Multifunctional structural additives, non-precious metal multi-component composite oxide catalysts, preparation methods and applications

Abstract

This invention relates to the field of biomass catalytic conversion technology, and particularly to a multi-functional additive non-precious metal multi-component composite oxide catalyst, its preparation method, and its applications. The catalyst comprises a first metal component, a second metal component, and an oxide support; the first metal component is selected from one or two of Co and Ni; the second metal component is selected from one or more of Pr, Mn, Ga, and Sc; the support metal component is selected from one or more of Zr, Al, Ti, Si, Mg, and Zn; based on the total weight of the catalyst, the oxide content of the first metal component is 20 wt.%~60 wt.%, the oxide content of the second metal component is 1 wt.%~20 wt%, and the oxide support content is 20 wt.%~70 wt%. The composite oxide framework structure formed by the co-precipitation of multiple metals is stable, and the interfacial interaction between the metal components and the support is strong, effectively inhibiting the sintering and loss of metal particles and improving the catalyst's cycle stability.

Description

Technical Field

[0001] This invention relates to the field of biomass catalytic conversion technology, and in particular to multifunctional additive non-precious metal multi-component composite oxide catalysts, their preparation methods, and applications. Background Technology

[0002] 1,5-Pentanediol is a high-value-added aliphatic diol. With its unique molecular structure and excellent physicochemical properties, it has become a promising "new cornerstone" chemical monomer in modern organic synthesis. As a core chemical intermediate, it can participate in a wide range of organic reactions such as polymerization, esterification, and etherification. It is a key raw material for the preparation of high-end polyesters, functional polyurethanes, pharmaceutical fine intermediates, environmentally friendly plasticizers, and high-end coating additives. Its downstream applications cover multiple core industrial sectors, including plastics processing, coatings and inks, biopharmaceuticals, daily chemical cosmetics, and textile materials, demonstrating extremely high industrial application value. Compared to traditional petroleum-based diols, 1,5-Pentanediol possesses superior low-temperature toughness, hydrolysis resistance, and thermal stability. Polymer materials synthesized from it exhibit significantly improved impact resistance and aging resistance, effectively compensating for the performance shortcomings of mainstream petroleum-based diols such as 1,6-hexanediol and 1,4-butanediol in the preparation of high-end materials. It has strong substitution potential in the high-end polyester and high-performance polyurethane markets and is gradually becoming one of the core raw materials for industry upgrading.

[0003] From the perspective of industry market structure, with the rapid expansion of downstream high-end new materials industries, the domestic market demand for 1,5-pentanediol continues to grow rapidly. In 2025, the market size of high-purity 1,5-pentanediol in China exceeded 1.27 billion yuan, with a year-on-year growth rate of 14.3%, far exceeding the global market average growth rate, indicating strong industry development momentum. Currently, high-end polyurethane is its largest application scenario, accounting for about 40% of the overall market demand. It is mainly used to synthesize high-end polycarbonate diol (PCDL), and then to prepare waterborne polyurethane coatings, high-end synthetic leather, elastomers and other materials. At the same time, its application share in high-end coatings, special polyester resins, pharmaceutical intermediates, and daily chemical moisturizing additives continues to increase, and the market demand continues to expand. However, contrary to this, the domestic industrial production capacity of 1,5-pentanediol is severely insufficient.

[0004] Currently, large-scale industrial production of 1,5-pentanediol still heavily relies on traditional petrochemical routes. After long-term industrial optimization, the mainstream mature processes mainly include three types: cyclopentadiene oxidation-hydrogenation, acrolein / ethylene ether condensation-hydrogenation, and glutaric acid and its esters hydrogenation. These three processes all use non-renewable petroleum-based chemicals as core raw materials and rely on a mature petrochemical industry chain to achieve mass production, forming the core support for the current global supply of 1,5-pentanediol. However, from the perspective of green chemical engineering and industrial upgrading and efficiency improvement, the traditional petroleum-based synthesis process has many inherent defects that are difficult to avoid: First, the reaction system often involves strong acids and highly corrosive raw materials, requiring production equipment made of highly corrosion-resistant special materials, resulting in extremely high equipment purchase and maintenance costs; Second, the reactions generally require harsh operating conditions of high temperature and high pressure, leading to high energy consumption and costs, which does not conform to current industrial policies on energy conservation and emission reduction; Third, the core raw material is a non-renewable petroleum derivative, and the supply of raw materials is subject to fluctuations in oil prices and limitations in petrochemical resource reserves, resulting in poor production cost stability. Furthermore, the production process generates a large number of byproducts and pollutants, leading to significant pressure on waste treatment and high environmental costs; Fourth, the overall process has low atom utilization, resulting in serious resource waste and insufficient economic efficiency and greenness. In summary, the many drawbacks of the traditional petroleum-based synthesis process are no longer suitable for the current trend of green chemical engineering development and the demand for low-cost, large-scale production of high-end materials. There is an urgent need to develop a new, green, environmentally friendly, mild, efficient, low-cost, and sustainable 1,5-pentanediol synthesis process.

[0005] Biomass resources, with their abundant reserves, wide availability, high renewability, and low-carbon environmental friendliness, have become the only organic carbon source in the industrial sector that can replace fossil resources. They are a core raw material for preparing green chemical intermediates and biodegradable polymer materials, and a research hotspot in the fields of new energy and new materials. Furfural is currently the only biomass platform compound globally to achieve large-scale industrial production, with an annual output exceeding 600,000 tons. Its industrialization technology is mature, raw material supply is sufficient, and costs are controllable, providing a foundation for large-scale application. From the perspective of the industrial chain structure, furfural's downstream products are concentrated, with approximately 75% of industrial furfural used to produce furfuryl alcohol. The continuously abundant production capacity provides ample raw material support for the deep processing and conversion of furfuryl alcohol.

[0006] Numerous studies have confirmed that furfuryl alcohol can be synthesized into 1,5-pentanediol via selective ring-opening hydrogenation after CO bond cleavage in the furan ring. This biomass conversion route perfectly aligns with the concept of green and sustainable chemical development. Compared to traditional petroleum routes, the core advantage of this process lies in its extremely high atom economy. All reactant atoms participate in the synthesis of the target product during the reaction, with no ineffective atom loss and minimal byproducts, significantly reducing emissions and resource waste. Simultaneously, the raw material is a renewable biomass derivative, eliminating dependence on petroleum fossil resources. The production process is low-carbon, environmentally friendly, and highly sustainable, making it an ideal technological route to replace traditional petroleum-based processes, possessing extremely high industrial R&D and application value. Currently, the biomass synthesis route for 1,5-pentanediol based on furfuryl alcohol hydrogenolysis has become a core research direction in the industry. Several domestic patents have disclosed related catalytic systems, but existing technologies still have significant shortcomings and have not yet achieved efficient and stable industrial-scale production.

[0007] Chinese invention patent CN102872897B discloses a classic technical scheme for the catalytic hydrogenolysis of furfuryl alcohol to prepare 1,5-pentanediol. This technology uses a hydrogen-form ultrastable Y molecular sieve (H-USY) as a support, loads platinum as the active component to construct a highly efficient catalytic system, and uses hydrochloric acid as a reaction promoter. The hydrogenolysis conversion of furfuryl alcohol is achieved under mild conditions of 100℃~140℃ and 0.5~2.5 MPa, resulting in relatively mild reaction conditions. Under optimal conditions, the yield of 1,5-pentanediol can reach up to 82.6%, showing a significant yield advantage compared to similar early biomass synthesis processes. However, this catalytic system has two major defects that restrict its industrial application: First, the catalyst activity and adaptability are insufficient. Even under optimal reaction conditions, the conversion rate of furfuryl alcohol reactants is only 86.1%, the raw material conversion is incomplete, and the raw material utilization rate and production efficiency are low. Second, the process system introduces hydrochloric acid as an acidic additive. During the reaction, hydrochloric acid will cause serious corrosion to the reaction equipment, which will not only significantly increase the investment and maintenance costs of equipment corrosion prevention, but also increase the difficulty of subsequent product separation and purification, and generate acidic wastewater pollutants. The environmental protection and industrial adaptability are poor, making it difficult to achieve large-scale industrial production.

