Supported ternary transition metal catalyst as well as preparation method and application thereof

Abstract

The invention discloses a supported ternary transition metal catalyst as well as a preparation method and application thereof. The chemical formula of the supported ternary transition metal catalyst is Ni < x > W < 1-x > Py: D, and D is a carrier, 0 lt; x < lt >; 1. The supported ternary transition metal catalyst provided by the invention has high activity, excellent cyclopentanol selectivity and excellent stability, and shows 99.9% of activity in a cyclopentyl formate hydrogenation reaction, and the selectivity of cyclopentanol in a product can reach 96% or above. Through a long-time stability test, the catalyst shows good stability, and the service life is as long as 1200 hours. Moreover, the technical scheme provided by the invention is mild in reaction condition and high in environmental friendliness in the production process, so that the method can be widely applied to the cyclopentanol preparation process in industrial production, and has remarkable economic benefits and application prospects.

Description

TECHNICAL FIELD

[0001] The present application relates to a preparation method of a catalyst, in particular to a supported ternary transition metal catalyst and a preparation method thereof, and application thereof in the preparation of cyclopentanol, and belongs to the technical field of organic chemical industry. BACKGROUND

[0002] Cyclopentanol is an important fine chemical raw material, which is widely used in the production and preparation of pharmaceuticals, pesticides, dye intermediates and perfumes, and can be used to prepare cyclopentanone, halogenated cyclopentane, antibacterial and antiallergic drugs, and is also an indispensable raw material for synthesizing the drugs for treating edema and hypertension, such as methazol and new non-barbiturate intravenous anesthetics ketamine. However, cyclopentanol only exists in a small number of plants in nature and has a low content, and is difficult to extract. At present, the main synthesis process of cyclopentanol in industry is to obtain cyclopentanone from adipic acid and its derivatives, and then to obtain cyclopentanol by hydrogenation. This route has problems of high price, long process route and pollutants in the production process, which limits its further industrialization.

[0003] In recent years, a two-step process has attracted much attention, which uses cyclopentene and organic acid as raw materials to obtain the corresponding cyclopentyl ester through esterification addition, and then obtains cyclopentanol from cyclopentyl ester. The commonly used catalysts such as platinum, palladium, nickel, etc. have high activity and selectivity, but their high cost and the problem of resource scarcity of some catalysts limit their wide application. Therefore, finding a cheaper and more efficient catalyst is still an important challenge. Chinese patent CN112194569A discloses a method for preparing cyclopentanol from cyclopentene via cyclopentyl formate: cyclopentene and formic acid generate cyclopentyl formate under the self-catalytic effect of formic acid, and the product is further reacted and then hydrolyzed with water to obtain cyclopentanol after separation and purification. Although the purity of the final cyclopentanol product can reach 99.1%, the use of formic acid as raw material requires high corrosion resistance of the equipment, resulting in high equipment cost. Chinese patent CN110818566A discloses a method for preparing cyclopentanol and ethanol from cyclopentene and acetic acid: cyclopentene and acetic acid are subjected to addition reaction under the action of an acid catalyst, and the obtained product is subjected to rectification and purification to obtain cyclopentyl acetate, which is subjected to hydrogenation reaction under the action of a metal catalyst to generate cyclopentanol and ethanol, but the process is still not mature, and the selectivity of cyclopentanol is about 50%, and the selectivity of ethanol is 30%-35%. Chinese patent CN10546115A discloses a method for preparing cyclopentanol from cyclopentene: cyclopentene and acetic acid are subjected to esterification reaction under the action of a modified sulfonic acid-based cation exchange resin to obtain cyclopentyl acetate, and the esterification reaction product is subjected to ester exchange reaction with methanol under the action of a catalyst CaO, but CaO is prone to deliquescence to form Ca(OH)2 or calcium acetate in the column, which not only blocks the reaction rectification column but also increases the difficulty of separation of subsequent materials. In addition, the ester exchange generated methyl acetate will form azeotrope with methanol, so the process also involves the separation of subsequent azeotrope.

[0004] On the other hand, in terms of reaction conditions, the current reaction usually requires high temperature and pressure, and requires corresponding hydrogen pressure. This not only increases energy consumption and operating cost, but also may cause side reactions to occur, affecting the yield and selectivity of the product.

