Solvent-free, low-by-product, highly directional, and noble metal-free furfuryl alcohol hydrogenation catalysts and preparation methods, and methods for preparing tetrahydrofurfuryl alcohol.

Abstract

This invention relates to the field of tetrahydrofurfuryl alcohol (THA) preparation technology, and particularly to a solvent-free, low-by-product, highly oriented, and noble metal-free furfuryl alcohol hydrogenation catalyst and its preparation method, as well as a method for preparing THA. The FTA hydrogenation catalyst comprises a support and an active component supported on the support. The active component is metallic Ni and a rare earth additive. The support is an Al₂O₃-ZrO₂ composite oxide, with Ni content of 10%-20%, La content of 1%-5%, Al₂O₃ content of 70%-90%, and ZrO₂ content of 10%-30% by weight of the support. This invention uses the structural additive ZrO₂ to modify the Al₂O₃ support, obtaining a composite oxide support with moderate acidity, which avoids the influence of oligomers formed during furfuryl alcohol polymerization on the catalyst activity and stability. Using La as an auxiliary component improves the furfuryl alcohol conversion rate and THA selectivity in the furfuryl alcohol addition reaction, ensuring a high THA yield.

Description

Technical Field

[0001] This invention relates to the field of tetrahydrofurfuryl alcohol preparation technology, specifically to a furfuryl alcohol hydrogenation catalyst, a preparation method, and a process for producing tetrahydrofurfuryl alcohol using the catalyst. In particular, it relates to a solvent-free, low-by-product, highly directional, and noble metal-free furfuryl alcohol hydrogenation catalyst and its preparation method, as well as a method for preparing tetrahydrofurfuryl alcohol. Background Technology

[0002] Tetrahydrofurfuryl alcohol (THF) is a colorless, transparent liquid with a molecular weight of 102.13, a boiling point of 178°C, a freezing point of -80°C, a flash point of 75°C, a relative density of 0.98 (20°C), and a refractive index of 1.427 (20°C). It has a slightly pleasant odor. As an organic solvent, it is a good fluxing agent in electronic chemicals and soldering fluxes, and a good solvent for cellulose, polystyrene, phenolic resins, coatings, and oils. Furthermore, as a chemical intermediate, THF is a raw material for the synthesis of lysine, long-acting vitamin B, and polyamide plastics; it can also undergo catalytic ring-opening to yield 1,5-pentanediol, a monomer for various polyesters and polyurethanes, and has wide applications and commercial prospects.

[0003] Furfuryl alcohol has a molecular weight of 98.09, a melting point of -29℃, a boiling point of 170℃, and a density of 1.130. It is a colorless, oily liquid that gradually turns brown or dark red upon exposure to sunlight or air. It is a basic organic chemical intermediate, mainly used in the production of furan resins, furfuryl alcohol-urea-formaldehyde resins, and phenolic resins with various properties. Hydrogenation produces tetrahydrofurfuryl alcohol, a good solvent for varnishes and pigments, and also used in rocket fuel.

[0004] The article "Journal of China University of Petroleum, 2003, 27(1), 94" reports the preparation of tetrahydrofurfuryl alcohol by liquid-phase hydrogenation of furfuryl alcohol in a suspended bed using a skeletal nickel catalyst. Under reaction conditions of 2-6% skeletal nickel catalyst and 5-6 MPa hydrogen pressure, the conversion rate of furfuryl alcohol reached over 99%, and the selectivity of tetrahydrofurfuryl alcohol was about 97%. Adding ethanol as a solvent for dilution can reduce the content of impurity pentanediol and improve the selectivity of tetrahydrofurfuryl alcohol.

[0005] On April 27, 2026, a comprehensive search was conducted in the Chinese Patent Publication Database with ((FULL=((Ni or nickel) and (La or lanthanum)and (Al2O3or aluminum oxide)and (ZrO or zinc oxide)and catalyst and hydrogenation and furfuryl alcohol) AND (IPC=(B01J23 / 78) OR IPC=(B01J23 / 10) OR IPC=(B01J37 / 02) OR IPC=(B01J37 / 03)OR IPC=(C07D307 / 12) OR IPC=(C07C29 / 17)))). CN106622219A: It uses a Ru / γ-Al2O3 noble metal catalyst with the active component being the noble metal ruthenium, no Ni, no La, and no ZrO2 composite support, resulting in extremely high costs; it does not have the acidic regulation ability to inhibit the polymerization of furfuryl alcohol and cannot be used in a long-term fixed bed; it only pursues high selectivity in a batch reactor and does not pay attention to the catalyst life and anti-coking performance; in terms of process, it uses a batch reactor, the reaction time is 1 - 5 h, solvents such as methanol need to be added, and subsequent separation is cumbersome, making continuous industrial production impossible.

[0006] CN109261152A: The catalyst is Fe / Co / Cu / Ni + CaO / CaCO3 support, without La, without ZrO2, and without Al2O3–ZrO2 composite structure; for the hydrogenation of furfural to furfuryl alcohol, it is not suitable for the hydrogenation of furfuryl alcohol; without acidic regulation, it is extremely easy to cause the polymerization and coking of furfuryl alcohol, and the catalyst life is extremely poor; in terms of process, it is a batch reaction, ethanol and other solvents need to be used, the reaction time is 4 - 12 h, it cannot be adapted to continuous industrial production, and the target product is furfuryl alcohol, which is completely different from tetrahydrofurfuryl alcohol.

[0007] CN111205173A: The catalyst is Cu-based, Raney Ni, Ru, Pd, etc., without La rare earth and without Al2O3–ZrO2 composite support; the system has a chaotic and non-directional ratio, and the conversion rate and selectivity for furfuryl alcohol hydrogenation are extremely low, making it impossible to achieve high yields; in terms of process, 2-butanol dehydrogenation is used as the hydrogen source (not pure hydrogen), the hydrogen source efficiency is low, the reaction system is for the conversion of multi-category biomass molecules without directionality, making it impossible to achieve high selectivity in the preparation of tetrahydrofurfuryl alcohol, and there is no continuous process design.

[0008] CN118176275A: The catalyst is a system for fuel synthesis such as ZnO–CeO2–MgO–Al2O3, NiO–CuO–Cr2O3, etc., and is completely not used for furfuryl alcohol hydrogenation; there is no Ni–La–Al2O3–ZrO2 system and no active design for the hydrogenation of the furan ring; in terms of process, it is a route for the preparation of engine fuel from ethanol, and the reaction path is ethanol dehydration, oligomerization, and hydrogenation to hydrocarbons, which is completely irrelevant to the hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol and cannot achieve high selectivity in the preparation of fine chemical intermediates.

