A catalyst and process for the co-production of XDA and BAC from XPN hydrogenation

Abstract

The present application provides a kind of XPN hydrogen coproduction XDA and BAC catalyst and method.The catalyst is composed of two parts A and B: catalyst A is composed of active component one and adjuvant one attached on carrier;The active component one is selected from one or more of metal Pt, Pd, Rh, Au, Ag, Fe, Ni, Co, Cu, Re, Ir, Sn and noble metal Ru, and the adjuvant one is selected from one or more of metal La, Ce, Ti, Ba, Zr;Catalyst B is composed of active component two and adjuvant two attached on carrier;The active component two is selected from one or more of metal Fe, Ni, Cu, Mo, Zn and metal Co;The adjuvant two is selected from one or more of metal Li, Na, k, Zn, Mn;The carrier is modified alumina.By coating catalyst B on the surface of A, the bifunctional catalyst of core-shell structure is formed.The present application can simultaneously realize the production of two products of phenyldimethylamine and cyclohexyldimethylamine, and the product ratio can be flexibly adjusted in a wide range.The production efficiency can be significantly improved, the production cost is reduced, and it is beneficial to industrial application.

Description

TECHNICAL FIELD

[0001] The present application relates to a catalyst and a method for hydrogenation of phthalonitrile to co-produce phenylenediamine and cyclohexanedimethylamine, and belongs to the field of amine compound synthesis. BACKGROUND

[0002] Phenylenediamine (XDA) mainly contains m-phenylenediamine (MXDA) and p-phenylenediamine (PXDA), both of which are important organic intermediates. MXDA has a wide application prospect in the field of water-based anticorrosive coatings due to its excellent heat resistance, water resistance and chemical corrosion resistance. Xylene diisocyanate (MXDI, PXDI) synthesized from MXDA and PXDA has low vapor pressure, high reactivity and other characteristics. In addition, the isocyanate group in the molecular structure is not directly connected to the benzene ring but is blocked by a methylene group, preventing resonance between the benzene ring and the isocyanate group. As a result, polyurethane prepared from MXDI and PXDI has unique advantages such as light stability, non-yellowing and good chemical stability, and is widely used in the fields of polyurethane coatings, polyurethane elastic fibers, synthetic leather, polyurethane rubber, high-end polyurethane lenses, etc. A new type of nylon resin, m-xylene nylon resin (MXD6), is prepared by using MXDA as a modified monomer. It is a crystalline aromatic nylon resin with high melting point, high mechanical strength, large elastic modulus, high glass transition temperature and high heat distortion temperature, and can maintain high strength and high rigidity in a wide temperature range, making it widely used in high-performance engineering plastics. In addition, due to its low water absorption and excellent barrier properties to gases such as oxygen and carbon dioxide, MXD6 is widely used in packaging, molding materials and fiber products, etc.

[0003] Cyclohexanedimethylamine (BAC) mainly contains 1,3-cyclohexanedimethylamine (1,3-BAC) and 1,4-cyclohexanedimethylamine (1,4-BAC), both of which are important fine chemical intermediates, mainly used as epoxy resin curing agents, and their downstream products can be used to synthesize polyamide, polyurethane, etc. As an epoxy curing agent, it has the advantages of fast curing speed and good toughness. The polyamide resin synthesized therefrom has high heat resistance and special applications in fiber and film materials. The polyurethane synthesized therefrom can be used to manufacture various light-resistant polyurethane coatings, elastomers and adhesives, etc. In addition, compared with MXDA and PXDA, 1,3-BAC and 1,4-BAC have the advantages of low freezing point, high low-temperature curing activity, low toxicity and anti-yellowing, further expanding the application range and scenarios of the products, and can be widely used in caulkants, automotive composites, etc.

[0004] Currently, the industrial production method of XDA and BAC is to use xylene as raw material, first prepare it into benzonitrile (XPN) by ammoxidation, then prepare XDA by hydrogenation, and then further hydrogenate XDA to prepare BAC. If using m-xylene as the starting material, the industry chain can obtain MXDA and 1,3-BAC two diamine products; if using p-xylene as the starting material, the industry chain can obtain PXDA and 1,4-BAC two diamine products.

[0005] The existing synthesis technology of benzene dimethylamine and cyclohexane dimethylamine is reported as follows:

[0006] Patent CN111036226B reports a catalyst system and method for preparing MXDA. The technology uses a fixed bed reactor, and Co-based and Ni-based catalysts are loaded in the reactor in sequence along the flow direction. A mixed solvent of alcohol, ether, aromatic hydrocarbon or amine (such as ethanol, tetrahydrofuran, toluene or MXDA) and liquid ammonia is used to obtain MXPN conversion rate > 99.9%, MXDA selectivity reaches more than 98%, and the catalyst has stable long-term operation performance.