[0005] In summary, the existing technology can realize the preparation of cyclopentanol, but still has many technical limitations and deficiencies. The future research directions include finding a cheaper and more efficient catalyst, optimizing the reaction conditions, improving the yield and selectivity, and improving the environmental friendliness, etc. Therefore, how to provide a complete cyclopentanol production process with cheap and efficient catalyst, mild reaction conditions, high yield and selectivity, and environmental friendliness is an urgent technical problem for those skilled in the art. SUMMARY

[0006] The main purpose of the present application is to provide a supported ternary transition metal catalyst and a preparation method thereof to solve the above and other potential problems of the prior art.

[0007] Another object of the present application is to provide an application of the supported ternary transition metal catalyst in the preparation of cyclopentanol.

[0008] To achieve the above objects, the technical solutions of the present application comprise:

[0009] The embodiment of the present application provides a supported ternary transition metal catalyst, which has a chemical formula of Ni x W 1-x P y :D, wherein D is a carrier, 0 < x < 1, and y is 0.5-2.

[0010] In some embodiments, the mass ratio of Ni x W 1-x P y to D is (14%-15%):(85%-86%), and the sum of Ni x W 1-x P y and D is 100%.

[0011] The embodiment of the present application also provides a preparation method of the supported ternary transition metal catalyst, which comprises:

[0012] activating the carrier to obtain an activated carrier;

[0013] mixing a nickel salt, a tungsten salt and a phosphorus salt with water to obtain a solid-phase precipitate, dissolving the solid-phase precipitate by adding a second acid, then adding the activated carrier for impregnation, and then sequentially performing filtration, drying and calcination to obtain a catalyst precursor;

[0014] performing reduction treatment on the catalyst precursor, and then performing passivation treatment to obtain the supported ternary transition metal catalyst.

[0015] The embodiment of the present application also provides an application of the supported ternary transition metal catalyst in the preparation of cyclopentanol.

[0016] Correspondingly, the embodiment of the present application also provides a preparation method of cyclopentanol, which comprises:

[0017] providing the supported ternary transition metal catalyst and performing activation treatment to obtain an activated catalyst;

[0018] performing hydrogenation reaction on cyclopentyl formate and hydrogen in the presence of the activated catalyst to obtain cyclopentanol.

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

[0020] The supported ternary transition metal catalyst prepared by the application has high activity, excellent cyclopentanol selectivity and excellent stability, exhibits 99.9% activity in the cyclopentyl formate hydrogenation reaction, and the selectivity of cyclopentanol in the product can reach more than 96%. After long-term stability test, the catalyst shows good stability and service life of up to 1200 hours. And the technical scheme of the application has mild reaction conditions in the production process and strong environmental friendliness, so it can be widely used in the preparation process of cyclopentanol in industrial production, and has significant economic benefits and application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments described in the application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0022] Figure 1 The nuclear magnetic spectrum of the product prepared by hydrogenation reaction of the embodiment 1 of the application;

[0023] Figure 2 The gas chromatogram of the product generated under 2MPa pressure in a typical embodiment of the application;

[0024] Figure 3 The gas chromatogram of the product generated under the condition of hydrogen material ratio of 119 in a typical embodiment of the application. DETAILED DESCRIPTION

[0025] In view of the problems existing in the prior art, the present inventors have long-term research and a large number of practices, and finally put forward the technical scheme of the application, which mainly proposes a supported ternary transition metal catalyst for cyclopentanol preparation and a preparation method thereof.

[0026] The technical scheme, its implementation process and principles will be further explained as follows. However, it should be understood that in the scope of the application, the above technical features of the application and the technical features specifically described in the following (embodiments) can be combined with each other to form new or preferred technical schemes. Limited by the length, they will not be listed one by one here.

[0027] As an aspect of the technical scheme of the application, the chemical formula of the supported ternary transition metal catalyst involved is Ni x W 1-x P y :D, wherein D is a carrier, 0 < x < 1, the value range of y is 0.5-2; Ni x W1-x P y The mass ratio of P to D is (14%~15%) : (85%~86%), and the mass ratio of Ni to D is (5%~6%) : (85%~86%). x W 1-x P y The total of P and D is 100%.

[0028] In some embodiments, the carrier can include one or more of SiO2, Al2O3, molecular sieve, etc., but not limited to.

[0029] Further, the molecular sieve can include one or both of MCM-41 and Y-type molecular sieve, but not limited to.