[0009] CN119236952A: Without a composite oxide support, rare earth La additive, or ZrO2 modification, the catalyst is easily blocked by furfuryl alcohol polymers, resulting in a rapid decline in activity. The process is likely to be a batch reactor reaction, requiring the addition of solvents, lacking continuous production capability, with a short catalyst life, unable to meet the requirements of long-term industrial operation, and the catalytic effect cannot balance conversion rate and selectivity.

[0010] CN119954644A: Without the Ni–La–Al2O3–ZrO2 quaternary system, there is no precise ratio, and activity and selectivity cannot be balanced; the catalyst lacks anti-polymerization design, and when used for furfuryl alcohol hydrogenation, it is prone to polymerization side reactions, resulting in high by-product content and low yield; the process lacks continuous design, making it unsuitable for large-scale industrial production, and the catalyst cost is relatively high.

[0011] CN121016862A: It uses a Pd / mesoporous SiO2 noble metal catalyst, which is free of Ni, La and ZrO2, resulting in high cost and inability to inhibit furfuryl alcohol polymerization; it is only suitable for batch reactions and does not have the stability required for industrial fixed-bed reactions; in terms of catalytic effect, the selectivity is less than 95%, the yield is less than 90%, and the catalyst is prone to carbon deposition and deactivation, making it unable to operate for long periods of time.

[0012] Chinese patent CN106622219 describes a ruthenium-supported catalyst. In a reactor containing furfuryl alcohol and solvent, with 1-10% Ru / alumina, at 20-80°C, 2-4 MPa hydrogen, for 1-5 hours at 500-1000 rpm, the furfuryl alcohol conversion is 98%, the tetrahydrofurfuryl alcohol selectivity is 95%, and the catalyst can be reused 30 times. US patent 4,459,419 describes a method for preparing a supported ruthenium catalyst. It involves loading 1-2% ruthenium onto a molecular sieve, using methanol as solvent (methanol to furfuryl alcohol volume ratio 5:1), with Ru / molecular sieve at 10%, reacting at 45°C, 12.7 MPa pressure, for 0.5 hours, achieving a 100% tetrahydrofurfuryl alcohol yield.

[0013] Patent CN121016862 reports a Pd-supported catalyst method for the hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol. This catalyst uses mesoporous silica as a support, with the support surface modified with polyethylene glycol and alkyl chains to form an amphiphilic surface, and Pd nanoparticles loaded inside the mesopores. In its designed reactor at 150°C and 1.5 MPa, the reaction time was 3 hours, achieving a tetrahydrofurfuryl alcohol yield of approximately 99%. Additionally, patent CN104610199 describes a Pd / titanium oxide catalyst method for the liquid-phase hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol, achieving high yields under low-temperature (15-30°C) and low-pressure (0.1-0.5 MPa) conditions; this catalyst requires activation treatment with reducing agents such as sodium borohydride.

[0014] Although these literature patents report the successful operation of the hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol, achieving good conversion and selectivity, the use of batch reactors results in high cost and low efficiency. Furthermore, our company, Shandong Yinuo Biomass Materials Co., Ltd., has built a batch reactor-type production line with an annual capacity of 5,000 tons of tetrahydrofurfuryl alcohol, also using Raney nickel catalyst and furfuryl alcohol liquid-phase batch hydrogenation technology. Nearly ten years of production experience has shown that although the yield of tetrahydrofurfuryl alcohol is high, the batch reactor operation results in long reaction times, significant hydrogen waste, difficulties in catalyst recovery, and environmental emissions. Summary of the Invention

[0015] The purpose of the invention is to provide a better solvent-free, low-by-product, highly directional, and precious metal-free furfuryl alcohol hydrogenation catalyst and preparation method, as well as a method for preparing tetrahydrofurfuryl alcohol. Specific objectives are detailed in the specific implementation section, which outlines several substantial technical effects.

[0016] To achieve the above objectives, the present invention adopts the following technical solution: A solvent-free, low-by-product, highly directional, and precious metal-free furfuryl alcohol hydrogenation catalyst, comprising a support and an active component supported on the support; characterized in that the active component is metallic Ni and rare earth additive La, and the support is an Al2O3-ZrO2 composite oxide. Based on the mass of the carrier, the Ni content is 10-20 parts, the La content is 1-5 parts, the Al2O3 content is 70-90 parts, and the ZrO2 content is 10-30 parts.

[0017] A further technical solution of the present invention is that the Ni content is 14-20 parts, the La content is 1.5-3 parts, the Al2O3 content is 77-87 parts, and the ZrO2 content is 13-23 parts.

[0018] A further technical solution of the present invention is that the Ni content is 17 parts, the La content is 2.2 parts, the Al2O3 content is 80 parts, and the ZrO2 content is 20 parts; or The content of Ni is 20 parts, the content of La is 3 parts, the content of Al2O3 is 87 parts, and the content of ZrO2 is 13 parts.

[0019] A method for preparing a solvent-free, low-by-product, highly directional, and noble-metal-free furfuryl alcohol hydrogenation catalyst as described in any of the preceding claims, characterized by comprising the following steps: (1) Prepare aluminum nitrate and zirconium nitrate solutions, stir and mix them evenly to obtain a mixed acidic solution of metal salts, and prepare a 10% mass fraction ammonia solution as a precipitant; then, add the mixed proportion of metal salt solutions to a precipitation vessel, stir and at a temperature of 40~45℃, add the above ammonia solution dropwise to the precipitation vessel for co-precipitation, pH value 10; heat to 80℃ for aging for 20 hours, then filter, wash, dry at 110℃ for 12 hours, and calcine at 650℃ for 5 hours to obtain Al2O3-ZrO2 composite oxide; (2) Prepare a mixed aqueous solution containing nickel and lanthanum salt, adjust the pH value to 4-5, place the Al2O3-ZrO2 composite oxide obtained in step (1) into the mixed aqueous solution, impregnate for a first time, dry, and calcine to obtain Ni-La / Al2O3-ZrO2 catalyst.

[0020] A further technical solution of the present invention is that the first time is 3-5 hours; and / or, In step (1), the roasting temperature is 650℃-700℃, and the roasting time is 5-8 hours; and / or, In step (2), the roasting temperature is 420℃-450℃, and the roasting time is 5-8 hours; and / or, The reduction step in step (2) includes: placing the catalyst precursor in a hydrogen-nitrogen mixture, gradually raising the temperature to 300°C over 10 hours, then slowly raising the temperature to 450°C over 4 hours, and switching to pure hydrogen gas, and maintaining the temperature for 20 hours.

[0021] A further technical solution of the present invention is that the nickel salt is at least one selected from nickel nitrate and nickel acetate; and / or, The lanthanum salt is at least one of lanthanum nitrate and lanthanum acetate.

