Preparation method of catalyst Ni-Co / NPHMC@mSiO2 and its application in preparing hydrogenated rosin by rosin hydrogenation

Abstract

The present invention belongs to the technical field of preparing hydrogenated rosin, and particularly relates to a method for preparing a catalyst Ni-Co / NPHMC@mSiO2 and its application in preparing hydrogenated rosin by hydrogenation of rosin. # Solvent naphtha is used as the solvent, a nano-nickel-cobalt alloy catalyst Ni‑Co / NPHMC@mSiO2 is introduced, and hydrogen is introduced to perform a catalytic hydrogenation reaction to produce hydrogenated rosin. The preparation method of the present invention effectively improves the conversion rate of rosin, and the resulting products, dihydroabietic acid and tetrahydroabietic acid, are highly selective. The preparation method is simple, the reagents used are safe, and it is beneficial for industrial production.

Description

Technical Field

[0001] The invention belongs to the technical field of preparing hydrogenated rosin, and particularly relates to a preparation method of a Ni-Co / NPHMC@mSiO2 catalyst and application of the catalyst in preparing hydrogenated rosin by hydrogenating rosin. Background Art

[0002] Rosin is a transparent, brittle resin obtained by distilling rosin. It is a compound containing various resin acids (such as alfalfa) and trace amounts of fatty acids. China is the world's largest rosin producer, but most of it is exported as raw material without further processing, resulting in significant economic losses. Rosin's primary component is abietic acid. Because abietic acid contains conjugated double bonds, it easily crystallizes in solvents and reacts with atmospheric oxygen, darkening the rosin's color, making it less stable, and degrading its quality. Catalytic hydrogenation of rosin modifies the double bond structure of abietic acid, stabilizing it. Hydrogenated rosin exhibits high thermal stability, reduced brittleness, improved oxidation resistance, and a lighter color. Hydrogenated rosin eliminates the drawbacks of rosin caused by the presence of conjugated double bonds, broadening its application areas. It is primarily used in industry, agriculture, medicine, cosmetics, and food.

[0003] In the related art, the active centers of the catalysts used in industrial catalytic hydrogenation of rosin to obtain hydrogenated rosin generally contain precious metals and non-precious metals. Catalysts with precious metals as active components have made good progress in the rosin hydrogenation reaction, but precious metals also have some inevitable disadvantages, such as high prices, relatively limited availability, and insufficient stability, which greatly increase the cost of their application in industrial production; non-precious metal catalysts have the disadvantages of high requirements for reaction equipment and harsh reaction conditions. Another relatively important aspect is that the mutual matching and synergy between the catalyst carrier and the catalyst active center plays a vital role in the rosin hydrogenation reaction. The catalytic activity and product selectivity of the catalyst obtained by compounding different catalyst carriers with catalytic active centers for the rosin hydrogenation reaction are also unpredictable. Summary of the Invention

[0004] In order to improve the conversion rate of rosin and to prepare dihydroabietic acid and tetrahydroabietic acid with high selectivity to obtain high-quality special-grade rosin, the present invention provides a preparation method of the catalyst Ni-Co / NPHMC@mSiO2 and its application in the preparation of hydrogenated rosin by rosin hydrogenation.

[0005] In order to achieve the above main invention objects, the present invention provides the following technical solutions:

[0006] The present invention provides an application of catalyst Ni-Co / NPHMC@mSiO2 in preparing hydrogenated rosin by hydrogenation of rosin, wherein rosin is used as raw material, water and 200 #Solvent oil is used as solvent, nano nickel-cobalt alloy catalyst Ni-Co / NPHMC@mSiO2 is used, H2 is added, and catalytic hydrogenation reaction is carried out to generate hydrogenated rosin.

[0007] Preferably, the mass ratio of the rosin to the catalyst Ni-Co / NPHMC@mSiO2 is 20:1.

[0008] Preferably, the reaction temperature of the catalytic hydrogenation reaction is 130-140°C, the reaction time is 4 h, and the pressure of H2 injected into the reaction process is 4 MPa.

[0009] Furthermore, after the catalytic hydrogenation reaction is completed, the catalyst and the hydrogenated rosin are separated by standing and aging.

