A multi-component supported metal catalyst, its preparation method and use

Abstract

The present application relates to a kind of multi-component load metal catalyst and its preparation method and application, belong to catalyst preparation technical field.Cashew phenol not only has phenolic hydroxyl group but also has a number of carbon-carbon double bond functional groups in long side chain.It can (partially) replace phenol, nonyl phenol to synthesize phenolic resin, modified epoxy resin, various coatings.Due to the reactivity of long side chain carbon-carbon double bond, self-condensation reaction is easy to occur, and the stability of phenolic hydroxyl group is affected by side chain olefin bond.The present application uses pseudo-boehmite precursor and ionic liquid to prepare alumina supported nickel-based metal catalyst, which is applied to cashew phenol hydrogenation reaction, and the catalytic activity is high.The side chain full hydrogenation product can reach 100% under relatively mild conditions, thereby effectively regulating and balancing the functionality, reactivity and stability of cashew phenol, which can be used to prepare high-weatherability, high-corrosion-resistance bio-based resin and coating.

Description

TECHNICAL FIELD

[0001] The application relates to a supported metal catalyst and selective catalytic hydrogenation of cardanol, and belongs to the technical field of catalyst preparation. BACKGROUND

[0002] Cardanol is a biomass-based phenolic compound from cashew nut shell and can be obtained through a series of physical / chemical treatment processes. Although the purity of refined cardanol can reach 95% or even higher, it is still a mixture. In addition to the phenolic hydroxyl group on the benzene ring, there is a long side chain containing 15 carbon atoms in the meta position. The long side chain has 31 hydrogen atoms, which is completely saturated, or contains one, two and three carbon-carbon double bonds, respectively, and the number of hydrogen atoms in the side chain is 29, 27 and 25, respectively. Depending on the different sources of cardanol, the relative content of the four long side chain-containing hydrocarbon phenols also differs, but overall, the content of the component with a saturated long side chain is the lowest, only a few percent. The content of the component with a three-olefin long side chain is the highest, about 40%, the content of the component with a one-olefin long side chain is slightly more than 30%, and the content of the component with a two-olefin long side chain is slightly more than 20%. Since cardanol not only has a phenolic hydroxyl group but also has a number of carbon-carbon double bond functional groups in the long side chain, it can undergo a series of chemical reactions. In recent years, it has been used as a renewable natural phenolic compound in the fields of coatings, adhesives, friction materials, ion exchange resins, surfactants, additives, etc. It can (partially) replace phenol, nonyl phenol to synthesize phenolic resin, modified epoxy resin, various coatings. Due to the reactivity of the long side chain carbon-carbon double bond, self-condensation reaction is easy to occur, and the side chain olefin bond affects the stability of the phenolic hydroxyl group. By selectively hydrogenating the carbon-carbon double bonds in the long side chain, the functionality, reactivity and stability of cardanol can be changed, so that it can be used to prepare bio-based coatings with high weather resistance and high corrosion resistance, and applied in the field of marine corrosion prevention, which has very important practical significance. SUMMARY

[0003] The application relates to the preparation of a supported nickel-based metal catalyst and its application in the selective hydrogenation of cardanol. The catalyst support is not only non-morphology-controlled alumina prepared by pseudo-boehmite, but also regular hexagonal flake alumina prepared by ionic liquid-directed growth and morphology control. Single, double and triple component metal salt precursors are introduced by impregnation or co-impregnation, and then the fresh catalyst is prepared through calcination and pre-reduction.

[0004] In order to solve the technical problem of the present application, the technical solution is provided: a preparation method of a nickel-based supported metal catalyst, comprising the following steps: a certain mass of AlCl3·6H2O is dissolved in a certain volume of deionized water to obtain an aluminum salt solution, a certain amount of 1-butyl-2,3-dimethylimidazole chloride is added, wherein the molar ratio of aluminum ions to 1-butyl-2,3-dimethylimidazole chloride (n[Al 3+ ]:n[Bdmim]Cl) is 0.5-1.5:1, a certain mass of (NH4)2CO3 is dissolved in deionized water to form a solution, and then added to the above mixture, and then hydrothermally treated at 160-200℃ for 12-24h to obtain hexagonal sheet-shaped γ-Al2O3;

[0005] The prepared hexagonal sheet-shaped alumina γ-Al2O3 carrier is added to a metal salt solution, which is a single metal nickel salt solution, a double metal nickel / cobalt salt solution, a double metal nickel / copper salt solution or a triple metal nickel / cobalt / copper salt solution, and then calcined and pre-reduced to obtain a nickel-based supported metal catalyst.