[0007] Patent CN110560065B reports a kind of metal as carrier, such as Fe, Zn, Al, etc. By means of electrolytic oxidation, part of the carrier metal and one of the second metal Ni, Co, Cu, etc. Form a supported bimetallic catalyst, using this catalyst, using fixed bed continuous hydrogenation process, MXDA and liquid ammonia mixture as solvent, MXPN conversion rate reaches 100%, MXDA selectivity reaches 99.9%, and the catalyst runs stably for 2000h.

[0008] Patent CN109772312A uses 4% Ru / hydrotalcite as catalyst, and uses lithium hydroxide to modify the catalyst. Using tetrahydrofuran as solvent, reaction temperature 130℃, pressure 5MPa, using intermittent process for MXDA hydrogenation, conversion rate reaches 100%, 1,3-BAC selectivity reaches 96.1%.

[0009] Patent CN102690203A uses 5% Ru-1% Pd / Al2O3 catalyst, uses liquid ammonia as solvent, substrate mass concentration is 20%, catalyst dosage is 0.2 times the mass of MXDA, then hydrogen is filled into the reactor to 10MPa, then heated to 130℃, and then reacted at this temperature for 10h, to obtain MXDA conversion rate of 99.9%, 1,3-BAC selectivity of 97.3%.

[0010] Patent US5741928A uses Ru / Al2O3 catalyst with a 2% loading rate for MXDA fixed-bed continuous hydrogenation, using liquid ammonia, 1,3-BAC, diethylamine, triethylamine and other small-molecule organic amines or their mixtures with alcohols as solvents, at a reaction temperature of about 120°C and a pressure of 10 MPa, to obtain a 1,3-BAC molar yield of about 95%.

[0011] Patent CN104788323A reports a synthesis method for 1,4-BAC: using an impregnation method to prepare alumina or silica-supported Ru catalyst and a high-pressure autoclave batch process for PXDA hydrogenation, with water, 1,4-BAC or a mixture of the two as solvent, and LiOH, NaOH or KOH as additive, to obtain a 1,4-BAC total yield of 96.8% after product rectification.

[0012] Patent US5371293A reports a method for one-step hydrogenation of aromatic dinitrile to prepare cyclohexanedimethylamine. Ru / Al2O3 catalyst with a Ru loading rate of 1-10% is used, with liquid ammonia or its mixture with dioxane as solvent, at a reaction temperature of 70-150°C and a pressure of 50-150 atm for MXPN hydrogenation, to obtain a 1,3-BAC molar yield of about 88%. The main hydrogenation by-products are m-tolylmethylamine, 1-aminomethyl-3-methylcyclohexane, 1-aminomethyl-3-cyanocyclohexane, m-xylylenediamine and a small amount of other high and low boiling point substances.

[0013] Patent US4070399A reports a method for one-step hydrogenation of terephthalonitrile to prepare 1,4-BAC, using Ru-Pd bimetallic catalyst supported on alumina, with liquid ammonia or its mixture with dioxane, diethylamine, etc. as solvent, to obtain a 1,4-BAC mass yield of up to 99wt%. If a single-metal catalyst Pd / Al2O3 is used, a large amount of deamination by-product p-tolylmethylamine is obtained, and no 1,4-BAC is generated.

[0014] Patent CN116444381A reports a technology for preparing XDA and BAC by catalytic hydrogenation of phthalic acid amide, which is prepared by amidation of phthalic acid with ammonia. The phthalic acid amide hydrogenation uses a catalyst with Lewis acid metal oxide such as Nb2O5, MoO3 or TiO2 supported with active components such as Pt, Rh or Au, and ammonia is introduced as an additive in the reaction system. After the reaction, desolventization and deamination, rectification, and finally 99.9% pure XDA and 99.9% pure BAC products are obtained. The total XDA two-step reaction yield is 66-72% and the total BAC two-step reaction yield is 9-12% based on phthalic acid.