[0010] Another object of the present invention is to provide a preparation method for the above-mentioned catalyst Ni-Co / NPHMC@mSiO2, which uses resorcinol and formaldehyde as carbon sources, ethylenediamine as a nitrogen source, octadecyltrimethylammonium bromide as a template, ethyl orthosilicate as a silicon source, and sodium hypophosphite as a phosphorus source, and synthesizes the amphiphilic mesoporous nanomaterial NPHMC@mSiO2 by high-temperature carbonization. Then, the metal Ni and Co active components are composited on the mesoporous nanomaterial, and the nano nickel-cobalt alloy catalyst Ni-Co / NPHMC@mSiO2 is generated by hydrogen reduction.

[0011] Preferably, the preparation method of the catalyst Ni-Co / NPHMC@mSiO2 specifically comprises the following steps:

[0012] 1) Amphiphilic mesoporous nanomaterial NPHMC@ m Preparation of SiO2: Octadecyltrimethylammonium bromide and ethylenediamine are dispersed in a mixed solution of ethanol and water, resorcinol is added and stirred, formaldehyde is added dropwise, and the mixture is stirred for reaction. Sodium triacetoxyborohydride and ethyl orthosilicate are added dropwise, stirring is continued, centrifugation is performed, and drying at room temperature yields a yellow solid. Sodium hypophosphite is placed near the inlet of a tube furnace, and the resulting yellow solid is placed near the gas outlet end of the tube furnace. Finally, the amphiphilic nanomaterial NPHMC@mSiO2 is carbonized at high temperature under an argon atmosphere.

[0013] 2) Nano nickel-cobalt alloy catalyst Ni-Co / NPHMC@ mPreparation of SiO2: The amphiphilic nanomaterial NPHMC@mSiO2 was used as a carrier and dispersed in ethanol. Ni(CH3COO)2·4H2O and Co(CH3COO)2 were then added and dispersed by ultrasonic treatment. The mixture was then stirred at room temperature. The ethanol was removed by rotary evaporation. After drying at room temperature, the black solid powder was reduced in a hydrogen-argon mixed gas atmosphere to generate a nano-nickel-cobalt alloy catalyst Ni-Co / NPHMC@mSiO2.

[0014] More specifically, the catalyst Ni-Co / NPHMC@mSiO2 can be prepared by the following specific steps:

[0015] 1) Amphiphilic mesoporous nanomaterial NPHMC@ m Preparation of SiO2: 0.12 g of octadecyltrimethylammonium bromide and 0.16 mL of EDA (ethylenediamine) were dispersed in a 50 mL mixture of ethanol and water. 0.16 g of resorcinol was added and stirred for 30 minutes. 0.24 mL of formaldehyde was added dropwise and stirred for 2 hours. 50 mg of sodium triacetoxyborohydride and 0.6 mL of LTEOS (ethyl orthosilicate) were added dropwise. Stirring continued for 4 hours, the mixture was centrifuged, and dried at room temperature to obtain a yellow solid. A porcelain boat containing 150 mg of sodium hypophosphite was placed near the inlet of a tube furnace, and the porcelain boat containing the yellow solid was placed near the gas outlet end of the tube furnace. Finally, the amphiphilic nanomaterial NPHMC@mSiO2 was carbonized at high temperature under an argon atmosphere to obtain the resulting product.

[0016] 2) Preparation of nano-nickel-cobalt alloy catalyst Ni-Co / NPHMC@mSiO2: 0.1 g of NPHMC@mSiO2 carrier was weighed and dispersed in 20 mL of ethanol. Then 53 mg of Ni(CH3COO)2·4H2O and 7.5 mg of Co(CH3COO)2 were added and dispersed by ultrasonic treatment for 30 min. The mixture was then stirred at room temperature for 4 h. The ethanol was removed by rotary evaporation. After drying at room temperature, the black solid powder was reduced in a hydrogen-argon mixed gas atmosphere (hydrogen accounted for 15% by volume of the mixed gas) to obtain a stable nano-nickel-cobalt alloy catalyst Ni-Co / NPHMC@mSiO2.

[0017] Furthermore, the volume ratio of ethanol to water in the mixed solution of ethanol and water is 3:7.

