Non-supported Ru-Ni monatomic alloy catalyst and method for catalyzing hydrogenation of orthophthalic plasticizers by using non-supported Ru-Ni monatomic alloy catalyst
The non-supported Ru-Ni single-atom alloy catalyst effectively addresses the low stability and selectivity issues of existing catalysts by hydrogenating phthalate esters to cyclohexane dicarboxylate esters with high stability and selectivity, leveraging Ru-Ni nano-particles and controlled electronic structure for benzene ring activation.
Patent Information
- Application Number
- CN202510471786.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-15
- Publication Date
- 2025-07-15
AI Technical Summary
The existing catalysts have insufficient stability and selectivity in the process of selective hydrogenation of phenylagen plasticizers to make cyclohexane plasticizers, making it difficult to meet environmental and economic needs.
The non-supported Ru-Ni single-atom alloy catalyst was used to catalyze the selective hydrogenation of phenylaid to form cyclohexane plasticizers under a hydrogen atmosphere. The Ru nanoparticles are pre-synthetic nanoparticles with reducing particle sizes of 2-3 nm. They were prepared by the synthesis route of Figure 1 using metal dispersants such as Zr, Al, Ni, and Si.
The selectivity of cyclohexanes for hydrogenation of ortho-phenyls is improved, and the catalyst has good structural stability and high activity, providing more active centers, and improving conversion and selectivity.
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Figure CN120305983A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of catalysts, and particularly relates to a non-supported Ru-Ni single-atom alloy catalyst and a method for catalyzing the hydrogenation of phthalate plasticizers Background Art
[0002] Phthalate esters are the largest category of plasticizers in the 21st century, and plasticizers are the plastic auxiliaries with the largest production and consumption so far. However, studies have found that phthalate compounds not only have toxicities such as mutagenicity, carcinogenicity, and teratogenicity, but are also environmental estrogens or endocrine disruptors with reproductive toxicity and developmental toxicity, and are considered to pose a serious threat to ecological safety and human health. There is an urgent need to develop and study new, non-toxic, and environmentally friendly plasticizers to replace the existing traditional plasticizers. Therefore, the synthesis of cyclohexanedicarboxylate has great economic value. The catalytic hydrogenation of phthalate esters to produce cyclohexanedicarboxylate has been rarely reported in the literature. We prepared a non-supported Ru1-Ni x based catalyst, taking phthalate ester (DOP) as the research object, reacting on a self-made fixed-bed reactor, with the catalyst loading of 50 mL, and investigated the effects of factors such as temperature, pressure, space velocity, and reaction time on the reaction of phthalate ester hydrogenation to produce cyclohexanedicarboxylate, and made a very beneficial exploration on the catalytic process conditions. The results show that 3 MPa, 160 °C, and 4 h are the optimal experimental conditions, and the hydrogenation selectivity of phthalate ester can reach 99.2%. The life test shows that this catalyst has good stability
[0003] The reducible groups in the phthalate ester molecular structure are the benzene ring and two esterified carboxyl groups. The hydrogenation of the benzene ring produces cyclohexanedicarboxylate, while the hydrogenation of the two esterified carboxyl groups produces benzoic acid (2-ethylhexyl) monoester. When both the benzene ring and the two esterified carboxyl groups are hydrogenated, 2-methylcyclohexanoic acid is produced. It is generally believed that compared with the hydrogenation of the benzene ring, the hydrogenation of the two esterified carboxyl groups is easier. Therefore, choosing a suitable catalyst and precise reaction conditions play a crucial role in achieving the preferential hydrogenation of the benzene ring, so as to be able to synthesize cyclohexanedicarboxylate
[0004] The hydrogenation reaction flow chart of phthalate plasticizers is as Figure 3 shown
[0005] To sum up, since the selective hydrogenation of phthalate plasticizers to cyclohexane-based plasticizers is of great significance, and the existing catalysts have low stability or low selectivity, it is necessary to prepare more suitable and efficient catalysts to synthesize cyclohexane-based plasticizers Summary of the Invention
[0006] To overcome the deficiencies of the prior art, the present invention aims to provide a non-supported Ru-Ni single-atom alloy catalyst and a method for catalyzing the hydrogenation of phthalate plasticizers
[0007] The technical solution of the present invention is a non-supported Ru-Ni single-atom alloy catalyst and a method for catalytic hydrogenation of phthalate plasticizers to cyclohexane plasticizers. Using the non-supported Ru-Ni single-atom alloy catalyst, under a hydrogen atmosphere and a pressure of 1 MPa - 3 MPa, with stirring and heating, catalytic selective hydrogenation of phthalates generates cyclohexanes; the non-supported Ru-Ni single-atom alloy catalyst is composed of a metal oxide dispersant and Ru-Ni nanoparticles.