[0015] In summary, the main problems existing in the prior art are: (1) The existing XPN hydrogenation process for preparing XDA generally introduces a large amount of liquid ammonia as a solvent and an amine removal inhibitor into the reaction system to achieve high conversion rate and selectivity. The XDA hydrogenation process for preparing BAC also uses the method of adding liquid ammonia or other inorganic strong base additives to improve the conversion rate and selectivity. The use of a large amount of liquid ammonia has the risk of leakage, which can easily pollute the production environment, and the recovery of liquid ammonia is difficult, which significantly increases the equipment investment and production cost. The addition of alkali metal hydroxide needs to be supplemented in the subsequent catalyst application due to the problem of alkali loss in the reaction process, and the addition amount is difficult to accurately control, which makes it difficult to maintain the stable activity and selectivity of the catalyst, thereby affecting the stability of production. On the other hand, the addition of a large amount of alkali metal hydroxide can easily cause equipment corrosion and other problems; (2) The patents US5371293A and US4070399A use the one-step hydrogenation method of XPN to synthesize BAC. Although the process flow is simplified, both of them use the batch process with low production efficiency. In order to inhibit the side reaction, a large amount of liquid ammonia is introduced into the reaction system, and both of the patents reported technologies have the problems of large catalyst consumption and easy deactivation of the catalyst in the application; (3) The patent CN116444381A uses phthalic acid diamide hydrogenation to obtain XDA and BAC as two products, but a large amount of hydrogenation intermediate aminomethyl benzamide is obtained in the process, which can be recovered and applied, but the total yield of XDA and BAC is only 85-92%. In addition, the main product obtained by using this process is XDA, and the amount of BAC generated is relatively small, the product ratio range is narrow, it is difficult to flexibly adjust the product ratio according to market demand, and the raw material isophthalic acid is not easy to obtain. SUMMARY

[0016] One of the purposes of the present application is to overcome the above various problems existing in the XPN hydrogenation process for preparing XDA, the XDA hydrogenation process for preparing BAC, the XPN hydrogenation process for preparing BAC, and the phthalic acid diamide hydrogenation process for co-producing XDA and BAC, and to provide an XPN hydrogenation process for co-producing XDA and BAC.

[0017] One of the purposes of the present application is to provide the above-mentioned catalyst for XPN hydrogenation for co-producing XDA and BAC.

[0018] Another purpose of the present application is to provide a preparation method of the above-mentioned catalyst.

[0019] Still another purpose of the present application is to provide the application of the above-mentioned catalyst in the XPN hydrogenation process for co-producing XDA and BAC.

[0020] To achieve the above-mentioned purposes, the present application adopts the following technical solutions:

[0021] A catalyst for XPN hydrogenation for co-producing XDA and BAC,

[0022] The catalyst comprises a bifunctional catalyst consisting of catalysts A and B;

[0023] The bifunctional catalyst is a core-shell type structure catalyst formed by coating B on the surface of A;

[0024] The catalyst A comprises a carrier, an active component one and an auxiliary agent one.

[0025] The active component one is selected from one or more of metals Pt, Pd, Rh, Au, Ag, Fe, Ni, Co, Cu, Re, Ir, Sn (M1) and noble metal Ru, preferably one or more of Rh, Au, Re and noble metal Ru.

[0026] The content of Ru in the catalyst A is 0.001% to 20% by mass of the carrier, preferably 0.05% to 10%; the content of M1 is 0.0005% to 10% by mass of the carrier, preferably 0.01% to 5%.

[0027] As a preferred solution, in the catalyst A, the mass ratio of M1 to noble metal Ru is 0.001:1 to 10:1, preferably 0.05:1 to 1:1.

[0028] The auxiliary agent one is selected from one or more of La, Ce, Ti, Ba and Zr, preferably Ce and / or Zr.

[0029] The content of the auxiliary agent one is 0.001% to 10% by mass of the carrier, preferably 0.01% to 5%.

[0030] The catalyst B comprises a carrier, an active component two and an auxiliary agent two.

[0031] The active component two is selected from one or more of metals Fe, Ni, Cu, Mo and Zn (M2) and metal Co, preferably one or more of Fe and Cu and metal Co.

[0032] The content of Co in the catalyst B is 0.01% to 30% by mass of the carrier, preferably 0.1% to 20%; the content of M2 is 0.001% to 15% by mass of the carrier, preferably 0.05% to 5%.

[0033] As a preferred solution, in the catalyst B, the mass ratio of M2 to metal Co is 0.001:1 to 100:1, preferably 0.05:1 to 10:1.

[0034] The auxiliary agent two is selected from one or more of Li, Na, K, Zn and Mn, preferably Mn and / or Na.

[0035] The content of the auxiliary agent two is 0.001% to 10% by mass of the carrier, preferably 0.01% to 5%.

[0036] The A and B catalyst carriers are both modified alumina.

[0037] The unmodified alumina raw powder is selected from one or more of γ-Al2O3, η-Al2O3, δ-Al2O3, θ-Al2O3, k-Al2O3, and α-Al2O3, preferably γ-Al2O3, according to crystal type classification.