[0006] Preferably, the metal nickel salt is Ni(NO3)2·6H2O or (COO)2Ni·2H2O, the metal copper salt is Cu(NO3)2·3H2O or (CH3CO2)2Cu·3H2O, and the metal cobalt salt is Co(NO3)2·6H2O or (CH3CO2)2Co·3H2O.

[0007] Preferably, according to the loading of 20wt%Ni, 3wt%Cu, and 0-5wt%Co, a certain amount of Ni(NO3)2·6H2O, Cu(NO3)2·3H2O, and Co(NO3)2·6H2O is dissolved in deionized water, and the corresponding amount of hexagonal sheet-shaped γ-Al2O3 carrier is added to the metal salt solution.

[0008] Preferably, according to the loading of 20wt%Ni, 3wt%Cu, and 5wt%Co, a certain amount of Ni(NO3)2·6H2O, Cu(NO3)2·3H2O, and Co(NO3)2·6H2O is dissolved in deionized water, and the corresponding amount of hexagonal sheet-shaped γ-Al2O3 carrier is added to the metal salt solution.

[0009] Preferably, the impregnated sample is preliminarily dried under an infrared lamp, then dried at 100℃ for 5h, then calcined at 400℃ in an air atmosphere for 4h, and then reduced at 450℃ in a 20vol% hydrogen-nitrogen mixed gas for 5h to obtain a nickel-based supported metal catalyst.

[0010] In order to solve the technical problem of the present application, another technical solution is provided: the nickel-based supported metal catalyst prepared by any of the above methods.

[0011] To solve the technical problem of the present application, another technical solution is proposed: the prepared nickel-based supported metal catalyst is applied to the reaction of cashew phenol hydrogenation.

[0012] Preferably, the selective hydrogenation of cashew phenol is carried out in a tank reactor, the reaction temperature is 90-110℃, the reaction time is 2.5-4.5h, the reaction pressure is 2.5-3.5MPa, the catalyst dosage is 5-10wt.% of the cashew phenol feed amount; the rotation speed is 400-500r / min, the cashew phenol concentration is 5-10wt.%, and n-butanol is used as the solvent.

[0013] To solve the technical problem of the present application, another technical solution is proposed: γ-Al2O3 carrier is prepared with pseudo-boehmite as precursor, metal salt solution is added, the metal salt solution is bimetallic nickel / cobalt salt solution, bimetallic nickel / copper salt solution or trimetallic nickel / cobalt / copper salt solution, double or triple component metal salt precursors are introduced by impregnation or co-impregnation method, and then the nickel-based supported metal catalyst is prepared by calcination and pre-reduction, which is used for selective hydrogenation reaction of cashew phenol.

[0014] Preferably, the diameter of the pseudo-boehmite small ball is 1-1.5mm, which is used as precursor, calcination is carried out under air atmosphere at 400-600℃ for 4h, the phase is converted into γ-Al2O3, the sample has a large specific surface area, a moderate pore volume and a pore diameter, and the sample is crushed to 20-40mesh for use as catalyst carrier.

[0015] Preparation of alumina carrier:

[0016] (1) Preparation with pseudo-boehmite as precursor: the pseudo-boehmite small ball with a diameter of 1-1.5mm provided by the Autocatalyst Catalyst Carrier Research Institute (Jiangyan, Jiangsu) is used as precursor, calcination is carried out under air atmosphere at 400-600℃ for 4h, the phase is converted into γ-Al2O3. The sample has a large specific surface area, a moderate pore volume and a pore diameter. The sample is crushed to 20-40mesh for use as catalyst carrier.

[0017] (2) Controllable preparation of morphology: a certain mass of AlCl3·6H2O is dissolved in a certain volume of deionized water to obtain an aluminum salt solution (0.13-0.3mol L -1 ). Then a certain amount of 1-butyl-2,3-dimethylimidazole chloride salt (0.002-0.004mol) is added. The molar ratio of aluminum ions to 1-butyl-2,3-dimethylimidazole chloride salt (n[Al 3+ ]:n[Bdmim]Cl) is 0.5-1.5. A certain mass of (NH4)2CO3 is dissolved in deionized water to form a solution (5.0-5.8mol L -1), and added to the above mixture. Then hydrothermal treatment at 160-200℃ for 12-24h. After the reactor naturally dropped to room temperature, centrifugal washing with ethanol and deionized water for several times, drying at 80℃ for 12h, and then heat treatment at 500-600℃ in air atmosphere for 3h, hexagonal sheet morphology γ-Al2O3 was obtained.