[0030] As another aspect of the technical solution of the present application, the preparation method of the supported ternary transition metal catalyst includes:

[0031] activating the carrier to obtain an activated carrier;

[0032] mixing a nickel salt, a tungsten salt, and a phosphorus salt with water to obtain a solid-phase precipitate, dissolving the solid-phase precipitate by adding a second acid, then adding the activated carrier for impregnation, and then sequentially performing filtration, drying, and calcination to obtain a catalyst precursor;

[0033] reducing the catalyst precursor, and then performing passivation treatment to obtain the supported ternary transition metal catalyst.

[0034] In some embodiments, the preparation method includes: impregnating the carrier in a solution containing a surfactant for 7-9 hours, mixing the carrier with a first acid after filtration, and performing activation treatment at room temperature for 2-4 hours.

[0035] In some embodiments, the carrier can include one or more of SiO2, Al2O3, molecular sieve, etc., but not limited to.

[0036] Further, the molecular sieve can include one or both of MCM-41 and Y-type molecular sieve, but not limited to.

[0037] In some embodiments, the surfactant can include, but not limited to, a mixture of one or more of SDBS, SDS, CTAB, Tween series, Pluronic F127, etc. The surfactant used in the activation treatment of the carrier surface of the present application can neutralize the surface charge of the carrier, stabilize the metal particles by electrostatic repulsion, inhibit the generation of carbon deposition, reduce the agglomeration of metal particles, prolong the catalytic life, and improve the selectivity by forming 3D interconnected mesopores. At the same time, the use of surfactants can increase the surface hydroxyl density, improve the wettability, enhance the anchoring ability, and improve the diffusion rate of macromolecules.

[0038] In some embodiments, the first acid comprises any one of nitric acid, hydrochloric acid, dilute sulfuric acid, and the like.

[0039] In some embodiments, the nickel salt can comprise, but is not limited to, a combination of one or more of nickel nitrate, nickel oxalate, nickel carbonate, nickel ammonium nitrate, and the like.

[0040] In some embodiments, the phosphorus salt can comprise, but is not limited to, a combination of one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, and ammonium phosphotungstate, and the like.

[0041] In some embodiments, the tungsten salt can comprise, but is not limited to, a combination of one or more of tungstate, metatungstate, paratungstate, and the like.

[0042] Further, the tungstate can comprise, but is not limited to, a combination of one or more of sodium tungstate, ammonium tungstate, potassium tungstate, magnesium tungstate, and the like.

[0043] Further, the metatungstate can comprise, but is not limited to, a combination of one or both of sodium metatungstate, ammonium metatungstate, and the like.

[0044] Further, the paratungstate can comprise, but is not limited to, a combination of one or both of ammonium paratungstate, sodium paratungstate, and the like.

[0045] In some embodiments, the molar ratio of the total amount of nickel salt and tungsten salt to the amount of phosphorus salt is (0.6-1.4):1.

[0046] In some embodiments, the molar ratio of the nickel salt to the tungsten salt is (1-9):1. The modified carrier used in the supported ternary transition metal catalyst prepared by the present application has a unique pore structure, which can better disperse during the preparation of the catalyst, is conducive to the formation of uniform active centers, and the unique pore structure of the carrier has more active sites, which is conducive to the catalytic reaction. The addition of an appropriate proportion of tungsten in the ternary system nickel tungsten phosphorus can disperse nickel and make its particles smaller, which is more conducive to the reduction of nickel from nickel phosphate to nickel phosphide, on the other hand, the addition of an appropriate proportion of tungsten can be more conducive to the formation of electronic vacancies of nickel to improve the catalytic results.

[0047] Further, the mass-volume ratio of the nickel salt to water is (5-10) g:(20-25) mL.

[0048] Further, the mass-volume ratio of the nickel salt to the second acid is (5-10) g:(2-3) mL.

[0049] In some embodiments, the second acid comprises any one of nitric acid, hydrochloric acid, dilute sulfuric acid, a mixed acid with phosphoric acid or citric acid or acetic acid. And, at least one of the first acid and the second acid comprises the same acid.

[0050] Further, the first acid and the second acid are preferably added dropwise.

[0051] In some embodiments, the reduction treatment is carried out under a hydrogen atmosphere, wherein the space velocity of hydrogen is 1800~2200h -1 .

[0052] In some embodiments, the temperature of the reduction treatment is 520~580℃, the time is 2~4h, and the heating rate is 3~5℃ / min.