[0038] The specific surface area of the unmodified alumina raw powder is 20-1000 m 2 / g, preferably 50-200 m 2 / g.

[0039] The pore volume of the unmodified alumina raw powder is 0.05-5 cm 3 / g, preferably 0.1-1 cm 3 / g.

[0040] The average pore diameter of the unmodified alumina raw powder is 2-200 nm, preferably 10-50 nm.

[0041] The preparation method of the modified alumina comprises the following steps: weighing a certain amount of a modifier precursor, dissolving it in water to prepare a uniform solution, adding a certain amount of alumina powder, stirring uniformly, immersing at room temperature for a period of time, drying at 80-120°C for 2-10 h, calcining at a certain temperature for 2-10 h, and then cooling to room temperature.

[0042] In the preparation method of the modified alumina, the modifier precursor is one or more of LiOH·H2O, LiNO3, Li2CO3, LiOOCH·H2O, LiOAc, NaOH, NaNO3, NaNO2, Na2CO3, NaHCO3, NaOOCH·H2O, NaOAc, Na3PO4, Na2HPO4, NaH2PO4, KOH, KNO3, KNO2, K2CO3, KHCO3, KOOCH·H2O, KOAc, K3PO4, K2HPO4, KH2PO4, NH4OH, NH4NO3, (NH4)2CO3, NH4HCO3, NH4OOCH·H2O, NH4OAc, (NH4)3PO4, (NH4)2HPO4, NH4H2PO4, H3PO4, La(NO3)3·6H2O, Ce(NO3)3·6H2O, ZrOCl2·2H2O, Ca(NO3)2, Ba(NO3)2, BaCl2, Mg(NO3)2·6H2O, Sr(NO3)2, preferably one or more of LiOOCH·H2O, Na3PO4, and Ca(NO3)2.

[0043] In the preparation method of the modified alumina, the mass ratio of the modifier precursor to the alumina is 0.0001:1-0.5:1, preferably 0.001:1-0.1:1.

[0044] In the preparation method of the modified alumina, the mass ratio of the modifier precursor solution to the alumina is 50:1-0.5:1, preferably 10:1-1:1.

[0045] In the preparation method of the modified alumina, the impregnation time is 1-100 h, preferably 5-20 h.

[0046] In the preparation method of the modified alumina, the calcination temperature is 200-1100℃, preferably 500-900℃.

[0047] Another aspect of the present application also provides a preparation method of the bifunctional catalyst, which comprises:

[0048] (1) Catalyst A preparation: a certain amount of modified alumina is weighed, water is added, stirred, and heated to a certain temperature (T1); a certain amount of ruthenium precursor, active component M1 precursor and additive one precursor are weighed, and a uniform mixed solution is prepared by adding water, and the solution and a certain amount of ammonia water are added to the suspension system of the carrier and water at the same time within 10-300 min, after the addition is completed, the stirring is continued for a period of time (t1), then the filtration is performed, the filter cake is dried at 80-120℃ for 3-20 h, then the temperature is lowered to room temperature, the filter cake is added to a certain amount of citric acid and water to form a particle material with a certain shape and size, dried at 80-120℃ for 2-10 h, then calcined at 200-800℃ in a muffle furnace for 2-20 h, then the temperature is lowered to room temperature, and the catalyst is ready for use;

[0049] (2) Catalyst B preparation: a certain amount of Co precursor and additive two precursor are weighed, a uniform mixed solution is prepared by adding water, and then a certain amount of modified alumina is weighed and added to the mixed solution, stirred uniformly, impregnated at a certain temperature (T2) for a period of time (t2), then dried at 80-120℃ for 1-20 h, the temperature is lowered to room temperature, the filter cake is added to a certain amount of M2 precursor aqueous solution, stirred uniformly, heated to 50-90℃, then a certain amount of alkali solution is added, after the addition is completed, the stirring is continued for a period of time (t3), then the filtration is performed, the filter cake is dried at 80-120℃ for 2-10 h, then calcined at 400-900℃ in a muffle furnace for 2-10 h, then the temperature is lowered to room temperature, and the catalyst is ready for use;

[0050] (3) Preparation of the core-shell type bifunctional catalyst: a certain amount of catalyst B prepared in step (2) is weighed, and a certain amount of organic acid and water are added to form a uniform paste; another certain amount of catalyst A prepared in step (1) is weighed, and the paste of catalyst B is uniformly coated on the surface of catalyst A, which is dried at 80-120℃ for 4-20h, then calcined at a certain temperature (T3) for 2-10h, and then cooled to room temperature for use.