[0018] Loading of metal components:

[0019] According to the loading of 20wt% Ni, 3wt% Cu, 0-5wt% Co, a certain amount of Ni(NO3)2·6H2O, Cu(NO3)2·3H2O, Co(NO3)2·6H2O was dissolved in deionized water (3-6mL), and the corresponding amount of alumina carrier was added to the metal salt solution, which could be a single metal nickel salt solution, a double metal nickel / cobalt or nickel / copper salt solution, or a triple metal nickel / cobalt / copper salt solution. The impregnated sample was initially dried under an infrared lamp, then dried at 100℃ for 5h, and then calcined at 400℃ in air atmosphere for 4h, and then reduced at 450℃ in 20vol.% hydrogen-nitrogen mixed gas for 5h (100ml / min) to obtain a fresh catalyst.

[0020] Evaluation of catalytic performance:

[0021] The selective hydrogenation of cardanol was carried out in a tank reactor. The reaction temperature was 90-110℃, the reaction time was 2.5-4.5h, the reaction pressure was 2.5-3.5MPa, the catalyst dosage was 5-10wt.% of the cardanol feed amount; the rotation speed was 400-500rpm, the cardanol concentration was 5-10wt.%, and n-butanol was used as the solvent. The product was analyzed by high performance liquid chromatography. The standard curve of each main component was established by establishing the relationship between the chromatographic peak area and the corresponding component concentration, and then the concentration change was obtained according to the peak area change of each component before and after the reaction, to determine the conversion rate and the proportion of saturated products / single olefin.

[0022] The catalyst for hydrogenation of cardanol according to the present application has high activity, and the side chain full hydrogenation product can reach 100%, or only diene / triene hydrogenation conversion can be achieved while retaining variable content of single olefin. Thus, the functionality, reactivity and stability of cardanol are effectively regulated and balanced, and the catalyst is applied to the synthesis of bio-based high-performance resins and coatings.

[0023] The technical advantages of the present application are embodied in:

[0024] 1. The hydrogenation reaction of long-chain alkene bonds in cashew phenol can be carried out using Raney nickel catalysts. However, the preparation of Raney nickel catalysts requires the use of large amounts of strong alkali to dissolve aluminum, making post-processing difficult. Moreover, Raney nickel catalysts are usually prone to deactivation, and regeneration is relatively difficult. Therefore, developing hydrogenation catalysts for the target reaction that are easy to prepare and have good activity and stability is a very attractive topic from a techno-economic perspective. This invention relates to the preparation of a supported nickel-based multi-component metal catalyst, on the one hand, by controlling the morphology of the alumina support to expose specific crystal facet structures (see attached diagram). Figure 1 2), thereby modulating the interaction and dispersion state between the metal salt precursor and the metal oxide intermediate and the support surface, and on the other hand, controlling the type and content of the metal components. In addition to the Ni main component, Cu and Co components are introduced to form bimetallic and trimetallic catalyst systems. After reduction, not only can the interaction between the metal components and the support be modulated, but also the interaction between the metal components and the electronic properties of the metal components can be modulated, thereby effectively controlling the catalytic performance of the catalyst. When the catalyst of this invention is applied to the selective hydrogenation of cashew nut shells, under milder reaction conditions, partial or complete hydrogenation of the long side-chain unsaturated alkene bonds of cashew nut shells can be achieved. Under milder conditions, the complete hydrogenation product of the side chain can reach 100%, or only the diene / triene can be hydrogenated and converted, while retaining the variable content of monoenes, thereby achieving effective modulation of the functionality, reactivity, and stability of cashew nut shells, laying an important foundation for the subsequent application of cashew nut shells.

[0025] 2. Catalysts prepared using hexagonal γ-Al2O3 as a support exhibit higher catalytic activity than those prepared using conventional γ-Al2O3. This is reflected in the fact that, although the reaction temperature is the same, the former can achieve the same catalytic performance at a lower catalyst / cashew phenol feed ratio, a shorter reaction time, and a lower reaction pressure (comparison between Example 10 and Example 7).

[0026] 3. The effect of supporting trimetallic catalysts is better than that of bimetallic or monometallic catalysts. This is reflected in the fact that trimetallic catalysts perform better under similar or milder reaction conditions (comparison of Example 7 with Examples 1, 2, and 6, and comparison of Example 10 with Example 13).

[0027] 4. The best results were achieved with a single trimetallic composition of 20wt% Ni, 3wt% Cu, and 5wt% Co (comparison between Example 7 and Examples 2 and 6).

[0028] 5. According to the literature (Mao et al., Ind. Eng. Chem. Res. 48 (2009) 9910-9914), compared with the catalyst of the present invention (Example 10), the Raney nickel catalyst requires a higher reaction temperature. Longer reaction time Higher hydrogen pressure The same catalytic performance can be achieved. Attached Figure Description

[0029] Figure 1 Fig. 6 SEM images of hexagonal plate-like morphology alumina at different magnifications.