[0053] In some embodiments, the passivation treatment employs a passivation gas which is a mixture of O2 and N2, wherein the concentration of O2 is 0.5~1.5vol%, i.e., 0.5~1.5vol% O2 / 6N2 mixed gas.

[0054] Further, the time of the passivation treatment is 3~5h.

[0055] In some more preferred embodiments, a preparation method of a supported ternary transition metal catalyst specifically comprises the following steps:

[0056] 1) Surface activation treatment of the carrier: first immerse the carrier in a surfactant solution, filter, pour into an A acid (i.e., the aforementioned first acid) solution for activation, then filter, wash and dry for standby;

[0057] 2) Mix nickel salt, tungsten salt and phosphorus salt in water to obtain a precipitate, then add B acid (i.e., the aforementioned second acid) to dissolve the precipitate, then immerse the carrier after activation treatment in step 1), then sequentially perform filtration, drying and calcination to obtain a catalyst precursor;

[0058] 3) Reduce the catalyst precursor obtained in step 2), after the reaction is complete, cool to room temperature for passivation treatment to obtain the supported ternary transition metal catalyst.

[0059] Further, the time of the immersion in step 1) is 7~9h.

[0060] Further, the time of the immersion in step 2) after adding the activated carrier is 2~4h.

[0061] Further, in step 2), the temperature of the drying is 100~120℃, and the time of the drying is 12~16h.

[0062] Furthermore, in step 2), the roasting temperature is 400~450℃ and the time is 3~5h.

[0063] As another aspect of the technical solution of the present invention, it also relates to the application of the supported ternary transition metal catalyst in the preparation of cyclopentanol.

[0064] Specifically, the application includes the use of the supported ternary transition metal catalyst in the hydrogenation reaction of cyclopentyl formate to prepare cyclopentanol.

[0065] Accordingly, as another aspect of the technical solution of the present invention, it also relates to a method for preparing cyclopentanol, which includes:

[0066] The supported ternary transition metal catalyst is provided and activated to obtain the activated catalyst;

[0067] In the presence of the activated catalyst, cyclopentyl formate is hydrogenated with hydrogen gas to obtain cyclopentanol.

[0068] In some embodiments, the activation treatment is carried out in a hydrogen atmosphere, wherein the pressure is preferably atmospheric pressure and the space velocity is preferably 1800-2200 h⁻¹. -1 .

[0069] In some embodiments, the activation treatment temperature is 450~550℃, the heating rate is 1~3℃ / min, and the activation treatment time is 3~6h.

[0070] In some embodiments, the hydrogenation reaction is carried out in a hydrogen atmosphere, with a hydrogen to cyclopentyl formate molar ratio of (51~150):1, preferably (51~136):1, and a weight hourly space velocity of 0.18~1.08 h⁻¹. -1 .

[0071] In some embodiments, the hydrogenation reaction is carried out at a temperature of 150-230°C for 2-4 hours and at a pressure of 1.0-3.0 MPa.

[0072] In summary, the supported ternary transition metal catalyst prepared by this invention exhibits high activity, excellent cyclopentanol selectivity, and outstanding stability. It demonstrates 99.9% activity in the hydrogenation reaction of cyclopentanol formate, and the selectivity for cyclopentanol in the product remains consistently above 96%. Extensive stability testing shows that the catalyst exhibits good stability and a service life of up to 1200 hours.

[0073] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0074] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0075] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0076] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be obvious to those skilled in the art. This application specification and embodiments are merely exemplary.

[0077] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0078] Unless otherwise specified, "room temperature" and "normal temperature" in this invention refer to 25±2℃.

[0079] All raw materials used in the following embodiments of the present invention are commercially available.

[0080] Example 1

[0081] The preparation method of supported ternary transition metal catalysts is as follows:

[0082] 1) Surface treatment of the carrier: First, 63 g of Al2O3 carrier was soaked in CTAB surfactant solution for 7 hours, filtered, and then activated in hydrochloric acid solution for 2 hours. After filtration and washing, it was dried at 100℃ for 16 hours for later use.

[0083] 2) Weigh out 0.05 mol of nickel carbonate, 0.01 mol of tungsten in sodium metatungstate, and 0.1 mol of ammonium dihydrogen phosphate and add them to 20 ml of deionized water to obtain a precipitate. Then add 2 ml of a mixture of hydrochloric acid and citric acid to dissolve the precipitate. Then add the activated Al2O3 support from 1) and soak it. Let it stand at room temperature for 4 h, filter it, dry it at 120 ℃ for 12 h, and then calcine it at 400 ℃ for 5 h to obtain the catalyst precursor.

