Hydrogenation of MTHPA to MHHPA over Ni-based catalysts: Al2O3 coating, Ru incorporation and kinetics

Because of its excellent performance, methyl hexahydrophthalic anhydride (MHHPA) is a new anhydride-based epoxy resin curing agent after methyl tetrahydrophthalic anhydride (MTHPA). To improve the activity and stability of conventional RANEY® nickel catalysts in the catalytic hydrogenation of MTHPA to MHHPA reaction, RANEY® nickel encapsulated with porous Al2O3 and alumina-supported Ni–Ru bimetallic catalysts were designed and synthesized in this study. The physicochemical properties and surface reactions over the catalysts were characterized by N2 adsorption and desorption, X-ray diffraction (XRD), hydrogen temperature-programmed reduction/desorption (H2-TPR/TPD), X-ray photoelectron spectroscopy (XPS), scanning electronic microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and in situ diffuse reflectance infrared Fourier transformations spectroscopy (DRIFTS). The kinetic model of MTHPA hydrogenation over NiRu/Al was established and the parameters were estimated using the least-square method. The results showed that the encapsulation of porous Al2O3 on the surface of RANEY® nickel enhanced the stability of the Ni skeleton and the adsorption ability of the reactant molecules, which improved its activity for the hydrogenation reaction. The introduction of Ru improved the dispersion and stability of metallic Ni, which greatly increased the conversion ability towards MTHPA hydrogenation, but it had a trend to cause C 
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Created by potrace 1.16, written by Peter Selinger 2001-2019
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 C bond transfer at lower temperatures, increasing the hydrogenation difficulties. The kinetic results based on Ni–Ru bimetallic catalyst showed that the MTHPA hydrogenation reaction rate was first-order with respect to MTHPA concentration and 0.5-order with respect to hydrogen partial pressure, and the apparent activation energy of the hydrogenation reaction was 37.02 ± 2.62 kJ mol−1.


Introduction
MHHPA as a new type of liquid anhydride curing agent for epoxy resin, has a wide application eld and increasing annual demand, owing to its advantages of light color, high stability, short curing time, etc. 1-3 MHHPA is derived from the catalytic hydrogenation of MTHPA as expressed by eqn (1). Besides the hydrogenation reaction, two types of side reactions also occur: on the one hand, the C]C within the MTHPA molecule is easily transferred when activated on the catalyst surface and tends to form p-p conjugation with C]O (eqn (2)), which increases the difficulty of hydrogenation; on the other hand, the anhydride is prone to occurring side reactions such as condensation, hydrogenolysis (eqn (3)) and cross-linking under hightemperature conditions, forming coke to deactivate the catalyst. Therefore, a catalyst with high activity and stability is the key to MTHPA hydrogenation.
(1) a College of Chemical Engineering, Zhejiang University of Technology, Changwang Road 18, Hangzhou 310032, China. E-mail: longpu@zjxu.edu.cn; yunjx@zjut.edu. cn (3) Industrially, the catalysts used for MTHPA hydrogenation is mainly RANEY® nickel which is widely used in catalytic hydrogenation of ne petrochemicals because it has a high surface of Ni skeleton and is inexpensive and insensitive to sulfur and arsenic poisoning. [4][5][6][7] However, its low mechanical strength and easy powdering loss limit its application in large tonnage continuous production units such as xed bed. 8 Usually, the RANEY® Ni catalyst is molded using inorganic or organic polymers as binders and calcined at high temperature to partially convert the Ni-Al alloy in the catalyst into a-Al 2 O 3 with higher mechanical strength. 9 Alternatively, the catalyst was prepared by incomplete alkali activation, thus the unactivated Ni-Al alloy phase with high mechanical strength could serve as support, but this also led to a decrease in the active sites, which was unfavorable to the MTHPA hydrogenation. 9 Ni-based catalysts are commonly used in the liquid-phase hydrogenation reaction of maleic anhydride due to their superior ability to cleave C-C bond. [10][11][12][13] Feng et al. prepared Ni particles with different sizes and polycrystalline structures by adding organic modiers in the reduction of nickel acetate by hydrazine hydrate, and found that the size and polycrystalline structure of Ni particles had a great inuence on the performance of the catalysts in the hydrogenation of maleic anhydride and the use of polar solvents could increase the diffusion of reactants and H 2 to the catalyst surface and facilitated the hydrogenation reaction. 