[0008] To optimize the shortcomings of traditional platinum-based catalytic systems and improve reaction efficiency and industrial applicability, the industry has continuously conducted research and development on non-precious metal catalytic systems. Patent CN118002169 discloses a nickel-lanthanum (NiLa) composite catalyst technology, providing a new pathway for the efficient conversion of furfuryl alcohol. This technology abandons the acidic promoter system and relies on the synergistic catalytic effect of the NiLa bimetallic active components to achieve 100% complete conversion of furfuryl alcohol by continuously catalyzing the reaction for 24 hours at 190℃ and 5 MPa hydrogen pressure. This completely solves the problem of incomplete raw material conversion and significantly improves raw material utilization. However, this technology still has significant process shortcomings, making industrialization difficult: on the one hand, the reaction cycle is as long as 24 hours, resulting in extremely low single-batch production efficiency, and the equipment utilization rate and capacity output efficiency are difficult to meet the needs of industrial-scale production; on the other hand, the selectivity of the target product is insufficient, with the selectivity of 1,5-pentanediol being only 78% under optimal operating conditions, and the reaction process easily generates byproducts such as pentanol and tetrahydrofurfuryl alcohol, making the purification of the target product difficult and the overall production yield low, which greatly reduces the economic efficiency of the process and cannot meet the core needs of efficient and low-cost mass production in industry.

[0009] In summary, existing patented technologies for the hydrogenolysis of furfuryl alcohol to prepare 1,5-pentanediol generally suffer from one or more problems, such as insufficient catalyst performance, harsh reaction conditions, low production efficiency, poor product selectivity, and equipment corrosion risks. These issues make it difficult to simultaneously meet the requirements of high conversion rate, high selectivity, environmental friendliness, and high efficiency and low cost for industrial production. Therefore, developing a novel catalytic system with excellent catalytic activity, strong stability, no corrosive additives, short reaction cycle, and high product selectivity, and constructing a green, efficient, and low-cost biomass-based 1,5-pentanediol synthesis process, is a core research topic urgently needing breakthroughs in this field. Summary of the Invention

[0010] Purpose of the invention: To provide a more effective multi-functional additive non-precious metal multi-component composite oxide catalyst, preparation method and application; specific objectives are detailed in the specific implementation section for several substantial technical effects.

[0011] To achieve the above objectives, the present invention adopts the following technical solution: A multi-functional additive non-precious metal multi-component composite oxide catalyst, characterized in that it comprises a first metal component, a second metal component, and an oxide support; The first metal component is selected from one or two of Co and Ni; The second metal component is selected from one or more of Pr, Mn, Ga, and Sc; The carrier metal component is selected from one or more of Zr, Al, Ti, Si, Mg, and Zn; Based on the total weight of the catalyst, the content of the first metal component oxide is 20 wt.% to 60 wt.%, the content of the second metal component oxide is 1 wt.% to 20 wt%, and the content of the oxide support is 20 wt.% to 70 wt%.

[0012] A further technical solution of the present invention is that the catalyst is a composite oxide formed by the co-precipitation of multiple metals, the metal components are atomically dispersed, and the surface has a controllable distribution of oxygen vacancies and basic sites; the catalyst can achieve tilted adsorption of furan reactants at the C2-end by adjusting the surface oxygen vacancy concentration and basic site density, and directionally break the C2-O1 bond of the furan ring.

[0013] A method for preparing a multi-functional additive non-noble metal multi-component composite oxide catalyst, characterized in that, The first metal component is selected from one or two of Co and Ni; The second metal component is selected from one or more of Pr, Mn, Ga, and Sc; The carrier metal component is selected from one or more of Zr, Al, Ti, Si, Mg, and Zn; Based on the total weight of the catalyst, the content of the first metal component oxide is 20 wt.%~60 wt.%, the content of the second metal component oxide is 1 wt.%~20 wt%, and the content of the oxide support is 20 wt.%~70 wt%. The complexation-homogeneous precipitation coupled soft template method is employed, including the following steps: (1) Dissolve the structure-regulating additive in an alcohol-water mixed solvent, then add the first metal soluble salt, the second metal soluble salt and the carrier metal soluble salt, stir at room temperature for 30 min ~ 120 min to form a clear and transparent multi-metal complex homogeneous solution. (2) Slowly add an alkaline precipitant to the homogeneous solution of the multi-metal complex, control the pH of the system to 9.0~13.0, and stir at a constant temperature of 35℃~60℃ for 30 min~180 min to achieve simultaneous co-precipitation of all metal ions; (3) The precipitate is subjected to two-stage gradient crystallization: the first stage is static aging at 40 ℃~80 ℃ for 2 h~8 h, and the second stage is hydrothermal crystallization at 90 ℃~150 ℃ for 2 h~4 h; (4) The crystallized product was washed alternately with deionized water and ethanol until the filtrate was neutral and no NO3⁻ was detected, and then subjected to gradient drying. (5) The dried precursor was calcined in air under programmed heating and then naturally cooled to obtain a non-precious metal multi-component composite oxide catalyst. During the preparation process: the structure-regulating additives not only coordinate with metal ions to form stable complexes, inhibiting the rapid nucleation and aggregation of metal ions, but also pyrolyze during calcination to form mesoporous channels, thereby regulating the specific surface area and pore structure of the catalyst and improving the diffusion efficiency of reactants and products.

[0014] A further technical solution of the present invention is that the structure regulating additive is selected from one or more of starch, sodium alginate, PEG, glycerol, and ethylene glycol, and the amount added is 2wt.% to 15wt.% of the total mass of all metal salts.

[0015] A further technical solution of the present invention is that the first metal soluble salt, the second metal soluble salt, and the carrier metal soluble salt are all selected from one or more of nitrates, acetates, and chlorides; in the alcohol-water mixed solvent, the volume ratio of deionized water to anhydrous ethanol is 1:1 to 6:1; and the alkaline precipitant is one or two of NaOH, Na2CO3, KOH, K2CO3, and ammonia. A further technical solution of this invention lies in the fact that Pr, Ga, and Sc are rare earth or rare earth-like metals with special electronic layer structures, which readily induce the precise generation of abundant oxygen vacancies on the catalyst surface; the density and intensity of basic sites on the catalyst surface can be finely controlled to construct synergistic active sites of "oxygen vacancy - basic site"; the electronic valence state of the main metal Co / Ni can be controlled to weaken metal particle agglomeration and achieve high atomic-level dispersion of metals; the metal-support interface interaction is strengthened, and metal sintering under high-temperature hydrogenation is inhibited, as well as the loss of polysaccharides, polyols, and PEG containing a large number of hydroxyl groups and ether bonds, which can interact with... , , , When metal ions form stable chelate complexes, the rapid nucleation of metal ions is slowed down and particle agglomeration is avoided, achieving homogeneous atomic-level dispersion of multi-metals; during the calcination process, the additives are gradually pyrolyzed and carbonized, and leave in situ, constructing regular mesoporous channels and layered lamellar structures, which greatly increases the specific surface area; the additive molecules are adsorbed on the surface of the crystal nuclei, inducing the crystals to grow preferentially along the lamellar direction, forming a hydrotalcite-like nanosheet stacked morphology with interconnected pores and low mass transfer resistance. The homogeneous complexation of fully soluble salts without the pre-existing solid carrier eliminates the problems of uneven loading and metal segregation at the source, achieving atomic-level mixing; gradient crystallization first aging at low temperature to regulate crystal nuclei, and then hydrothermal crystallization to assemble a lamellar structure, making crystal defects controllable and oxygen vacancy concentration precisely adjustable; gradient drying first removes free water in vacuum at low temperature, and then dries bound water with forced air, avoiding hard agglomeration of particles and maintaining the lamellar structure of the precursor; programmed temperature calcination with slow temperature rise ensures the gradual decomposition of additives and the stable formation of oxide crystal phases, preserving abundant defects and pore structures; It exhibits strong interfacial bonding between the metal and the support, resists sintering and leaching, and boasts a service life and cycle stability far exceeding those of traditional non-precious metal catalysts.