[0030] Figure 2 Fig. 7 (a1) TEM image of hexagonal plate-like morphology alumina; (a2) selected area electron diffraction pattern of the sample (inset is the TEM image); (a3) exposed crystal face and structure schematic diagram. DETAILED EMBODIMENTS

[0031] Example 1

[0032] Take pseudo-boehmite pellets 10 g, calcine at 400°C for 4 h in air atmosphere. Then crush the sample to 20-40 mesh. According to 20 wt% Ni loading, dissolve 1.0 g Ni(NO3)2·6H2O in 3 mL deionized water, add 0.8 g alumina carrier to the above metal salt solution. The impregnated sample is preliminarily dried under infrared lamp, then dried at 100°C for 5 h, then calcined at 400°C in air atmosphere for 4 h, and then reduced at 450°C in 20 vol.% hydrogen-nitrogen mixed gas for 5 h to obtain a fresh catalyst.

[0033] The selective hydrogenation of cardanol was carried out in a tank reactor. The reaction temperature was 100°C, the reaction time was 3.5 h, the reaction pressure was 3.5 MPa, the cardanol feed was 2.74 g, the rotation speed was 500 rpm, n-butanol was used as the solvent, the cardanol concentration was 7.5 wt.%, and the catalyst was 0.27 g. The product was analyzed by high performance liquid chromatography, the conversion rate was 73%, the side chain saturated product accounted for 75%, and the mono-olefin accounted for 21%.

[0034] Example 2

[0035] Take pseudo-boehmite pellets 10 g, calcine at 400°C for 4 h in air atmosphere. Then crush the sample to 20-40 mesh. According to 20 wt% Ni loading, 3 wt% Cu loading, dissolve 1.0 g Ni(NO3)2·6H2O, 0.11 g Cu(NO3)2·3H2O in 5 mL deionized water, add 0.77 g alumina carrier to the above metal salt solution. The impregnated sample is preliminarily dried under infrared lamp, then dried at 100°C for 5 h, then calcined at 400°C in air atmosphere for 4 h, and then reduced at 450°C in 20 vol.% hydrogen-nitrogen mixed gas for 5 h to obtain a fresh catalyst.

[0036] The selective hydrogenation of cardanol was carried out in a batch reactor. The reaction temperature was 90 °C, the reaction time was 2.5 h, the reaction pressure was 3.5 MPa, the cardanol feed was 1.83 g, the rotation speed was 500 rpm, n-butanol was used as the solvent, the cardanol concentration was 5.0 wt.%, and the catalyst was 0.18 g. The product was analyzed by high performance liquid chromatography, the conversion rate was 76%, the side chain saturated product accounted for 78%, and the mono-olefin accounted for 19%.

[0037] Example 3

[0038] Pseudo-boehmite pellets 10 g were calcined at 600 °C for 4 h under air atmosphere. The sample was then crushed to 20-40 mesh. According to a 20 wt.% Ni loading, 5 wt.% Co loading, 1.0 g Ni(NO3)2·6H2O, 0.25 g Co(NO3)2·6H2O were dissolved in 5 mL deionized water, and 0.75 g of the alumina support was added to the above metal salt solution. The impregnated sample was initially dried under an infrared lamp, then dried at 100 °C for 5 h, and then calcined at 400 °C under air atmosphere for 4 h, and then reduced at 450 °C under 20 vol.% hydrogen-nitrogen mixture for 5 h to obtain a fresh catalyst.

[0039] The selective hydrogenation of cardanol was carried out in a batch reactor. The reaction temperature was 110 °C, the reaction time was 3.5 h, the reaction pressure was 2.5 MPa, the cardanol feed was 3.65 g, the rotation speed was 500 rpm, n-butanol was used as the solvent, the cardanol concentration was 10.0 wt.%, and the catalyst was 0.27 g. The product was analyzed by high performance liquid chromatography, the conversion rate was 91%, the side chain saturated product accounted for 85%, and the mono-olefin accounted for 11%.

[0040] Example 4

[0041] Pseudo-boehmite pellets 10 g were calcined at 500 °C for 4 h under air atmosphere. The sample was then crushed to 20-40 mesh. According to a 20 wt.% Ni loading, 3 wt.% Cu loading, 5 wt.% Co loading, 1.0 g Ni(NO3)2·6H2O, 0.11 g Cu(NO3)2·3H2O, 0.25 g Co(NO3)2·6H2O were dissolved in 6 mL deionized water, and 0.72 g of the alumina support was added to the above metal salt solution. The impregnated sample was initially dried under an infrared lamp, then dried at 100 °C for 5 h, and then calcined at 400 °C under air atmosphere for 4 h, and then reduced at 450 °C under 20 vol.% hydrogen-nitrogen mixture for 5 h to obtain a fresh catalyst.