[0084] 3) The catalyst precursor obtained in step 2) is reduced in a hydrogen atmosphere, wherein the hydrogen space velocity is 1800 h⁻¹. -1 The reduction reaction was carried out at 520℃ for 2 hours at a heating rate of 3℃ / min. After the reaction, the temperature was lowered to room temperature and passivated with a 0.5 vol% O2 / 6N2 mixed gas for 3 hours. This yielded the supported ternary transition metal catalyst. In this catalyst, Ni... x W 1-x P y The mass ratio of Ni to Al2O3 is 14%:86%; the molar ratio (Ni+W):P is 1:1.

[0085] 2. The preparation process of cyclopentanol is as follows:

[0086] 1) The supported ternary transition metal catalyst was subjected to atmospheric pressure and a space velocity of 1800 h⁻¹. -1 The catalyst was activated under a hydrogen atmosphere at a temperature of 450℃, a heating rate of 1℃ / min, and an activation time of 6 hours. The activated catalyst was then obtained.

[0087] 2) The activated catalyst was used to hydrogenate cyclopentyl formate at 150℃ and 3.0 MPa for 2 h, with a hydrogen to cyclopentyl formate molar ratio of 51:1 and a weight hourly space velocity of 0.18 h⁻¹. -1 The reaction yields cyclopentanol.

[0088] Under the conditions of this example, the conversion rate of cyclopentyl formate was 99.8%, and the selectivity of cyclopentanol was 96.0%.

[0089] Example 2

[0090] 1. The preparation method of supported ternary transition metal catalysts is as follows:

[0091] 1) Surface treatment of the carrier: First, 34g of SiO2 carrier was soaked in the surfactant SDBS solution for 8 hours, filtered, and then poured into nitric acid solution for activation for 3 hours. After that, it was filtered, washed, and dried at 110℃ for 14 hours for later use.

[0092] 2) Weigh out 0.0595 mol of nickel nitrate, 0.01 mol of sodium tungstate, and 0.0695 mol of diammonium hydrogen phosphate and add them to 23 ml of deionized water to obtain a precipitate. Then, add 2.4 ml of a mixed acid of nitric acid and phosphoric acid dropwise to dissolve the precipitate. Then, add the activated SiO2 support from 1) and soak it. Let it stand at room temperature for 3 h, filter it, dry it at 110 ℃ for 14 h, and then calcine it at 420 ℃ for 4 h to obtain the catalyst precursor.

[0093] 3) The catalyst precursor obtained in step 2) is reduced in a hydrogen atmosphere, wherein the hydrogen space velocity is 2000 h⁻¹. -1 The reduction reaction was carried out at 550℃ for 3 hours at a heating rate of 4℃ / min. After the reaction, the temperature was lowered to room temperature and passivated with a 1 vol% O2 / 6N2 mixed gas for 4 hours. This yielded the supported ternary transition metal catalyst. In this catalyst, Ni... x W 1-x P y The mass ratio of Ni to SiO2 is 15%:85%; the molar ratio (Ni+W):P = 1:1.

[0094] 2. The preparation process of cyclopentanol is as follows:

[0095] 1) The supported ternary transition metal catalyst was subjected to atmospheric pressure and a space velocity of 2000 h⁻¹. -1 The catalyst was activated under a hydrogen atmosphere at a temperature of 500℃, a heating rate of 2℃ / min, and a activation time of 4 hours. The activated catalyst was then obtained.

[0096] 2) The activated catalyst was used to hydrogenate cyclopentyl formate at 200℃ and 2.5 MPa for 3 h, with a hydrogen to cyclopentyl formate molar ratio of 100:1 and a weight hourly space velocity (WHSV) of 0.6 h⁻¹. -1 The reaction yields cyclopentanol.

[0097] Figure 1 The NMR spectrum of the product prepared in this embodiment confirms the formation of cyclopentanol.

[0098] Under the conditions of this example, the conversion rate of cyclopentyl formate was 99.6%, and the selectivity of cyclopentanol was 96.5%.