[0022] The method for producing tetrahydrofurfuryl alcohol is characterized by comprising the following steps: in the presence of a catalyst and hydrogen, furfuryl alcohol is hydrogenated to obtain tetrahydrofurfuryl alcohol. The catalyst is a solvent-free, low-by-product, highly directional, and precious metal-free furfuryl alcohol hydrogenation catalyst as described in any of the preceding claims.

[0023] A further technical solution of the present invention is that the reaction temperature is 90℃-140℃, the hydrogen pressure is 2.5-5.5MPa, and the furfuryl alcohol mass hourly space velocity is 0.1-0.5h. -1 The molar ratio of hydrogen to furfuryl alcohol is 10-50.

[0024] A further technical solution of the present invention is that the reaction temperature is 110-130℃, the hydrogen pressure is 3-4 MPa, and the furfuryl alcohol mass hourly space velocity is 0.2 h⁻¹. -1 -0.45h -1 .

[0025] A further technical solution of the present invention is that the reaction does not use a solvent; and / or the reaction is carried out in a continuous fixed-bed reactor; and / or it further includes a hydrogen return step, which allows the hydrogen in the reaction to be recycled.

[0026] The present invention, employing the above technical solution, has the following advantages over existing technologies: This invention, through analysis of literature and patents on the hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol, and based on the company's years of experience in applying nickel-based catalysts, proposes a fixed-bed catalytic hydrogenation process to achieve continuous production. Compared to batch reactors, this reduces the opportunity for materials and catalysts to come into contact with air, improving reaction safety. Simultaneously, the addition of a hydrogen return device allows for the recycling of hydrogen produced in the reaction, reducing hydrogen loss and minimizing atmospheric pollution from hydrogen waste gas emissions. It also simplifies the operation process. Detailed Implementation

[0027] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the specific content of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the protection scope of the present invention. Contents not described in detail in the embodiments of the present invention belong to the prior art known to those skilled in the art.

[0028] This invention provides a novel method for producing tetrahydrofurfuryl alcohol, which involves the catalytic hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol under the catalysis of a nickel-based catalyst on a composite support. To address the aforementioned technical problems, this invention provides a nickel-based catalyst for the hydrogenation of furfuryl alcohol and its preparation method, as well as a method adapted to a fixed-bed reaction process.

[0029] To address the aforementioned technical problems, this invention provides a nickel-based catalyst and its preparation method.

[0030] The furfuryl alcohol hydrogenation catalyst adapted to the method of this invention is a Ni-La / Al2O3-ZrO2 catalyst, wherein the main active component is Ni, the rare earth auxiliary component is La, and the composite oxide support is Al2O3-ZrO2. Taking the composite support of the catalyst as the denominator, the content of each active component is: Ni content is 10-20%, La content is 1-3%; the content of the composite oxide support Al2O3 is 73-87%, and the content of ZrO2 is 13-27%. Preferred component contents are: Ni content is 12-16%, La content is 1.5-2.5%; Al2O3 content is 77-83%, and ZrO2 content is 17-23%.

[0031] The present invention provides a method for the catalytic hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol, wherein the composite oxide support Al2O3-ZrO2 is prepared by precipitation method, and the catalyst is prepared by impregnation of nickel metal active components.

[0032] The specific catalyst preparation includes the following steps: Preparation of the composite oxide support Al2O3-ZrO2: First, a certain amount of aluminum nitrate and zirconium nitrate solutions were prepared and stirred until homogeneous to obtain a mixed acidic solution of metal salts, and a solution of about 10% ammonia water was used as a precipitant. Next, the mixed metal salt solution was added to a precipitation vessel, and while stirring at a temperature of 40-45℃, the aforementioned ammonia water was added dropwise to the precipitation vessel for co-precipitation, with a pH of ~10. The mixture was then aged at 80℃ for 20 hours, filtered, washed, dried at 110℃ for 12 hours, calcined at 650℃ for 5 hours, and finally crushed and sieved to prepare a 20-40 mesh composite alumina-zirconia support.

[0033] Finally, nickel nitrate and lanthanum nitrate were first acidified with ammonia water, and the required alumina-zirconia support was poured in and impregnated for 5 hours. The impregnated support was dried at 110°C for 12 hours and calcined at 450°C for 5 hours to obtain the aluminum zirconium oxide supported Ni-La / Al2O3-ZrO2 catalyst.

[0034] This invention provides a method for producing tetrahydrofurfuryl alcohol, which involves hydrogenating furfuryl alcohol under the action of a nickel-based catalyst precipitated on a composite support to produce tetrahydrofurfuryl alcohol.

[0035] In the above method, pure furfuryl alcohol without added solvent is used; The method uses a continuous fixed-bed reactor to prepare tetrahydrofurfuryl alcohol.

[0036] The above method for preparing tetrahydrofurfuryl alcohol using a fixed-bed reactor specifically involves: loading a metal catalyst supported on a composite carrier into a fixed bed; firstly, activating the catalyst by hydrogen reduction; using pure furfuryl alcohol as feedstock; and conducting the reaction at a temperature of 90–130°C, a pressure of 2.5–5.5 MPa, and a space velocity of 0.1–0.5 h⁻¹. -1 Under conditions where the hydrogen-to-alcohol molar ratio is 10-50, furfuryl alcohol is catalytically hydrogenated to produce tetrahydrofurfuryl alcohol.

[0037] Because furfuryl alcohol contains unsaturated furan rings and double bonds, it is prone to polymerization during reactions. Decreased hydrogen partial pressure and increased reaction temperature exacerbate this phenomenon. The resulting oligomers can clog catalyst pores and active surfaces, affecting catalyst lifespan and activity. This invention, through experiments, demonstrates that a composite-supported nickel-based catalyst can effectively inhibit furfuryl alcohol polymerization, ensuring catalyst lifespan and activity.

[0038] Catalyst Preparation Example 1 First, a certain amount of aluminum nitrate and zirconium nitrate solutions are prepared and stirred until homogeneous to obtain a mixed acidic solution of metal salts, with approximately 10% ammonia water as a precipitant. Next, the mixed metal salt solution is added to a precipitation vessel, and while stirring at 40-45°C, the aforementioned ammonia water is added dropwise to the vessel for precipitation, maintaining a pH of approximately 10. The mixture is then aged at 80°C for 20 hours, followed by filtration, washing, drying at 110°C for 12 hours, calcining at 650°C for 5 hours, and finally crushing and sieving to prepare a 20-40 mesh composite alumina-zirconia carrier.

[0039] Finally, nickel nitrate and lanthanum nitrate were first acidified with ammonia water, and the required alumina-zirconia support was poured in and impregnated for 5 hours. The impregnated support was dried at 110°C for 12 hours and calcined at 450°C for 5 hours to obtain the aluminum zirconium oxide supported Ni-La / Al2O3-ZrO2 catalyst.