[0018] The present invention provides a preparation method of a Ni-Co / NPHMC@mSiO2 catalyst and its application in preparing hydrogenated rosin by hydrogenating rosin.

[0019] The present invention uses the prepared amphiphilic nanomaterial NPHMC@mSiO2 as a catalyst carrier. Its internal cavity is lipophilic, which is beneficial to the mass transfer and enrichment of reactants, and the introduction of the hydrophilic layer improves the dispersibility of the catalyst in the aqueous medium. The introduction of the P element gives the material weak acid sites, which will promote the hydrogenation reaction to a certain extent. The loaded alloy nanoparticles Ni-Co serve as active centers, and their performance is significantly better than that of a single non-precious metal catalyst. They have a strong ability to adsorb and crack hydrogen molecules, further improving the catalytic activity of the catalyst. The most important aspect is that the present invention uses Ni-Co alloy particles as active centers to cooperate and synergize with the carrier NPHMC@mSiO2, giving the catalyst high activity and stability, and high selectivity for the products dihydroabietic acid and tetrahydroabietic acid.

[0020] Throughout the catalytic hydrogenation reaction, a three-phase interface is formed between the solid catalyst, the rosin oil phase, and the hydrogen. This reduces mass transfer resistance, facilitates the reaction, and enables the catalytic hydrogenation reaction to proceed under mild conditions. These mild reaction conditions result in higher catalytic efficiency and better selectivity for hydrogenated products. After the reaction, the catalyst can be easily separated and reused, maintaining high catalytic activity.

[0021] Test results show that the catalyst provided by the present invention effectively improves the rosin conversion rate when used for catalytic rosin hydrogenation, reaching a rosin conversion rate of over 98%. It also produces dihydroabietic acid and tetrahydroabietic acid with high selectivity, resulting in high-quality premium rosin, with selectivities exceeding 62% and 33%, respectively. The above technical solutions demonstrate that the preparation method of the present invention can effectively improve the rosin conversion rate, and the resulting products, dihydroabietic acid and tetrahydroabietic acid, have high selectivity. The preparation method is simple, the reagents used are safe, and it is beneficial for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a scanning electron microscope image of the amphiphilic nanomaterial NPHMC@mSiO2 provided by the present invention;

[0023] Figure 2 This is a transmission electron microscope image of the amphiphilic nanomaterial NPHMC@mSiO2 provided by the present invention;

[0024] Figure 3 This is a picture of the temperature-programmed desorption (NH3-TPD) of ammonia of the amphiphilic nanomaterial NPHMC@mSiO2 provided by the present invention;

[0025] Figure 4 This is a high-resolution transmission electron microscope image of the catalyst Ni-Co / NPHMC@mSiO2 provided by the present invention and a particle size distribution diagram of nickel-cobalt alloy nanoparticles. DETAILED DESCRIPTION

[0026] The present invention discloses a method for preparing a catalyst Ni-Co / NPHMC@mSiO2 and its application in the hydrogenation of rosin to prepare hydrogenated rosin. Those skilled in the art can refer to the contents of this article and appropriately improve the process parameters to achieve the desired results. It should be noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in the present invention. The methods and applications of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the methods and applications described herein without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.

[0027] In order to enable those skilled in the art to better understand the present invention, the present invention is further described in detail below in conjunction with specific embodiments.

[0028] Example 1 Preparation of Ni-Co / NPHMC@mSiO2 catalyst

[0029] 1) Preparation of the Amphiphilic Mesoporous Nanomaterial NPHMC@mSiO2: 0.12 g of STAB (octadecyltrimethylammonium bromide) and 0.16 mL of EDA (ethylenediamine) were dispersed in 50 mL of a mixture of ethanol and water (the volume ratio of ethanol to water was 3:7). 0.16 g of resorcinol was added and stirred for 30 minutes. 0.24 mL of formaldehyde was added dropwise and stirred for 2 hours. 50 mg of STAB and 0.6 mL of TEOS (tetraethyl orthosilicate) were added dropwise and stirred for another 4 hours. The mixture was centrifuged and dried at room temperature to obtain a yellow solid. A porcelain boat containing 150 mg of sodium hypophosphite was placed near the inlet of a tube furnace, and the porcelain boat containing the yellow solid was placed near the gas outlet of the tube furnace. Finally, the amphiphilic nanomaterial NPHMC@mSiO2 was carbonized at high temperature under an argon atmosphere to obtain the resulting product.