[0099] Example 3

[0100] 1. The preparation method of supported ternary transition metal catalysts is as follows:

[0101] 1) Surface treatment of the carrier: First, soak 18g of MCM-41 molecular sieve carrier in a solution of surfactant Pluronic F127 for 9 hours, filter it, and then pour it into a solution of tretinoin acid and dilute sulfuric acid for 4 hours. Then filter, wash and dry at 120℃ for 12 hours for later use.

[0102] 2) Weigh out 0.0357 mol of nickel oxalate, 0.01 mol of sodium paratungstate containing tungsten, and 0.0326 mol of ammonium phosphate and add them to 25 ml of deionized water to obtain a precipitate. Then, add 3 ml of a mixture of dilute sulfuric acid and acetic acid dropwise to dissolve the precipitate. Then, add the activated MCM-41 molecular sieve support from 1) and soak it. Let it stand at room temperature for 2 h, filter it, dry it at 100℃ for 16 h, and then calcine it at 450℃ for 3 h to obtain the catalyst precursor.

[0103] 3) The catalyst precursor obtained in step 2) is reduced in a hydrogen atmosphere, wherein the hydrogen space velocity is 2200 h⁻¹. -1 The reduction reaction was carried out at 580℃ for 4 hours at a heating rate of 5℃ / min. After the reaction, the temperature was lowered to room temperature and passivated with a 1.5 vol% O2 / 6N2 mixed gas for 5 hours. This yielded the supported ternary transition metal catalyst. In this catalyst, Ni... x W 1-x P y The mass ratio of Ni to MCM-41 molecular sieve is 15%:85%; the molar ratio (Ni+W):P is 1:1.

[0104] 2. The preparation process of cyclopentanol is as follows:

[0105] 1) The supported ternary transition metal catalyst was subjected to atmospheric pressure and a space velocity of 2200 h⁻¹. -1 The catalyst was activated under a hydrogen atmosphere at a temperature of 550℃, a heating rate of 3℃ / min, and an activation time of 3 hours. The activated catalyst was then obtained.

[0106] 2) The activated catalyst was used to hydrogenate cyclopentyl formate at 230℃ and 1.0 MPa for 4 h, with a hydrogen to cyclopentyl formate molar ratio of 150:1 and a weight hourly space velocity of 1.08 h⁻¹. -1 The reaction yields cyclopentanol.

[0107] Under the conditions of this example, the conversion rate of cyclopentyl formate was 99.9%, and the selectivity of cyclopentanol was 98.5%.

[0108] Example 4

[0109] The difference between this embodiment and Example 1 is that the pressure in the preparation of cyclopentanol is 2 MPa.

[0110] Figure 2 This is a gas chromatogram of the product generated at a pressure of 2 MPa in this embodiment.

[0111] Example 5

[0112] The difference between this embodiment and Example 1 is that the molar ratio of hydrogen to cyclopentyl formate in the preparation of cyclopentanol is 119:1.

[0113] Figure 3 This is a gas chromatogram of the product generated in this embodiment under a hydrogen-to-feed ratio of 119.

[0114] The supported ternary transition metal catalyst of this invention exhibited high activity, excellent cyclopentanol selectivity, and outstanding stability in repeated experiments. Even after 18 days of continuous repeated use of the supported ternary transition metal catalyst, the cyclopentanol selectivity remained as high as 96.43%. Furthermore, the consistently high yield throughout the repeated experiments indicates that the reaction has been optimized in terms of catalyst selection and reaction condition control, resulting in a significant improvement in both the conversion rate of the raw materials and the yield of the target product. Simultaneously, this also means that fewer byproducts and wastes are generated during the reaction, achieving green and sustainable chemical production.

[0115] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0116] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A supported ternary transition metal catalyst, characterized in that: The chemical formula of the supported ternary transition metal catalyst is Ni. x W 1-x P y :D, where D is the carrier, 0 < x < 1, and y is 0.5~2.

2. The supported ternary transition metal catalyst according to claim 1, characterized in that: Ni x W 1-x P y The mass ratio of Ni to D is (14%~15%):(85%~86%), and Ni x W 1-x P y The sum of D and D is 100%.

3. The supported ternary transition metal catalyst according to claim 1, characterized in that: The carrier includes one or more of SiO2, Al2O3, and molecular sieves; preferably, the molecular sieve includes one or a combination of MCM-41 and Y-type molecular sieves.