10 The supported Ni catalysts are also widely used for liquid-phase hydrogenation reactions and the type of support can change the morphology of Ni 0 and the metal-support interaction, which have a great inuence on the hydrogenation reaction. [11][12][13] The acidity and basicity of the support have a great inuence on the conversion and selectivity during hydrogenation process, and it has been found that the acidic sites can improve the conversion of hydrogenation while the basic sites can inhibit the further hydrogenation of C]O. 14 Among several common acidic oxide supports (Al 2 O 3 , TiO 2 , SiO 2 ), Al 2 O 3 exhibits excellent hydrogenation performance due to its high surface area and acidic sites. 15 Compared to Al 2 O 3 , mesoporous CeO 2 has better Ni dispersion due to its lattice oxygen vacancies and proper pore structure, resulting in an excellent performance in the hydrogenation reaction of maleic anhydride. 16 Similarly, the lattice oxygen vacancies within ZrO 2 can also form a synergistic catalytic interaction with metallic Ni to improve the activity and selectivity of the catalyst in the hydrogenation reaction of maleic anhydride. 17 Mesoporous TiO 2 with pure anatase phase is a good support candidate for the catalytic hydrogenation due to its strong metal-support interaction (SMSI), high chemical stability and acid-base properties, and large surface area, which is extremely favorable for metal dispersion. 18 In addition, supported noble metal catalysts, such as Pt, Pd, and Ru, are also commonly used in catalytic hydrogenation reactions. [19][20][21] The noble metals are usually loaded on porous carbon materials, such as activated carbon, carbon nanotubes, and bio-based carbon materials. Compared with transition metal catalysts, noble metal catalysts have high activity and selectivity, and fewer side reactions such as condensation, cross-linking and hydrogenolysis. However, the noble metal catalysts are very sensitive to the poisoning of sulfur and arsenic in the reactants, making the hydrogenation cost substantially higher. By adding second metals such as Co, Ce, Cr, Sn, etc., the hydrogenation ability and sulfur poisoning resistance of Pdbased catalysts can be improved. 22 Among these second metals, Co has better anti-poisoning effect because it can form an alloy with Pd to make some electrons missing from the surface of Pd, thus reduce the adsorption of sulde. 22 The Ndoped carbon material as a support can not only improve the stability and dispersion of Pd, but also provide additional electron activation for Pd metal. 23 However, the study on various porous and non-porous oxides supported Pd catalysts indicated that the support did not signicantly change the electronic state of Pd, and its activity in the hydrogenation reaction of maleic anhydride depended on the average distance between adjacent Pd particles. 24 Ru-based catalysts are considered promising for liquid-phase hydrogenation reactions 25 owing to their high hydrogenation activity and low price 26,27 compared with other noble metal catalysts.
Currently, the literature related to the study of MTHPA hydrogenation is quite rare. The technology of MHHPA production via MTHPA hydrogenation in China is relatively backward, mostly intermittent reaction process. It is urgent to develop a highly active catalyst to achieve continuous production. In our previous study, the sintering resistance of Ni nanoparticles at high temperatures was improved by coating (2) porous Al 2 O 3 (ref. [28][29][30] and the catalytic performance in steam reforming reactions was enhanced by employing supported Ni-Ru bimetallic catalysts. 31,32 Therefore, in this study, we proposed strategies to strengthen the stability of the RANEY® nickel catalyst by encapsulating porous Al 2 O 3 outside and to improve the catalytic performance by employing Ni-Ru bimetallic catalyst. The effects of porous Al 2 O 3 coating and Ru incorporation on the catalyst structure and performance in the MTHPA hydrogenation reaction were investigated. The difference in surface reactions over Ni and Ni-Ru bimetallic catalysts was elucidated by the in situ DRIFTS technique. The kinetic model of MTHPA hydrogenation over the highly active Ni-Ru catalyst was established to provide a theoretical basis for the future reactor design.

Catalyst preparation
2.2.1 Activation of RANEY® nickel catalyst. RANEY® nickel was activated using an aqueous NaOH solution. Typically, 10 g of RANEY® nickel was added into 50 mL of aqueous sodium hydroxide (20 wt%) and the suspension was stirred for 40 min at 50°C. Aer activation, the powders were ltered and washed with distilled water until the pH was 7. Before use, the activated RANEY® nickel was stored in anhydrous ethanol. The activated RANEY® nickel was denoted as R-Ni.