[0030] The scanning electron microscope images and transmission electron microscope images of the obtained nanomaterial NPHMC@mSiO2 are shown in Figure 1 and Figure 2 The obtained ammonia temperature programmed desorption (NH3-TPD) graph of the nanomaterial NPHMC@mSiO2 is shown in Figure 3 . Figure 1 and Figure 2 It can be seen that the catalyst carrier has uniform particle size and a relatively large specific surface area, which can increase the contact area between the substrate and the catalyst and promote the reaction. Figure 3 It can be seen that there is a desorption peak at 188 °C, which means that the support material has a weak acid center.

[0031] 2) Preparation of nano-nickel-cobalt alloy catalyst Ni-Co / NPHMC@mSiO2 0.1 g of the obtained amphiphilic nanomaterial NPHMC@mSiO2 was weighed and dispersed in 20 mL of ethanol, and then 53 mg of Ni(CH3COO)2·4H2O and 7.5 mg of Co(CH3COO)2 were added and dispersed by ultrasonic treatment for 30 min. Then, the mixture was stirred at room temperature for 4 h, and the ethanol was removed by rotary evaporation. After drying at room temperature, the black solid powder was reduced in a hydrogen (hydrogen accounts for 15% by volume of the mixed gas) and argon mixed gas atmosphere to obtain a stable nano-catalyst Ni-Co / NPHMC@mSiO2.

[0032] The high-resolution transmission electron microscopy image of the obtained catalyst Ni-Co / NPHMC@mSiO2 and the particle size distribution of nickel-cobalt alloy nanoparticles are shown in Figure 4 . Figure 4 Nickel-cobalt alloy nanoparticles immobilized on the amphiphilic nanomaterials can be clearly observed, and the particle size of the alloy nanoparticles is concentrated in the range of 7~8 nm.

[0033] Example 2 Preparation of Hydrogenated Rosin by Hydrogenation of Rosin

[0034] Weigh 1 g of rosin and add it to a stainless steel mechanical stirring kettle, then add 5 mL of water, 10 mL of 200 # Solvent oil was added, 50 mg of the catalyst Ni-Co / NPHMC@mSiO2 prepared in Example 1 was weighed and mixed evenly, the gas in the autoclave was replaced three times with 4 MPa hydrogen, and then 4 MPa hydrogen was added. The mixture was mechanically stirred and reacted at 130 °C for 4 h. After the reaction was completed, the catalyst and the product were separated by standing. The upper product phase was collected and quantitatively analyzed by chromatography. The conversion rate of rosin, the selectivity of dihydroabietic acid, the selectivity of tetrahydroabietic acid and the selectivity of dehydroabietic acid were 98.1%, 64.2%, 33.7% and 2.1%, respectively.

[0035] Example 3 Preparation of Hydrogenated Rosin by Hydrogenation of Rosin

[0036] Weigh 1 g of rosin and add it to a stainless steel mechanical stirring kettle, then add 5 mL of water, 10 mL of 200 # Solvent oil was added, 50 mg of the catalyst Ni-Co / NPHMC@mSiO2 prepared in Example 1 was weighed and mixed evenly, the gas in the autoclave was replaced three times with 4 MPa hydrogen, and then 4 MPa hydrogen was added. The mixture was mechanically stirred and reacted at 140 °C for 4 h. After the reaction was completed, the mixture was allowed to stand to separate the catalyst and the product. The conversion rate of rosin, the selectivity of dihydroabietic acid, the selectivity of tetrahydroabietic acid, and the selectivity of dehydroabietic acid could reach 98.7%, 62.7%, 35.6%, and 1.7%, respectively.