[0051] In the preparation method of the catalyst, the mass ratio of water to modified alumina in step (1) is 1000:1-5:1, preferably 50:1-10:1.

[0052] In the preparation method of the catalyst, the temperature T1 in step (1) is 0-90℃, preferably 40-80℃.

[0053] In the preparation method of the catalyst, the ruthenium precursor in step (1) is selected from one or more of Ru(OAc)3, K2RuCl6, (NH4)2RuCl6, K2RuCl5·nH2O, RuCl3·3H2O, (NH4)2[RuCl4], Ru2Cl2(CO)6, Ru(NO)(NO3)3, preferably one or more of RuCl3·3H2O and Ru(NO)(NO3)3.

[0054] In the preparation method of the catalyst, the M1 precursor in step (1) is selected from one or more of H2PtCl6, PdCl2, RhCl3·3H2O, AuCl3, AgNO3, Fe(NO3)3·9H2O, Ni(NO3)2·6H2O, Co(NO3)2·6H2O, Cu(NO3)2·3H2O, KReCl6, IrCl3·3H2O, SnCl4, preferably one or more of RhCl3·3H2O, AuCl3 and KReCl6.

[0055] In the preparation method of the catalyst, the auxiliary agent I precursor in step (1) is selected from one or more of La(NO3)3·6H2O, Ce(NO3)3·6H2O, TiCl4, Ba(NO3)2 and Zr(NO3)4, preferably Ce(NO3)3·6H2O and / or Zr(NO3)4.

[0056] In the preparation method of the catalyst, in the mixed solution of the ruthenium precursor, the M1 precursor and the auxiliary agent I precursor in step (1), the mass ratio of water to the total mass of the three precursors is 1000:1-5:1, preferably 100:1-10:1.

[0057] In the preparation method of the catalyst, in step (1), the concentration of ammonia water is 1-50%, preferably 10-30%.

[0058] In the preparation method of the catalyst, in step (1), the mass ratio of the ammonia water to the total mass of the three precursors is 50:1-0.5:1, preferably 10:1-1:1.

[0059] In the preparation method of the catalyst, in step (1), the time t1 is 10-500 min, preferably 30-200 min.

[0060] In the preparation method of the catalyst, in step (1), the mass ratio of the citric acid to the modified alumina in the catalyst A forming step is 0.5:1-0.001:1, preferably 0.2:1-0.01:1.

[0061] In the preparation method of the catalyst, in step (1), the mass ratio of the water to the modified alumina in the catalyst A forming step is 5:1-0.5:1, preferably 3:1-1:1.

[0062] In the preparation method of the catalyst, in step (2), the Co precursor is selected from one or more of Co(NO3)2·6H2O and CoCl2·6H2O, preferably Co(NO3)2·6H2O.

[0063] In the preparation method of the catalyst, in step (2), the M2 precursor is selected from one or more of Fe(NO3)3·9H2O, Ni(NO3)2·6H2O, Cu(NO3)3·3H2O, (NH4)2MoO4 and Zn(NO3)2·6H2O, preferably Fe(NO3)3·9H2O and / or Cu(NO3)3·3H2O.

[0064] In the preparation method of the catalyst, in step (2), the second additive precursor is selected from one or more of LiOH·H2O, NaNO3, KNO3, Zn(NO3)2·6H2O and Mn(NO3)2·4H2O, preferably NaNO3 and / or Mn(NO3)2·4H2O.

[0065] In the preparation method of the catalyst, in step (2), in the mixed solution of the Co precursor and the second additive precursor, the mass ratio of the water to the total mass of the two precursors is 100:1-2:1, preferably 20:1-5:1.

[0066] In the preparation method of the catalyst, in step (2), the temperature T2 is 10-90℃, preferably 40-70℃.

[0067] In the preparation method of the catalyst, in step (2), the time t2 is 20-1000 min, preferably 60-300 min.

[0068] In the preparation method of the catalyst, the mass ratio of water to the M2 precursor in the aqueous solution of the M2 precursor in step (2) is 1000:1 to 1:1, preferably 50:1 to 5:1.

[0069] In the preparation method of the catalyst, the base in step (2) is one or more of Li2CO3, Na2CO3, K2CO3, and (NH4)2CO3, preferably (NH4)2CO3.

[0070] In the preparation method of the catalyst, the mass ratio of water to the base in the base solution in step (2) is 100:1 to 10:1, preferably 50:1 to 20:1.

[0071] In the preparation method of the catalyst, the mass ratio of the base to the M2 precursor in step (2) is 50:1 to 0.1:1, preferably 5:1 to 0.5:1.

[0072] In the preparation method of the catalyst, the time t3 in step (2) is 5 to 300 min, preferably 30 to 100 min.