[0016] A further technical solution of the present invention is that the gradient drying is: first, vacuum drying at 60℃ for 6 h to 10 h, then forced air drying at 100℃ for 2 h to 8 h; the programmed temperature calcination is: increasing to 350℃ to 550℃ at a rate of 1℃ / min to 3℃ / min, and holding at that temperature for 3 h to 6 h; and also includes an optional reduction step: reducing the calcined catalyst at 300℃ to 500℃ for 1 h to 5 h in a 30% V H2 / N2 mixed atmosphere. The application of the multi-functional additive non-precious metal multi-component composite oxide catalyst described above in the hydrogenation of furfuryl alcohol to prepare 1,5-pentanediol. A method for preparing 1,5-pentanediol by hydrogenation of furfuryl alcohol using a multi-functional additive non-precious metal multi-component composite oxide catalyst, characterized in that the reaction conditions are: reaction temperature 150 ℃~200 ℃, hydrogen pressure 2 MPa~6 MPa, reaction time 2 h~10 h, and the reaction solvent is selected from ethanol, isopropanol, water or a mixture thereof.

[0017] A multi-functional additive non-precious metal multi-component composite oxide catalyst, characterized in that the catalyst is any one of the following: Option 1: Co-Mn / ZrO2 catalyst (additive: starch) (1) Catalyst preparation: Mix 300 mL of deionized water with 100 mL of anhydrous ethanol, add 5.0 g of starch, and stir until completely dissolved (60 g / mL). o (C) Heating-assisted dissolution to form a homogeneous solvent system; 48.4 g of cobalt nitrate hexahydrate, 9.6 g of manganese nitrate hexahydrate, and 50.3 g of zirconium nitrate pentahydrate were added sequentially, and the mixture was stirred at room temperature for 90 min to form a transparent homogeneous complex solution; under stirring, a mixed alkaline solution of NaOH and Na2CO3 was slowly added dropwise to adjust the pH of the system to 10.0, and the solution was maintained at 50°C. o Stir at C for 120 min to complete simultaneous co-precipitation; then transfer the suspension to a hydrothermal reactor, first at 70 °C. o Static aging at 6°C for 6 hours, then heated to 100°C. o Hydrothermal crystallization at C for 3 h; the product was washed alternately with deionized water and anhydrous ethanol until neutral (pH=7.0), then at 60 °C. o Vacuum dry at C for 8 hours, then at 100°C. o Dry in a forced-air environment for 3 hours; then dry in air at 2°C. o The heating rate was increased to 500 °C / min. o C, calcined for 4 h to obtain a composite oxide precursor; in a 30 vol.% H2 / N2 mixed atmosphere, 350 oC reduction for 3 h yielded a Co / Mn2O3-ZrO2 catalyst; wherein the mass fraction of CoO was 40%, the mass fraction of Mn2O3 was 8%, and the mass fraction of ZrO2 was 52%. Option 2: Ni-Ga / Al2O3 catalyst (additive: sodium alginate) (1) Catalyst preparation: 400 mL of deionized water and 100 mL of anhydrous ethanol were mixed, and 3.2 g of sodium alginate was added. The mixture was stirred until completely dissolved to form a homogeneous solvent system. 30.2 g of nickel nitrate hexahydrate, 5.10 g of gallium nitrate, and 72.3 g of aluminum nitrate nonahydrate were added sequentially. The mixture was stirred at room temperature for 120 min until homogeneous and transparent. NaOH alkaline solution was added dropwise while stirring to adjust the pH of the system to 9.5. The suspension was then transferred to a hydrothermal reactor and heated at 45°C. o Stirring at C for 150 min completes co-precipitation; then sequentially subjected to 65... o C aging for 8 hours, 95 o Gradient crystallization was performed using hydrothermal crystallization at C for 4 h; then the suspension was washed until neutral and crystallized at 60 °C. o Vacuum drying at C for 6 h, then at 110 o Drying at 2°C with forced air for 4 hours; o Temperature increased to 500 °C / min o C, calcined for 5 h; then heated at 380 °C in a 30 vol.% H2 / N2 atmosphere. o C reduction for 3 h yielded a Ni / Ga2O3-Al2O3 catalyst; wherein the mass fraction of NiO was 40%, the mass fraction of Ga2O3 was 9.6%, and the mass fraction of Al2O3 was 50.4%. Option 3: Co-Pr / ZnO catalyst (additives: glycerol + ethylene glycol) (1) Catalyst preparation method: Mix 300 mL of deionized water with 100 mL of ethanol, add 3 mL of glycerol and 3 mL of ethylene glycol, and stir until completely dissolved to form a homogeneous solvent system; add 43.5 g of cobalt nitrate hexahydrate, 6.2 g of praseodymium nitrate hexahydrate, and 49.5 g of zinc nitrate hexahydrate in sequence, and stir for 90 min to form a homogeneous complex solution. Under stirring conditions, add KOH alkaline solution dropwise until the pH is 10.0. o Stirring at 70°C for 120 min completes co-precipitation; then transfer the suspension to a hydrothermal reactor, first at 70°C... o C aging for 6 hours, 100 o C hydrothermal crystallization for 3 h; after washing until neutral, 60 o Vacuum drying at 100°C for 7 hours. o C. Blow dry for 3 hours; 500 oCalcination at C for 4 h; then calcined at 30 vol.% H2 / N2 atmosphere at 300 °C. o C reduction for 4 h yields Co / Pr6O 11 -ZnO catalyst; wherein the mass fraction of CoO is 41%, and Pr6O 11 The mass fraction of ZnO is 9%, and the mass fraction of ZnO is 50%. Option 4: Ni-Mn / MgO catalyst (additive: PEG-6000) (1) Mix 350 mL of deionized water with 70 mL of ethanol, add 4.50 g of PEG-6000, stir to dissolve, and form a homogeneous solvent system; add 30.8 g of nickel nitrate hexahydrate, 9.6 g of manganese nitrate hexahydrate, and 68 g of magnesium nitrate hexahydrate in sequence, and stir for 80 min to form a homogeneous complex solution; under stirring conditions, add a mixed alkaline solution of NaOH and Na2CO3 dropwise until pH=10.1, 55 o Stir at C for 100 min to complete co-precipitation; then transfer the suspension to a hydrothermal reactor, first at 80°C. o C aging for 4 hours, 110 o C hydrothermal crystallization for 2 h; washing until neutral, then 60 o Vacuum drying at 105°C for 8 hours o C-air drying for 3 hours; 550 o Calcination at C for 3 h; then calcined at 350 °C in a 30 vol.% H2 / N2 atmosphere. o C reduction for 4 h yielded a Ni-Mn / MgO catalyst; wherein the mass fraction of NiO was 40%, the mass fraction of Mn2O3 was 13.3%, and the mass fraction of MgO was 46.7%. Option 5: Co-Ga / ZnO catalyst (additives: starch + sodium alginate) (1) Mix 300 mL of deionized water with 100 mL of ethanol, add 2.5 g of starch and 2.0 g of sodium alginate, and stir until completely dissolved (60 g / mL). o (C heating assisted) to form a homogeneous solvent system, 50.9 g of cobalt nitrate hexahydrate, 6.6 g of gallium nitrate, and 53.9 g of zinc nitrate hexahydrate were added sequentially, and the mixture was stirred for 90 min to form a homogeneous complex solution; under stirring conditions, a mixed alkaline solution of KOH and K2CO3 was added dropwise until the pH reached 9.5, and then the suspension was transferred to a hydrothermal reactor, first heated to 50... o Stir at C for 120 min to complete co-precipitation; 75 o C aging for 5 hours, 105 o C hydrothermal crystallization for 3 h; after washing until neutral, 60 oVacuum drying at 100°C for 7 hours. o C. Blow dry for 3 hours; 500 o Calcination at C for 4 h; then calcined at 380 °C in a 30 vol.% H2 / N2 atmosphere. o C reduction for 2 h yielded a Co / Ga2O3-ZnO catalyst; wherein the mass fraction of CoO was 42%, the mass fraction of Ga2O3 was 8%, and the mass fraction of ZnO was 50%.