[0042] The selective hydrogenation of cardanol was carried out in a batch reactor. The reaction temperature was 110 °C, the reaction time was 4.5 h, the reaction pressure was 3.5 MPa, the cardanol feed was 2.74 g, the rotation speed was 500 rpm, n-butanol was used as the solvent, the cardanol concentration was 7.5 wt.%, and the catalyst was 0.27 g. The product was analyzed by high performance liquid chromatography, the conversion rate was 99%, the side chain saturated product accounted for 96%, and the mono-olefin accounted for 3%.

[0043] Example 5

[0044] Pseudo-boehmite pellets 10 g were calcined at 500 °C for 4 h under air atmosphere. The sample was then crushed to 20-40 mesh. According to a 20 wt.% Ni loading, a 3 wt.% Cu loading, and a 5 wt.% Co loading, 1.0 g of Ni(NO3)2·6H2O, 0.11 g of Cu(NO3)2·3H2O, and 0.25 g of Co(NO3)2·6H2O were dissolved in 6 mL of deionized water, and 0.72 g of the alumina support was added to the metal salt solution. The impregnated sample was initially dried under an infrared lamp, then dried at 100 °C for 5 h, and then calcined at 400 °C under air atmosphere for 4 h, and then reduced at 450 °C under 20 vol.% hydrogen-nitrogen mixture for 5 h to obtain a fresh catalyst.

[0045] The selective hydrogenation of cardanol was carried out in a batch reactor. The reaction temperature was 105 °C, the reaction time was 4.5 h, the reaction pressure was 3.5 MPa, the cardanol feed was 2.74 g, the rotation speed was 500 rpm, n-butanol was used as the solvent, the cardanol concentration was 7.5 wt.%, and the catalyst was 0.27 g. The product was analyzed by high performance liquid chromatography, the conversion rate was 98%, the side chain saturated product accounted for 96.5%, and the mono-olefin accounted for 3%.

[0046] Example 6

[0047] Pseudo-boehmite pellets 10 g were calcined at 550 °C for 4 h under air atmosphere. The sample was then crushed to 20-40 mesh. According to a 20 wt.% Ni loading, a 3 wt.% Co loading, 1.0 g of Ni(NO3)2·6H2O and 0.15 g of Co(NO3)2·6H2O were dissolved in 6 mL of deionized water, and 0.77 g of the alumina support was added to the metal salt solution. The impregnated sample was initially dried under an infrared lamp, then dried at 100 °C for 5 h, and then calcined at 400 °C under air atmosphere for 4 h, and then reduced at 450 °C under 20 vol.% hydrogen-nitrogen mixture for 5 h to obtain a fresh catalyst.

[0048] The selective hydrogenation of cardanol was carried out in a batch reactor. The reaction temperature was 110 °C, the reaction time was 3.5 h, the reaction pressure was 3.5 MPa, the cardanol feed was 1.83 g, the rotation speed was 500 rpm, n-butanol was used as the solvent, the cardanol concentration was 5.0 wt.%, and the catalyst was 0.18 g. The product was analyzed by high performance liquid chromatography, the conversion rate was 97%, the side chain saturated product accounted for 92%, and the mono-olefin accounted for 7%.

[0049] Example 7

[0050] Pseudo-boehmite pellets 10 g were calcined at 550 °C for 4 h under air atmosphere. The sample was then crushed to 20-40 mesh. According to a 20 wt% Ni loading, a 3 wt% Cu loading, and a 5 wt% Co loading, 1.0 g of Ni(NO3)2·6H2O, 0.11 g of Cu(NO3)2·3H2O, and 0.25 g of Co(NO3)2·6H2O were dissolved in 6 mL of deionized water, and 0.72 g of the alumina support was added to the metal salt solution. The impregnated sample was initially dried under an infrared lamp, then dried at 100 °C for 5 h, and then calcined at 400 °C under air atmosphere for 4 h, and then reduced at 450 °C under 20 vol.% hydrogen-nitrogen mixture for 5 h to obtain a fresh catalyst.

[0051] The selective hydrogenation of cardanol was carried out in a batch reactor. The reaction temperature was 110 °C, the reaction time was 4.5 h, the reaction pressure was 3.5 MPa, the cardanol feed was 2.74 g, the rotation speed was 500 rpm, n-butanol was used as the solvent, the cardanol concentration was 7.5 wt.%, and the catalyst was 0.27 g. The product was analyzed by high performance liquid chromatography, the conversion rate was 100%, and the side chain saturated product accounted for >99%.