[0037] Example 4 Recycling of catalyst

[0038] Weigh 1 g of rosin and add it to a stainless steel autoclave, then add 5 mL of water, 10 mL of 200 # Solvent oil was added, 50 mg of the catalyst Ni-Co / NPHMC@mSiO2 prepared in Example 1 was weighed and mixed evenly, the gas in the kettle was replaced three times with 4 MPa hydrogen, and then 4 MPa hydrogen was added. The reaction was carried out at 130 ° C with mechanical stirring for 4 h. After the reaction was completed, the catalyst was separated from the product, and the separated catalyst was reused. The above experimental steps were repeated, and the catalyst was reused 5 times. The conversion rate of rosin, the selectivity of dihydroabietic acid, the selectivity of tetrahydroabietic acid and the selectivity of dehydroabietic acid could reach 95.2%, 65.5%, 30.7% and 3.8% respectively, indicating that the catalyst had good reuse performance.

[0039] Example 5 Selection of Temperature for Preparation of Hydrogenated Rosin by Hydrogenation of Rosin

[0040] Weigh 1 g of rosin and add it to a stainless steel mechanical stirring kettle, then add 5 mL of water, 10 mL of 200 # Solvent oil was mixed with 50 mg of the Ni-Co / NPHMC@mSiO2 prepared in Example 1. The atmosphere in the reactor was replaced three times with 4 MPa hydrogen, then filled with 4 MPa hydrogen. The reaction was mechanically stirred at above 150°C for 4 h. After the reaction was completed, the catalyst and product were separated by standing. The upper product phase was collected and quantitatively analyzed by chromatography. The conversion of rosin, selectivity for dihydroabietic acid, selectivity for tetrahydroabietic acid, and selectivity for dehydroabietic acid reached 99.2%, 60.6%, 37.9%, and 1.5%, respectively. The catalytic efficiency remained essentially unchanged as the temperature increased. For safety and equipment cost savings in actual production, the effective catalytic temperature of this catalyst was selected to be 130-140°C.

[0041] Effect of different catalysts on rosin hydrogenation reaction

[0042] 1 g of rosin, 50 mg of the catalysts listed in Table 1, 5 mL of water, and 10 mL of 200 # Solvent oil was added to a stainless steel mechanical reactor and mixed evenly. The solvent oil was replaced with 4 MPa hydrogen three times and then filled with 4 MPa hydrogen. The reaction was carried out at 130 °C with magnetic stirring for 4 h. After the reaction was completed, the catalyst and the product were separated by standing. The upper product phase was collected and quantitatively analyzed by chromatography. The conversion rate of rosin, selectivity of dihydroabietic acid, selectivity of tetrahydroabietic acid, and selectivity of dehydroabietic acid are shown in Table 1.

[0043] Table 1 Effects of different catalysts on rosin catalytic hydrogenation

[0044] Catalyst Conversion / % Dihydroabietic acid / % Tetrahydroabietic acid / % Dehydroabietic acid / % <![CDATA[Ru / NPHMC@mSiO2]]> 89.7 67.2 26.6 6.2 <![CDATA[Pd / NPHMC@mSiO2]]> 99.4 60.5 38.3 1.2 <![CDATA[Ni-Co / NPHMC@mSiO2]]> 98.1 64.2 33.7 2.1 <![CDATA[Co / NPHMC@mSiO2]]> 74.5 62.8 27.7 9.5 <![CDATA[Ni / NPHMC@mSiO2]]> 89.1 71.3 22.4 6.3 Pd / C 76.9 77.1 19.1 3.8 Ru / C 60.4 83.9 6.9 9.2 <![CDATA[Ni-Co / mSiO2]]> 28.3 56.3 31.2 12.5 <![CDATA[Ni-Co / CxNy@mSiO2]]> 85.3 60.6 30.8 8.6 Ni-Co / N-MCHS@MS 82.3 58.6 32.2 9.2

[0045] The data in Table 1 show that the catalyst Ni-Co / NPHMC@mSiO2 provided by the present invention exhibits excellent catalytic activity and product selectivity for the rosin hydrogenation reaction under the same conditions, and its effect is significantly better than that of other non-precious metal catalysts; at the same time, it is better than the precious metal catalyst Pd / C in terms of selectivity.

