Catalyst as well as preparation method and application thereof

Abstract

The invention discloses a catalyst as well as a preparation method and application thereof, and relates to the technical field of catalysts. The catalyst comprises a metal nickel-based active component and a metal oxide deposited on the surface of the metal nickel-based active component; wherein the metal oxide comprises any one or a combination of at least two of vanadium oxide, molybdenum oxide or tungsten oxide. The catalyst has high activity and high selectivity for preparation of gamma-butyrolactone through hydrogenation reduction of maleic anhydride or succinic anhydride, the preparation process is simple to operate, the catalytic process is high in safety, the catalyst has excellent stability, the quality and quality stability of the product are improved, the process cost is reduced, the catalyst synthesis and modification cost is low, and the catalyst is suitable for industrial production. The large-scale production is facilitated.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and in particular to a catalyst and a preparation method and application thereof. Background Art

[0002] γ-Butyrolactone (GBL) is an important chemical raw material and intermediate, widely used in fiber, polyester, agriculture and medicine. Due to its excellent solubility, conductivity and thermal stability, γ-butyrolactone is favored by solar cells and lithium-ion batteries as a high-boiling point solvent. Therefore, the efficient and green synthesis of γ-butyrolactone is of great significance to the development of fine chemicals, but also a major challenge.

[0003] Maleic anhydride hydrogenation is a method of preparing γ-butyrolactone by directly hydrogenating maleic anhydride in one step. In 1971, Mitsubishi Chemical Company of Japan built the first 1,000-ton industrial unit using maleic anhydride liquid phase hydrogenation process. With the maturity of the process route of preparing maleic anhydride by oxidation of n-butane, the raw material maleic anhydride has sufficient sources and low prices, becoming the most powerful competitive process route for preparing γ-butyrolactone from 1,4-butanediol. For example, in 2019, Jiang et al. reported that Ni-PS catalyst can produce γ-butyrolactone at 200℃ and 5MPa H 2 The catalytic hydrogenation of maleic anhydride in atmosphere for 3 h can achieve a 70% yield of γ-butyrolactone (J.Phys.Chem.C2019,123,9779); in the same year, Zhao et al. 2 For catalyst at 210℃5MPaH 2 In 2022, Zheng et al. used 40Ni-2Zr-MFI as catalyst at 200 °C and 6 MPa H to obtain γ-butyrolactone with a yield of 65.8% after 3 hours of reaction under atmosphere (Catalysts 2019, 9, 366). 2 Under atmosphere, the reaction was carried out for 3 h to obtain a γ-butyrolactone yield of 64.2% (J.Catal.2022,410,69), while the introduction of a dehydrating agent into the system could achieve a γ-butyrolactone yield of 95.2%.

[0004] It is not difficult to see that the current catalyst activity of maleic anhydride hydrogenation method is low, the reaction requires high temperature and pressure, harsh conditions, and a complex reaction path, with many by-products and generally low intrinsic selectivity of the catalyst, which greatly increases the equipment cost and processing cost of the enterprise. Therefore, a catalyst with high catalytic efficiency and good stability is urgently needed.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] The object of the present invention is to provide a catalyst and a preparation method and application thereof, wherein the catalyst comprises a metal nickel-based active component and a metal oxide deposited on the surface of the metal nickel-based active component; wherein the metal oxide comprises any one of vanadium oxide, molybdenum oxide or tungsten oxide or a combination of at least two thereof. The catalyst of the present invention modifies the metal nickel-based active component by the above-mentioned metal oxide, and the catalyst can be used for the hydrogenation reduction of substrates such as maleic anhydride and succinic anhydride to prepare butyrolactone, and the catalyst has high reaction activity, high selectivity, good stability, and can further improve the quality and quality stability of the product and reduce the process cost.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a catalyst, comprising a metal nickel-based active component and a metal oxide deposited on the surface of the metal nickel-based active component;

[0009] The metal oxide includes any one of vanadium oxide, molybdenum oxide or tungsten oxide, or a combination of at least two of them.

[0010] Furthermore, the 2p orbital binding energy of the vanadium element in the vanadium oxide is between 510 and 530 eV.

[0011] Furthermore, the 4f orbital binding energy of the tungsten element in the tungsten oxide is between 30 and 42 eV.

[0012] Furthermore, the 3d orbital binding energy of the molybdenum element in the molybdenum oxide is between 228 and 239 eV.

[0013] Furthermore, the mass ratio of the metal oxide to the metal nickel-based active component is (0.001-4.000):1.

[0014] Furthermore, the metallic nickel-based active component includes a nickel-based catalyst.

[0015] Furthermore, the nickel-based catalyst is selected from any one or a combination of at least two of a supported nickel-based catalyst, a Raney nickel catalyst or nickel nanoparticles.

[0016] Furthermore, when the metal nickel-based active component is a supported nickel-based catalyst, the mass ratio of the metal oxide to the metal nickel-based active component is (0.001-4.000):1.

[0017] Furthermore, when the metal nickel-based active component is a Raney nickel catalyst and / or nickel nanoparticles, the mass ratio of the metal oxide to the metal nickel-based active component is (0.001-2.000):1.

[0018] Furthermore, the supported nickel-based catalyst includes a carrier and nickel particles supported on the carrier.

[0019] Furthermore, the loading amount of the nickel particles accounts for 0.1 to 60 wt% of the total mass of the supported nickel-based catalyst;

[0020] Furthermore, the carrier is selected from carbon carrier, Al 2 O 3 、TiO 2 、ZrO 2 、CeO 2 , Fe 2 O 3 or SiO 2 Any one or a combination of at least two of the following:

[0021] Furthermore, the carbon carrier is selected from any one of activated carbon, carbon nanotubes, carbon black or mesoporous carbon, or a combination of at least two thereof.

[0022] In a second aspect, the present invention provides a method for preparing the catalyst as described in the first aspect, the method for preparing the catalyst comprising the following steps:

[0023] The metal oxide precursor and the metal nickel-based active component are mixed and calcined to obtain the catalyst; wherein the metal oxide precursor includes any one of vanadate, tungstate, tungsten polyacid, molybdate or molybdenum polyacid or a combination of at least two thereof.

[0024] Furthermore, the metallic nickel-based active component includes a nickel-based catalyst.

[0025] Furthermore, the nickel-based catalyst is selected from any one or a combination of at least two of a supported nickel-based catalyst, a Raney nickel catalyst or nickel nanoparticles.

[0026] Furthermore, the vanadate is selected from any one of sodium metavanadate, sodium pyrovanadate, ammonium metavanadate or sodium orthovanadate, or a combination of at least two thereof.

[0027] Furthermore, the tungstate is selected from any one of ammonium metatungstate, ammonium paratungstate, ammonium tungstate or tungstates, or a combination of at least two thereof.

[0028] Furthermore, the heteropolytungstic acid is selected from silicotungstic acid and / or phosphotungstic acid.

[0029] Furthermore, the molybdate is selected from any one of ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate or sodium molybdate, or a combination of at least two thereof.

[0030] Furthermore, the molybdenum heteropoly acid is selected from silicomolybdic acid and / or phosphomolybdic acid.

[0031] Furthermore, the mass ratio of the metal oxide precursor to the metal nickel-based active component is (0.001-4.000):1.

[0032] Furthermore, when the metal nickel-based active component is a supported nickel-based catalyst, the mass ratio of the metal oxide precursor to the metal nickel-based active component is (0.001-4.000):1.

[0033] Furthermore, when the metal nickel-based active component is a Raney nickel catalyst and / or nickel nanoparticles, the mass ratio of the metal oxide precursor to the metal nickel-based active component is (0.001-2.000):1.

[0034] Furthermore, the calcination is carried out under a protective gas atmosphere; wherein the protective gas is selected from any one of nitrogen, argon or hydrogen, or a combination of at least two of them.

[0035] Furthermore, the calcination temperature is 50 to 500° C., and the calcination time is 1 to 12 hours.

[0036] Furthermore, the supported nickel-based catalyst is prepared by the following steps: allowing the carrier to adsorb the nickel salt precursor, and then reducing and calcining to obtain the supported nickel-based catalyst.

[0037] Furthermore, the supported nickel-based catalyst is prepared by the following steps:

[0038] (a) first preparing a nickel salt solution and a carrier solution respectively, then mixing the nickel salt solution and the carrier solution, stirring and drying to obtain a solid phase;

[0039] (b) calcining the solid phase in an atmosphere of reducing gas to obtain the supported nickel-based catalyst.