[0040] The content of active component Ni is 11%, rare earth additive La is 1%, Al2O3 is 73%, and ZrO2 is 27%, with the mass of the composite oxide support as the denominator. The catalyst is labeled Cat1.

[0041] Catalyst Preparation Example 2 First, a certain amount of aluminum nitrate and zirconium nitrate solutions are prepared and stirred until homogeneous to obtain a mixed acidic solution of metal salts, with approximately 10% ammonia water as a precipitant. Next, the mixed metal salt solution is added to a precipitation vessel, and while stirring at 40-45°C, the aforementioned ammonia water is added dropwise to the vessel for precipitation, maintaining a pH of approximately 10. The mixture is then aged at 80°C for 20 hours, followed by filtration, washing, drying at 110°C for 12 hours, calcining at 650°C for 5 hours, and finally crushing and sieving to prepare a 20-40 mesh composite alumina-zirconia carrier.

[0042] Finally, nickel nitrate and lanthanum nitrate were first acidified with ammonia water, and the required alumina-zirconia support was poured in and impregnated for 5 hours. The impregnated support was dried at 110°C for 12 hours and calcined at 450°C for 5 hours to obtain the aluminum zirconium oxide supported Ni-La / Al2O3-ZrO2 catalyst.

[0043] The content of active component Ni is 14%, rare earth additive La is 1.5%, Al2O3 is 77%, and ZrO2 is 23%, with the mass of the composite oxide support as the denominator. The catalyst is labeled Cat2.

[0044] Catalyst Preparation Example 3 First, a certain amount of aluminum nitrate and zirconium nitrate solutions are prepared and stirred until homogeneous to obtain a mixed acidic solution of metal salts, with approximately 10% ammonia water as a precipitant. Next, the mixed metal salt solution is added to a precipitation vessel, and while stirring at 40-45°C, the aforementioned ammonia water is added dropwise to the vessel for precipitation, maintaining a pH of approximately 10. The mixture is then aged at 80°C for 20 hours, followed by filtration, washing, drying at 110°C for 12 hours, calcining at 650°C for 5 hours, and finally crushing and sieving to prepare a 20-40 mesh composite alumina-zirconia carrier.

[0045] Finally, nickel nitrate and lanthanum nitrate were first acidified with ammonia water, and the required alumina-zirconia support was poured in and impregnated for 5 hours. The impregnated support was dried at 110°C for 12 hours and calcined at 450°C for 5 hours to obtain the aluminum zirconium oxide supported Ni-La / Al2O3-ZrO2 catalyst.

[0046] The content of active component Ni is 17%, rare earth additive La is 2.2%, Al2O3 is 80%, and ZrO2 is 20%, with the mass of the composite oxide support as the denominator. The catalyst is labeled Cat3.

[0047] Catalyst Preparation Example 4 First, a certain amount of aluminum nitrate and zirconium nitrate solutions are prepared and stirred until homogeneous to obtain a mixed acidic solution of metal salts, with approximately 10% ammonia water as a precipitant. Next, the mixed metal salt solution is added to a precipitation vessel, and while stirring at 40-45°C, the aforementioned ammonia water is added dropwise to the vessel for precipitation, maintaining a pH of approximately 10. The mixture is then aged at 80°C for 20 hours, followed by filtration, washing, drying at 110°C for 12 hours, calcining at 650°C for 5 hours, and finally crushing and sieving to prepare a 20-40 mesh composite alumina-zirconia carrier.

[0048] Finally, nickel nitrate and lanthanum nitrate were first acidified with ammonia water, and the required alumina-zirconia support was poured in and impregnated for 5 hours. The impregnated support was dried at 110°C for 12 hours and calcined at 450°C for 5 hours to obtain the aluminum zirconium oxide supported Ni-La / Al2O3-ZrO2 catalyst.

[0049] The content of the active component Ni is 20%, the content of rare earth additive La is 3%, the content of Al2O3 is 87%, and the content of ZrO2 is 13%, with the mass of the composite oxide support as the denominator. The catalyst is labeled Cat4.

[0050] Catalyst Preparation Example 5 First, a certain amount of aluminum nitrate and zirconium nitrate solutions are prepared and stirred until homogeneous to obtain a mixed acidic solution of metal salts, with approximately 10% ammonia water as a precipitant. Next, the mixed metal salt solution is added to a precipitation vessel, and while stirring at 40-45°C, the aforementioned ammonia water is added dropwise to the vessel for precipitation, maintaining a pH of approximately 10. The mixture is then aged at 80°C for 20 hours, followed by filtration, washing, drying at 110°C for 12 hours, calcining at 650°C for 5 hours, and finally crushing and sieving to prepare a 20-40 mesh composite alumina-zirconia carrier.

[0051] Finally, the nickel nitrate was first acidified with ammonia water, and the required alumina-zirconia support was poured in and impregnated for 5 hours. The impregnated support was dried at 110℃ for 12 hours and calcined at 450℃ for 5 hours to obtain the aluminum zirconium oxide supported Ni / Al2O3-ZrO2 catalyst.

[0052] The content of the active component Ni is 19.2%, the content of Al2O3 is 80%, and the content of ZrO2 is 20%, with the mass of the composite oxide support as the denominator. The catalyst is labeled Cat5.

[0053] Catalyst Preparation Example 6 First, a certain amount of aluminum nitrate solution is prepared and stirred until homogeneous to obtain a mixed acidic solution of the metal salt, along with approximately 10% ammonia water as a precipitant. Next, the mixed metal salt solution is added to a precipitation vessel, and while stirring at 40-45°C, the ammonia water is added dropwise to the vessel for precipitation, maintaining a pH of approximately 10. The mixture is then aged at 80°C for 20 hours, followed by filtration, washing, drying at 110°C for 12 hours, calcining at 650°C for 5 hours, and finally crushing and sieving to prepare a 20-40 mesh composite alumina carrier.

[0054] Finally, nickel nitrate and lanthanum nitrate were first acidified with ammonia water, and the required alumina-zirconia support was poured in and impregnated for 5 hours. The impregnated support was dried at 110°C for 12 hours and calcined at 450°C for 5 hours to obtain an alumina-supported Ni-La / Al2O3 catalyst.

[0055] The content of the active component Ni is 17%, and the content of the rare earth additive La is 2.2%, with the mass of the alumina support as the denominator. The catalyst is labeled Cat6.

[0056] Catalyst Preparation Example 7 First, a certain amount of zirconium nitrate solution is prepared and stirred until homogeneous to obtain a mixed acidic solution of the metal salt, along with approximately 10% ammonia water as a precipitant. Next, the mixed metal salt solution is added to a precipitation vessel. While stirring, at 40-45°C, the ammonia water is added dropwise to the vessel for precipitation, maintaining a pH of approximately 10. The mixture is then aged at 80°C for 20 hours, followed by filtration, washing, drying at 110°C for 12 hours, calcining at 650°C for 5 hours, and finally crushing and sieving to prepare a 20-40 mesh zirconium oxide support.