4. The method for preparing the supported ternary transition metal catalyst according to any one of claims 1-3, characterized in that, include: The carrier is activated to obtain the activated carrier; Nickel salt, tungsten salt, and phosphate salt are mixed with water to obtain a solid precipitate. A second acid is added to dissolve the solid precipitate. Then, the activated support is added for impregnation. The mixture is then filtered, dried, and calcined to obtain a catalyst precursor. The catalyst precursor was reduced and then passivated to obtain a supported ternary transition metal catalyst.

5. The preparation method according to claim 4, characterized in that, include: The carrier is immersed in a solution containing surfactant for 7-9 hours, filtered, and then mixed with the first acid and activated at room temperature for 2-4 hours. Preferably, the surfactant includes one or a mixture of SDBS, SDS, CTAB, Tween series, and Pluronic F127; Preferably, the first acid includes any one of nitric acid, hydrochloric acid, and dilute sulfuric acid; And / or, the support comprises one or more of SiO2, Al2O3, and molecular sieves; preferably, the molecular sieve comprises one or a combination of MCM-41 and Y-type molecular sieves.

6. The preparation method according to claim 4, characterized in that: The nickel salt includes one or more combinations of nickel nitrate, nickel oxalate, nickel carbonate, and nickel ammonium nitrate; And / or, the tungsten salt includes one or more combinations of tungstate, metatungstate, and paratungstate; preferably, the tungstate includes one or more combinations of sodium tungstate, ammonium tungstate, potassium tungstate, and magnesium tungstate; preferably, the metatungstate includes one or two combinations of sodium metatungstate and ammonium metatungstate; preferably, the paratungstate includes one or two combinations of ammonium paratungstate, potassium paratungstate, and sodium paratungstate. And / or, the phosphate salt comprises one or more combinations of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, and ammonium phosphotungstate; And / or, the molar ratio of the total amount of nickel salt and tungsten salt added to the amount of phosphate salt added is (0.6~1.4):1; And / or, the molar ratio of the nickel salt to the tungsten salt is (1~9):1; And / or, the mass-to-volume ratio of the nickel salt to water is (5~10) g : (20~25) mL; And / or, the mass-to-volume ratio of the nickel salt to the second acid is (5~10) g : (2~3) mL; And / or, the second acid includes any one of nitric acid, hydrochloric acid, dilute sulfuric acid, or a mixture of phosphoric acid, citric acid, or acetic acid; preferably, the first acid and the second acid contain at least one of the same acid; preferably, the first acid and the second acid are added dropwise. And / or, the impregnation time after adding the activated carrier is 2-4 hours; And / or, the drying temperature is 100~120℃, and the drying time is 12~16h; And / or, the calcination temperature is 400~450℃ and the time is 3~5h.

7. The preparation method according to claim 4, characterized in that: The reduction process is carried out in a hydrogen atmosphere, wherein the hydrogen space velocity is 1800~2200 h⁻¹. -1 ; and / or, the reduction treatment is performed at a temperature of 520~580℃ for 2~4h, with a heating rate of 3~5℃ / min; And / or, the passivation gas used in the passivation treatment is a mixture of O2 and N2, wherein the concentration of O2 is 0.5~1.5 vol%, and the passivation treatment time is 3~5 h.

8. The application of the supported ternary transition metal catalyst according to any one of claims 1-3 in the preparation of cyclopentanol, preferably, the application includes: Application of the supported ternary transition metal catalyst in the hydrogenation reaction of cyclopentyl formate to prepare cyclopentanol.

9. A method for preparing cyclopentanol, characterized in that, include: Provide a supported ternary transition metal catalyst according to any one of claims 1-3, and perform activation treatment to obtain an activated catalyst; In the presence of the activated catalyst, cyclopentyl formate is hydrogenated with hydrogen to produce cyclopentanol.

10. The preparation method according to claim 9, characterized in that: The activation treatment is carried out under a hydrogen atmosphere, wherein the pressure is atmospheric pressure and the space velocity is 1800~2200 h⁻¹. -1 ; And / or, the activation treatment temperature is 450~550℃, the heating rate is 1~3℃ / min, and the activation treatment time is 3~6h; And / or, the hydrogenation reaction is carried out in a hydrogen atmosphere, with a molar ratio of hydrogen to cyclopentyl formate of (51~150):1, preferably (51~136):1, and a weight hourly space velocity of 0.18~1.08 h⁻¹. -1 ; And / or, the hydrogenation reaction is carried out at a temperature of 150~230℃, for a time of 2~4h, and at a pressure of 1.0~3.0MPa.

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