[0040] Furthermore, in step (a), the mixing method is: dropping the nickel salt solution into the carrier solution;

[0041] Furthermore, the nickel salt includes any one of nickel chloride, nickel nitrate, nickel acetate, nickel formate or nickel acetylacetonate, or a combination of at least two thereof.

[0042] Furthermore, the solvents in the nickel salt solution and the carrier solution include any one of water, methanol, ethanol, tetrahydrofuran or N,N-dimethylformamide, or a combination of at least two thereof.

[0043] Furthermore, the reducing gas includes any one of hydrogen, hydrogen / argon mixed gas, carbon monoxide, methane or acetylene, or a combination of at least two thereof.

[0044] Furthermore, in step (b), the calcination temperature is 200 to 600° C., and the calcination time is 1 to 12 hours.

[0045] In a third aspect, the present invention provides a catalyst as described in the second aspect, or a catalyst obtained by the method for preparing the catalyst as described in the second aspect, used as a catalyst for preparing butyrolactone by hydrogenation reduction.

[0046] In a fourth aspect, the present invention provides a method for preparing γ-butyrolactone, the preparation method comprising the following steps:

[0047] In the presence of the catalyst described in the first aspect or the catalyst obtained by the preparation method of the catalyst described in the second aspect, maleic anhydride and / or succinic anhydride are subjected to a hydrogenation reduction reaction to obtain the γ-butyrolactone.

[0048] Furthermore, the preparation method of γ-butyrolactone specifically comprises the following steps:

[0049] After the catalyst is placed in a continuous fixed bed reaction device, maleic anhydride and / or succinic anhydride raw material liquid is injected to carry out a hydrogenation reduction reaction to obtain the gamma-butyrolactone.

[0050] Preferably, the reaction pressure of the hydrogenation reduction reaction is 0.1 to 5.0 MPa;

[0051] Preferably, the temperature of the hydrogenation reduction reaction is 80 to 240°C;

[0052] Preferably, the hydrogen-anhydride ratio of the hydrogenation reduction reaction is 2 to 300;

[0053] Preferably, the mass space velocity of the hydrogenation reduction reaction is 0.01 to 2.0 h -1 ;

[0054] Furthermore, the raw material liquid also includes a solvent, and the solvent includes any one or a combination of at least two of γ-butyrolactone, methanol, ethanol, isopropanol, N,N-dimethylformamide, dimethyl sulfoxide, dichloromethane, 1,4-dioxane or tetrahydrofuran.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] (1) The present invention improves the catalytic activity and selectivity of the metal nickel-based active component by modifying the metal nickel-based active component with tungsten oxide, molybdenum oxide or vanadium oxide, and achieves the desired effect under the more stringent reaction conditions (5-8 MPaH) compared to the conventional literature. 2 , yield of about 60% to 80%), vanadate, tungstate or molybdate modified catalysts can be used under mild conditions (2.5MPaH 2) can achieve a 99% butyrolactone yield and is expected to be applied in the field of chemical production.

[0057] (2) The catalyst prepared by the present invention has high activity. Under the high mass space velocity (WHSV=1.0), the catalyst can achieve a butyrolactone yield of more than 95% at 180°C and a butyrolactone yield of more than 99% at 200°C. Under mild conditions, the substrate can be rapidly converted with high selectivity, and the activity is higher than that of the traditional process.

[0058] (3) The vanadium oxide, tungsten oxide or molybdenum oxide modified in the catalyst provided by the present invention can act as a passivation layer, that is, the metal nickel-based active catalyst modified by vanadate, tungstate or molybdate has certain antioxidant properties, which can effectively prevent the catalyst from being violently oxidized and burned when exposed to air, greatly improving the experimental, safety and industrial applicability of the metal nickel-based catalyst.

[0059] (4) The present invention abandons the traditional high-pressure reactor-type butyrolactone production process and adopts an advanced continuous flow high-pressure fixed bed process, which optimizes the overall butyrolactone production process structure, greatly reduces the butyrolactone production cost, significantly improves the practicability, continuity and safety of the production process, and provides convenience for large-scale production.

[0060] (5) The modification method of the present invention for the metal nickel-based active catalyst is simple to operate, has a low modification cost, is conducive to large-scale production, and can be promoted and applied to catalysts such as nickel powder, Raney nickel, and supported nickel-based nanomaterials, thus providing convenience for the industrialization of catalyst preparation. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0062] Figure 1 The Ni@VO prepared in Example 1 x High-resolution transmission electron microscopy characterization of / C-2.5% catalyst.

[0063] Figure 2 Ni / C and Ni@VO prepared in Example 1 x / C-2.5% catalyst XRD characterization diagram.

[0064] Figure 3 Ni@VO prepared in Example 1 x X-ray photoelectron spectrum of vanadium element of / C-2.5% catalyst.

[0065] Figure 4 Ni@VO prepared in Example 1 x / C-2.5% catalyst maleic anhydride hydrogenation stability test chart.

[0066] Figure 5 Ni@WO prepared in Example 34 x Tungsten X-ray photoelectron spectrum of / C-2.5% catalyst.

[0067] Figure 6 Ni@MoO prepared in Example 39 x X-ray photoelectron spectrum of molybdenum element of / C-2.5% catalyst. DETAILED DESCRIPTION

[0068] Unless otherwise defined herein, scientific and technical terms used in conjunction with the present invention shall have the meanings commonly understood by those of ordinary skill in the art. The meaning and scope of the terms should be clear, however, in the case of any potential ambiguity, the definitions provided herein take precedence over any dictionary or external definitions. In this application, unless otherwise stated, the use of "or" means "and / or". In addition, the use of the term "including" and other forms is non-limiting.

[0069] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0070] Terminology

[0071] In the present invention, "room temperature" refers to ambient temperature, which may be 10-40°C, 15-35°C, or 20-30°C; in some embodiments, 22-28°C; in some embodiments, 24-26°C; in some embodiments, 25°C.

[0072] In the above text of the present invention, regardless of whether the words "about" or "approximately" are used, all the numbers disclosed herein are approximate values. Based on the disclosed numbers, the value of each number may vary by less than ±10% or reasonable differences considered by those skilled in the art, such as ±1%, ±2%, ±3%, ±4% or ±5%.

[0073] In the present invention, "WHSV" means the catalyst mass space velocity, which refers to the mass of the reactants in the catalyst bed passing through the reactor per unit time, and can be expressed in kg / (kg·h) or h -1 To express.

[0074] In the present invention, the term "optionally", "optionally" or "optionally" means that the event or situation described later may but does not necessarily occur. For example, "optionally, the reaction pressure of the reductive amination reaction is 0.5 to 3 MPa" means that the situation of "the reaction pressure of the reductive amination reaction is 0.5 to 3 MPa" may or may not exist.

[0075] As used herein, the term "weight percent" or "percent by weight" or "wt %" is defined as the weight of a single component in a composition divided by the total weight of all components of the composition multiplied by 100%.

[0076] In the present invention, the term "and / or" should be understood to mean any one of the optional items or a combination of any two or more of the optional items.

[0077] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0078] In the description of this specification, "MPa" means megapascal; "℃" means degrees Celsius; "h" means hour; "M" means mole per liter; "g" means gram; "mg" means milligram; "eV" means electron volt; "%" means percentage; "wt%" means mass percentage, "vol%" means volume percentage; "Ni" means nickel; "VO" means nickel; x " indicates vanadium oxide; "WO x " stands for tungsten oxide; "MoO x ” stands for molybdenum oxide and “C” stands for carbon.

[0079] In addition, the technical features involved in different embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0080] In a first aspect, the present invention provides a catalyst comprising a metal nickel-based active component and a metal oxide deposited on the surface of the metal nickel-based active component; wherein the metal oxide comprises any one of vanadium oxide, molybdenum oxide or tungsten oxide, or a combination of at least two thereof.

[0081] In the present invention, the metal nickel-based active component is modified by any one or a combination of at least two of tungsten oxide, molybdenum oxide or vanadium oxide, thereby significantly improving the catalytic reaction activity and selectivity of the metal nickel-based active component, so that it can catalytically hydrogenate and reduce to prepare γ-butyrolactone under mild conditions, and can also achieve high selectivity and rapid conversion of substrates, and has higher activity than traditional processes. In addition, the metal oxide can act as a passivation layer, has certain antioxidant properties, and can effectively prevent the catalyst from being exposed to air and violently oxidized and burned, thereby further improving the experimental, safety and industrial applicability of the catalyst.

[0082] In a preferred embodiment of the present invention, the metal oxide is vanadium oxide.