2.2.2 RANEY® nickel encapsulated with porous Al 2 O 3 . The porous Al 2 O 3 was coated to the activated RANEY® nickel using a similar method as we previously reported in the literature. 28,29 Typically, 0.5 g of aluminum isopropoxide and 0.5 g of CTAB were dissolved in 100 mL of anhydrous ethanol. 5 g of activated RANEY® nickel was dispersed into the above solution by 30 min of ultra-sonication. Subsequently, 10 mL of deionized water was added dropwise under vigorous stirring at room temperature and kept for 24 h. The samples were separated by centrifugation and then washed several times with deionized water and anhydrous ethanol. The obtained RANEY® nickel encapsulated with porous Al 2 O 3 was denoted as R-Ni@Al.
2.2.3 Al 2 O 3 supported Ni or Ni-Ru catalysts. The catalyst with 15 wt% Ni was prepared by the incipient wetness impregnation method. Typically, 3.497 g of Ni(NO 3 ) 2 $6H 2 O was dissolved in 10 mL of deionized water. 4 g of g-alumina was ultrasonically dispersed into the above solution, and then the water was slowly evaporated in a sand bath at 80°C. The samples were dried at 120°C for 2 h and calcined at 600°C for 5 h. Before use, the catalyst was reduced using 30 mL min −1 of H 2 at 600°C for 1 h. The reduced catalyst was denoted as Ni/Al-R. Similarly, using Ni(NO 3 ) 2 $6H 2 O and RuCl 3 as precursors, 2 wt% Ru and 15 wt% Ni were successively loaded to the alumina support to prepare the Ni-Ru bimetallic catalyst. The calcined and reduced Ni-Ru bimetallic catalysts were denoted as NiRu/Al and NiRu/Al-R, respectively. A schematic illustration of the catalyst synthesis is presented in Scheme 1.

Catalyst characterization
The BET surface area and pore volume of the samples were obtained from N 2 adsorption-desorption isotherms at liquid nitrogen temperature (−196°C) in a BSD-PS1 specic surface & pore volume analyzer (BSD Corp.). Before analysis, the samples were degassed at 300°C for 3 h to remove water and impurities. The micropore volumes of the samples were calculated from the N 2 adsorption-desorption isotherms by the N-K (original) method. XRD analysis of the samples was performed in a 7000X XRD instrument (SHIMADZU) with Cu-Ka radiation (40 kV, 30 mA). The samples were scanned in the 2 theta range of 20 to 80°w ith a step size of 0.02°. XPS spectra of the samples were Scheme 1 Schematic illustration of synthesis process of catalysts.
recorded with an ESCALAB 250Xi spectrometer (Thermo Fisher Scientic Corp.). TEM images were recorded with a JEM-2100F microscope operating at 200 kV. SEM-EDS analysis of the samples was performed in an S-4800 microscope (Hitachi). H 2 -TPR/TPD was recorded with a chemisorption instrument equipped with a gas residual analyzer (Standford RGA-200). For H 2 -TPR analysis, the temperature was linearly increased to 900°C at 10°C min −1 in 6.25 vol% H 2 /He ow. For H 2 -TPD analysis, the sample was rst in situ reduced at 600°C for 30 min using H 2 , then cooled down to room temperature and remained for 30 min. The H 2 -TPD analysis was performed from room temperature to 600°C at 10°C min −1 . 13 C-NMR and 1 H-NMR analysis of the products was conducted in a Bruker 600 MHz spectrometer (AV4600) using dimethyl sulfoxide as the solvent. FTIR analysis of the samples was performed in an IRTracer-100 FTIR spectrometer (SHIMADZU). The samples were scanned 20 times in the range of 400 to 4000 cm −1 at a resolution of 4 cm −1 . DRIFTS of the samples was performed in an FTIR spectrometer (IRTracer-100, SHIMADZU) equipped with a high-pressure diffuse reectance reaction cell (HVC-DRM, Harric) with KBr windows. Approximately 20 mg of the sample was loaded and reduced with 30 mL min −1 of H 2 at 600°C for 30 min. Aer the temperature decreased to room temperature, 40 mg of MTHPA was loaded onto the catalyst. The background was subtracted when the hydrogen pressure was maintained at 1.0 MPa with a ow rate of 30 mL min −1 . The samples were in situ scanned 20 times at different temperatures in the range of 700-4000 cm −1 at a resolution of 4 cm −1 . Before each analysis, the samples were kept for 10 min at each specied temperature.