[0046] The data in Table 1 show that the catalyst Ni-Co / NPHMC@mSiO2 provided by the present invention exhibits excellent catalytic activity and product selectivity in the rosin hydrogenation catalytic reaction, compared with the catalyst Ni-Co / mSiO2 without a hollow structure, the hollow catalyst Ni-Co / CxNy@mSiO2 not doped with P element, and the hollow catalyst Ni-Co / N-MCHS@MS not doped with P element and synthesized with dopamine as the carbon source and nitrogen source. The total conversion rate of rosin and the content of dihydroabietic acid and tetrahydroabietic acid in the product are higher.

[0047] It can be seen from this that the catalysts used in the rosin hydrogenation catalytic reaction, and the catalysts obtained by compounding different catalyst carriers and catalytic active centers for the rosin hydrogenation reaction are also unpredictable. The nano nickel-cobalt alloy catalyst Ni-Co / NPHMC@mSiO2 prepared by the present invention has unexpectedly high catalytic activity and product selectivity due to the mutual matching and synergistic effect between its alloy particles Ni-Co and the P-doped carrier NPHMC@mSiO2.

[0048] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. Catalyst Ni-Co / NPHMC@ m The application of SiO2 in the preparation of hydrogenated rosin by hydrogenation of rosin is characterized in that: Take rosin as raw material, water and 200 # Solvent oil is used as solvent, and nano nickel-cobalt alloy catalyst Ni-Co / NPHMC@ m SiO2, filled with H2, undergoes catalytic hydrogenation reaction to produce hydrogenated rosin; The catalyst Ni-Co / NPHMC@ m The preparation method of SiO2 specifically comprises the following steps: 1) Amphiphilic mesoporous nanomaterial NPHMC@ m Preparation of SiO2: Octadecyltrimethylammonium bromide and ethylenediamine were dispersed in a mixed solution of ethanol and water, resorcinol was added and stirred, formaldehyde was added dropwise, and the mixture was stirred for reaction. Sodium triacetoxyborohydride was added, and ethyl orthosilicate was added dropwise. The mixture was stirred continuously, centrifuged, and dried at room temperature to obtain a yellow solid. Sodium hypophosphite was placed near the inlet of a tube furnace, and the obtained yellow solid was placed near the gas outlet end of the tube furnace. Finally, the amphiphilic nanomaterial NPHMC@ was obtained by high-temperature carbonization under an argon atmosphere. m SiO2; 2) Nano nickel-cobalt alloy catalyst Ni-Co / NPHMC@ m Preparation of SiO2 amphiphilic nanomaterial NPHMC@ m SiO2 was dispersed in ethanol as a carrier, and then Ni(CH3COO)2·4H2O and Co(CH3COO)2 were added and dispersed by ultrasonic treatment. After stirring at room temperature, the ethanol was removed by rotary evaporation. After drying at room temperature, the black solid powder was reduced in a hydrogen-argon mixed gas atmosphere to generate a nano-nickel-cobalt alloy catalyst Ni-Co / NPHMC@mSiO2.

2. The use according to claim 1, characterized in that The rosin and the catalyst Ni-Co / NPHMC@ m The mass ratio of SiO2 is 20:

1.

3. The use according to claim 1, characterized in that The reaction temperature of the catalytic hydrogenation reaction is 130-140° C., the reaction time is 4 h, and the H2 pressure during the reaction is 4 MPa.

4. The use according to claim 2 or 3, characterized in that After the catalytic hydrogenation reaction is completed, the catalyst and the hydrogenated rosin are separated by standing and aging.

5. The use according to claim 1, characterized in that The volume ratio of ethanol to water in the mixed solution of ethanol and water is 3:

7.

6. The catalyst Ni-Co / NPHMC@ used in any one of claims 1 to 4 m The preparation method of SiO2 is characterized in that: The amphiphilic mesoporous nanomaterial NPHMC@ was synthesized by high-temperature carbonization using resorcinol and formaldehyde as carbon sources, ethylenediamine as nitrogen source, octadecyltrimethylammonium bromide as template, ethyl orthosilicate as silicon source, and sodium hypophosphite as phosphorus source. m SiO2, and then the metal Ni and Co active components are composited on the mesoporous nanomaterials, and the nano nickel-cobalt alloy catalyst Ni-Co / NPHMC@ is generated by hydrogen reduction. m SiO2.

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