[0018] The present invention, employing the above technical solution, has the following beneficial effects compared to the prior art: The present invention achieves a breakthrough improvement in catalytic performance through multi-component synergy and innovative preparation process, and its core mechanism of action is as follows: (1) Homogeneous complexation of fully soluble salts: The support dissolves and complexes with the active metal salt in the form of soluble salts, avoiding the problem of uneven metal dispersion caused by solid supports in traditional supported catalysts, realizing atomic-level mixing of metal components and greatly increasing the number of active sites; (2) Dual role of complexation-soft template: The additive not only coordinates with metal ions to form stable complexes, inhibiting the rapid nucleation and aggregation of metal ions, but also pyrolyzes during the calcination process to form mesoporous channels, thereby regulating the specific surface area and pore structure of the catalyst and improving the diffusion efficiency of reactants and products. (3) Gradient process control of structure: Gradient crystallization makes the crystal structure more regular, and gradient drying avoids hard agglomeration of particles, ultimately obtaining a thin-layer, highly dispersed composite oxide structure. (4) Synergistic optimization of oxygen vacancies and alkalinity: The introduction of the second metal component and the precise control of the calcination process simultaneously regulate the concentration of oxygen vacancies and the density of alkaline sites on the catalyst surface, so that furfuryl alcohol is bound to the catalyst surface in a C2-end tilted adsorption mode, effectively overcoming the steric hindrance of furan ring opening, directionally breaking the C2-O1 bond, and inhibiting the occurrence of side reactions. (5) Enhanced structural stability: The composite oxide skeleton formed by the co-precipitation of multiple metals has a stable structure and strong interfacial interaction between the metal components and the support, which effectively inhibits the sintering and loss of metal particles and improves the cycle stability of the catalyst. Attached Figure Description

[0019] To further illustrate the present invention, the following description is provided in conjunction with the accompanying drawings: Figure 1 Electron micrograph of the precursor after calcination; Figure 2 A bar chart showing the effects of the invention. Detailed Implementation The present invention will be further described in detail below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0020] The present invention will be further illustrated by the following embodiments, but is not limited to the following embodiments.

[0021] Example 1: Co-Mn / ZrO2 catalyst (additive: starch) (1) Catalyst preparation: Mix 300 mL of deionized water with 100 mL of anhydrous ethanol, add 5.0 g of starch, and stir until completely dissolved (60 g / mL). o (Heating-assisted dissolution) to form a homogeneous solvent system. 48.4 g of cobalt nitrate hexahydrate, 9.6 g of manganese nitrate hexahydrate, and 50.3 g of zirconium nitrate pentahydrate were added sequentially, and the mixture was stirred at room temperature for 90 min to form a transparent homogeneous complex solution. While stirring, a mixed alkaline solution of NaOH and Na₂CO₃ was slowly added dropwise to adjust the pH of the system to 10.0, maintaining a constant temperature of 50°C. o Stir at 70°C for 120 minutes to complete simultaneous co-precipitation. Then transfer the suspension to a hydrothermal reactor and heat at 70°C. o Static aging at 6°C for 6 hours, then heated to 100°C. o Hydrothermal crystallization at C for 3 h. The product was washed alternately with deionized water and anhydrous ethanol until neutral (pH=7.0), then at 60 °C. o Vacuum dry at C for 8 hours, then at 100°C. o Dry in a forced-air environment for 3 hours. Then, under air conditions, dry at 2... o The heating rate was increased to 500 °C / min. o C, calcined for 4 h, to obtain the composite oxide precursor. In a 30 vol.% H2 / N2 mixed atmosphere, at 350 °C... o C reduction for 3 h yielded a Co / Mn2O3-ZrO2 catalyst. The catalyst contained 40% CoO, 8% Mn2O3, and 52% ZrO2 by mass.

[0022] (2) Evaluation of catalytic performance: 1) The activated catalyst is loaded into a high-pressure reactor, furfuryl alcohol is added, and pure hydrogen is introduced to carry out the hydrogenation reaction; 2) The product after the reaction was separated by centrifugation to obtain the upper layer product, which was then analyzed by gas chromatography; 3) At a reaction temperature of 160°C o At C, with a pressure of 5 MPa H2, the reaction was carried out in ethanol solvent for 2 h, resulting in a furfuryl alcohol conversion of 100% and a 1,5-pentanediol selectivity of 98.7%.

[0023] Example 2 Ni-Ga / Al2O3 catalyst (additive: sodium alginate) (1) Catalyst preparation: 400 mL of deionized water and 100 mL of anhydrous ethanol were mixed, and 3.2 g of sodium alginate was added. The mixture was stirred until completely dissolved to form a homogeneous solvent system. 30.2 g of nickel nitrate hexahydrate, 5.10 g of gallium nitrate, and 72.3 g of aluminum nitrate nonahydrate were added sequentially, and the mixture was stirred at room temperature for 120 min until homogeneous and transparent. NaOH alkaline solution was added dropwise while stirring to adjust the pH of the system to 9.5. The suspension was then transferred to a hydrothermal reactor and heated at 45°C. o Stirring at C for 150 min completes co-precipitation. Then, sequentially pass through 65°C... o C aging for 8 hours, 95 o Gradient crystallization was performed using hydrothermal crystallization at C for 4 h. The suspension was then washed until neutral and then crystallized at 60 °C. o Vacuum drying at C for 6 hours, then at 110 o Drying at 2°C using forced air for 4 hours. o Temperature increased to 500 °C / min o C, calcined for 5 h. Then, in a 30 vol.% H2 / N2 atmosphere, at 380 °C. o The Ni / Ga₂O₃-Al₂O₃ catalyst was obtained by reduction with C for 3 h. The mass fraction of NiO was 40%, the mass fraction of Ga₂O₃ was 9.6%, and the mass fraction of Al₂O₃ was 50.4%.

[0024] (2) Catalytic performance 1) Follow the operating steps in Example 1: 2) At a reaction temperature of 160°C o At C, under a pressure of 5 MPa, the reaction was carried out in a mixed solvent of ethanol and water for 2 h, with a furfuryl alcohol conversion of 100% and a 1,5-pentanediol selectivity of 98.2%.