[0008] In some embodiments, the Ru nanoparticles are pre-synthesized nanoparticles with reducibility.
[0009] In some embodiments, with stirring and heating, the stirring rate is 600 - 1000 rpm, and the heating temperature is 120 - 180 °C.
[0010] In some embodiments, the particle size of the Ru-Ni nanoparticles is 2 - 3 nm, and the particle size is small and uniform.
[0011] In some embodiments, the metal dispersant used is one of Zr, Al, Ni, and Si.
[0012] The non-supported Ru-Ni single-atom alloy catalyst in the present invention is prepared by Figure 1 the synthesis route shown.
[0013] Beneficial effects
[0014] The method of the embodiment of the present invention has advantages such as good structural stability, high catalyst activity and selectivity compared with the traditional catalytic reaction process.
[0015] In the method of the embodiment of the present invention, through the non-supported Ru-Ni single-atom alloy catalyst and its catalytic hydrogenation of phthalate plasticizers to cyclohexane, Ru nanocrystals can be evenly dispersed in phthalate substances, providing more active centers. Ni regulates the electronic structure of Ru, plays an adsorption and activation role on the benzene ring in the molecular structure of phthalate substances, and plays an adsorption and dissociation role on hydrogen molecules.
[0016] When this method is applied to the phthalate plasticizer hydrogenation system, it can effectively improve the selectivity of phthalate hydrogenation to generate cyclohexanes. Brief description of the drawings
[0017] Figure 1 It is a synthesis and preparation flow chart of the non-supported Ru-Ni single-atom alloy catalyst.
[0018] Figure 2TEM and particle size distribution diagram of the non-supported Ru-Ni single-atom alloy catalyst. Each small white dot in the TEM image is a Ru atom, and each 2-3 nm patch is a Ru-Ni single-atom alloy nanoparticle (i.e., the red circle in the figure).
[0021] Figure 3 Catalytic hydrogenation roadmap of phthalate plasticizers.
[0022] Figure 4 Experimental catalytic data graph, including catalytic data in all examples, including reaction time, temperature, conversion rate, and selectivity. Specific implementation examples
[0023] Example 1
[0024] Preparation of Ru1-Ni8 catalyst
[0025] Dissolve RuCl3·3H2O (1 mmol, 262.42 mmg) and Ni(NO3)2·6H2O (8 mmol, 2325.52 mmg) in 100 ml of distilled water. Rapidly add 100 ml of 20% NaOH solution under stirring and stir at 80 °C for 10 min to complete precipitation. Transfer the obtained mixed solution to a GS-1 Hastelloy autoclave, heat it to 150 °C under a H2 pressure of 3.0 MPa and a stirring rate of 900 r / min, take it out after reduction for 5 h, and wash it with distilled water until neutral to obtain the non-supported Ru1-Ni8 catalyst.
[0026] Ru1-Ni8 as a catalyst for catalytic reaction
[0027] Activate the Ru1-Ni8 catalyst in a vacuum oven at 140 °C for 12 h. Weigh 20 mg of the activated catalyst into a ZrO2 liner, add 15 mL of ethanol as a solvent and ultrasonically mix evenly; then add 120 μL of phthalate and a clean rotor, assemble the high-pressure autoclave and introduce hydrogen. The reaction conditions are set as follows: reaction time 3 h, hydrogen pressure 2 MPa, reaction temperature 140 °C. Use GC to detect phthalate and its hydrogenation products. The results are as follows: conversion rate is about 70.0%, and the selectivity of the main product cyclohexanedicarboxylate is about 94.3%.