Hydrogenation of MTHPA to MHHPA
The hydrogenation of MTHPA to MHHPA was carried out in a high-pressure stainless-steel batch reactor equipped with a temperature and pressure control system. 15 g of MTHPA was dissolved with 100 g of ethyl acetate and added to the 300 mL Teon liner together with 0.15 g of the pre-reduced catalyst. Before the reaction, the reactor was replaced with hydrogen at 1.0 MPa three times to exhaust the air. Aer the temperature and pressure reached the specied values, the reaction was carried out under vigorous stirring at 500 rpm. Aer the reaction, the catalyst was separated by centrifugation and the composition of the liquid product was analyzed by GC-FID (9790, FULI) equipped with an OV-17 capillary column (30 m × 0.32 mm × 0.25 mm). The column was programmed to ramp up to 80°C for 1 min, then to 180°C at a rate of 5°C min −1 , and nally to 260°C at a rate of 20°C min −1 for 10 min. GC-MS of the products was conducted in an Agilent 7890 series gas chromatograph with an Agilent 5975A series mass spectrometer.
The conversion of MTHPA (a A ) and selectivity (S A ) of MHHPA were calculated according to the following equations.
Kinetic experiments over NiRu/Al were designed according to the following steps. First, product concentrations were measured at different reaction times at 50, 60, 70 and 80°C under 2 MPa. Then the conversion of MTHPA was kept within 50% to determine the reaction order of reaction rate versus concentration and calculate activation energy. Hydrogen pressure was varied (1.5, 2.0, 2.5, and 3.0 MPa) at 80°C for a reaction time of 2 h to determine the reaction order of reaction rate versus hydrogen pressure. All kinetic experiments were carried out using the integral idea, i.e. the reaction order was rst assumed, then the reaction kinetic equations were integrated and nally, the integral equations were tted and veried by experimental data.

Textural and structural features of the catalysts
The BET surface area and pore volume of the catalysts are listed in Table 1. The surface area of unactivated RANEY® nickel is only 0.14 m 2 g −1 , indicating its non-porous structure, which is because RANEY® nickel is mainly composed of nickelaluminum alloy. Aer activation under alkaline conditions, the surface area of the activated RANEY® nickel (R-Ni) increased to 27.98 m 2 g −1 because the metallic Al phase was etched away and the Ni skeleton with high active sites was formed. Due to the presence of porous Al 2 O 3 , the pore structure of the R-Ni@Al catalyst was greatly improved with a surface area of 60.67 m 2 g −1 . According to our previous study, the porous alumina shell was proven to be robust and thermally stable. 28 Therefore, the coating of porous alumina was expected to improve the mechanical strength and attrition resistance of the RANEY® nickel skeleton. However, using this strategy, MTHPA need to diffuse to the Ni surface, which was not favorable for the contact between reactants and active sites. The alumina-coated RANEY® nickels showed poorer pore structures than the alumina-supported Ni and Ni-Ru catalysts because of the smaller alumina coating amount to ensure a better MTHPA diffusion. The incorporation of Ni and Ru could block the alumina pores, leading to a decrease in surface area, and some pore structures of Al 2 O 3 also underwent collapse during the calcination procedure. 31 However, it is noteworthy that the surface area of NiRu/Al (166.54 m 2 g −1 ) is larger than that of Ni/ Al (133.60 m 2 g −1 ) under the same preparation conditions, suggesting that the pre-loaded Ru inhibited the elimination of alumina pore at high temperature. This may be owing to the strong interaction between Ru and Ni, which greatly improves the Ni sintering resistance under high-temperature conditions. Fig. 1a  phase. This indicates that the nickel-aluminum alloy is mainly composed of Al 3 Ni and Al 3 Ni 2 , which are the raw phases to form a metallic Ni skeleton. The content of Al 3 Ni was related to the particle size of the powder, while Al 3 Ni 2 was more resistant to dealloying in the base environment. 33 Besides, another diffraction peak at 38.5°was observed owing to the eutectic phase. 34 The activated RANEY® nickel (R-Ni) showed diffraction peaks of metallic Ni 0 at 44.50, 51.85, and 76.38°(JCPDS 87-0712), indicating that Al was gradually etched away under alkaline conditions to form active Ni skeletons. Meanwhile, the diffraction peak associated with AlNi also appeared at 44.37°(JCPDS 20-0019), indicating that some Al remained in the catalyst and formed an AlNi alloy. RANEY® nickel encapsulated with porous Al 2 O 3 (R-Ni@Al) showed diffraction peaks consistent with R-Ni, indicating that the coating of porous Al 2 O 3 did not change the original crystalline structure of Ni. Because of the amorphous state of the coated Al 2 O 3 , 28 no diffraction peaks of Al 2 O 3 were observed in the XRD pattern of R-Ni@Al. Aer reduction at 600°C , the diffraction peaks of Ni in R-Ni@Al only suffered from a slight increase in intensity, indicating that the Ni skeleton was well preserved because of the protection of the robust alumina shell, showing high resistance to Ni agglomeration under severe conditions.