[0083] In an optional embodiment, the 2p orbital binding energy of the vanadium element in the vanadium oxide is 510-530eV, for example, it can be 510eV, 512eV, 514eV, 516eV, 518eV, 520eV, 522eV, 524eV, 526eV, 528eV, 530eV, etc.

[0084] In an optional embodiment, the 4f orbital binding energy of the tungsten element in the tungsten oxide is 30-42eV, for example, it can be 30eV, 31eV, 32eV, 33eV, 34eV, 35eV, 36eV, 37eV, 38eV, 39eV, 40eV, 41eV, 42eV, etc.

[0085] In an optional embodiment, the 3d orbital binding energy of the molybdenum element in the molybdenum oxide is between 228 and 239 eV, for example, 228 eV, 229 eV, 230 eV, 231 eV, 232 eV, 233 eV, 234 eV, 235 eV, 236 eV, 237 eV, 238 eV, 239 eV, etc.

[0086] In an optional embodiment, the mass ratio of the metal oxide to the metal nickel-based active component is (0.001-4.000):1, for example, it can be 0.001:1, 0.002:1, 0.004:1, 0.006:1, 0.008:1, 0.010:1, 0.020:1, 0.040:1, 0.050:1, 0.060:1, 0.080:1, 0.100:1, 0.200:1, 0.400:1, 0.500:1, 0.600:1, 0.800:1, 1.000:1, 1.500:1, 2.000:1, 2.500:1, 3.000:1, 3.500:1, 4.000:1, etc.

[0087] In an optional embodiment, the metallic nickel-based active component includes a nickel-based catalyst.

[0088] In an optional embodiment, the nickel-based catalyst is selected from any one or a combination of at least two of a supported nickel-based catalyst, a Raney nickel catalyst or nickel nanoparticles.

[0089] In an optional embodiment, when the metal nickel-based active component is a supported nickel-based catalyst, the mass ratio of the metal oxide to the metal nickel-based active component is (0.001-4.000):1, for example, it can be 0.001:1, 0.002:1, 0.004:1, 0.006:1, 0.008:1, 0.010:1, 0.020:1, 0.040:1, 0.050:1, 0.060:1, 0.080:1, 0.100:1, 0.200:1, 0.400:1, 0.500:1, 0.600:1, 0.800:1, 1.000:1, 1.500:1, 2.000:1, 2.500:1, 3.000:1, 4.000:1, etc.

[0090] In an optional embodiment, when the metal nickel-based active component is a Raney nickel catalyst and / or nickel powder, the mass ratio of the metal oxide to the metal nickel-based active component is (0.001-2.000):1, for example, it can be 0.001:1, 0.002:1, 0.004:1, 0.006:1, 0.008:1, 0.010:1, 0.020:1, 0.040:1, 0.050:1, 0.060:1, 0.080:1, 0.100:1, 0.200:1, 0.400:1, 0.500:1, 0.600:1, 0.800:1, 1.000:1, 1.500:1, 2.000:1, etc.

[0091] In an optional embodiment, the supported nickel-based catalyst includes a carrier and nickel particles supported on the carrier.

[0092] In an optional embodiment, the loading of the nickel particles is 0.1 to 50 wt% of the total mass of the supported nickel-based catalyst, for example, 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt% and the like.

[0093] In an optional embodiment, the carrier is selected from a carbon carrier, an Al2 O 3 、TiO 2 、ZrO 2 、CeO 2 , Fe 2 O 3 or SiO 2 Any one or a combination of at least two of the following.

[0094] In an alternative embodiment, the carrier is selected from a carbon carrier.

[0095] In an optional embodiment, the carbon carrier is selected from any one of activated carbon, carbon nanotubes, carbon black or mesoporous carbon, or a combination of at least two thereof.

[0096] In an optional embodiment, the supported nickel-based catalyst includes any one of a carbon carrier-supported nickel catalyst, an aluminum oxide-supported nickel catalyst, a titanium dioxide-supported nickel catalyst, a zirconium dioxide-supported nickel catalyst, a ceria-supported nickel catalyst, an iron oxide-supported nickel catalyst or a silicon dioxide-supported nickel catalyst, or a combination of at least two thereof.

[0097] In an optional embodiment, the supported nickel-based catalyst includes a carbon-supported nickel catalyst.

[0098] In an optional embodiment, the supported nickel-based catalyst includes an activated carbon-supported nickel catalyst.

[0099] In a second aspect, the present invention provides a method for preparing the catalyst as described in the first aspect, the method for preparing the catalyst comprising the following steps:

[0100] The metal oxide precursor and the metal nickel-based active component are mixed and calcined to obtain the catalyst; wherein the metal oxide precursor includes any one of vanadate, tungstate, tungsten heteropoly acid, molybdate or molybdenum heteropoly acid or a combination of at least two thereof.

[0101] In an optional embodiment, the metallic nickel-based active component includes a nickel-based catalyst.

[0102] In an optional embodiment, the nickel-based catalyst is selected from any one or a combination of at least two of a supported nickel-based catalyst, a Raney nickel catalyst or nickel powder.

[0103] In an optional embodiment, the vanadate is selected from any one or a combination of at least two of sodium metavanadate, sodium pyrovanadate, ammonium metavanadate or sodium orthovanadate.

[0104] In an optional embodiment, the tungstate is selected from any one of ammonium metatungstate, ammonium paratungstate, ammonium tungstate or tungstates, or a combination of at least two thereof.

[0105] In an optional embodiment, the heteropolytungstic acid is selected from silicotungstic acid and / or phosphotungstic acid.

[0106] In an optional embodiment, the molybdate is selected from any one of ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate or sodium molybdate, or a combination of at least two thereof.

[0107] In an optional embodiment, the molybdenum heteropoly acid is selected from silicomolybdic acid and / or phosphomolybdic acid.

[0108] In an optional embodiment, the mass ratio of the metal oxide precursor to the metal nickel-based active component is (0.001-4.000):1, for example, it can be 0.001:1, 0.002:1, 0.004:1, 0.006:1, 0.008:1, 0.010:1, 0.020:1, 0.040:1, 0.050:1, 0.060:1, 0.080:1, 0.100:1, 0.200:1, 0.400:1, 0.500:1, 0.600:1, 0.800:1, 1.000:1, 1.500:1, 2.000:1, 2.500:1, 3.000:1, 3.500:1, 4.000:1, etc.

[0109] In an optional embodiment, when the metallic nickel-based active component is a supported nickel-based catalyst, the mass ratio of the metal oxide precursor to the metallic nickel-based active component is (0.001-4.000):1, for example, it can be 0.001:1, 0.002:1, 0.004:1, 0.006:1, 0.008:1, 0.010:1, 0.020:1, 0.040:1, 0.050:1, 0.060:1, 0.080:1, 0.100:1, 0.200:1, 0.400:1, 0.500:1, 0.600:1, 0.800:1, 1.000:1, 1.500:1, 2.000:1, 2.500:1, 3.000:1, 3.500:1, 4.000:1, etc.

[0110] In an optional embodiment, when the metal nickel-based active component is a Raney nickel catalyst and / or nickel nanoparticles, the mass ratio of the metal oxide precursor to the metal nickel-based active component is (0.001-1.000):1, for example, it can be 0.001:1, 0.002:1, 0.004:1, 0.006:1, 0.008:1, 0.010:1, 0.020:1, 0.040:1, 0.050:1, 0.060:1, 0.080:1, 0.100:1, 0.200:1, 0.400:1, 0.500:1, 0.600:1, 0.800:1, 1.000:1, 1.500:1, 2.000:1, etc.

[0111] In an optional embodiment, the calcination is performed under a protective gas atmosphere.

[0112] In an optional embodiment, the protective gas is selected from any one of nitrogen, argon or hydrogen, or a combination of at least two of them.

[0113] In an optional embodiment, the protective gas is a mixed gas of argon and hydrogen (hereinafter referred to as hydrogen-argon mixed gas).

[0114] In an optional embodiment, the volume percentage of hydrogen in the hydrogen-argon mixture is 0.1-50 vol%, for example, it can be 0.1 vol%, 0.5 vol%, 1 vol%, 2 vol%, 3 vol%, 4 vol%, 5 vol%, 6 vol%, 7 vol%, 8 vol%, 9 vol%, 10 vol%, 15 vol%, 20 vol%, 25 vol%, 30 vol%, 40 vol%, 45 vol%, 50 vol%, etc.

[0115] In an optional embodiment, the calcination temperature is 50-500°C, for example, it can be 50°C, 60°C, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, 240°C, 260°C, 280°C, 300°C, 320°C, 340°C, 360°C, 380°C, 400°C, 420°C, 440°C, 460°C, 480°C, 500°C, etc.