[0025] Example 3 Co-Pr / ZnO catalyst (additives: glycerol + ethylene glycol) (1) Catalyst preparation method: Mix 300 mL of deionized water with 100 mL of ethanol, add 3 mL of glycerol and 3 mL of ethylene glycol, and stir until completely dissolved to form a homogeneous solvent system. Add 43.5 g of cobalt nitrate hexahydrate, 6.2 g of praseodymium nitrate hexahydrate, and 49.5 g of zinc nitrate hexahydrate sequentially, and stir for 90 min to form a homogeneous complex solution. Under stirring conditions, add KOH alkaline solution dropwise until the pH reaches 10.0. o Stir at 70°C for 120 min to complete co-precipitation. Then transfer the suspension to a hydrothermal reactor and heat at 70°C. o C aging for 6 hours, 100 o Hydrothermal crystallization at C for 3 hours. After washing until neutral, at 60°C... o Vacuum drying at 100°C for 7 hours.o C. Blow dry for 3 hours. 500 o Calcination at C for 4 h. Then, in a 30 vol.% H2 / N2 atmosphere, at 300 °C. o C reduction for 4 h yields Co / Pr6O 11 -ZnO catalyst. The mass fraction of CoO is 41%, and Pr6O is... 11 The mass fraction of ZnO is 9%, and the mass fraction of ZnO is 50%.

[0026] (2) Catalytic performance 1) The operation method according to Example 1 2) At a reaction temperature of 170°C o At C, under a pressure of 4 MPaH2, the reaction was carried out in isopropanol solvent for 4 h, with a furfuryl alcohol conversion of 100% and a 1,5-pentanediol selectivity of 97.3%.

[0027] Example 4 Ni-Mn / MgO catalyst (additive: PEG-6000) (1) Mix 350 mL of deionized water with 70 mL of ethanol, add 4.50 g of PEG-6000, stir to dissolve, and form a homogeneous solvent system. Add 30.8 g of nickel nitrate hexahydrate, 9.6 g of manganese nitrate hexahydrate, and 68 g of magnesium nitrate hexahydrate sequentially, and stir for 80 min to form a homogeneous complex solution. Under stirring conditions, add a mixed alkaline solution of NaOH and Na2CO3 dropwise until the pH reaches 10.1. o Stir at C for 100 min to complete co-precipitation. Then transfer the suspension to a hydrothermal reactor and heat at 80°C. o C aging for 4 hours, 110 o Hydrothermal crystallization at C for 2 hours. After washing until neutral, at 60°C... o Vacuum drying at 105°C for 8 hours o C. Blow dry for 3 hours. 550 o Calcination at C for 3 h. Then, in a 30 vol.% H2 / N2 atmosphere, at 350 °C. o The Ni-Mn / MgO catalyst was obtained by reduction with C for 4 h. The mass fraction of NiO was 40%, the mass fraction of Mn2O3 was 13.3%, and the mass fraction of MgO was 46.7%.

[0028] (2) Catalytic performance 1) The operation method according to Example 1 4) At a reaction temperature of 160°C o At C, under a pressure of 6 MPa H2, the reaction was carried out in a mixed solvent of isopropanol and water for 2 h, with a furfuryl alcohol conversion of 100% and a 1,5-pentanediol selectivity of 96.8%.

[0029] Example 5 Co-Ga / ZnO catalyst (additives: starch + sodium alginate) (1) Mix 300 mL of deionized water with 100 mL of ethanol, add 2.5 g of starch and 2.0 g of sodium alginate, and stir until completely dissolved (60 g / mL). o (Heating assisted by C) to form a homogeneous solvent system, 50.9 g of cobalt nitrate hexahydrate, 6.6 g of gallium nitrate, and 53.9 g of zinc nitrate hexahydrate were added sequentially, and the mixture was stirred for 90 min to form a homogeneous complex solution. Under stirring conditions, a mixed alkaline solution of KOH and K₂CO₃ was added dropwise until the pH reached 9.5. The suspension was then transferred to a hydrothermal reactor and heated at 50 °C. o Stir at C for 120 min to complete co-precipitation. 75 o C aging for 5 hours, 105 o Hydrothermal crystallization at C for 3 hours. After washing until neutral, at 60°C... o Vacuum drying at 100°C for 7 hours. o C. Blow dry for 3 hours.

[0030] 500 o Calcination at C for 4 h. Then, in a 30 vol.% H2 / N2 atmosphere, at 380 °C. o C reduction for 2 h yielded a Co / Ga2O3-ZnO catalyst. The mass fraction of CoO was 42%, Ga2O3 was 8%, and ZnO was 50%.

[0031] (2) Catalytic performance 1) The operation method according to Example 1 2) At a reaction temperature of 150°C o At C, under a pressure of 6 MPa and H2, the reaction was carried out in ethanol solvent for 2 h, with a furfuryl alcohol conversion of 100% and a 1,5-pentanediol selectivity of 97.6%.

[0032] Example 6: The catalyst prepared in Example 1 was recycled 6 times under the conditions of Example 1. The catalyst activity and product selectivity did not decrease significantly. Figure 2 This indicates that the catalyst has excellent stability.

[0033] Comparative Example 1 (no additives, traditional co-precipitation) Except for the absence of any structure-regulating additives, the other components, dosages, calcination and reduction conditions were exactly the same as in Example 1.

[0034] (2) Catalytic performance 1) The operation method according to Example 1 2) At a reaction temperature of 160°C oAt C, with a pressure of 5 MPa H2, the reaction time was 4 h, resulting in a furfuryl alcohol conversion of 80% and a 1,5-pentanediol selectivity of 42%.

[0035] Comparative Example 2 (Conventional Impregnation Method, Solid Carrier) (1) Solid Al2O3 was used as a carrier, and Ni and Ga active components were loaded by the traditional impregnation method. The proportions of other components, calcination and reduction conditions were the same as in Example 2.

[0036] (2) Catalytic performance 1) The operation method according to Example 1 2) At a reaction temperature of 150°C o At C, with a pressure of 6 MPa H2, the reaction time was 4 h, and the conversion rate of furfuryl alcohol was 83%, while the selectivity of 1,5-pentanediol was 38.2%. The catalytic selectivity was significantly lower than that of the embodiments of the present invention.

[0037] The above experiments show that the prepared catalyst significantly improves the catalyst's activity, selectivity, and stability, and has high industrial application value.

[0038] Compared to the shortcomings of existing technologies, the traditional petrochemical synthesis process of 1,5-pentanediol involves strong acids and highly corrosive raw materials, requiring production equipment made of highly corrosion-resistant special materials, resulting in high equipment purchase and maintenance costs. This patent innovatively and non-obviously adopts a biomass-based furfuryl alcohol as raw material and a non-precious metal multi-component composite oxide catalyst system without acidic additives. It does not introduce strong acids or highly corrosive reagents throughout the process, and the reaction system is a neutral / weakly alkaline environment. It does not require special anti-corrosion equipment, thus avoiding equipment corrosion problems from the source and significantly reducing equipment investment and operation and maintenance costs.

[0039] Compared to the shortcomings of existing technologies, traditional petroleum-based processes require harsh conditions of high temperature and high pressure, resulting in high energy consumption and costs, which violate carbon reduction and energy conservation policies. This patent innovatively and non-obviously limits the reaction temperature for the hydrogenation of furfuryl alcohol to 1,5-pentanediol to 150 ℃-200 ℃ and the hydrogen pressure to 2 MPa-6 MPa. The operating conditions are mild, eliminating the need for extreme high temperature and high pressure environments, significantly reducing production energy consumption, and meeting the requirements of green chemical energy conservation and emission reduction.