[0028] Example 2
[0029] Ru1-Ni 10 Catalyst preparation
[0030] Dissolve RuCl3·3H2O (1 mmol, 262.42 mg) and Ni(NO3)2·6H2O (10 mmol, 2906.9 mg) in 100 ml of distilled water. While stirring, quickly add 100 ml of 20% NaOH solution by mass. Stir at 80 °C for 10 min until precipitation is complete. Transfer the resulting mixed solution to a GS-1 type Hastelloy reactor, heat it to 150 °C under a H2 pressure of 3.0 MPa and a stirring rate of 900 r / min, take it out after reduction for 5 h, and wash it with distilled water until neutral to obtain non-supported Ru1-Ni 10 catalyst.
[0031] Ru1-Ni 10 As a catalyst for catalytic reaction
[0032] Take Ru1-Ni 10 The catalyst is activated in a vacuum oven at 120 °C for 12 h. Weigh 20 mg of the activated catalyst into a ZrO2 liner, add 15 mL of ethanol as a solvent and ultrasonically mix evenly; then add 120 μL of phthalate and a clean rotor, assemble the high-pressure reactor and introduce hydrogen. The reaction conditions are set as follows: reaction time 3 h, hydrogen pressure 2 MPa, reaction temperature 140 °C. Use GC to detect phthalate and its hydrogenation products. The results are: the conversion rate is about 85.0%, and the selectivity of the main product cyclohexanedicarboxylate is about 99.6%.
[0033] Example 3
[0034] Ru1-Ni 14 Preparation of catalyst
[0035] Dissolve RuCl3·3H2O (1 mmol, 262.42 mg) and Ni(NO3)2·6H2O (14 mmol, 4069.66 mg) in 100 ml of distilled water. While stirring, quickly add 100 ml of 20% NaOH solution by mass. Stir at 80 °C for 10 min until precipitation is complete. Transfer the resulting mixed solution to a GS-1 type Hastelloy reactor, heat it to 150 °C under a H2 pressure of 3.0 MPa and a stirring rate of 900 r / min, take it out after reduction for 5 h, and wash it with distilled water until neutral to obtain non-supported Ru1-Ni 14 catalyst.
[0036] Ru1-Ni 14 As a catalyst for catalytic reaction
[0037] Take Ru1-Ni 10The catalyst was activated in a vacuum oven at 120 °C for 12 h. 20 mg of the activated catalyst was weighed into a ZrO2 liner, and 15 mL of ethanol was added as a solvent and sonicated to mix evenly. Then, 120 μL of phthalate and a clean rotor were added, the high-pressure reactor was assembled and hydrogen was introduced. The reaction conditions were set as follows: reaction time 3 h, hydrogen pressure 2 MPa, reaction temperature 140 °C. GC was used to detect the phthalate and its hydrogenation products. The results were: conversion rate was about 80.1%, and the selectivity of the main product cyclohexanedicarboxylate was about 93.8%.
[0038] Example 4
[0039] Ru1-Ni 10 As a catalyst, the catalytic reaction was carried out at a reaction time of 2 h
[0040] The catalyst of Example 2 was activated in a vacuum oven at 120 °C for 12 h. 20 mg of the activated catalyst was weighed into a ZrO2 liner, and 15 mL of ethanol was added as a solvent and sonicated to mix evenly. Then, 120 μL of phthalate and a clean rotor were added, the high-pressure reactor was assembled and hydrogen was introduced. The reaction conditions were set as follows: reaction time 2 h, hydrogen pressure 2 MPa, reaction temperature 140 °C. GC was used to detect the phthalate and its hydrogenation products. The results were: conversion rate was about 66.4%, and the selectivity of the main product cyclohexanedicarboxylate was about 98.7%.