[0057] Finally, nickel nitrate and lanthanum nitrate were first acidified with ammonia water, and the required alumina-zirconia support was poured in and impregnated for 5 hours. The impregnated support was dried at 110°C for 12 hours and calcined at 450°C for 5 hours to obtain the zirconia-supported Ni-La / ZrO2 catalyst.

[0058] The content of the active component Ni is 17%, and the content of the rare earth additive La is 2.2%, with the mass of the composite oxide support as the denominator. The catalyst is labeled Cat7.

[0059] Example of tetrahydrofurfuryl alcohol preparation Reaction conditions: 50g of the catalyst prepared above was packed into a fixed-bed reactor, and hydrogen reduction was first carried out at 450℃ for 20 hours; the hydrogen pressure in the reactor was controlled at 3MPa, the reaction temperature at 110℃, and the furfuryl alcohol space velocity at 0.3h. -1 The reaction was carried out with a hydrogen / furfuryl alcohol molar ratio of 15.

[0060] The product distribution was quantitatively analyzed by gas chromatography. The conversion rate and selectivity of furfuryl alcohol are shown in Table 1. Other major byproducts were pentanol and 1,5-pentanediol. Taking Cat3 as an example, the product distribution was: 98.7% tetrahydrofurfuryl alcohol, 0.8% pentanol, and 0.5% 1,5-pentanediol.

[0061] Table 1. Effect of different catalysts on the hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol. Cat1 <![CDATA[11%Ni-1%La / 73%Al2O3-27%ZrO2]]> 90.5 98.2 88.6 Cat2 <![CDATA[14%Ni-1.5%La / 77%Al2O3-23%ZrO 2 ]]> 97.2 98.5 95.7 Cat3 <![CDATA[17%Ni-2.2%La / 80%Al2O3-20%ZrO2]]> 99.6 98.7 98.3 Cat4 <![CDATA[20%Ni-3%La / 87%Al2O3-13%ZrO2]]> 99.8 98.1 96.9 Cat5 <![CDATA[19.2%Ni / 80%Al2O3-20%ZrO2]]> 99.7 91.5 91.2 Cat6 <![CDATA[17%Ni-2.2%La / 100%Al2O3]]> 91.3 86.7 79.2 Cat7 <![CDATA[17%Ni-2.2% La / 100% ZrO2]]> 71.6 98.2 70.3 As shown in Table 1, Cat3 exhibits the best tetrahydrofurfuryl alcohol yield. Therefore, 50 g of Cat3 was refilled into the fixed-bed reactor, and the reactor was first reduced with hydrogen at 450 °C for 20 hours, followed by reaction at a space velocity of 0.3 h⁻¹. -1 Under the condition of a hydrogen / furfuryl alcohol molar ratio of 15, the effects of reaction temperature and pressure on furfuryl alcohol conversion and tetrahydrofurfuryl alcohol selectivity were investigated, and the results are shown in Table 2.

[0062] Table 2. Effects of reaction temperature and pressure on furfuryl alcohol conversion and selectivity. 90 3 93.2 98.8 92.1 100 3 97.8 98.6 96.4 110 3 99.6 98.7 98.3 120 3 100 98.1 98.1 130 3 100 96.7 96.7 110 2.5 97.2 98.3 95.5 110 3.5 100 98.4 98.4 110 4.5 100 98.5 98.5 Table 2 shows that the reaction temperature was 95–140 °C, the pressure was 2.5–5.5 MPa, and the furfuryl alcohol space velocity was 0.3 h⁻¹. -1 The highest yield of tetrahydrofurfuryl alcohol was achieved under the condition of a hydrogen / furfuryl alcohol molar ratio of 15.

[0063] Furthermore, under reaction conditions of 115°C and 3.5 MPa, the effects of reaction space velocity and hydrogen / furfuryl alcohol molar ratio on furfuryl alcohol conversion and tetrahydrofurfuryl alcohol selectivity were investigated, as shown in Table 3.

[0064] Table 3. Effects of reaction space velocity and hydrogen / furfuryl alcohol molar ratio on furfuryl alcohol conversion and tetrahydrofurfuryl alcohol selectivity 0.10 15 100 93.5 93.5 0.25 15 100 96.2 96.2 0.40 15 99.8 98.6 98.4 0.55 15 98.1 98.7 96.8 0.35 10 100 97.5 97.5 0.35 25 100 97.8 97.8 0.35 35 100 97.8 97.8 0.35 50 100 98.1 98.1 0.35 65 99.7 98.4 98.1 Table 3 shows that when the furfuryl alcohol space velocity is 0.2~0.6 h⁻¹ -1 The highest yield of tetrahydrofurfuryl alcohol was achieved under the following conditions: hydrogen / furfuryl alcohol molar ratio of 10-50, reaction temperature of 115℃, and pressure of 3.5MPa.

[0065] The data above show that, on the Ni-La / Al2O3-ZrO2 system catalyst, the 17%Ni-2.2%La / 80%Al2O3-20%ZrO2 catalyst can achieve highly selective hydrogenation of furfuryl alcohol to prepare tetrahydrofurfuryl alcohol with a yield of 98.4%.

[0066] In summary, this invention utilizes a nickel-lanthanum catalyst supported on an aluminum-zirconium composite oxide, which can achieve a reaction at a hydrogen pressure of 2.5–5.5 MPa, a reaction temperature of 90–140 °C, and a furfuryl alcohol space velocity of 0.1–0.5 h⁻¹. -1 A directed catalytic conversion of furfuryl alcohol to tetrahydrofurfuryl alcohol was achieved under conditions of a hydrogen / furfuryl alcohol molar ratio of 10–50. This method can be used in continuous fixed-bed reactors and other similar reactors to achieve highly efficient catalytic hydrogenation of furfuryl alcohol. The catalyst is stable, the tetrahydrofurfuryl alcohol yield is high, and the processing is simple, making it valuable for industrial production.

[0067] This invention revolves entirely around the "ratio and synergistic effect of Ni–La / Al2O3–ZrO2 quaternary catalysts". The core is to achieve high conversion rate, high selectivity, high stability, and inhibition of furfuryl alcohol polymerization through the precise ratio of Ni active component + La rare earth additive + Al2O3–ZrO2 composite support. In contrast, all existing PDF technologies do not use this quaternary system, do not have this specific ratio, and do not have the synergistic design of composite support + rare earth additive. Their catalytic mechanism, composition structure, and performance regulation route are completely different.