The XRD patterns of Ni/Al and NiRu/Al before and aer reduction are shown in Fig. 1b , their intensities in NiRu/Al are much weaker than those in Ni/Al, indicating that NiRu/Al has a better Ni dispersion and smaller alumina particle size. This is consistent with BET results that the incorporation of Ru inhibits the metal sintering and agglomeration of Al 2 O 3 nanoparticles, showing a good pore structure. Due to the small loading amount of Ru with high dispersion, 35 no diffraction peaks associated with the RuO 2 phase were observed in the XRD patterns of NiRu/Al. For the reduced state, both Ni/Al-R and NiRu/Al-R showed diffraction peaks at 44.50, 51.85, and 76.38°c orresponding to Ni, indicating that NiO was transformed to metallic Ni 0 which is the active sites for MTHPA hydrogenation. Compared to Ni/Al-R, NiRu/Al-R showed smaller full width at half maximum for the diffraction peaks of Ni, indicating that the introduction of Ru improved the Ni sintering resistance under reducing conditions, which may be explained by the strong interaction between Ru and Ni, forming more stable Ni-Ru clusters. 31 It is noteworthy that the diffraction peak of NiO appears in NiRu/Al-R, indicating that the reduced highly active Ni is easily re-oxidized aer exposed to air.
The results of H 2 -TPR analysis of Ni/Al, NiRu/Al as well as pure NiO prepared by calcining Ni(NO 3 ) 2 at 550°C are shown in Fig. 2a. The reduction of NiO is related with the particle size, Nialumina interaction, and Ni-Ru interaction. Depending on different Ni sizes, the reduction peaks of pure NiO appeared at 300-600°C. There are three reduction peaks for NiRu/Al, which appear mainly in the low-temperature region (152-600°C). The peak at ∼230°C is related to the reduction of RuO 2 , 35 the peak at ∼330°C is attributed to the reduction of NiO, and the peak at 275°C is supposed to be the reduction of Ni that has interaction with Ru. It is revealed that Ni-Ru interaction makes the reduction temperature lower forming Ni-Ru clusters, which can increase the type and number of active sites in the reduction process. On the contrary, the reduction peaks of Ni/Al mainly appear in the high-temperature region (367-900°C), where the reduction peaks from 400 to 600°C are due to the reduction of bulk NiO, while the reduction peaks from 480 to 725°C are associated with the reduction of NiO that interacts with Al 2 O 3 . 35 The reduction peak above 725°C is probably due to the formation of NiAl 2 O 4 species. 28,29,35 The strong Ni-Al interaction increases the reduction temperature, resulting in the difficult reduction of NiO and decrease in active sites during the reduction procedure.