[0116] In an optional embodiment, the calcination time is 1 to 12 h, for example, it can be 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h, 10 h, 10.5 h, 11 h, 1.5 h, 12 h, etc.

[0117] In an optional embodiment, the supported nickel-based catalyst is prepared by the following steps: allowing the support to adsorb a nickel salt precursor, followed by reduction calcination to obtain the supported nickel-based catalyst.

[0118] In an optional embodiment, the supported nickel-based catalyst is prepared by the following steps:

[0119] (a) first preparing a nickel salt solution and a carrier solution respectively, then mixing the nickel salt solution and the carrier solution, stirring and drying to obtain a solid phase;

[0120] (b) calcining the solid phase in an atmosphere of reducing gas to obtain the supported nickel-based catalyst.

[0121] In an optional embodiment, in step (a), during the mixing process, the mass ratio of the nickel salt to the carrier is (0.01-1):1, for example, it can be 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.15:1, 0.2:1, 025:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, etc.

[0122] In an optional embodiment, in step (a), the mixing method is: adding the nickel salt solution dropwise into the carrier solution.

[0123] In an optional embodiment, the nickel salt includes any one of nickel chloride, nickel nitrate, nickel acetate, nickel formate or nickel acetylacetonate, or a combination of at least two thereof.

[0124] In an optional embodiment, the solvent in the nickel salt solution and the carrier solution includes any one of water, methanol, ethanol, tetrahydrofuran or N,N-dimethylformamide, or a combination of at least two thereof.

[0125] In an optional embodiment, in step (a), the stirring time is 0.1 to 10 h, for example, 0.1 h, 0.2 h, 0.3 h, 0.4 h, 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, etc.

[0126] In an optional embodiment, in step (a), the drying temperature is 20-140°C, for example, it can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, etc.

[0127] In an optional embodiment, in step (a), the drying time is 1 to 48 hours, for example, 1 hour, 2 hours, 4 hours, 6 hours, 12 hours, 18 hours, 24 hours, 30 hours, 36 hours, 42 hours, 48 ​​hours, etc.

[0128] In an optional embodiment, in step (b), the reducing gas includes any one of hydrogen, a hydrogen / argon mixture, carbon monoxide, methane or acetylene, or a combination of at least two thereof.

[0129] In an optional embodiment, in step (b), the reducing gas is a mixed gas of argon and hydrogen (hereinafter referred to as hydrogen-argon mixed gas).

[0130] In an optional embodiment, in step (b), the reducing gas is a hydrogen-argon mixture, and the volume percentage of hydrogen in the hydrogen-argon mixture is 5 to 100 vol%, for example, it can be 5 vol%, 6 vol%, 7 vol%, 8 vol%, 9 vol%, 10 vol%, 15 vol%, 20 vol%, 25 vol%, 30 vol%, 40 vol%, 45 vol%, 50 vol%, 60 vol%, 70 vol%, 80 vol%, 90 vol%, 99 vol%, 99.99 vol%, etc.

[0131] In an optional embodiment, in step (b), the calcination temperature is 200-600°C, for example, it can be 200°C, 220°C, 240°C, 260°C, 280°C, 300°C, 320°C, 340°C, 360°C, 380°C, 400°C, 420°C, 440°C, 460°C, 480°C, 500°C, 520°C, 540°C, 560°C, 580°C, 600°C, etc.

[0132] In an optional embodiment, in step (b), the calcination time is 1 to 12 h, for example, it can be 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h, 10 h, 10.5 h, 11 h, 1.5 h, 12 h, etc.

[0133] In a third aspect, the present invention provides a use of the catalyst described in the first aspect, or a catalyst obtained by the method for preparing the catalyst described in the second aspect, as a catalyst for preparing γ-butyrolactone.

[0134] In an optional embodiment, the raw materials for preparing γ-butyrolactone include but are not limited to maleic anhydride and / or succinic anhydride.

[0135] In an optional embodiment, the reaction for preparing γ-butyrolactone is a hydrogenation reduction reaction.

[0136] In a fourth aspect, the present invention provides a method for preparing γ-butyrolactone, the preparation method comprising the following steps:

[0137] In the presence of the catalyst described in the first aspect or the catalyst obtained by the preparation method of the catalyst described in the second aspect, maleic anhydride and / or succinic anhydride are subjected to a hydrogenation reduction reaction to obtain the γ-butyrolactone.

[0138] In an optional embodiment, the method for preparing γ-butyrolactone specifically comprises the following steps:

[0139] After the catalyst is placed in a continuous fixed bed reaction device, maleic anhydride and / or succinic anhydride raw material liquid is injected to carry out a hydrogenation reduction reaction to obtain the gamma-butyrolactone.

[0140] In an optional embodiment, the method for preparing γ-butyrolactone specifically comprises the following steps:

[0141] The catalyst is placed in a continuous fixed bed reaction device; maleic anhydride or succinic anhydride and a solvent are mixed to obtain a raw material liquid; in an atmosphere of reducing gas, the raw material liquid is injected into the reaction device through an injection pump, and a hydrogenation reduction reaction is carried out under certain pressure and temperature conditions to obtain the γ-butyrolactone.

[0142] The present invention provides a method for preparing γ-butyrolactone, wherein the metal catalyst is first placed in a continuous fixed bed reaction device; then, a reaction solution of maleic anhydride or succinic anhydride is injected into the continuous fixed bed reaction device under a reducing gas atmosphere for hydrogenation reduction reaction to obtain γ-butyrolactone. The method for preparing γ-butyrolactone of the present invention abandons the traditional high-pressure reactor type butyrolactone production process, adopts an advanced continuous flow high-pressure fixed bed process, optimizes the overall butyrolactone production process structure, greatly reduces the butyrolactone production cost, and significantly improves the practicality, continuity and safety of the production process.

[0143] In an optional embodiment, the reaction pressure of the hydrogenation reduction reaction is 0.1 to 4.0 MPa, for example, it can be 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.5 MPa, 0.6 MPa, 0.8 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa, 2.5 MPa, 3.0 MPa, 3.5 MPa, 4.0 MPa, etc.

[0144] In an optional embodiment, the temperature of the hydrogenation reduction reaction is 80-240°C, for example, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, 240°C, etc., preferably 160-200°C.

[0145] In an optional embodiment, the hydrogen anhydride ratio of the hydrogenation reduction reaction is 2 to 300, for example, it can be 2, 5, 10, 20, 50, 100, 150, 200, 250, 300, etc., preferably 5 to 50, and more preferably 30.

[0146] In an optional embodiment, the raw material solution also includes a solvent, and the solvent includes any one or a combination of at least two of γ-butyrolactone, methanol, ethanol, isopropanol, N,N-dimethylformamide, dimethyl sulfoxide, dichloromethane, 1,4-dioxane or tetrahydrofuran.

[0147] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0148] Note: In the following examples and comparative examples, “VO x " indicates vanadium oxide; "WO x " stands for tungsten oxide; "MoO x ” stands for molybdenum oxide; “C” stands for carbon.

[0149] Example 1

[0150] This embodiment provides a catalyst, which is prepared by the following steps:

[0151] S1. Preparation of carbon-supported nickel catalyst:

[0152] 1.62 g of nickel chloride hexahydrate was weighed and dissolved in 50 mL of ultrapure water to obtain a nickel chloride solution; at the same time, 1.6 g of an activated carbon carrier was weighed and dispersed in 20 mL of ultrapure water to obtain an activated carbon carrier dispersion; the nickel nitrate solution was added dropwise to the activated carbon carrier dispersion, and the mixture was stirred for 30 min. The water solvent was evaporated at 120° C. to obtain a carbon-supported nickel catalyst precursor with a loading of 20 wt %; the carbon-supported nickel catalyst precursor was placed in an alumina crucible, and the crucible was placed in a tubular furnace. A 5% hydrogen-argon mixed gas was introduced at 25° C. for 60 min to remove oxygen in the pipeline, and then the temperature was raised to 400° C. at a rate of 4° C. / min, and the mixture was reduced at 400° C. for 3 h in a 5% hydrogen-argon mixed atmosphere to prepare a carbon-supported nickel catalyst.

[0153] S2. Preparation of catalyst:

[0154] 50 mg of ammonium metavanadate was mixed with 2.0 g of the carbon-supported nickel catalyst obtained in S1, placed in an alumina crucible, and placed in a tube furnace. A 5% hydrogen-argon mixed gas was introduced for 60 min to remove oxygen in the tube. The temperature was then raised to 200 °C at a rate of 3 °C / min, and calcined at 200 °C for 1 h in a 5% hydrogen-argon mixed atmosphere to prepare vanadium oxide-modified Ni@VO x / C-2.5% catalyst.