[0040] Compared to the shortcomings of existing technologies, traditional processes rely on non-renewable petroleum derivatives as their core raw materials. Raw material costs are highly susceptible to oil price fluctuations, and production results in numerous byproducts, high pollutant emissions, and high environmental treatment costs. This patent innovatively and non-obviously utilizes the biomass platform compound furfuryl alcohol / furfural as a raw material, leveraging renewable agricultural and forestry biomass resources to break free from dependence on petroleum fossil resources. This ensures a stable raw material supply and controllable costs. Furthermore, by utilizing the selective catalytic effect of the catalyst to directionally break the C2-O1 bond of the furan ring, byproducts are minimal, atom utilization is high, and emissions of waste and environmental treatment pressures are significantly reduced.

[0041] Compared to the shortcomings of existing technologies, traditional petroleum-based synthesis processes suffer from low atom utilization, serious resource waste, and difficulty in meeting the needs of modern chemical industry development in terms of production economy and greenness. This patent innovatively and non-obviously utilizes the atomic-level dispersion of active sites in non-precious metal multi-component composite oxides and the synergistic effect of oxygen vacancies and basic sites to achieve tilted adsorption and directional ring-opening hydrogenation of furan reactants at the C2-end. The reaction has extremely high atom economy, with reactant atoms participating efficiently in the synthesis of 1,5-pentanediol without any ineffective atom loss, thus balancing production economy and green process.

[0042] Compared to existing technologies that use platinum-based molecular sieve-supported catalysts, which achieve only 86.1% conversion of furfuryl alcohol reactants and have low raw material utilization, this patent innovatively constructs a multi-component composite oxide atomic-level dispersed catalytic system with Co / Ni as the main active component, Pr / Mn / Ga / Sc as the auxiliary metal, and Zr / Al / Ti as the support. This system, combined with synergistic active sites of oxygen vacancies and basic sites, significantly enhances the activation and conversion capacity of furfuryl alcohol, achieving near-complete conversion. Furthermore, no acidic additives such as hydrochloric acid are added throughout the process, eliminating corrosive media in the reaction system, avoiding equipment corrosion and acidic wastewater pollution, and simplifying subsequent product separation and purification processes.

[0043] Compared to existing technologies, the NiLa composite catalyst has a long reaction cycle of up to 24 hours, resulting in insufficient equipment utilization and large-scale production capacity. The selectivity of the target product, 1,5-pentanediol, is only 78%, and it easily generates byproducts such as pentanol and tetrahydrofurfuryl alcohol, leading to high purification costs and low overall yield. This patent innovatively and non-obviously employs a complexation-homogeneous precipitation coupled soft template method, a two-stage gradient crystallization + gradient drying + programmed temperature calcination method to prepare the catalyst. It precisely controls the surface oxygen vacancy concentration and basicity site density, forcibly achieving directional breakage of the C2-O1 bond in the furan ring, suppressing side reactions, and significantly improving the selectivity of 1,5-pentanediol. At the same time, the reaction time is limited to 2 to 10 hours, which greatly shortens the working time compared to the existing 24-hour reaction cycle, improves the efficiency of single-batch production and equipment utilization, and meets the needs of continuous industrial production.

[0044] Compared to the shortcomings of existing technologies, conventional non-precious metal catalysts are prone to metal component agglomeration and poor dispersibility. Under high-temperature hydrogenation conditions, metals are easily sintered and lost, resulting in short catalyst life and insufficient cycle stability. This patent innovatively introduces Pr, Ga, and Sc rare earth / rare earth-like metal components in a non-obvious manner. The special electronic layer structure precisely controls the electronic valence state of the main metal Co / Ni, weakening metal particle agglomeration. At the same time, it strengthens the metal-support interface interaction, inhibits metal sintering and active component loss during high-temperature hydrogenation, and combines the chelating and complexing effects of structural additives such as starch, sodium alginate, and PEG to achieve high atomic-level dispersion of multi-metal components, significantly improving catalyst life and cycle stability.

[0045] Compared to existing technologies, traditional supported catalysts suffer from uneven metal loading, component segregation, irregular pores, low specific surface area, and high resistance to diffusion and mass transfer between reactants and products, thus limiting catalytic reaction efficiency. This patent innovatively and non-obviously employs a homogeneous complexation process with fully soluble salts, eliminating the need for a pre-existing solid support and fundamentally eliminating the problems of uneven loading and metal segregation. By relying on the in-situ construction of regular mesoporous channels and layered double hydroxide-like nanosheets through the calcination and pyrolysis of structure-regulating additives, the pores are interconnected, the specific surface area is significantly increased, the mass transfer resistance between reactants and products is reduced, and the catalytic reaction efficiency is further enhanced.

[0046] Compared to the shortcomings of existing technologies, the current furfuryl alcohol hydrogenolysis catalytic system struggles to simultaneously meet the multiple industrial requirements of high furfuryl alcohol conversion, high selectivity of 1,5-pentanediol, mild reaction conditions, no corrosive additives, short reaction cycle, and long catalyst life. This patent innovatively and non-obviously addresses the industry's pain points across all dimensions—conversion rate, selectivity, corrosion under operating conditions, production efficiency, and catalyst stability—through an integrated design that precisely proportions the main metal-cooperating metal-support ternary components, synergistically regulates oxygen vacancies and basic sites, and controls the atomic-level dispersion morphology. Combined with a solvent system that limits temperature, pressure, and time, this patent provides a one-stop solution to these issues. It can be directly adapted for the green and large-scale industrial production of 1,5-pentanediol.

[0047] Figure 1 shows the SEM microstructure of the non-noble metal multi-component composite oxide catalyst. The test scale is 500 nm, the magnification is 20.0 kx, the characterization current is 62 pA, and the working distance is 4.51 mm.

[0048] From a microstructural perspective, the catalyst exhibits a regular stacked morphology of nanosheets, with uniform particle dispersion and no obvious agglomeration or clumping. It forms a continuous mesoporous channel structure with well-developed and uniform pore size, and the interwoven layers create a three-dimensional, interconnected network. This microstructure benefits from the patented complexation-homogeneous precipitation coupled soft template method, the coordination and chelation effect of structure-regulating additives, and the gradient crystallization and gradient drying processes: the additives inhibit rapid nucleation of metal ions and particle agglomeration, inducing preferential crystal growth along the layer direction. Simultaneously, the pyrolysis of the additives after calcination forms regular mesopores in situ, giving the catalyst a large specific surface area, abundant pore structure, and sufficient surface defect sites.

[0049] Figure 2 shows the performance correlation between the number of catalyst cycles and furfuryl alcohol conversion and 1,5-pentanediol selectivity. The horizontal axis represents the number of catalyst cycles, and the vertical axis represents the percentage. It includes two indicators: furfuryl alcohol conversion and 1,5-pentanediol selectivity.

[0050] As can be seen from the graph trends, the furfuryl alcohol conversion rate remained at a high level close to 100% with increasing catalyst recycling rates, showing no significant decline; the 1,5-pentanediol selectivity remained stable above 80%, with only slight fluctuations after multiple cycles, without a substantial decrease. Overall, it exhibits excellent catalytic activity stability, product selectivity stability, and cycle life.

[0051] Figure 1 shows that the microstructure characterization fully demonstrates that the present invention uses a complexation-homogeneous precipitation coupled soft template method with multi-functional structural additives to successfully prepare a multi-component composite oxide catalyst with atomic-level metal dispersion, nanosheet stacking, and regular mesoporous structure. It achieves the controllable construction of oxygen vacancies and basic sites as synergistic active sites at the microstructural level, effectively solving the drawbacks of traditional non-noble metal catalysts such as metal agglomeration, disordered pore structure, and low specific surface area.

[0052] Figure 2 shows the catalytic cycle performance, which strongly demonstrates that the non-precious metal multi-component composite oxide catalyst, when applied to the hydrogenation of furfuryl alcohol to 1,5-pentanediol, not only exhibits excellent initial catalytic activity and target product selectivity, but also strong resistance to sintering and leaching, and extremely slow performance degradation during recycling. It possesses the long-cycle stability and practical value required for industrial catalytic applications.