[0073] In the preparation method of the catalyst, the organic acid in step (3) is one or more of formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, and citric acid, preferably acetic acid and citric acid.

[0074] In the preparation method of the catalyst, the mass ratio of the organic acid to catalyst B in step (3) is 0.001:1 to 0.5:1, preferably 0.01:1 to 0.5:1.

[0075] In the preparation method of the catalyst, the mass ratio of water to catalyst B in step (3) is 5:1 to 0.5:1, preferably 3:1 to 1:1.

[0076] In the preparation method of the catalyst, the mass ratio of catalyst A to catalyst B in step (3) is 20:1 to 0.05:1, preferably 10:1 to 0.1:1.

[0077] In the preparation method of the catalyst, the calcination temperature T3 in step (3) is 300 to 900°C, preferably 400 to 600°C.

[0078] In another aspect of the present application, the use of the above-mentioned catalyst in catalyzing the hydrogenation of XPN to co-produce XDA and BAC is disclosed: in preferred embodiments, the use comprises: using XPN as the hydrogenation reaction substrate in a fixed bed reactor, using a reaction solvent selected from one or more of methanol, ethanol, isopropanol, n-butanol, cyclohexanol, tetrahydrofuran, dioxane, toluene, dimethylbenzene, trimethylbenzene, cyclohexane, methylcyclohexane, dimethylcyclohexane, diethylamine, triethylamine, tert-butylamine, ethanolamine, isopropanolamine, hexanediamine, cyclohexylamine, 1,4-cyclohexanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanedimethylamine, 1,4-cyclohexanedimethylamine, aniline, m-xylylenediamine, preferably one or more of tetrahydrofuran, m-xylylenediamine, 1,3-cyclohexanedimethylamine; the substrate mass concentration is 1-50%, preferably 5-20%; the reaction temperature is 40-200°C, preferably 80-160°C; the reaction pressure is 2-16 MPa, preferably 5-10 MPa; the reaction space velocity is 0.005-1.0 h -1 , preferably 0.05-0.5 h -1 , and the H2 / XPN molar ratio is 5-500, preferably 10-50.

[0079] The present application has the following beneficial effects:

[0080] (1) By modifying the alumina carrier, the strong acid sites on the surface of the carrier can be eliminated, and only a small amount of weak acid sites are retained, the elimination of the strong acid sites is conducive to inhibiting the deamination side reaction, and the retention of a small amount of weak acid sites is conducive to the adsorption and dispersion of the active metal precursor on the surface of the carrier, so that a high-activity and high-selectivity catalyst can be prepared;

[0081] (2) The bifunctional catalyst with core-shell structure prepared by the present application can first hydrogenate XPN on the surface coated with B catalyst to generate XDA, part of the XDA is desorbed from the active site and diffuses into the material bulk phase, and part of the XDA further diffuses into the A catalyst to generate BAC through benzene ring hydrogenation reaction, so that the same reactor and the same catalyst can be used to co-produce XDA and BAC two products;

[0082] (3) By adjusting the catalyst formula and process conditions, the ratio of XDA and BAC two products can be controlled in a very wide range, so that the industrialization can be flexibly adjusted according to the changes of product market situation; in addition, the same set of devices can be used for the synthesis and separation of XDA and BAC by using the present application, which greatly reduces the equipment investment and land occupation.

[0083] By the present application, the XPN hydrogenation conversion rate can be >99.9%, and the BAC+XDA comprehensive molar yield can be >98%;

[0084] The content of XDA in the product is 5-95%, and the content of BAC is 5-95%;

[0085] The molar ratio of BAC / XDA in the product is 1:20-20:1, preferably 1:10-10:1. DETAILED DESCRIPTION

[0086] The embodiments of the present application are described in detail below, and the specific embodiments described below are exemplary and are intended to explain the present application, and cannot be understood as a limitation of the present application.

[0087] Gas chromatograph: Agilent 7890B, FID detector, HP-INNOWAX chromatographic column, injection port temperature 240℃, FID detector temperature 250℃, column flow rate 1.2mL / min, hydrogen flow rate 40mL / min, air flow rate 400mL / min, the program temperature rising mode is 50℃ for 2min, then 5℃ / min to 80℃, then 15℃ / min to 240℃, and keep for 10min.

[0088] The external standard method is used for quantitative analysis, and the conversion rate of raw materials and the yield of products are calculated.