[0041] Ru1-Ni 10 As a catalyst, the catalytic reaction was carried out at a reaction time of 4 h
[0042] The catalyst of Example 2 was activated in a vacuum oven at 120 °C for 12 h. 20 mg of the activated catalyst was weighed into a ZrO2 liner, and 15 mL of ethanol was added as a solvent and sonicated to mix evenly. Then, 120 μL of phthalate and a clean rotor were added, the high-pressure reactor was assembled and hydrogen was introduced. The reaction conditions were set as follows: reaction time 4 h, hydrogen pressure 2 MPa, reaction temperature 140 °C. GC was used to detect the phthalate and its hydrogenation products. The results were: conversion rate was about 95.2%, and the selectivity of the main product cyclohexanedicarboxylate was about 99.1%.
[0043] Example 5
[0044] Ru1-Ni 10 As a catalyst, the catalytic reaction was carried out at a hydrogen pressure of 1.0 MPa
[0045] The catalyst of Example 2 was activated in a vacuum oven at 120 °C for 12 h. 20 mg of the activated catalyst was weighed into a ZrO2 inner lining, and 15 mL of ethanol was added as a solvent and mixed evenly by ultrasonic; then 120 μL of phthalate and a clean rotor were added, the high-pressure reactor was assembled and hydrogen was introduced. The reaction conditions were set as follows: reaction time 4 h, hydrogen pressure 1 MPa, reaction temperature 140 °C. GC was used to detect phthalate and its hydrogenation products, and the results were as follows: the conversion rate was about 73.5%, and the selectivity of the main product cyclohexanedicarboxylate was about 98.5%.
[0046] Example 6
[0047] Ru1-Ni 10 As a catalyst, the catalytic reaction was carried out under a hydrogen pressure of 3 MPa
[0048] The catalyst of Example 2 was activated in a vacuum oven at 120 °C for 12 h. 20 mg of the activated catalyst was weighed into a ZrO2 inner lining, and 15 mL of ethanol was added as a solvent and mixed evenly by ultrasonic; then 120 μL of phthalate and a clean rotor were added, the high-pressure reactor was assembled and hydrogen was introduced. The reaction conditions were set as follows: reaction time 4 h, hydrogen pressure 3 MPa, reaction temperature 140 °C. GC was used to detect phthalate and its hydrogenation products, and the results were as follows: the conversion rate was about 98.5%, and the selectivity of the main product cyclohexanedicarboxylate was about 99.5%.
[0049] Example 7
[0050] Ru1-Ni 10 As a catalyst, the catalytic reaction was carried out at a reaction temperature of 160 °C
[0051] The catalyst of Example 2 was activated in a vacuum oven at 120 °C for 12 h. 20 mg of the activated catalyst was weighed into a ZrO2 inner lining, and 15 mL of ethanol was added as a solvent and mixed evenly by ultrasonic; then 120 μL of phthalate and a clean rotor were added, the high-pressure reactor was assembled and hydrogen was introduced. The reaction conditions were set as follows: reaction time 4 h, hydrogen pressure 3 MPa, reaction temperature 160 °C. GC was used to detect phthalate and its hydrogenation products, and the results were as follows: the conversion rate was about 99.9%, and the selectivity of the main product cyclohexanedicarboxylate was about 99.2%.
[0052] Example 8
[0053] Ru1-Ni 10 As a catalyst, the catalytic reaction was carried out at a reaction temperature of 180 °C
[0054] The catalyst of Example 2 was activated in a vacuum oven at 120 °C for 12 h. 20 mg of the activated catalyst was weighed and placed in a ZrO2 inner liner, and 15 mL of ethanol was added as a solvent and mixed uniformly by ultrasonic treatment. Then, 120 μL of phthalate and a clean rotor were added, and the high-pressure reactor was assembled and hydrogen was introduced. The reaction conditions were set as follows: reaction time 4 h, hydrogen pressure 3 MPa, and reaction temperature 180 °C. GC was used to detect phthalate and its hydrogenation products. The results were as follows: the conversion rate was approximately 99.9%, and the selectivity of the main product cyclohexanedicarboxylate was approximately 93.4%.