H 2 -TPD analysis can characterize the type of hydrogen adsorbed on the catalyst surface 36 and the results are presented in Fig. 2b. It is observed that the H 2 desorption peaks for all samples are mainly concentrated between 200 and 400°C. In addition, H 2 desorption peaks with different intensities are also present in the low and high-temperature regions, representing different types of adsorbed H 2 species. The amount of hydrogen adsorbed on the surface of the samples was calculated by peak tting and the dispersion was calculated based on the Ni content as shown in Table 1. It is noticed that the average dispersion of Ni and Ru for NiRu/Al is much higher compared to that of Ni/Al, indicating that the addition of Ru can improve the dispersion of Ni. Considering the H 2 -TPR results, it appears that this is mainly due to the Ni-Ru interaction resulting in a lower reduction temperature and exposure of more active sites. In contrast, the dispersion of R-Ni and R-Ni@Al is lower, mainly due to their higher Ni content, which makes it more difficult to achieve high dispersion. The Ni dispersion of R-Ni@Al is higher than that of R-Ni, indicating that the Al encapsulation improves the dispersion of RANEY® nickel. This is probably due to the encapsulation of Al making the RANEY® nickel structure more stable and improving the sintering resistance during the H 2 reduction procedure. Fig. 3 presents the XPS spectra of the samples. From the XPS surveys, it is observed that the peaks of Ni 2p, O 1s, and Al 2p appear in the samples with different intensities. The peak intensities of Ni 2p in Ni/Al and NiRu/Al are weaker than those  TEM images of catalysts are presented in Fig. 5. The reduced metallic Ni is mainly concentrated in the black region. 28 For the Ni/Al sample, less metallic Ni is formed in the black region due to the strong interaction between Ni-Al resulting in a smaller reduction of NiO. For the NiRu/Al sample, on the other hand, the reduction temperature of Ni decreases due to the Ni-Ru interaction and much more metallic Ni is formed. The activated RANEY® nickel is mainly a Ni-based skeleton structure. The Ni body surrounded by grey regions of Al 2 O 3 can be observed in Fig. 5d.
The FTIR spectra of MTHPA and products over R-Ni@Al and NiRu/Al are shown in Fig. 6  effect on the hydrogenation degree due to the steric and conjugation effects caused by the C]O groups. The absorption peak at this location is large for the raw MTHPA owing to the existence of many unsaturated C]C bonds in the molecules. Aer hydrogenation over R-Ni@Al and NiRu/Al, these peaks almost disappear, indicating that the C]C bond is converted to a C-C bond, accompanying the growth of the C-H absorption peak at 2935 and 2859 cm −1 . It is noteworthy that for NiRu/Al, a new absorption peak appears at 1584 cm −1 corresponding to C]C stretching vibration, indicating that the C]C transfer reaction may occur during the hydrogenation process, forming a new isomer of MTHPA. The C]C transfer towards anhydride groups will increase the hydrogenation difficulty because of conjugation and steric effects, causing a decrease in the MHHPA selectivity. Fig. 7 shows the DRIFTS results of MTHPA hydrogenation over R-Ni@Al and NiRu/Al at different temperatures. Because the partial pressure of the reaction intermediates in the gas phase increases with the rising temperature, the intensity of all  the absorption peaks for the two types of catalysts gradually increases. For either catalyst, no signicant change in the relative ratios of the C-H bond absorption peaks (at 2935 and 2859 cm −1 ) to the C-C absorption peaks (971 and 923 cm −1 ) at different temperatures was observed, but only the intensity changed with the temperature. Compared to MTHPA, the absorption peaks corresponding to C]C stretching vibration at 1645 and 1394 cm −1 receded and almost did not change with the rising temperature, indicating that the degree of MTHPA hydrogenation reached a limit. Moreover, a high temperature is not always favorable to the hydrogenation reaction because of its exothermic features. By comparing the two catalysts, it is obvious that the percentage of C-H over NiRu/Al is larger than that of R-Ni@Al, indicating its stronger hydrogenation ability. This is mainly because the introduction of Ru gives a better Ni dispersion and forms highly active Ni-Ru clusters. 31,37 However, the NiRu/Al catalyst showed a new absorption peak at 1584 cm −1 associated with the C]C stretching vibration and its intensity became larger with the increasing temperature, revealing that the introduction of Ru promoted the C]C transfer in the ring and this was favored by the high temperature. The transfer of C]C will increase the difficulty of hydrogenation, resulting in a decrease in the MHHPA selectivity, thus the reaction temperature should not be too high.  hydrogenation the peak of MHHPA in this region almost disappears, indicating that the hydrogenation reaction occurs. Similarly, the position, number, and intensity of the corresponding peaks at 1, 2, 5, 6 and 7 change accordingly due to the disappearance of C]C and the formation of isomers. Fig. S2 † shows the GC-MS spectra of MTHPA and MHHPA. Consistent with the results of the NMR, MTHPA showed two signal peaks at 11.9 and 13.3 min, representing the two isomers of MTHPA. The small peak at 14.80 min, for butylated hydroxytoluene, indicates the presence of a small amount of stabilizer in the feedstock. In the MHHPA product aer hydrogenation, besides the large peak at 13.11 min, a smaller signal peak at 12.06 min appeared, reecting the hydrogenation of two different methyl-positioned MTHPA isomers. Furthermore, some small signal peaks about MTHPA were also present, indicating the occurrence of C]C transfer during the hydrogenation process.