[0052] Example 8

[0053] An aluminum salt solution was prepared by dissolving 0.483 g of AlCl3-6H2O in 10 mL of deionized water. Then 0.38 g of 1-butyl-2,3-dimethylimidazolium chloride was added. An ammonium carbonate solution was prepared by dissolving 4.805 g of (NH4)2CO3 in 10 mL of deionized water and added to the above mixture. The mixture was then hydrothermally treated at 180 °C for 12 h. After the reactor was allowed to cool to room temperature, the product was washed by centrifugation with ethanol and deionized water several times, dried at 80 °C for 12 h, and calcined at 500 °C for 3 h in air to obtain hexagonal plate-shaped γ-Al2O3. The above procedure was repeated to prepare multiple batches of alumina, which were stored for later use. A catalyst precursor solution was prepared by dissolving 1.0 g of Ni(NO3)2-6H2O, 0.11 g of Cu(NO3)2-3H2O, and 0.25 g of Co(NO3)2-6H2O in 6 mL of deionized water. Then 0.72 g of the hexagonal plate-shaped alumina support was added to the metal salt solution. The impregnated sample was dried under an infrared lamp and then at 100 °C for 5 h, followed by calcination at 400 °C for 4 h in air and reduction at 450 °C for 5 h in 20 vol.% H2-N2. The fresh catalyst was obtained.

[0054] The selective hydrogenation of cardanol was carried out in a batch reactor. The reaction temperature was 100 °C, the reaction time was 3 h, the reaction pressure was 3.5 MPa, the cardanol feed was 2.74 g, the rotation speed was 500 rpm, n-butanol was used as the solvent, the cardanol concentration was 7.5 wt.%, and the catalyst was 0.27 g. The product was analyzed by high-performance liquid chromatography. The conversion rate was 99% and the side chain saturated product accounted for >99%.

[0055] Example 9

[0056] An aluminum salt solution was prepared by dissolving 0.724 g of AlCl3-6H2O in 10 mL of deionized water. Then 0.38 g of 1-butyl-2,3-dimethylimidazolium chloride was added. An ammonium carbonate solution was prepared by dissolving 4.805 g of (NH4)2CO3 in 10 mL of deionized water and added to the above mixture. The mixture was then hydrothermally treated at 160 °C for 24 h. After the reactor was allowed to cool to room temperature, the product was washed by centrifugation with ethanol and deionized water several times, dried at 80 °C for 12 h, and then calcined at 500 °C for 3 h in air to obtain hexagonal plate-shaped γ-Al2O3. The above procedure was repeated to prepare multiple batches of alumina, which were stored for later use. A catalyst precursor solution was prepared by dissolving 1.0 g of Ni(NO3)2-6H2O, 0.11 g of Cu(NO3)2-3H2O, and 0.25 g of Co(NO3)2-6H2O in 6 mL of deionized water. Then 0.72 g of the hexagonal plate-shaped alumina support was added to the metal salt solution. The impregnated sample was dried under an infrared lamp, then at 100 °C for 5 h, and then calcined at 400 °C for 4 h in air and reduced at 450 °C for 5 h in 20 vol.% H2-N2 to obtain a fresh catalyst.

[0057] The selective hydrogenation of cardanol was carried out in a tank reactor. The reaction temperature was 90 °C, the reaction time was 2.5 h, the reaction pressure was 2.5 MPa, the cardanol feed was 1.83 g, the rotation speed was 500 rpm, n-butanol was used as the solvent, the cardanol concentration was 5.0 wt.%, and the catalyst was 0.18 g. The product was analyzed by high performance liquid chromatography. The conversion rate was 95%, the side chain saturated product accounted for 90%, and the mono-olefin accounted for 8%.

[0058] Example 10

[0059] An aluminum salt solution was prepared by dissolving 0.483 g of AlCl3-6H2O in 15 mL of deionized water. Then 0.75 g of 1-butyl-2,3-dimethylimidazolium chloride was added. A solution of 5.765 g of (NH4)2CO3 was prepared by dissolving in 10 mL of deionized water and added to the above mixture. The reactor was then hydrothermally treated at 200 °C for 12 h. After the reactor was allowed to cool to room temperature, the product was washed by centrifugation with ethanol and deionized water several times, dried at 80 °C for 12 h, and then calcined at 500 °C for 3 h in air to obtain hexagonal plate-shaped γ-Al2O3. The above procedure was repeated to prepare multiple batches of alumina, which were collected for later use. A solution of 1.0 g of Ni(NO3)2-6H2O, 0.11 g of Cu(NO3)2-3H2O, and 0.25 g of Co(NO3)2-6H2O was prepared by dissolving in 6 mL of deionized water. Then 0.72 g of the hexagonal plate-shaped alumina support was added to the above metal salt solution. The impregnated sample was dried under an infrared lamp, then dried at 100 °C for 5 h, and then calcined at 400 °C for 4 h in air, and then reduced at 450 °C for 5 h in 20 vol.% hydrogen-nitrogen mixture to obtain a fresh catalyst.