[0055] Comparative Example 1
[0056] Preparation of Ru catalyst
[0057] Accurately weigh 3.00 g of CeO2 and 0.06 g (0.285 mmol) of ruthenium trichloride, and add them to 60 mL of deionized water. After stirring for 30 min, it was designated as dispersion A. Subsequently, an aqueous sodium hydroxide solution with a concentration of 0.1 mol / L was slowly added dropwise to dispersion A until the pH was adjusted to 13, and stirring was continued for 24 h. Finally, the mixture was filtered, washed with deionized water, and dried (at 80 °C) for 12 h to obtain a black solid, which was the Ru catalyst.
[0058] Ru was used as a catalyst for the catalytic reaction
[0059] The Ru catalyst was activated in a vacuum oven at 120 °C for 12 h. 20 mg of the activated catalyst was weighed and placed in a ZrO2 inner liner, and 15 mL of ethanol was added as a solvent and mixed uniformly by ultrasonic treatment. Then, 120 μL of phthalate and a clean rotor were added, and the high-pressure reactor was assembled and hydrogen was introduced. The reaction conditions were set as follows: reaction time 3 h, hydrogen pressure 3 MPa, and reaction temperature 160 °C. GC was used to detect phthalate and its hydrogenation products. The results were as follows: the conversion rate was approximately 95.0%, and the selectivity of the main product cyclohexanedicarboxylate was approximately 84.6%.
[0060] Comparative Example 2
[0061] Preparation of Ni catalyst
[0062] Accurately weigh 3.00 g of CeO2 and 0.06 g (0.206 mmol) of Ni(NO3)2·6H2O, and add them to 60 mL of deionized water. After stirring for 30 min, it was designated as dispersion A. Subsequently, an aqueous sodium hydroxide solution with a concentration of 0.1 mol / L was slowly added dropwise to dispersion A until the pH was adjusted to 13, and stirring was continued for 24 h. Finally, the mixture was filtered, washed with deionized water, and dried (at 80 °C) for 12 h to obtain a black solid, which was the Ni catalyst.
[0063] Ni was used as a catalyst for the catalytic reaction
[0064] The Ni catalyst was activated in a vacuum oven at 120 °C for 12 h. 20 mg of the activated catalyst was weighed and placed in a ZrO2 inner lining, and 15 mL of ethanol was added as a solvent and ultrasonically mixed evenly; then 120 μL of phthalate and a clean rotor were added, the high-pressure reactor was assembled and hydrogen was introduced. The reaction conditions were set as follows: reaction time 3 h, hydrogen pressure 3 MPa, reaction temperature 160 °C. GC was used to detect phthalate and its hydrogenation products, and the results were as follows: the conversion rate was about 36.0%, and the selectivity of the main product cyclohexanedicarboxylate was about 90.1%.
[0065] The present invention is not limited to the above-mentioned optimal implementation manner. Any other products identical or similar to the present invention obtained by anyone under the inspiration of the present invention fall within the protection scope of the present invention.
Claims
1. A non-supported Ru-Ni single-atom alloy catalyst and its method for catalyzing the hydrogenation of phthalate plasticizers, characterized in that, The Ru-Ni catalyst using an integrated metal promoter, under the conditions of a hydrogen atmosphere and a pressure of 1 MPa - 3 MPa, with stirring and heating, the rate of the stirring is 600 - 1000 rpm, and the temperature of the heating is 120 - 180 °C, catalyzes the selective hydrogenation of phthalate plasticizers to produce cyclohexane plasticizers; The unsupported Ru-Ni single-atom alloy catalyst is composed of a metal oxide dispersant and Ru-Ni nanoparticles. The metal dispersant used is one of Zr, Al, Ni, and Si; the Ru-Ni nanoparticles have a particle size of 2 - 3 nm and are Ru-Ni nanoparticles with reducibility.
2. The non-supported Ru-Ni single-atom alloy catalyst according to claim 1 and its method for catalyzing the hydrogenation of phthalate plasticizers, characterized in that, The Ru nanocrystals contained can be uniformly dispersed in phthalate substances, providing more active centers. Ni adsorbs and activates the benzene rings in the molecular structure of phthalate substances by regulating the electronic structure of Ru, and plays a role in adsorbing and dissociating hydrogen molecules.