducing olefin selectivity.

[0351] Compared to Example 5, the use of ZrO2 as the support in Comparative Example 4 resulted in a decrease in CO conversion from 56.1% to 15.6%; the selectivity for CO2 increased from 2.3% to 2.8%. 2+ The selectivity for olefins decreased from 75.2% to 55.1%, C 5+ The selectivity for olefins increased from 30.9% to 52.3% (an increase of 69.3%), C 2+ Olefins and C 5+ The selectivity for alkanes decreased from 93.4% to 76.6%. This is likely because, compared to SiO2, the ZrO2 support has a stronger metal-support interaction, resulting in a reduction in the number of active sites exposed by Ru.

[0352] Compared with Comparative Example 5, Example 1 demonstrates that the catalyst prepared by the hydrothermal synthesis method in Example 1 has a narrower particle size distribution, ranging from 3 to 5.0 nm, with a relative standard deviation (RSD, obtained by statistical analysis of electron micrographs using Nano Measurer 1.2 software) ≤10%, and a smaller particle size, with an average particle size D.50 The wavelength is 3.22 ± 0.32 nm, indicating better dispersion (e.g., ...). Figure 3 (As shown); while the catalyst prepared by the impregnation method (Comparative Example 5) has a wider particle size distribution, ranging from 4 to 15 nm, with a relative standard deviation of about 30%, and a larger particle size, with an average particle size D. 50 The wavelength is 9.64 ± 2.61 nm, and the exposed active surface area is even lower (e.g., Figure 4 (As shown). The reason for this is probably that the hydrothermal method used in this invention to prepare ruthenium-based catalysts is a homogeneous and synchronous nucleation and growth process, which easily produces small-sized, highly uniform Ru particles; while the impregnation method results in uneven precursor distribution, easy agglomeration at high temperatures, and large particle size with high deviation.

[0353] Long-term performance comparison of Example 1: Samples were taken at 30, 78, 124, 165, and 199 hours to test conversion rate, with a maximum duration of 220 hours. High conversion rate and selectivity were observed. Figure 5 As shown. Among them, olefin selectivity refers to C... 2+ Olefin selectivity, specifically olefin-containing distillate oil selectivity, refers to C 2+ Olefins and C 5+ The sum of selectivity for alkanes.

[0354] from Figure 5 It can be seen that during operation for 30-199 hours, the CO conversion rate remained between 50-60%; the CO2 selectivity remained below 3.1%; the olefin selectivity remained between 65-80%; and the olefin-containing distillate oil selectivity remained between 85-96%.

[0355] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A catalyst for producing olefin-rich distillate oil from syngas, characterized in that, The catalyst includes a support and oxides of a first metal element and a second metal element supported on the support; the first metal element is selected from alkali metals, and the second metal element is selected from one or more of Mg, Ca, Sr, Ba, Zn, Cu, Cr, Ce, La, Pr and Sm. Based on the total mass of ruthenium, the oxide of the first metal element, the oxide of the second metal element, and the carrier, the content of ruthenium is 0.5-5 wt%, the content of the first metal element is 0.01-2 wt%, and the content of the oxide of the second metal element is 0.01-5 wt%.

2. The catalyst according to claim 1, characterized in that, The alkali metal element is selected from one or more of Na, K, Cs, and Rb; And / or, the type of support is selected from one or more of SiO2, Al2O3 and TiO2; And / or, the carrier is in the form of columnar particles; And / or, the average particle size D of the catalyst 50 The wavelength range is 2~4.0nm.

3. The catalyst as described in claim 2, characterized in that, The specific surface area of ​​the carrier is 100~400 m². 2 / g, with a pore size of 5~30 nm.

4. The method for preparing the catalyst according to any one of claims 1 to 3, characterized in that, Includes the following steps: 1) The ruthenium-based salt, surfactant, and support undergo a hydrothermal reaction in the first solvent to obtain a ruthenium-based catalyst; the salts corresponding to the first and second metal elements dissolve in the second solvent to form a mixed solution. 2) The ruthenium-based catalyst is impregnated in the mixed solution, dried, and calcined to obtain the catalyst.

5. The preparation method according to claim 4, characterized in that, The salt corresponding to the ruthenium element is selected from one or two of ruthenium nitrite, ruthenium chloride, and ruthenium acetate; And / or, the salt corresponding to the first metal element is selected from one or more of nitrates, sulfates, chlorides, acetates, and carbonates; And / or, the salt corresponding to the second metal element is selected from one or more of nitrates, sulfates, chlorides, acetates, and carbonates; And / or, the surfactant is selected from one or more of polyvinylpyrrolidone, vinylpyrrolidone, polyethylene glycol, chitosan, citric acid, polyvinyl alcohol, and ethylenediamine; And / or, the first solvent and the second solvent are independently selected from water, N,N-dimethylformamide, ethylene glycol and glycerol; And / or, the mass ratio of the ruthenium element to the surfactant is (1~280):

1.

6. The preparation method according to claim 4, characterized in that, In step 1), the temperature of the hydrothermal reaction is 50~80 °C; And / or, in step 1), the hydrothermal reaction time is 1~24 h; And / or, in step 2), the calcination temperature is 300~600 ℃; And / or, in step 2), the calcination time is 2~24 h.

7. The use of the catalyst according to any one of claims 1 to 3 in the production of olefin-rich distillate oil from catalytic syngas.

8. The application as described in claim 7, characterized in that, Prior to catalysis, the catalyst is further subjected to a reduction treatment in a reducing atmosphere; And / or, when the catalyst catalyzes the synthesis gas, the selectivity for olefins is >65%; Preferably, the reducing atmosphere comprises H2; preferably, it further comprises a diluent gas selected from one or more of N2, Ar, and He; Preferably, the temperature of the reduction treatment is 300~600 ℃; Preferably, the reduction process takes 2 to 24 hours. Preferably, the volume hourly space velocity of the reducing atmosphere is 1000~10000 h⁻¹. -1 .

9. A method for producing olefin-rich distillate oil from syngas, characterized in that, Synthetic gas is produced by catalytic synthesis using the catalyst described in any one of claims 1 to 3.

10. The method as described in claim 9, characterized in that, The synthesis gas comprises H2 and CO, and the molar ratio of H2 to CO is (0.2~3):1: And / or, the catalytic temperature is 240~300 °C; And / or, the pressure of the catalyst is 0.1~5 MPa; And / or, the catalytic time is not less than 12 hours; And / or, the volume hourly space velocity of the synthesis gas is 500~10000 h⁻¹. -1 .

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