[0060] The selective hydrogenation of cardanol was carried out in a tank reactor. The reaction temperature was 110 °C, the reaction time was 2.5 h, the reaction pressure was 2.5 MPa, the cardanol feed was 3.66 g, the rotation speed was 500 rpm, n-butanol was used as the solvent, the cardanol concentration was 10.0 wt.%, and the catalyst was 0.27 g. The product was analyzed by high performance liquid chromatography. The conversion was 100% and the side chain saturated product accounted for 100%.

[0061] Example 11

[0062] An aluminum salt solution was prepared by dissolving 0.483 g of AlCl3-6H2O in 10 mL of deionized water. Then 0.38 g of 1-butyl-2,3-dimethylimidazolium chloride was added. An ammonium carbonate solution was prepared by dissolving 4.805 g of (NH4)2CO3 in 10 mL of deionized water and added to the above mixture. The mixture was then hydrothermally treated at 200 °C for 24 h. After the reactor was allowed to cool to room temperature, the product was washed by centrifugation with ethanol and deionized water several times, dried at 80 °C for 12 h, and then calcined at 500 °C for 3 h in air to obtain hexagonal plate-shaped γ-Al2O3. The above procedure was repeated to prepare multiple batches of alumina, which were stored for later use. A catalyst precursor was prepared by dissolving 1.0 g of Ni(NO3)2-6H2O, 0.11 g of Cu(NO3)2-3H2O, and 0.25 g of Co(NO3)2-6H2O in 6 mL of deionized water and adding 0.72 g of the hexagonal plate-shaped alumina support to the metal salt solution. The impregnated sample was dried under an infrared lamp, then at 100 °C for 5 h, and then calcined at 400 °C for 4 h in air and reduced at 450 °C for 5 h in 20 vol.% H2-N2 to obtain a fresh catalyst.

[0063] The selective hydrogenation of cardanol was carried out in a batch reactor. The reaction temperature was 100 °C, the reaction time was 2.5 h, the reaction pressure was 3.0 MPa, the cardanol feed was 2.74 g, the rotation speed was 500 rpm, n-butanol was used as the solvent, the cardanol concentration was 7.5 wt.%, and the catalyst was 0.27 g. The product was analyzed by high performance liquid chromatography, and the conversion rate was 99% with the side chain saturated product accounting for 99%.

[0064] Example 12

[0065] Example 1 0.483 g of AlCl3-6H2O was dissolved in 15 mL of deionized water to obtain an aluminum salt solution. Then 0.38 g of 1-butyl-2,3-dimethylimidazolium chloride was added. 4.805 g of (NH4)2CO3 was dissolved in 10 mL of deionized water and added to the above mixture. Then hydrothermal treatment was carried out at 180 °C for 20 h. After the reactor was naturally cooled to room temperature, the product was washed by centrifugation with ethanol and deionized water for several times, dried at 80 °C for 12 h, and then heat treated at 500 °C in air for 3 h to obtain hexagonal plate-shaped γ-Al2O3. Several portions of alumina were prepared in parallel by the above process and collected for later use. According to a 20 wt% Ni loading, 1.0 g of Ni(NO3)2-6H2O was dissolved in 6 mL of deionized water, and 0.75 g of hexagonal plate-shaped alumina support was added to the above metal salt solution. The impregnated sample was preliminarily dried under an infrared lamp, then dried at 100 °C for 5 h, and then calcined at 400 °C in air for 4 h, and then reduced at 450 °C in 20 vol.% hydrogen-nitrogen mixed gas for 5 h to obtain a fresh catalyst.

[0066] The selective hydrogenation of cardanol was carried out in a tank reactor. The reaction temperature was 90 °C, the reaction time was 3.5 h, the reaction pressure was 3.0 MPa, the cardanol feed was 2.74 g, the rotation speed was 500 rpm, n-butanol was used as the solvent, the cardanol concentration was 7.5 wt.%, and the catalyst was 0.21 g. The product was analyzed by high performance liquid chromatography, the conversion rate was 73%, and the side chain saturated product accounted for 68%, and the mono-olefin accounted for 27%.

[0067] Example 13

[0068] 0.483 g of AlCl3-6H2O was dissolved in 15 mL of deionized water to obtain an aluminum salt solution. Then 0.38 g of 1-butyl-2,3-dimethylimidazolium chloride was added. 4.805 g of (NH4)2CO3 was dissolved in 10 mL of deionized water and added to the above mixture. Then hydrothermal treatment was carried out at 200 °C for 16 h. After the reactor was naturally cooled to room temperature, the product was washed by centrifugation with ethanol and deionized water for several times, dried at 80 °C for 12 h, and then heat treated at 500 °C in air for 3 h to obtain hexagonal plate-shaped γ-Al2O3. Several portions of alumina were prepared in parallel by the above process and collected for later use. According to a 20 wt% Ni loading, 1.0 g of Ni(NO3)2-6H2O was dissolved in 5 mL of deionized water, and 0.80 g of hexagonal plate-shaped alumina support was added to the above metal salt solution. The impregnated sample was preliminarily dried under an infrared lamp, then dried at 100 °C for 5 h, and then calcined at 400 °C in air for 4 h, and then reduced at 450 °C in 20 vol.% hydrogen-nitrogen mixed gas for 5 h to obtain a fresh catalyst.