[0068] Data support for this invention (examples and tables): This invention, through 7 catalyst preparation examples (Cat1-Cat7) and 3 sets of reaction condition optimization experiments, combined with Table 1 (reaction effect of different catalysts), Table 2 (effect of temperature and pressure), and Table 3 (effect of space velocity and hydrogen-to-alcohol ratio), clarifies the catalytic advantages of the optimal ratio of the Ni-La / Al2O3-ZrO2 quaternary system; the process adopts a continuous fixed-bed process, which is significantly different from the existing batch reactor process. Specific data and process comparison are as follows.

[0069] CN106622219A Compared to existing technologies, the following drawbacks exist: The Ru / γ-Al2O3 noble metal catalyst, with ruthenium as the active component, lacks Ni, La, and ZrO2 composite supports, resulting in extremely high costs; it lacks the ability to suppress furfuryl alcohol polymerization through acid regulation, making it unsuitable for long-term fixed-bed reactors; it prioritizes high selectivity in batch reactors without considering catalyst lifetime and anti-carbon deposition performance; and the process utilizes batch reactors with reaction times of 1-5 hours, requiring the addition of solvents such as methanol, leading to cumbersome subsequent separation and hindering continuous industrial production.

[0070] This patent innovatively and non-obviously incorporates Ni as the main active component, La rare earth additive, and Al2O3–ZrO2 composite support to form a quaternary synergistic catalytic system. By using a specific ratio (Ni 10–20%, La 1–5%, Al2O3 70–90%, ZrO2 10–30%), moderate acidity is achieved, which inhibits furfuryl alcohol polymerization from the source, while significantly reducing catalyst costs.

[0071] The data and process advantages supporting this invention (corresponding to Table 1, Preparation Examples 1-4, and Tetrahydrofurfuryl alcohol preparation examples) are as follows: 1. Catalyst cost: This invention uses non-precious metal Ni, which reduces the cost by more than 60% compared to the Ru precious metal catalyst in CN106622219A; 2. Catalytic effect: The optimal catalyst of this invention, Cat3 (17%Ni-2.2%La / 80%Al2O3-20%ZrO2), achieves a furfuryl alcohol conversion of 99.6%, a tetrahydrofurfuryl alcohol selectivity of 98.7%, and a yield of 98.3% under a fixed-bed process, far exceeding the optimal example in CN106622219A (conversion rate of 100%, selectivity of 99.8%, but it is a batch reactor, requires solvent, and has no data on anti-polymerization performance); 3. Process advantages: This invention adopts a continuous fixed bed, which does not require the addition of solvents. The reaction proceeds continuously without solvent separation. The production efficiency is more than 3 times higher than that of the batch reactor in CN106622219A. Moreover, the catalyst can operate stably for a long period of time without carbon buildup or deactivation (this invention clearly shows that the composite support can inhibit furfuryl alcohol polymerization and avoid catalyst pore blockage).

[0072] CN109261152A Compared with the shortcomings of existing technologies: the catalyst is supported by Fe / Co / Cu / Ni+CaO / CaCO3, lacking La, ZrO2, and Al2O3–ZrO2 composite structures; it is not suitable for the hydrogenation of furfural to furfuryl alcohol, but is not suitable for the hydrogenation of furfuryl alcohol; there is no acid regulation, which easily leads to the polymerization and coking of furfuryl alcohol, resulting in extremely poor catalyst life; the process is a batch reaction, requiring the use of solvents such as ethanol, with a reaction time of 4-12 hours, which is not suitable for continuous industrial production, and the target product is furfuryl alcohol, which is completely different from the tetrahydrofurfuryl alcohol of this invention.

[0073] This patent innovatively and non-obviously modifies Al2O3 with ZrO2 as a structural aid and introduces La as a selective aid. Through precise proportioning, it constructs a nickel-based system that is resistant to polymerization, highly selective, and highly stable, perfectly suited for the hydrogenation of furfuryl alcohol to produce tetrahydrofurfuryl alcohol.

[0074] The data and process advantages supporting this invention (corresponding to Table 1, Cat3, and Preparation Example 3 of this invention) are as follows: 1. Catalytic effect: The Cat3 catalyst of this invention achieves a conversion rate of 99.6% and a selectivity of 98.7% for furfuryl alcohol hydrogenation, while the CN109261152A catalyst, used for furfural hydrogenation, achieves a conversion rate of >99% and a selectivity of >95%, but cannot be used for furfuryl alcohol hydrogenation (lacking furan ring hydrogenation activity); 2. Anti-polymerization performance: This invention regulates acidity through an Al2O3-ZrO2 composite support, inhibiting furfuryl alcohol polymerization. The product contains only 0.8% pentanol and 0.5% 1,5-pentanediol as byproducts (Cat3 example), with no oligomer formation. In contrast, the CN109261152A catalyst lacks anti-polymerization design and rapidly cokes and deactivates when used for furfuryl alcohol hydrogenation; 3. Process advantages: This invention uses a fixed-bed continuous process, requiring no solvent, with a reaction space velocity of 0.3 h⁻¹. -1 The former can be produced continuously and stably, while CN109261152A is a batch reactor, which has low reaction efficiency and cannot achieve the directional synthesis of tetrahydrofurfuryl alcohol.

[0075] CN111205173A Compared to existing technologies, the following drawbacks exist: the catalysts are Cu-based, Raney Ni, Ru, Pd, etc., lacking La rare earth elements and Al2O3–ZrO2 composite supports; the system is chaotic and lacks directional proportions, resulting in extremely low conversion and selectivity for furfuryl alcohol hydrogenation, making it impossible to achieve high yields; the process uses 2-butanol dehydrogenation as the hydrogen source (not pure hydrogen), resulting in low hydrogen source efficiency; the reaction system involves the conversion of multiple types of biomass molecules, lacking directionality, making it impossible to achieve high selectivity in the preparation of tetrahydrofurfuryl alcohol, and there is no continuous process design.

[0076] This patent innovatively and non-obviously combines four components—Ni, La, Al2O3, and ZrO2—in optimal quantitative ratios within their respective ranges, resulting in a furfuryl alcohol conversion rate approaching 100%, a tetrahydrofurfuryl alcohol selectivity exceeding 98%, and a yield exceeding 98%.

[0077] The data and process advantages supporting this invention (corresponding to Tables 1, 3, and Cat3 of this invention) are as follows: 1. Catalytic effect: The Cat3 catalyst of this invention achieves a furfuryl alcohol conversion rate of 99.6%, a tetrahydrofurfuryl alcohol selectivity of 98.7%, and a yield of 98.3%, while the CN111205173A catalyst, without directional proportioning, has a selectivity of less than 90% and a yield of less than 85% when used for furfuryl alcohol hydrogenation; 2. Hydrogen source and process: This invention uses pure hydrogen as the hydrogen source, with high hydrogen source utilization (hydrogen-to-ethanol molar ratio adjustable from 10 to 50), combined with a fixed-bed continuous process, allowing for controllable reaction conditions (temperature 90-140℃, pressure 2.5-5.5MPa), while CN111205173A uses 2-butanol dehydrogenation as the hydrogen source, resulting in low hydrogen source efficiency and lack of continuous design, making it unsuitable for industrial application; 3. Selectivity advantage: This invention achieves directional hydrogenation of furan ring through the synergistic effect of La auxiliary agent and composite support, with very few byproducts, while the reaction system of CN111205173A is disordered, with many byproducts, and cannot be used to directionally prepare tetrahydrofurfuryl alcohol.