[0155] The catalyst prepared above was characterized:

[0156] Figure 1 The Ni@VO prepared in Example 1 x / C-2.5% catalyst high-resolution transmission electron microscopy characterization diagram. Figure 1 As shown, for Ni@VO x / C-2.5% catalyst was characterized by transmission electron microscopy, and the results showed that the surface nickel-based nanoparticles were evenly distributed on the surface of the carbon support.

[0157] Figure 2 The Ni / C and Ni@VO prepared in Example 1 x / C-2.5% catalyst XRD characterization diagram. Figure 2 As shown, the lattice of the nickel-based nanocatalyst on the surface of the carbon carrier does not change before and after the modification, that is, the oxide of the modification strategy provided by the present invention is mainly deposited on the surface of the nickel-based catalyst and does not diffuse into the nickel lattice.

[0158] Figure 3 The Ni@VO prepared in Example 1 x X-ray photoelectron spectrum of vanadium element in / C-2.5% catalyst. Figure 3 As shown, Ni@VO x / C-2.5% catalyst has obvious V element signal, which further verifies the above experimental conclusions. Therefore, the method of modifying nickel-based catalyst with vanadate provided by the present invention can effectively modify the surface of nickel-based catalyst.

[0159] Example 2

[0160] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the amount of ammonium metavanadate used is 0.2 mg, and the remaining preparation steps and material selection are the same as the embodiment 1 to prepare Ni@VO x / C-0.01% catalyst.

[0161] Example 3

[0162] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the amount of ammonium metavanadate used is 1 mg, and the remaining preparation steps and material selection are the same as the embodiment 1, to prepare Ni@VO x / C-0.01% catalyst.

[0163] Example 4

[0164] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the amount of ammonium metavanadate used is 2 mg, and the remaining preparation steps and material selection are the same as the embodiment 1 to prepare Ni@VO x / C-0.1% catalyst.

[0165] Example 5

[0166] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the amount of ammonium metavanadate used is 10 mg, and the remaining preparation steps and material selection are the same as the embodiment 1 to prepare Ni@VO x / C-0.5% catalyst.

[0167] Example 6

[0168] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the amount of ammonium metavanadate used is 20 mg, and the remaining preparation steps and material selection are the same as the embodiment 1, to prepare Ni@VO x / C-1% catalyst.

[0169] Example 7

[0170] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the amount of ammonium metavanadate used is 100 mg, and the remaining preparation steps and material selection are the same as the embodiment 1 to prepare Ni@VO x / C-5% catalyst.

[0171] Example 8

[0172] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the amount of ammonium metavanadate used is 200 mg, and the remaining preparation steps and material selection are the same as the embodiment 1, to prepare Ni@VO x / C-10% catalyst.

[0173] Example 9

[0174] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the amount of ammonium metavanadate used is 400 mg, and the remaining preparation steps and material selection are the same as the embodiment 1, to prepare Ni@VO x / C-20% catalyst.

[0175] Example 10

[0176] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the amount of ammonium metavanadate used is 1.0 g, and the remaining preparation steps and material selection are the same as the embodiment 1 to prepare Ni@VO x / C-50% catalyst.

[0177] Embodiment 11

[0178] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the amount of ammonium metavanadate used is 2.0 g, and the remaining preparation steps and material selection are the same as the embodiment 1 to prepare Ni@VO x / C-100% catalyst.

[0179] Test Example 1

[0180] Study on the Effect of Vanadate Amount on Catalytic Activity of Catalyst

[0181] Test sample: catalyst provided in Examples 1 to 11;

[0182] Test method: 2g of Ni@VO x The catalyst was placed in a quartz tube and fixed to a continuous high-pressure reaction device. The hydrogen pressure in the reaction device system was adjusted to 2.0 MPa H 2 , and the temperature of the reaction bed was adjusted to 200°C. The maleic anhydride solution prepared in advance was pumped into the reaction bed through an injection pump. After the maleic anhydride solution passed through the bed catalyst, it underwent a hydrogenation reaction in a hydrogen atmosphere to generate γ-butyrolactone and the reaction liquid was enriched through a condensing reflux tower. During the reaction, the mass space velocity was controlled to be 1.0h -1 , the hydrogen anhydride ratio is 30, the reaction liquid is collected and analyzed by gas chromatography, and the yield of γ-butyrolactone is detected by the gas chromatography analysis results.

[0183] The test results are shown in Table 1 below:

[0184] Table 1

[0185]

[0186]

[0187] It can be seen from Table 1 that with the increase in the amount of vanadate used, the activity of the modified catalyst increases significantly, and the yield of γ-butyrolactone increases from 73.1% to 99.5%. Therefore, the method of modifying the nickel-based catalyst with vanadate provided by the present invention can effectively improve the catalytic efficiency of the catalyst for maleic anhydride hydrogenation reaction.

[0188] Furthermore, the Ni@VO obtained in Example 1 x The stability test of the / C-2.5% catalyst was carried out under the same conditions. Figure 4The Ni@VO prepared in Example 1 x / C-2.5% catalyst maleic anhydride hydrogenation stability test chart. Figure 4 As shown, the catalyst of the present invention can run stably for 200 hours, and the yield of γ-butanediol is always maintained at about 99.5%, which shows that the catalyst has excellent stability and can realize the continuous production of γ-butanediol.

[0189] In summary, the method for vanadate-modified nickel-based catalyst provided by the present invention can effectively modify the surface of the nickel-based catalyst, realize the geometric and electronic regulation of the surface and interface structure of the nickel-based catalyst, and thus effectively improve the catalytic efficiency of the catalyst for maleic anhydride hydrogenation reaction, and ensure the high activity and high stability of the catalyst.

[0190] Example 12

[0191] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the calcination temperature of S2 is 50°C, and the remaining preparation steps and material selection are the same as the embodiment 1 to prepare vanadium oxide modified Ni@VO x / C-2.5% catalyst.

[0192] Embodiment 13

[0193] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the calcination temperature of S2 is 100°C, and the remaining preparation steps and material selection are the same as those in the embodiment 1 to prepare vanadium oxide-modified Ni@VO x / C-2.5% catalyst.

[0194] Embodiment 14

[0195] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the calcination temperature of S2 is 150°C, and the remaining preparation steps and material selection are the same as the embodiment 1 to prepare vanadium oxide modified Ni@VO x / C-2.5% catalyst.

[0196] Embodiment 15

[0197] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the calcination temperature of S2 is 250°C, and the remaining preparation steps and material selection are the same as the embodiment 1 to prepare vanadium oxide modified Ni@VO x / C-2.5% catalyst.

[0198] Example 16

[0199] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the calcination temperature of S2 is 300°C, and the remaining preparation steps and material selection are the same as those in the embodiment 1, to prepare vanadium oxide modified Ni@VOx / C-2.5% catalyst.

[0200] Embodiment 17

[0201] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the calcination temperature of S2 is 400°C, and the remaining preparation steps and material selection are the same as those in the embodiment 1, to prepare vanadium oxide modified Ni@VO x / C-2.5% catalyst.

[0202] Embodiment 18

[0203] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the calcination temperature of S2 is 500°C, and the remaining preparation steps and material selection are the same as those in the embodiment 1 to prepare vanadium oxide modified Ni@VO x / C-2.5% catalyst.

[0204] Test Example 2

[0205] Study on the Effect of Calcination Temperature on Catalytic Activity of Catalyst

[0206] Test samples: the catalyst provided in Example 1, and the catalysts provided in Examples 12 to 18;

[0207] Test method: Same as test example 1.

[0208] The test results are shown in Table 2 below:

[0209] Table 2

[0210]

[0211]

[0212] As can be seen from Table 2, the calcination temperature of the vanadate-modified nickel-based catalyst has a significant effect on the hydrogenation performance of the catalyst. As the calcination temperature increases from 50°C to 250°C, the yield of γ-butyrolactone gradually increases; when the calcination temperature is 300°C, the yield of γ-butyrolactone can also reach more than 98%; and when the calcination temperature is further increased, the catalyst performance decreases. Therefore, the activity of the catalyst obtained by using a calcination temperature of 150-300°C is the best.

[0213] Embodiment 19

[0214] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the calcination atmosphere of S2 is nitrogen, and the remaining preparation steps and material selection are the same as the embodiment 1, to prepare vanadium oxide modified Ni@VO x / C-2.5% catalyst.