[0053] In summary, this invention relates to the field of biomass catalytic conversion technology, and particularly to a multi-functional additive non-precious metal multi-component composite oxide catalyst, its preparation method, and its applications. It comprises a first metal component, a second metal component, and an oxide support; the first metal component is selected from one or two of Co and Ni; the second metal component is selected from one or more of Pr, Mn, Ga, and Sc; the support metal component is selected from one or more of Zr, Al, Ti, Si, Mg, and Zn; based on the total weight of the catalyst, the oxide content of the first metal component is 20 wt.%~60 wt.%, the oxide content of the second metal component is 1 wt.%~20 wt%, and the oxide support content is 20 wt.%~70 wt%. The composite oxide framework formed by the co-precipitation of multiple metals has a stable structure, and the interfacial interaction between the metal components and the support is strong, effectively inhibiting the sintering and loss of metal particles and improving the catalyst's cycle stability.

Claims

1. A multi-functional additive non-precious metal multi-component composite oxide catalyst, characterized in that, It comprises a first metal component, a second metal component, and an oxide support; The first metal component is selected from one or two of Co and Ni; The second metal component is selected from one or more of Pr, Mn, Ga, and Sc; The carrier metal component is selected from one or more of Zr, Al, Ti, Si, Mg, and Zn; Based on the total weight of the catalyst, the content of the first metal component oxide is 20 wt.% to 60 wt.%, the content of the second metal component oxide is 1 wt.% to 20 wt%, and the content of the oxide support is 20 wt.% to 70 wt%.

2. The multi-functional additive non-precious metal multi-component composite oxide catalyst as described in claim 1, characterized in that, The catalyst is a composite oxide formed by the co-precipitation of multiple metals, with the metal components dispersed at the atomic level and the surface having a controllable distribution of oxygen vacancies and basic sites. The catalyst can achieve tilted adsorption of furan reactants at the C2-end by adjusting the surface oxygen vacancy concentration and basic site density, and directionally break the C2-O1 bond of the furan ring.

3. A method for preparing a multi-functional additive non-precious metal multi-component composite oxide catalyst, characterized in that, The first metal component is selected from one or two of Co and Ni; The second metal component is selected from one or more of Pr, Mn, Ga, and Sc; The carrier metal component is selected from one or more of Zr, Al, Ti, Si, Mg, and Zn; Based on the total weight of the catalyst, the content of the first metal component oxide is 20 wt.%~60 wt.%, the content of the second metal component oxide is 1 wt.%~20 wt%, and the content of the oxide support is 20 wt.%~70 wt%. The complexation-homogeneous precipitation coupled soft template method is employed, including the following steps: (1) Dissolve the structure-regulating additive in an alcohol-water mixed solvent, then add the first metal soluble salt, the second metal soluble salt and the carrier metal soluble salt, stir at room temperature for 30 min ~ 120 min to form a clear and transparent multi-metal complex homogeneous solution. (2) Slowly add an alkaline precipitant to the homogeneous solution of the multi-metal complex, control the pH of the system to 9.0~13.0, and stir at a constant temperature of 35℃~60℃ for 30 min~180 min to achieve simultaneous co-precipitation of all metal ions; (3) The precipitate is subjected to two-stage gradient crystallization: the first stage is static aging at 40 ℃~80 ℃ for 2 h~8 h, and the second stage is hydrothermal crystallization at 90 ℃~150 ℃ for 2 h~4 h; (4) The crystallized product was washed alternately with deionized water and ethanol until the filtrate was neutral and free of NO3. - Detected, then subjected to gradient drying; (5) The dried precursor was calcined in air under programmed heating and then naturally cooled to obtain a non-precious metal multi-component composite oxide catalyst. During the preparation process: the structure-regulating additives not only coordinate with metal ions to form stable complexes, inhibiting the rapid nucleation and aggregation of metal ions, but also pyrolyze during calcination to form mesoporous channels, thereby regulating the specific surface area and pore structure of the catalyst and improving the diffusion efficiency of reactants and products.

4. The preparation method of the multi-functional additive non-precious metal multi-component composite oxide catalyst as described in claim 3, characterized in that, The structure-regulating additive is selected from one or more of starch, sodium alginate, PEG, glycerol, and ethylene glycol, and the amount added is 2 wt.% to 15 wt.% of the total mass of all metal salts.

5. The preparation method of the multi-functional additive non-precious metal multi-component composite oxide catalyst as described in claim 3, characterized in that, The first metal soluble salt, the second metal soluble salt, and the carrier metal soluble salt are all selected from one or more of nitrates, acetates, and chlorides; in the alcohol-water mixed solvent, the volume ratio of deionized water to anhydrous ethanol is 1:1 to 6:1; the alkaline precipitant is one or two of NaOH, Na2CO3, KOH, K2CO3, and ammonia.

6. The preparation method of the multi-functional additive non-precious metal multi-component composite oxide catalyst as described in claim 3, characterized in that, Pr, Ga, and Sc are rare earth or rare earth-like metals with special electronic structures, which can easily induce the generation of abundant oxygen vacancies on the catalyst surface. They can finely control the density and intensity of basic sites on the catalyst surface, constructing "oxygen vacancy-basic site" synergistic active sites. They can also control the electronic valence state of the main metal Co / Ni, weaken metal particle agglomeration, and achieve high atomic-level dispersion of metals. Strengthening the metal-carrier interface and inhibiting metal sintering and loss of polysaccharides, polyols, and PEGs under high-temperature hydrogenation. PEGs contain numerous hydroxyl groups and ether bonds, which can interact with... , , , When metal ions form stable chelate complexes, the rapid nucleation of metal ions is slowed down and particle agglomeration is avoided, achieving homogeneous atomic-level dispersion of multi-metals; during the calcination process, the additives are gradually pyrolyzed and carbonized, and leave in situ, constructing regular mesoporous channels and layered lamellar structures, which greatly increases the specific surface area; the additive molecules are adsorbed on the surface of the crystal nuclei, inducing the crystals to grow preferentially along the lamellar direction, forming a hydrotalcite-like nanosheet stacked morphology with interconnected pores and low mass transfer resistance. The homogeneous complexation of fully soluble salts without the pre-existing solid carrier eliminates the problems of uneven loading and metal segregation at the source, achieving atomic-level mixing; gradient crystallization first aging at low temperature to regulate crystal nuclei, and then hydrothermal crystallization to assemble the lamellar structure, making crystal defects controllable and oxygen vacancy concentration precisely adjustable; gradient drying first removes free water in vacuum at low temperature, and then dries bound water by air, avoiding hard agglomeration of particles and maintaining the lamellar structure of the precursor. The slow temperature rise during programmed calcination ensures the gradual decomposition of additives and the stable formation of oxide crystal phases, while preserving abundant defects and pore structures. It exhibits strong interfacial bonding between the metal and the support, resists sintering and leaching, and boasts a service life and cycle stability far exceeding those of traditional non-precious metal catalysts.

7. The preparation method of the multi-functional additive non-precious metal multi-component composite oxide catalyst as described in claim 3, characterized in that, The gradient drying process involves first vacuum drying at 60 °C for 6 to 10 hours, followed by forced-air drying at 100 °C for 2 to 8 hours. The programmed temperature calcination process involves increasing the temperature to 350 °C to 550 °C at a rate of 1 °C / min to 3 °C / min and holding for 3 to 6 hours. The process also includes an optional reduction step: reducing the calcined catalyst at 300 °C to 500 °C for 1 to 5 hours in a 30% V H2 / N2 mixed atmosphere.