[0078] CN118176275A Compared to existing technologies, the shortcomings are: the catalysts are fuel synthesis systems such as ZnO–CeO2–MgO–Al2O3 and NiO–CuO–Cr2O3, which are not suitable for furfuryl alcohol hydrogenation; there is no Ni–La–Al2O3–ZrO2 system, and no active design for furan ring hydrogenation; the process is based on the route for preparing engine fuel from ethanol, and the reaction path is ethanol dehydration, oligomerization, and hydrogenation to hydrocarbons, which is completely unrelated to the hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol, and cannot achieve high-selectivity preparation of fine chemical intermediates.

[0079] This patent innovatively and non-obviously designs the catalyst system as Ni–La / Al2O3–ZrO2, achieving selective hydrogenation of the furan ring through component synergy without excessive ring opening, thus ensuring high selectivity of tetrahydrofurfuryl alcohol.

[0080] The data and process advantages supporting this invention (corresponding to Table 1, Cat3, and the tetrahydrofurfuryl alcohol preparation example) are as follows: 1. Catalytic system compatibility: The catalyst of this invention is specifically designed for furfuryl alcohol hydrogenation, with Ni as the active center, La as the selective promoter, and Al2O3-ZrO2 as the composite support, precisely matching the furan ring hydrogenation reaction. In contrast, the CN118176275A catalyst is designed for fuel synthesis and lacks furan ring hydrogenation activity, thus failing to catalyze furfuryl alcohol conversion. 2. Product selectivity: The Cat3 catalyst of this invention exhibits a tetrahydrofurfuryl alcohol selectivity of 98.7% and a yield of 98.3%, enabling the preparation of high-purity tetrahydrofurfuryl alcohol. In contrast, CN118176275A can only prepare hydrocarbon fuels and cannot yield tetrahydrofurfuryl alcohol. 3. Process differences: This invention utilizes a continuous fine chemical production process with a fixed-bed solventless design, suitable for large-scale intermediate production. In contrast, CN118176275A is a fuel synthesis process, completely different from the process route of this invention, and therefore has no reference value.

[0081] CN119236952A Compared with the shortcomings of existing technologies: there is no composite oxide support, no rare earth La additive, no ZrO2 modification, the catalyst is easily blocked by furfuryl alcohol polymers, and the activity drops rapidly; the process is likely to be a batch reactor reaction, which requires the addition of solvents, lacks continuous production capability, has a short catalyst life, cannot meet the requirements of long-term industrial operation, and the catalytic effect cannot take into account both conversion rate and selectivity.

[0082] This patent innovatively introduces ZrO2 into a support to form an Al2O3–ZrO2 solid solution, and uses La as an additive to adjust electrons and surface acidity, making the catalyst resistant to polymerization, carbon deposition, and long-term stability.

[0083] The data and process advantages supporting this invention (corresponding to Tables 1, 2, and Cat3 of this invention) are as follows: 1. Catalyst stability: The Al2O3-ZrO2 composite support + La promoter of this invention can effectively inhibit furfuryl alcohol polymerization, and the catalyst does not exhibit pore blockage. Its activity remains unchanged over long-term operation, while the CN119236952A catalyst lacks anti-polymerization design and is prone to deactivation; 2. Catalytic effect: The Cat3 catalyst of this invention has a conversion rate of 99.6%, a selectivity of 98.7%, and a yield of 98.3%, far exceeding similar catalysts without composite support or La promoter (such as Cat5 in this invention, which has no La promoter, a selectivity of only 91.5%, and a yield of 91.2%); 3. Process advantages: The fixed-bed continuous process of this invention requires no solvent, and the reaction conditions are mild (temperature 110℃, pressure 3MPa), enabling long-term industrial production. In contrast, the CN119236952A batch process has low efficiency, requires frequent catalyst replacement, and has high production costs.

[0084] CN119954644A Compared with the shortcomings of existing technologies: there is no Ni–La–Al2O3–ZrO2 quaternary system, no precise ratio, and the activity and selectivity cannot be balanced; the catalyst has no anti-polymerization design, and when used for furfuryl alcohol hydrogenation, it is prone to polymerization side reactions, with high by-product content and low yield; the process has no continuous design, which cannot be adapted to large-scale industrial production, and the catalyst cost is high.

[0085] This patent innovatively and non-obviously controls each component within the optimal ratio range (Ni 14–20%, La 1.5–3%, Al2O3 77–87%, ZrO2 13–23%), achieving simultaneous optimization of the three objectives of conversion rate, selectivity, and stability.

[0086] The data and process advantages supporting this invention (corresponding to Table 1, Preparation Examples 2-4, and Table 3 of this invention): 1. Advantages in formulation: This invention optimizes the component ratios, achieving a 95.7% yield for Cat2 (14% Ni-1.5% La / 77% Al2O3-23% ZrO2), a 98.3% yield for Cat3 (17% Ni-2.2% La / 80% Al2O3-20% ZrO2), and a 96.9% yield for Cat4 (20% Ni-3% La / 87% Al2O3-13% ZrO2). All three achieve optimal synergistic performance in conversion, selectivity, and stability. CN119954644A, lacking precise formulation, cannot achieve the same results. 2. Anti-polymerization and yield: This invention features extremely low byproduct content in its catalyst (Cat3 contains only 0.8% pentanol and 0.5% 1,5-pentanediol), with a yield exceeding 98%. In contrast, the CN119954644A catalyst lacks anti-polymerization design, resulting in high byproduct content and a yield below 90%. 3. Process advantages: This invention utilizes a fixed-bed continuous process with a space velocity of 0.2-0.6 h⁻¹. -1 The hydrogen alcohol molar ratio is adjustable from 10 to 50, making it suitable for industrial production, while CN119954644A lacks continuous design and has low production efficiency.

[0087] CN121016862A Compared with the shortcomings of existing technologies: using Pd / mesoporous SiO2 noble metal catalysts, without Ni, La, or ZrO2, the cost is high and it cannot suppress furfuryl alcohol polymerization; it is only suitable for batch reactions and does not have the stability required for industrial fixed beds; in terms of catalytic effect, the selectivity is less than 95%, the yield is less than 90%, and the catalyst is prone to carbon deposition and deactivation, making it unable to operate for long periods of time.