[0215] Embodiment 20

[0216] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the calcination atmosphere of S2 is argon, and the remaining preparation steps and material selection are the same as those of the embodiment 1 to prepare vanadium oxide modified Ni@VO x / C-2.5% catalyst.

[0217] Embodiment 21

[0218] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the calcination atmosphere of S2 is hydrogen, and the remaining preparation steps and material selection are the same as the embodiment 1, to prepare vanadium oxide modified Ni@VO x / C-2.5% catalyst.

[0219] Embodiment 22

[0220] This embodiment provides a catalyst, which is different from the embodiment 1 only in that the calcination atmosphere of S2 is carbon monoxide, and the remaining preparation steps and material selection are the same as the embodiment 1, to prepare vanadium oxide modified Ni@VO x / C-2.5% catalyst.

[0221] Test Example 3

[0222] Investigation of different calcination atmospheres on the catalytic activity of catalysts

[0223] Test samples: the catalyst provided in Example 1, and the catalysts provided in Examples 19 to 22;

[0224] Test method: Same as test example 1.

[0225] The test results are shown in Table 3 below:

[0226] Table 3

[0227] sample Reducing atmosphere γ-Butyrolactone yield (%) Example 1 Hydrogen-Argon Mixture 99.3 Embodiment 19 Nitrogen 99.6 Embodiment 20 Argon 99.7 Embodiment 21 hydrogen 99.3 Embodiment 22 Carbon monoxide 29.9

[0228] As can be seen from Table 3, when the vanadate-modified nickel-based catalyst is calcined in an inert gas atmosphere such as nitrogen or argon, the yield of butyrolactone is further improved and maintained at more than 99.5%; when a reducing atmosphere of hydrogen or a hydrogen-argon mixture is used, the yield of butyrolactone is slightly reduced, but still maintained at more than 99%; and when CO is used as the calcination atmosphere, the catalyst performance is significantly reduced, which is presumably due to the carbon accumulation on the surface of the catalyst caused by CO treatment. Therefore, the catalyst obtained by using the calcination atmosphere of inert gas nitrogen or argon has the best activity.

[0229] Embodiment 23

[0230] This embodiment provides a catalyst, which is different from the embodiment 1 in that 1.70 g of nickel acetate tetrahydrate is used as a nickel salt precursor to prepare Ni@VO x / C-2.5%-Ni catalyst.

[0231] Embodiment 24

[0232] This embodiment provides a catalyst, which is different from the embodiment 1 in that 1.98 g of nickel nitrate hexahydrate is used as a nickel salt precursor to prepare Ni@VO x / C-2.5%-Ni catalyst.

[0233] Embodiment 25

[0234] This embodiment provides a catalyst, which is different from the embodiment 1 in that 1.75 g of nickel acetylacetonate is used as a nickel salt precursor to prepare Ni@VO x / C-2.5%-Ni catalyst.

[0235] Embodiment 26

[0236] This embodiment provides a catalyst, which is different from the embodiment 1 in that 1.25 g of nickel formate dihydrate is used as a nickel salt precursor to prepare Ni@VO x / C-2.5%-Ni catalyst.

[0237] Test Example 4

[0238] Investigation of the effect of different nickel salt precursors on the catalytic activity of catalysts

[0239] Test samples: the catalyst provided in Example 1, and the catalysts provided in Examples 23 to 26;

[0240] Test method: Same as test example 1.

[0241] The test results are shown in Table 4 below:

[0242] Table 4

[0243] Example Nickel salts catalyst γ-Butyrolactone yield (%) Example 1 Nickel chloride hexahydrate <![CDATA[Ni@VO x / C-2.5%]]> 99.3 Embodiment 23 Nickel acetate tetrahydrate <![CDATA[Ni@VO x / C-2.5%]]> 99.1 Embodiment 24 Nickel nitrate hexahydrate <![CDATA[Ni@VO x / C-2.5%]]> 99.3 Embodiment 25 Nickel acetylacetonate <![CDATA[Ni@VO x / C-2.5%]]> 49.7 Embodiment 26 Nickel formate dihydrate <![CDATA[Ni@VO x / C-2.5%]]> 61.3

[0244] It can be seen from Table 4 that the catalyst synthesis can achieve a butyrolactone yield of more than 99% for the catalysts prepared using different nickel salt precursors, proving that the method of the present invention has a certain universality for different nickel salts; however, due to the poor solubility of nickel acetylacetonate and nickel formate dihydrate in water, the synthesized precursor nickel salt is unevenly distributed, so the catalytic performance of the synthesized catalyst is poor.

[0245] Embodiment 27

[0246] This embodiment provides a catalyst, which is different from the embodiment 1 only in that alumina is used as a carrier, and the reduction temperature when preparing the supported nickel catalyst (i.e., the reduction temperature in the 5% hydrogen-argon mixed atmosphere in step S2 of the embodiment 1) is 500°C, and Ni@VO is prepared.x / Al 2 O 3 -2.5% catalyst.

[0247] Embodiment 28

[0248] This embodiment provides a catalyst, which is different from the embodiment 1 only in that silicon dioxide is used as a carrier, and the reduction temperature when preparing the supported nickel catalyst (i.e., the reduction temperature in the 5% hydrogen and argon mixed atmosphere in step S2 of the embodiment 1) is 500°C, and Ni@VO is prepared. x / SiO 2 -2.5% catalyst.

[0249] Embodiment 29

[0250] This embodiment provides a catalyst, which is different from the embodiment 1 only in that titanium dioxide is used as a carrier, and the reduction temperature when preparing the supported nickel catalyst (i.e., the reduction temperature in the 5% hydrogen-argon mixed atmosphere in step S2 of the embodiment 1) is 500°C, and Ni@VO is prepared. x / TiO 2 -2.5% catalyst.

[0251] Embodiment 30

[0252] This embodiment provides a catalyst, which is different from the embodiment 1 only in that ceria is used as a carrier, and the reduction temperature when preparing the supported nickel catalyst (i.e., the reduction temperature in the 5% hydrogen-argon mixed atmosphere in step S2 of the embodiment 1) is 500°C, and Ni@VO is prepared. x / CeO 2 -2.5% catalyst.

[0253] Test Example 5

[0254] Investigation of the effect of different supports on the catalytic activity of catalysts

[0255] Test samples: the catalyst provided in Example 1, and the catalysts provided in Examples 27 to 29;

[0256] Test method: Same as test example 1.

[0257] The test results are shown in Table 5 below:

[0258] Table 5

[0259] sample catalyst γ-Butyrolactone yield (%) Example 1 <![CDATA[Ni@VO x / C-2.5%]]> 99.3 Embodiment 27 <h2 style=";text-align:left;direction:ltr"><![CDATA[Ni@VO <h2 style=";text-align:left;direction:ltr"> x <h2 style=";text-align:left;direction:ltr"> / Al<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> O<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> -2.5%]]><h2 style=";text-align:left;direction:ltr"> 99.2 Embodiment 28 <![CDATA[Ni@VO x / No 2 -2.5%]]> 99.0 Embodiment 29 <![CDATA[Ni@VO x / TiO 2 -2.5%]]> 99.4 Embodiment 30 <![CDATA[Ni@VO x / CeO 2 -2.5%]]> 99.3

[0260] It can be seen from Table 5 that the catalyst synthesis can achieve a butyrolactone yield of more than 99% for catalysts prepared using different nickel salt precursors, which proves that the method of the present invention has a certain universality for different carriers.

[0261] Embodiment 31

[0262] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 2.0g of Raney nickel catalyst to prepare Raney Ni@VO x -2.5% catalyst.

[0263] Embodiment 32

[0264] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 2.0g of nickel nanoparticle catalyst to prepare Raney Ni@VO x -2.5% catalyst.

[0265] Test Example 6

[0266] Investigation of the catalytic activity of different nickel-based catalysts

[0267] Test samples: the catalyst provided in Example 1, and the catalysts provided in Examples 31 to 32;

[0268] Test method: Same as test example 1.

[0269] The test results are shown in Table 6 below:

[0270] Table 6

[0271] sample catalyst γ-Butyrolactone yield (%) Example 1 <![CDATA[Ni@VO x / C-2.5%]]> 99.3 Embodiment 31 <![CDATA[Raney Ni@VO x -2.5%]]> 99.5 Embodiment 32 <![CDATA[Nano Ni@VO x -2.5%]]> 99.8

[0272] It can be seen from Table 6 that the catalyst synthesis can achieve a butyrolactone yield of more than 99% for catalysts prepared using different nickel-based catalysts, which proves that the preparation method of the catalyst of the present invention has a certain universality for different nickel-based catalysts.