Catalytic performance in MTHPA hydrogenation
The comparison of the catalytic performance of different catalysts in MTHPA hydrogenation is shown in Fig. 9. As shown in Fig. 9a, all the catalysts showed the conversions of MTHPA gradually increased with the increasing reaction time. NiRu/Al showed the best catalytic performance, which was mainly attributed to the improved Ni dispersion and formed highly active Ni-Ru clusters due to the incorporation of Ru. On the contrary, the Ni/Al catalysts showed the lowest catalytic activity due to their poor pore structure and low metal dispersion. R-Ni also showed poor activity because the activated Ni skeleton was easily oxidized by air although they were stored in ethanol. R-Ni@Al showed a higher conversion than R-Ni, indicating that the encapsulation of porous Al 2 O 3 promoted the catalytic performance of RANEY® Ni, which is owing to the better adsorption of reactants in the porous alumina and easier interaction with the dissociated H on the Ni surface. In addition, the coating of the porous alumina also enhanced the stability of the activated Ni skeleton and inhibited oxidation by air. As shown in Fig. 9b, the MHHPA selectivity over R-Ni and R-Ni@Al is higher than that of NiRu/Al. This is consistent with the DRIFTS analysis that the introduction of Ru promotes the C]C transfer, forming hard hydrogenated MTHPA isomers.
The effect of reaction temperature on the conversion of MTHPA and selectivity of MHHPA over NiRu/Al is shown in Fig. 10. The conversion of MTHPA and the reaction rate (slope of conversion versus time) increases with the rising temperature. The effect of temperature on the selectivity of MHHPA is  small, showing an increasing trend, indicating that the C]C transfer over NiRu/Al has to low sensitivity to the temperature than the hydrogenation reaction. Although the selectivity of MHHPA can be improved by appropriately increasing the temperature, high temperature also promotes the hydrogenation reaction of C]O, forming aldehydes, acids, and other byproducts, which decreases the content of anhydride in the product. 39 The conversion of MTPHA and selectivity of MHHPA over NiRu/Al at different H 2 pressures are presented in Fig. 11. Both the conversion of MTPHA and the selectivity of MHHPA showed a rising trend with the increasing pressure due to the increased amount of dissociated H on the catalyst surface. The more H species could accelerate the hydrogenation of MTHPA, showing a higher MHHPA selectivity. Fig. S5 † presents the hydrogenation cycle test of the NiRu/Al catalyst. It is observed that aer four cycle tests, the conversion of MTHPA only undergoes a slight decrease. The main reason for the decrease in NiRu/Al activity is the weight loss during recycling and partial oxidation when exposed to air.

Kinetics of MTHPA hydrogenation over NiRu/Al
Under present conditions, the MTHPA hydrogenation reaction is not limited by thermodynamic equilibrium. To make it convenient for subsequent reactor design, the reaction rate is dened as the consumed MTHPA per unit time per unit mass of catalyst. The reaction rate (r A ) is related to the MTHPA concentration (x A ) and the H 2 pressure (p H ), which can be written as the following equations.   where n A is the mole number of MTHPA; w is the amount of catalyst (g); t is the reaction time (min); p H is the H 2 pressure (MPa); n is the reaction order with respect to H 2 pressure; k is the reaction rate constant (mol g −1 min −1 MPa −n ). Because the pressure is kept constant during the reaction, p H n and k can be combined into k ′ Therefore, the reaction rate equation can be written as.
where n T is the total mole number in the reaction system; a A is the conversion of MTHPA.