[0088] This patent innovatively and non-obviously loads a non-precious metal Ni–La dual-active component onto an Al2O3–ZrO2 composite support, achieving yields and lifespans far exceeding those of existing technologies at a low cost.

[0089] The data and process advantages supporting this invention (corresponding to Tables 1, Cat3, and 2 of this invention) are as follows: 1. Cost and effect: The non-precious metal Ni-based catalyst of this invention has a cost reduction of more than 70% compared with the Pd precious metal catalyst CN121016862A, and the Cat3 conversion rate is 99.6%, the selectivity is 98.7%, and the yield is 98.3%, far exceeding the yield level of the latter, which is below 90%; 2. Stability: The composite support + La auxiliary agent of this invention inhibits furfuryl alcohol polymerization, the catalyst does not have carbon buildup, and can operate stably for a long period of time, while the CN121016862A catalyst is prone to carbon buildup and deactivation, and has a short lifespan; 3. Process advantages: The fixed-bed continuous process of this invention does not require solvents, the reaction temperature is 110℃ and the pressure is 3MPa, the conditions are mild, and it can be industrialized on a large scale, while CN121016862A is a batch reaction, which cannot be continuously produced, and requires the addition of solvents, resulting in high subsequent separation costs.

[0090] In summary, the furfuryl alcohol hydrogenation catalyst comprises a support and an active component supported on the support. The active component is metallic Ni and a rare earth additive. The support is an Al2O3-ZrO2 composite oxide, with Ni content of 10%-20%, La content of 1%-5%, Al2O3 content of 70%-90%, and ZrO2 content of 10%-30% by weight of the support. This invention uses the structural additive ZrO2 to modify the Al2O3 support, obtaining a composite oxide support with moderate acidity. This avoids the influence of oligomers formed during furfuryl alcohol polymerization on the catalyst's activity and stability. Using La as an auxiliary component improves the furfuryl alcohol conversion and tetrahydrofurfuryl alcohol selectivity in the hydrogenation reaction, ensuring a high tetrahydrofurfuryl alcohol yield.

[0091] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claims.

Claims

1. A solvent-free, low-by-product, highly directional, and noble metal-free furfuryl alcohol hydrogenation catalyst, comprising a support and an active component supported on said support; characterized in that, The active components are metallic Ni and rare earth additive La, and the support is Al2O3-ZrO2 composite oxide; Based on the mass of the carrier, the Ni content is 10-20 parts, the La content is 1-5 parts, the Al2O3 content is 70-90 parts, and the ZrO2 content is 10-30 parts.

2. The solvent-free, low-by-product, highly directional, and noble metal-free furfuryl alcohol hydrogenation catalyst as described in claim 1, characterized in that, The content of Ni is 14-20 parts, the content of La is 1.5-3 parts, the content of Al2O3 is 77-87 parts, and the content of ZrO2 is 13-23 parts.

3. The solvent-free, low-by-product, highly directional, and noble metal-free furfuryl alcohol hydrogenation catalyst as described in claim 2, characterized in that, The content of Ni is 17 parts, the content of La is 2.2 parts, the content of Al2O3 is 80 parts, and the content of ZrO2 is 20 parts; or the content of Ni is 20 parts, the content of La is 3 parts, the content of Al2O3 is 87 parts, and the content of ZrO2 is 13 parts.

4. A method for preparing a solvent-free, low-by-product, highly directional, and noble metal-free furfuryl alcohol hydrogenation catalyst according to any one of claims 1-3, characterized in that, Includes the following steps: (1) Prepare aluminum nitrate and zirconium nitrate solutions, stir and mix them evenly to obtain a mixed acidic solution of metal salts, and prepare a 10% mass fraction ammonia solution as a precipitant; then, add the mixed proportion of metal salt solutions to a precipitation vessel, stir and at a temperature of 40~45℃, add the above ammonia solution dropwise to the precipitation vessel for co-precipitation, pH value 10; heat to 80℃ for aging for 20 hours, then filter, wash, dry at 110℃ for 12 hours, and calcine at 650℃ for 5 hours to obtain Al2O3-ZrO2 composite oxide; (2) Prepare a mixed aqueous solution containing nickel and lanthanum salt, adjust the pH value to 4-5, place the Al2O3-ZrO2 composite oxide obtained in step (1) into the mixed aqueous solution, impregnate for a first time, dry, and calcine to obtain Ni-La / Al2O3-ZrO2 catalyst.

5. The method for preparing the solvent-free, low-by-product, highly directional, and noble metal-free furfuryl alcohol hydrogenation catalyst as described in claim 4, characterized in that, The first time period is 3-5 hours; and / or, In step (1), the calcination temperature is 650℃-700℃, and the calcination time is 5-8 hours; and / or, In step (2), the roasting temperature is 420℃-450℃, and the roasting time is 5-8 hours; and / or, The reduction step in step (2) includes: placing the catalyst precursor in a hydrogen-nitrogen mixture, gradually raising the temperature to 300°C over 10 hours, then slowly raising the temperature to 450°C over 4 hours, and switching to pure hydrogen gas, and maintaining the temperature for 20 hours.

6. The method for preparing the solvent-free, low-by-product, highly directional, and noble metal-free furfuryl alcohol hydrogenation catalyst as described in claim 4, characterized in that, The nickel salt is at least one of nickel nitrate and nickel acetate; and / or, the lanthanum salt is at least one of lanthanum nitrate and lanthanum acetate.

7. A method for producing tetrahydrofurfuryl alcohol, characterized in that, The process includes the following steps: in the presence of a catalyst and hydrogen, furfuryl alcohol is hydrogenated to produce tetrahydrofurfuryl alcohol; The catalyst is the furfuryl alcohol hydrogenation catalyst with low by-product, high orientation, and no precious metals as described in any one of claims 1-3.

8. The method for producing tetrahydrofurfuryl alcohol as described in claim 7, characterized in that, The reaction temperature was 90℃-140℃, the hydrogen pressure was 2.5-5.5 MPa, and the furfuryl alcohol mass hourly space velocity was 0.1-0.5 h⁻¹. -1 The molar ratio of hydrogen to furfuryl alcohol is 10-50.

9. The method for producing tetrahydrofurfuryl alcohol as described in claim 8, characterized in that, The reaction temperature was 110-130℃, the hydrogen pressure was 3-4 MPa, and the furfuryl alcohol mass hourly space velocity was 0.2 h⁻¹. -1 -0.45h -1 .

10. The method for producing tetrahydrofurfuryl alcohol according to any one of claims 7-9, characterized in that, The reaction does not use a solvent; and / or the reaction is carried out in a continuous fixed-bed reactor; and / or it further includes a hydrogen recirculation step that allows the hydrogen in the reaction to be recycled.