[0273] Embodiment 33

[0274] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 50 mg sodium vanadate to replace ammonium metavanadate to prepare Ni@VO x / C-2.5%-Na catalyst.

[0275] Embodiment 34

[0276] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 50 mg of ammonium metatungstate to replace ammonium metavanadate to prepare Ni@WO x / C-2.5%-AMT catalyst.

[0277] Embodiment 35

[0278] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 50 mg of ammonium paratungstate to replace ammonium metavanadate to prepare Ni@WO x / C-2.5%-APT catalyst.

[0279] Embodiment 36

[0280] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 50 mg of ammonium tungstate to replace ammonium metavanadate to prepare Ni@WO x / C-2.5%-AT catalyst.

[0281] Embodiment 37

[0282] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 50 mg of phosphotungstic acid to replace ammonium metavanadate to prepare Ni@WO x / C-2.5%-P catalyst.

[0283] Embodiment 38

[0284] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 50 mg of silicotungstic acid to replace ammonium metavanadate to prepare Ni@WO x / C-2.5%-Si catalyst.

[0285] Embodiment 39

[0286] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 50 mg of ammonium molybdate to replace ammonium metavanadate to prepare Ni@WO x / C-2.5%-AM catalyst.

[0287] Embodiment 40

[0288] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 50 mg of ammonium paramolybdate to replace ammonium metavanadate to prepare Ni@MoO x / C-2.5-APM catalyst.

[0289] Embodiment 41

[0290] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 50 mg of phosphomolybdic acid to replace ammonium metavanadate to prepare Ni@MoO x / C-2.5-P catalyst.

[0291] Embodiment 42

[0292] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 50 mg of phosphomolybdic acid to replace ammonium metavanadate to prepare Ni@MoO x / C-2.5-Si catalyst.

[0293] Embodiment 43

[0294] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses a mixture of 25 mg of ammonium metavanadate and 25 mg of ammonium metatungstate to replace ammonium metavanadate to prepare Ni@VWO x / C-2.5 catalyst.

[0295] Embodiment 44

[0296] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses a mixture of 25 mg of ammonium metavanadate and 25 mg of ammonium molybdate to replace ammonium metavanadate to prepare Ni@VMoO x / C-2.5 catalyst.

[0297] Embodiment 45

[0298] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses a mixture of 25 mg of ammonium metatungstate and 25 mg of ammonium molybdate to replace ammonium metavanadate to prepare Ni@WMoO x / C-2.5 catalyst.

[0299] Embodiment 46

[0300] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 18 mg of ammonium metatungstate, 16 mg of ammonium metatungstate and 16 mg of ammonium molybdate mixture to replace ammonium metavanadate to prepare Ni@VWMoO x / C-2.5-111 catalyst.

[0301] Embodiment 47

[0302] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 25 mg of ammonium metatungstate, 12.5 mg of ammonium metatungstate and 12.5 mg of ammonium molybdate mixture to replace ammonium metavanadate to prepare Ni@VWMoO x / C-2.5-211 catalyst.

[0303] Embodiment 48

[0304] This embodiment provides a catalyst, which is different from the embodiment 1 only in that S2 uses 10 mg of ammonium metatungstate, 20 mg of ammonium metatungstate and 20 mg of ammonium molybdate mixture to replace ammonium metavanadate to prepare Ni@VWMoO x / C-2.5-122 catalyst.

[0305] Test Example 7

[0306] Investigation of the effect of different metal oxide precursors on the catalytic activity of catalysts

[0307] Test sample: catalyst provided in Examples 33 to 48;

[0308] Test method: Same as test example 1.

[0309] The test results are shown in Table 7 below:

[0310] Table 7

[0311]

[0312]

[0313] As can be seen from Table 7, from the results of Examples 33 to 48, the catalysts prepared using sodium vanadate, ammonium metatungstate, ammonium paratungstate, ammonium tungstate, phosphotungstic acid, silicotungstic acid, ammonium molybdate, ammonium paramolybdate, phosphomolybdic acid or silicomolybdic acid and any mixture thereof as precursors all have excellent activity.

[0314] Figure 5 Ni@WO prepared in Example 34 x Tungsten X-ray photoelectron spectrum of / C-2.5% catalyst; Figure 5 As shown, Ni@WO x / C-2.5% The XPS signal of W element was obviously detected on the surface of the catalyst, indicating that the tungsten oxide modified nickel-based catalyst technology provided by the present invention can effectively realize the deposition of tungsten oxide on the surface of the nickel catalyst, realize the regulation of the surface and interface structure of the nickel-based catalyst, thereby greatly improving the maleic anhydride hydrogenation activity of the nickel-based catalyst.

[0315] Similarly, Figure 6 Ni@MoO prepared in Example 39 x Molybdenum X-ray photoelectron spectrum of / C-2.5% catalyst; Figure 6 As shown, Ni@MoO x / C-2.5% The XPS signal of Mo element was obviously detected on the surface of the catalyst, indicating that the molybdenum oxide modified nickel-based catalyst technology provided by the present invention can effectively realize the deposition of tungsten oxide on the surface of the nickel catalyst, and realize the regulation of the surface geometry and electronic state of the nickel-based catalyst, thereby greatly improving the maleic anhydride hydrogenation activity of the nickel-based catalyst.

[0316] Application Example 1

[0317] This application example provides a method for preparing γ-butyrolactone by catalytic hydrogenation of succinic anhydride. The preparation method comprises the following steps: placing 2 g of the catalyst provided in the above-mentioned Example 1 in a quartz tube, fixing it in a continuous high-pressure reaction device, and adjusting the hydrogen pressure in the reaction device system to 2.0 MPa H 2 , and the temperature of the reaction bed was adjusted to 200°C. The prepared succinic anhydride solution was pumped into the reaction bed through an injection pump. After the succinic anhydride solution passed through the bed catalyst, it underwent a hydrogenation reaction in a hydrogen atmosphere to generate γ-butyrolactone and the reaction liquid was enriched through a condensing reflux tower. During the reaction, the mass space velocity was controlled to be 1.0h -1 , the hydrogen anhydride ratio is 30, the reaction liquid is collected and analyzed by gas chromatography, and the yield of γ-butyrolactone is detected by the gas chromatography analysis results.

[0318] Test Case 8

[0319] Investigation of different substrates

[0320] Test sample: the reaction solution provided in Application Example 1;

[0321] The test results are shown in Table 8 below:

[0322] Table 8

[0323] sample Substrate γ-Butyrolactone yield (%) Application Example 1 Succinic anhydride 99.8

[0324] It can be seen from Table 8 that, with succinic anhydride as the substrate, the catalyst provided by the present invention has a butyrolactone yield of 99.8%, which has an excellent catalytic effect.

[0325] Comparative Example 1

[0326] Comparative Example 1 uses the same preparation conditions as Example 1 to prepare a 20 wt% carbon-supported nickel catalyst, except that no vanadate, tungstate or molybdate modification is performed, and the catalytic conditions are the same as Example 1.

[0327] Comparative Example 2

[0328] Comparative Example 2: 20 wt% Al 2 O 3 The supported nickel catalyst is different in that no modification with vanadate, tungstate or molybdate is performed, and the catalytic conditions are the same as those in Example 1.

[0329] Comparative Example 3

[0330] Comparative Example 3: 20 wt% SiO 2The supported nickel catalyst is different in that no modification with vanadate, tungstate or molybdate is performed, and the catalytic conditions are the same as those in Example 1.

[0331] Comparative Example 4

[0332] Comparative Example 4: 20 wt% TiO 2 The supported nickel catalyst is different in that no modification with vanadate, tungstate or molybdate is performed, and the catalytic conditions are the same as those in Example 1.

[0333] Comparative Example 5

[0334] Comparative Example 5: 20 wt% CeO 2 The supported nickel catalyst is different in that no modification with vanadate, tungstate or molybdate is performed, and the catalytic conditions are the same as those in Example 1.

[0335] Comparative Example 6

[0336] Comparative Example 6 uses the same Raney nickel catalyst as Example 31, except that no vanadate, tungstate or molybdate modification is performed, and the catalytic conditions are the same as Example 1.

[0337] Comparative Example 7

[0338] Comparative Example 7 uses the same nickel nanoparticle catalyst as Example 31, except that no vanadate, tungstate or molybdate modification is performed, and the catalytic conditions are the same as Example 1.

[0339] Comparative Example 8

[0340] Comparative Example 8 uses vanadium oxide as a catalyst, and the catalytic conditions are the same as those of Example 1.