The mass transfer has a strong inuence on liquid-phase hydrogenation over porous catalysts. 40 To obtain intrinsic kinetic data for the MTHPA hydrogenation reaction, the effect of internal and external diffusion of the reaction process needs to be eliminated. As shown in Fig. S4, † by varying the stirring speed of the reaction process (500, 600, and 800 rpm), no signicant change in the rate of the hydrogenation reaction was observed, indicating that the external diffusion has been eliminated. On the other hand, the effect of internal diffusion can also be neglected since the estimated C wp = 4.0 × 10 −5 according to Weisz-Prater internal diffusion criterion is rather small. As shown in Fig. 12, −ln(1 − a) and reaction time at different reaction temperatures showed a good linear relationship, indicating that the reaction rate is rst order with respect to the MTHPA concentration. The parameter k ′ in the model was obtained using the least-squares method and the results are listed in Table 2.
The relationship between k ′ and T is in accordance with the Arrhenius equation.
where A ′ is the pre-exponential factor aer combining the H 2 pressure terms (mol g −1 min −1 ), E a is the apparent activation energy (kJ mol −1 ), and R is the molar gas constant.
As shown in Fig. 12b, ln k ′ and 1/T showed a good linear relationship. The parameters were estimated by linear tting and the results are E a = 37.02 ± 2.62 kJ mol −1 and A ′ = 10 537.66 ± 2.53 mol g −1 min −1 .
To determine the reaction order with respect to the hydrogen pressure, the following equation can be obtained by integrating eqn (4) and taking the logarithm on both sides.
The relationship between ln p H and ln[−ln(1 − a A )] is presented in Fig. 13a and the slope of the line is 0.5266 by linear regression of the data. Therefore, the reaction order with respect to hydrogen pressure is 0.5. The parameters of the kinetic model were optimized by the least-square method, obtaining the pre-exponential factor A = 7908.62 mol g −1 min −1 MPa −0.5 .
Table S1 † shows the comparison of experimental and modelpredicted values of MTHPA conversion under different reaction conditions. The model-predicted values are similar to the experimental values with relative errors mostly within 10%. Although the absolute errors of some data points were not large, the relative errors were more than 10%, due to the low conversion of MTHPA under some experimental conditions. As shown   Fig. 13b, all data points distribute uniformly on both sides of the diagonal, indicating that the established kinetic model has good reliability.

Possible hydrogenation mechanism over NiRu/Al
Fig. 14 illustrates the possible mechanism of the hydrogenation of MTHPA over NiRu/Al catalysts, where Ni interacts with Ru to form highly active Ni-Ru sites. H 2 adsorbs and dissociates into H on the surface of the Ni-Ru active site under certain pressure, then reacts with the C]C of MTHPA to generate MHHPA. On the other hand, the Ni-Ru active site also activates the C]C in MTHPA, causing its transfer and increasing the difficulty of hydrogenation. The activation of H 2 on the Ni-Ru surface is related to the partial pressure of H 2 , and the concentration of H increases with the increasing partial pressure of H 2 . The higher pressure can make the Ni-Ru surface occupied by more H, reducing the chance of contact with C]C in MTHPA, thus improving the hydrogenation activity and selectivity. When the Ni-Ru surface is saturated with H adsorption, the effect of pressure on the hydrogenation reaction becomes less pronounced.

Conclusions
In this study, porous Al 2 O 3 -coated RANEY® nickel and aluminasupported Ni-Ru bimetallic catalysts were prepared to improve the activity and stability of catalysts in the hydrogenation of MTHPA to MHHPA. The results showed that the coating of porous Al 2 O 3 not only improved the mechanical strength of the RANEY® nickel skeleton but also provided more adsorption sites for the reactant molecules, which is favorable to the hydrogenation reaction. The incorporation of Ru improved the dispersion and sintering resistance of Ni, boosting the catalytic performance signicantly. However, C]C transfer in the carbon ring was facilitated over Ru, increasing the difficulty of hydrogenation. The selectivity of MHHPA can be improved by appropriately elevating the temperature and increasing the pressure. The results of the kinetic study over the NiRu/Al showed that the reaction orders with respect to the concentration of MHHPA and hydrogen pressure were 1 and 0.5, respectively, and the apparent activation energy was 37.02 ± 2.62 kJ mol −1 . The established kinetic model well predicted the conversions of MTHPA under the present conditions, which could provide a theoretical basis for the subsequent reactor design.

Conflicts of interest
There are no conicts to declare.