[0069] The selective hydrogenation of cardanol was carried out in a batch reactor. The reaction temperature was 105°C, the reaction time was 4.5h, the reaction pressure was 3.0MPa, the cardanol feed was 2.74g, the rotation speed was 500rpm, n-butanol was used as the solvent, the cardanol concentration was 7.5wt.%, and the catalyst was 0.27g. The product was analyzed by high performance liquid chromatography, the conversion rate was 87%, the side chain saturated product accounted for 82%, and the mono-olefin accounted for 16%.

[0070] Example 14

[0071] An aluminum salt solution was prepared by dissolving 0.483g of AlCl3-6H2O in 15mL of deionized water. Then, 0.38g of 1-butyl-2,3-dimethylimidazolium chloride was added. A solution of 5.765g of (NH4)2CO3 was prepared by dissolving it in 10mL of deionized water and then added to the above mixture. The mixture was then hydrothermally treated at 200°C for 12h. After the reactor was naturally cooled to room temperature, the product was washed by centrifugation with ethanol and deionized water several times, dried at 80°C for 12h, and then calcined at 500°C in air for 3h to obtain hexagonal plate-shaped γ-Al2O3. Several portions of the aluminum oxide were prepared in parallel using the above process and stored for later use. A solution of 1.0g of Ni(NO3)2-6H2O, 0.11g of Cu(NO3)2-3H2O, and 0.15g of Co(NO3)2-6H2O was prepared by dissolving them in 6mL of deionized water, and 0.74g of the hexagonal plate-shaped aluminum oxide support was added to the above metal salt solution. The impregnated sample was initially dried under an infrared lamp, then dried at 100°C for 5h, and then calcined at 400°C in air for 4h, and then reduced at 450°C in a 20vol.% hydrogen-nitrogen mixture for 5h to obtain a fresh catalyst.

[0072] The selective hydrogenation of cardanol was carried out in a batch reactor. The reaction temperature was 100°C, the reaction time was 2.5h, the reaction pressure was 3.0MPa, the cardanol feed was 3.66g, the rotation speed was 400rpm, n-butanol was used as the solvent, the cardanol concentration was 10.0wt.%, and the catalyst was 0.27g. The product was analyzed by high performance liquid chromatography, the conversion rate was 93%, the side chain saturated product accounted for 89%, and the mono-olefin accounted for 9%.

Claims

1. A nickel-based supported metal catalyst used in the hydrogenation reaction of cashew nut shellac, characterized in that: 0.483 g of AlCl3·6H2O was dissolved in 15 mL of deionized water to obtain an aluminum salt solution; then 0.38 g of 1-butyl-2,3-dimethylimidazolium chloride was added; 4.805 g of (NH4)2CO3 was dissolved in 10 mL of deionized water and added to the above mixture; subsequently, the mixture was hydrothermally treated at 180°C for 20 h. After the reactor cooled naturally to room temperature, it was washed multiple times by centrifugation with ethanol and deionized water, dried at 80°C for 12 h, and then heat-treated in air at 500°C for 3 h to obtain hexagonal γ-Al2O3. 3； Multiple alumina samples were prepared in parallel using the above process and collected for later use. Based on a Ni loading of 20 wt% and a Co loading of 5 wt%, 1.0 g Ni(NO3)2·6H2O and 0.25 g Co(NO3)2·6H2O were dissolved in 6 mL of deionized water, and 0.75 g of hexagonal alumina support was added to the above metal salt solution. The impregnated samples were initially dried under an infrared lamp, then dried at 100℃ for 5 h, then calcined at 400℃ in air atmosphere for 4 h, and then reduced at 450℃ for 5 h in a 20 vol.% hydrogen-nitrogen mixture to obtain a fresh catalyst. Selective hydrogenation of cashew nut shellac was carried out in a batch reactor at a reaction temperature of 90°C for 3.5 h and a reaction pressure of 3.0 MPa. The cashew nut shellac feed rate was 2.74 g, the rotation speed was 500 rpm, n-butanol was used as the solvent, the cashew nut shellac concentration was 7.5 wt.%, and the catalyst was 0.21 g. The product was analyzed by high performance liquid chromatography, and the conversion rate was 73%, with 68% being side-chain saturated products and 27% being mono-enes.

Images