[0341] Comparative Example 9

[0342] Comparative Example 9 uses tungsten oxide as a catalyst, and the catalytic conditions are the same as those of Example 1.

[0343] Comparative Example 10

[0344] Comparative Example 10 uses molybdenum oxide as a catalyst, and the catalytic conditions are the same as those of Example 1.

[0345] Test Example 9

[0346] Investigation of different catalysts

[0347] Test sample: the catalyst provided in Comparative Examples 1 to 10.

[0348] The test results are shown in Table 9 below:

[0349] Table 9

[0350]

[0351]

[0352] It can be seen from Table 1-Table 9 that compared with the nickel-based nanocatalysts (i.e., Comparative Examples 1-7), vanadium oxide (Comparative Example 8), tungsten oxide (Comparative Example 9), and molybdenum oxide (Comparative Example 10) that have not been modified by any vanadate, tungstate, or molybdate, the nickel-based catalysts (such as Examples 1-48) modified by vanadate, tungstate, or molybdate provided by the present invention have a significant improvement in the catalytic activity of maleic anhydride / succinic anhydride hydrogenation reaction, from 58.4% before modification to 99.5%, indicating that the vanadate, tungstate, or molybdate modification strategy (such as Examples 1-48) developed by the present invention has a synergistic effect in the catalytic activity of maleic anhydride / succinic anhydride hydrogenation reaction, and has an unexpected technical effect. Therefore, modifying the nickel-based catalyst by vanadate, tungstate, or molybdate is an effective strategy to improve the activity and selectivity of the catalyst itself in the hydrogenation of maleic anhydride / succinic anhydride to butyrolactone, and successfully developed a nickel-based catalyst with low cost, high efficiency, high selectivity, and high antioxidant performance.

[0353] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A catalyst, It is characterized in that The catalyst comprises a metal nickel-based active component and a metal oxide deposited on the surface of the metal nickel-based active component; The metal oxide includes any one of vanadium oxide, molybdenum oxide or tungsten oxide, or a combination of at least two of them.

2. The catalyst according to claim 1, It is characterized in that The 2p orbital binding energy of the vanadium element in the vanadium oxide is 510 to 530 eV; And / or, the 4f orbital binding energy of the tungsten element in the tungsten oxide is 30 to 42 eV; And / or, the 3d orbital binding energy of the molybdenum element in the molybdenum oxide is between 228 and 239 eV.

3. The catalyst according to claim 1, It is characterized in that The mass ratio of the metal oxide to the metal nickel-based active component is (0.001-4.000):1; Preferably, the metallic nickel-based active component comprises a nickel-based catalyst; Preferably, the nickel-based catalyst is selected from any one or a combination of at least two of a supported nickel-based catalyst, a Raney nickel catalyst or nickel nanoparticles; Preferably, when the metal nickel-based active component is a supported nickel-based catalyst, the mass ratio of the metal oxide to the metal nickel-based active component is (0.001-4.000):1; Preferably, when the metal nickel-based active component is a Raney nickel catalyst and / or nickel nanoparticles, the mass ratio of the metal oxide to the metal nickel-based active component is (0.001-2.000):1; Preferably, the supported nickel-based catalyst comprises a carrier and nickel nanoparticles supported on the carrier; Preferably, the loading amount of the nickel nanoparticles accounts for 0.1 to 60 wt % of the total mass of the supported nickel-based catalyst; Preferably, the carrier is selected from carbon carrier, Al 2 O 3 、TiO 2 、ZrO 2 、CeO 2 , Fe 2 O 3 or SiO 2 Any one or a combination of at least two of the following: Preferably, the carbon carrier is selected from any one of activated carbon, carbon nanotubes, carbon black or mesoporous carbon, or a combination of at least two thereof.

4. A method for preparing the catalyst according to any one of claims 1 to 3, It is characterized in that The preparation method of the catalyst comprises the following steps: The metal oxide precursor and the metal nickel-based active component are mixed and calcined to obtain the catalyst; wherein the metal oxide precursor includes any one of vanadate, tungstate, tungsten heteropoly acid, molybdate or molybdenum heteropoly acid or a combination of at least two thereof.

5. A method for preparing a catalyst according to claim 4, It is characterized in that The metal nickel-based active component includes a nickel-based catalyst; Preferably, the nickel-based catalyst is selected from any one or a combination of at least two of a supported nickel-based catalyst, a Raney nickel catalyst or nickel nanoparticles; Preferably, the vanadate is selected from any one or a combination of at least two of sodium metavanadate, sodium pyrovanadate, ammonium metavanadate or sodium orthovanadate; Preferably, the tungstate is selected from any one or a combination of at least two of ammonium metatungstate, ammonium paratungstate, ammonium tungstate or tungstate; Preferably, the heteropolytungstic acid is selected from silicotungstic acid and / or phosphotungstic acid; Preferably, the molybdate is selected from any one of ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate or sodium molybdate, or a combination of at least two thereof; Preferably, the molybdenum heteropoly acid is selected from silicomolybdic acid and / or phosphomolybdic acid.

6. The method for preparing the catalyst according to claim 4, It is characterized in that The mass ratio of the metal oxide precursor to the metal nickel-based active component is (0.001-4.000):1; Preferably, when the metal nickel-based active component is a supported nickel-based catalyst, the mass ratio of the metal oxide precursor to the metal nickel-based active component is (0.001-4.000):1; Preferably, when the metal nickel-based active component is a Raney nickel catalyst and / or nickel powder, the mass ratio of the metal oxide precursor to the metal nickel-based active component is (0.001-2.000):1; Preferably, the calcination is carried out under a protective gas atmosphere; wherein the protective gas is selected from any one of nitrogen, argon or hydrogen, or a combination of at least two thereof; Preferably, the calcination temperature is 50-500° C., and the calcination time is 1-12 hours.

7. The method for preparing the catalyst according to claim 5, It is characterized in that The supported nickel-based catalyst is prepared by the following steps: allowing the support to adsorb the nickel salt precursor, and then reducing and calcining to obtain the supported nickel-based catalyst; Preferably, the supported nickel-based catalyst is prepared by the following steps: (a) first preparing a nickel salt solution and a carrier solution respectively, then mixing the nickel salt solution and the carrier solution, stirring and drying to obtain a solid phase; (b) calcining the solid phase under a reducing gas atmosphere to obtain the supported nickel-based catalyst; Preferably, in step (a), the mixing method is: dropping the nickel salt solution into the carrier solution; Preferably, the nickel salt includes any one of nickel chloride, nickel nitrate, nickel acetate, nickel formate or nickel acetylacetonate, or a combination of at least two thereof; Preferably, the solvent in the nickel salt solution and the carrier solution includes any one of water, methanol, ethanol, tetrahydrofuran or N,N-dimethylformamide or a combination of at least two thereof; Preferably, in step (b), the reducing gas comprises any one of hydrogen, hydrogen / argon mixed gas, carbon monoxide, methane or acetylene, or a combination of at least two thereof; Preferably, in step (b), the calcination temperature is 200-600° C., and the calcination time is 1-12 hours.

8. Use of the catalyst according to any one of claims 1 to 3 or the catalyst obtained by the method for preparing the catalyst according to any one of claims 4 to 7 as a catalyst for preparing γ-butyrolactone.

9. A method for preparing γ-butyrolactone, It is characterized in that The preparation method comprises the following steps: In the presence of the catalyst according to any one of claims 1 to 3 or the catalyst obtained by the method for preparing the catalyst according to any one of claims 4 to 7, maleic anhydride and / or succinic anhydride are subjected to a hydrogenation reduction reaction to obtain the γ-butyrolactone.

10. The method for preparing γ-butyrolactone according to claim 9, It is characterized in that The preparation method specifically comprises the following steps: After placing the catalyst in a continuous fixed bed reaction device, maleic anhydride and / or succinic anhydride raw material liquid is injected to carry out a hydrogenation reduction reaction to obtain the γ-butyrolactone; Preferably, the reaction pressure of the hydrogenation reduction reaction is 0.1 to 5.0 MPa; Preferably, the temperature of the hydrogenation reduction reaction is 80 to 240°C; Preferably, the hydrogen-anhydride ratio of the hydrogenation reduction reaction is 2 to 300; Preferably, the mass space velocity of the hydrogenation reduction reaction is 0.01 to 2.0 h -1 ; Preferably, the raw material solution also includes a solvent, and the solvent includes any one or a combination of at least two of methanol, ethanol, isopropanol, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, dichloromethane, 1,4-dioxane or tetrahydrofuran.

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