8. The application of the multi-functional additive non-precious metal multi-component composite oxide catalyst according to any one of claims 1–3 in the hydrogenation of furfuryl alcohol to prepare 1,5-pentanediol.

9. A method for preparing 1,5-pentanediol by hydrogenation of furfuryl alcohol using a multi-functional additive non-precious metal multi-component composite oxide catalyst, characterized in that, The reaction conditions are: reaction temperature 150 ℃~200 ℃, hydrogen pressure 2 MPa~6 MPa, reaction time 2 h~10 h, and the reaction solvent is selected from ethanol, isopropanol, water or a mixture thereof.

10. A multi-functional additive non-precious metal multi-component composite oxide catalyst, characterized in that, The catalyst is any one of the following: Option 1: Co-Mn / ZrO2 catalyst (additive: starch) (1) Catalyst preparation: Mix 300 mL of deionized water with 100 mL of anhydrous ethanol, add 5.0 g of starch, and stir until completely dissolved (60 g / mL). o (C) Heating-assisted dissolution to form a homogeneous solvent system; 48.4 g of cobalt nitrate hexahydrate, 9.6 g of manganese nitrate hexahydrate, and 50.3 g of zirconium nitrate pentahydrate were added sequentially, and the mixture was stirred at room temperature for 90 min to form a transparent homogeneous complex solution; under stirring, a mixed alkaline solution of NaOH and Na2CO3 was slowly added dropwise to adjust the pH of the system to 10.0, and the solution was maintained at 50°C. o Stir for 120 min at C to complete simultaneous co-precipitation; The suspension was then transferred to a hydrothermal reactor and heated at 70°C. o Static aging at C for 6 hours, then heating to 100°C o Hydrothermal crystallization at C for 3 h; the product was washed alternately with deionized water and anhydrous ethanol until neutral (pH=7.0), then at 60 °C. o Vacuum dry at C for 8 hours, then at 100°C. o Dry in a forced-air environment for 3 hours; then dry in air at 2°C. o The heating rate was increased to 500 °C / min. o C, calcined for 4 h to obtain a composite oxide precursor; in a 30 vol.% H2 / N2 mixed atmosphere, 350 o C reduction for 3 h yielded a Co / Mn2O3-ZrO2 catalyst; wherein the mass fraction of CoO was 40%, the mass fraction of Mn2O3 was 8%, and the mass fraction of ZrO2 was 52%. Option 2: Ni-Ga / Al2O3 catalyst (additive: sodium alginate) (1) Catalyst preparation: 400 mL of deionized water and 100 mL of anhydrous ethanol were mixed, and 3.2 g of sodium alginate was added. The mixture was stirred until completely dissolved to form a homogeneous solvent system. 30.2 g of nickel nitrate hexahydrate, 5.10 g of gallium nitrate, and 72.3 g of aluminum nitrate nonahydrate were added sequentially. The mixture was stirred at room temperature for 120 min until homogeneous and transparent. NaOH alkaline solution was added dropwise while stirring to adjust the pH of the system to 9.

5. The suspension was then transferred to a hydrothermal reactor and heated at 45°C. o Stirring at C for 150 min completes co-precipitation; then sequentially subjected to 65... o C aging for 8 hours, 95 o Gradient crystallization was performed using hydrothermal crystallization at C for 4 h; then the suspension was washed until neutral and crystallized at 60 °C. o Vacuum drying at C for 6 hours, then at 110 o Drying at 2°C with forced air for 4 hours; o Temperature increased to 500°C / min o C, calcined for 5 h; then in a 30 vol.% H2 / N2 atmosphere, at 380 °C. o C reduction for 3 h yielded a Ni / Ga2O3-Al2O3 catalyst; wherein the mass fraction of NiO was 40%, the mass fraction of Ga2O3 was 9.6%, and the mass fraction of Al2O3 was 50.4%. Option 3: Co-Pr / ZnO catalyst (additives: glycerol + ethylene glycol) (1) Catalyst preparation method: Mix 300 mL of deionized water with 100 mL of ethanol, add 3 mL of glycerol and 3 mL of ethylene glycol, and stir until completely dissolved to form a homogeneous solvent system; add 43.5 g of cobalt nitrate hexahydrate, 6.2 g of praseodymium nitrate hexahydrate, and 49.5 g of zinc nitrate hexahydrate in sequence, and stir for 90 min to form a homogeneous complex solution. Under stirring conditions, add KOH alkaline solution dropwise until the pH is 10.

0. o Stir for 120 min at C to complete co-precipitation; The suspension was then transferred to a hydrothermal reactor and heated at 70°C. o C aging for 6 hours, 100 o C hydrothermal crystallization for 3 h; after washing until neutral, 60 o Vacuum drying at 100°C for 7 hours. o C. Blow dry for 3 hours; 500 o Calcination at C for 4 h; then calcined at 30 vol.% H2 / N2 atmosphere for 300 h. o C reduction for 4 h yields Co / Pr6O 11 -ZnO catalyst; wherein the mass fraction of CoO is 41%, and Pr6O 11 The mass fraction of ZnO is 9%, and the mass fraction of ZnO is 50%. Option 4: Ni-Mn / MgO catalyst (additive: PEG-6000) (1) Mix 350 mL of deionized water with 70 mL of ethanol, add 4.50 g of PEG-6000, stir to dissolve, and form a homogeneous solvent system; add 30.8 g of nickel nitrate hexahydrate, 9.6 g of manganese nitrate hexahydrate, and 68 g of magnesium nitrate hexahydrate in sequence, and stir for 80 min to form a homogeneous complex solution; under stirring conditions, add a mixed alkaline solution of NaOH and Na2CO3 dropwise until pH=10.1, 55 o Stir at C for 100 min to complete co-precipitation; then transfer the suspension to a hydrothermal reactor, first at 80°C. o C aging for 4 hours, 110 o C hydrothermal crystallization for 2 h; washing until neutral, then 60 o Vacuum drying at 105°C for 8 hours o C-air drying for 3 hours; 550 o Calcination at C for 3 h; then calcined at 350 °C in a 30 vol.% H2 / N2 atmosphere. o C reduction for 4 h yielded a Ni-Mn / MgO catalyst; wherein the mass fraction of NiO was 40%, the mass fraction of Mn2O3 was 13.3%, and the mass fraction of MgO was 46.7%. Option 5: Co-Ga / ZnO catalyst (additives: starch + sodium alginate) (1) Mix 300 mL of deionized water with 100 mL of ethanol, add 2.5 g of starch and 2.0 g of sodium alginate, and stir until completely dissolved (60 g / mL). o (C heating assisted) to form a homogeneous solvent system, 50.9 g of cobalt nitrate hexahydrate, 6.6 g of gallium nitrate, and 53.9 g of zinc nitrate hexahydrate were added sequentially, and the mixture was stirred for 90 min to form a homogeneous complex solution; under stirring conditions, a mixed alkaline solution of KOH and K2CO3 was added dropwise until the pH reached 9.5, and then the suspension was transferred to a hydrothermal reactor, first heated to 50... o Stir at C for 120 min to complete co-precipitation; 75 o C aging for 5 hours, 105 o C hydrothermal crystallization for 3 h; after washing until neutral, 60 o Vacuum drying at 100°C for 7 hours. o C. Blow dry for 3 hours; 500 o Calcination at C for 4 h; then calcined at 380 °C in a 30 vol.% H2 / N2 atmosphere. o C reduction for 2 h yielded a Co / Ga2O3-ZnO catalyst; wherein the mass fraction of CoO was 42%, the mass fraction of Ga2O3 was 8%, and the mass fraction of ZnO was 50%.

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