[0089] The main raw material source information in the examples and comparative examples of the present application is as follows, and other raw materials and reagents are purchased through ordinary commercial channels if not otherwise specified:

[0090] MXPN (isophthalonitrile) and PXPN (p-phthalonitrile) are provided by Aladdin;

[0091] The related information of the alumina carrier is as shown in Table 1:

[0092] Table 1 Alumina carrier

[0093]

[0094] Carrier modification example 1

[0095] 8.07g of LiOOCH·H2O is weighed, dissolved in 400g of water to prepare a uniform solution, then 800g of γ-Al2O3 powder is added, stirred uniformly, immersed at room temperature for 3h, dried at 110℃ for 8h, then calcined at 1000℃ in a muffle furnace for 8h, and then cooled to room temperature for use. The modified carrier is recorded as G-Al2O3-1#.

[0096] Carrier modification example 2

[0097] Take 570.23 g Na3PO4, add water 7400 g to dissolve and prepare a uniform solution, then add 800 g γ-Al2O3 powder, stir well, immerse at room temperature for 10 h, dry at 120 °C for 20 h, then calcine in a muffle furnace at 600 °C for 6 h, then cool to room temperature, and wait for use. The modified carrier is recorded as G-Al2O3-2#.

[0098] Carrier modification example 3

[0099] Take 327.52 g Ca(NO3)2, add water 3700 g to dissolve and prepare a uniform solution, then add 800 g δ-Al2O3 powder, stir well, immerse at room temperature for 20 h, dry at 110 °C for 12 h, then calcine in a muffle furnace at 800 °C for 4 h, then cool to room temperature, and wait for use. The modified carrier is recorded as G-Al2O3-3#.

[0100] Carrier modification example 4

[0101] Take 79.49 g LiNO3, add water 700 g to dissolve and prepare a uniform solution, then add 800 g γ-Al2O3 powder, stir well, immerse at room temperature for 50 h, dry at 90 °C for 6 h, then calcine in a muffle furnace at 300 °C for 3 h, then cool to room temperature, and wait for use. The modified carrier is recorded as G-Al2O3-4#.

[0102] Catalyst preparation example 1

[0103] (1) Catalyst A preparation: take 200 g of modified alumina G-Al2O3-1# into a glass container with stirring and heating, add 500 g of water, stir, and heat to 60 °C; take 4.10 g of RuCl3·3H2O, 5.12 g of RhCl3·3H2O and 3.10 g of Ce(NO3)3·6H2O, add 50 g of water to prepare a uniform mixed solution, add the solution and 49 g of 20% concentration ammonia water to the suspension system of the carrier and water at the same time within 30 min, continue to stir for 120 min after the dropwise addition is completed, filter and wash to neutral, dry the filter cake at 120 °C for 6 h, then cool to room temperature, add 20 g of citric acid and 400 g of water to form small balls with a diameter of 3 mm, dry at 110 °C for 6 h, then calcine in a muffle furnace at 600 °C for 8 h, then cool to room temperature, and wait for use. The prepared catalyst is recorded as A-1;

[0104] (2) Catalyst B preparation: 20.00 g of Co(NO3)2-6H2O and 4.57 g of Mn(NO3)2-4H2O were weighed and dissolved in 240 g of water to form a homogeneous solution. Then 200 g of modified alumina G-Al2O3-1# was added to the solution and stirred until homogeneous. The mixture was then impregnated at 50°C for 4 h and dried at 90°C for 10 h. The mixture was then cooled to room temperature and added to a solution of 600 g of water and 14.47 g of Fe(NO3)3-9H2O. The mixture was stirred until homogeneous and heated to 80°C. Then a homogeneous solution of 440 g of water and 14.47 g of (NH4)2CO3 was added. The mixture was stirred for another 60 min and then filtered. The filter cake was dried at 120°C for 5 h and then calcined in a muffle furnace at 500°C for 4 h. The catalyst was then cooled to room temperature and ready for use. The prepared catalyst was labeled as B-1.

[0105] (3) Preparation of core-shell type bifunctional catalyst: 200 g of catalyst B-1 was weighed and added to 10 g of acetic acid and 400 g of water to form a homogeneous paste. Then 200 g of catalyst A-1 was weighed and the catalyst B-1 paste was evenly coated on the surface of catalyst A-1. The mixture was dried at 110°C for 10 h and then calcined in a muffle furnace at 500°C for 8 h. The catalyst was then cooled to room temperature and ready for use. The prepared catalyst was labeled as C-1.

[0106] Catalyst preparation example 2

[0107] (1) Catalyst A preparation: 200 g of modified alumina G-Al2O3-2# was weighed and added to a glass container with stirring and heating. 500 g of water was added and stirred. The temperature was raised to 60°C. Then 41.05 g of RuCl3-3H2O, 0.03 g of AuCl3 and 0.074 g of Zr(NO3)4 were weighed and dissolved in 800 g of water to form a homogeneous solution. The solution and 412 g of 20% ammonia water were added to the suspension of the carrier and water simultaneously within 60 min. The mixture was stirred for another 180 min and then filtered. The filter cake was washed to neutral and then dried at 110°C for 5 h. The mixture was then cooled to room temperature and added to 20 g of citric acid and 400 g of water to form small balls with a diameter of 3 mm. The mixture was dried at 110°C for 6 h and then calcined in a muffle furnace at 800°C for 6 h. The catalyst was then cooled to room temperature and ready for use. The prepared catalyst was labeled as A-2.

[0108] (2) Catalyst B preparation: 2 g of Co(N03)2-6H20 and 36.55 g of Mn(N03)2-4H20 were weighed and dissolved in 400 g of water to form a homogeneous solution. 200 g of modified alumina G-Al203-2# was weighed and added to the mixed solution, stirred uniformly, and impregnated at 60°C for 6 h, then dried at 100°C for 10 h. The temperature was lowered to room temperature, and the mixture was added to an aqueous solution prepared by dissolving 300 g of water and 0.38 g of Cu(N03)2-3H20, stirred uniformly, and heated to 80°C. A homogeneous solution prepared by dissolving 20 g of water and 0.38 g of (NH4)2CO3 was added, and stirring was continued for 90 min after the addition was completed. The filter cake was dried at 120°C for 5 h, then calcined at 700°C for 6 h in a muffle furnace, and then cooled to room temperature. The prepared catalyst was labeled as B-2.

[0109] (3) Preparation of a core-shell type bifunctional catalyst: 200 g of catalyst B-2 was weighed and added to 10 g of citric acid and 300 g of water to form a homogeneous paste. 200 g of catalyst A-2 was weighed, and the catalyst B-2 paste was uniformly coated on the surface of the A-2 catalyst. The coated catalyst was dried at 110°C for 10 h, then calcined at 500°C for 8 h in a muffle furnace, and then cooled to room temperature. The prepared catalyst was labeled as C-2.

[0110] Catalyst preparation example 3

[0111] (1) Catalyst A preparation: 200 g of modified alumina G-Al203-3# was weighed and added to a glass container with stirring and heating, and 500 g of water was added and stirred. The temperature was raised to 60°C. 20.52 g of RuCl3-3H20, 15.38 g of ReCl6, and 30.99 g of Ce(N03)3-6H20 were weighed and dissolved in 700 g of water to form a homogeneous solution. The solution and 67 g of 20% ammonia water were simultaneously added to the suspension of the carrier and water over 90 min. After the addition was completed, stirring was continued for 30 min, and the filter cake was washed to neutral. The filter cake was dried at 110°C for 5 h, then cooled to room temperature, and added to 2 g of citric acid and 800 g of water to form small balls with a diameter of 3 mm. The small balls were dried at 110°C for 6 h, then calcined at 800°C for 6 h in a muffle furnace, and then cooled to room temperature. The prepared catalyst was labeled as A-3.

[0112] (2) Catalyst B preparation: 50 g of Co(N03)2-6H20 and 0.09 g of Mn(N03)2-4H20 were weighed and dissolved in 500 g of water to form a homogeneous solution. 200 g of modified alumina G-AI203-3# was weighed and added to the solution, stirred and impregnated at 80°C for 2 h, then dried at 110°C for 6 h. The mixture was cooled to room temperature and added to an aqueous solution prepared from 1400 g of water and 144.67 g of Fe(N03)3-9H20. The mixture was stirred and heated to 80°C, and a homogeneous solution prepared from 900 g of water and 28.93 g of (NH4)2C03 was added. The mixture was stirred for 60 min, filtered, and the filter cake was dried at 120°C for 5 h, then calcined at 800°C in a muffle furnace for 4 h, and cooled to room temperature. The prepared catalyst was labeled as B-3.

[0113] (3) Preparation of a core-shell type bifunctional catalyst: 200 g of catalyst B-3 was weighed and added to 2 g of adipic acid and 400 g of water to form a homogeneous paste. 200 g of catalyst A-3 was weighed and the catalyst B-3 paste was evenly coated on the surface of the A-3 catalyst. The mixture was dried at 110°C for 10 h, then calcined at 600°C in a muffle furnace for 8 h, and cooled to room temperature. The prepared catalyst was labeled as C-3.

[0114] Catalyst preparation example 4

[0115] (1) Catalyst A preparation: 200 g of modified alumina G-AI203-4# was weighed and added to a glass container with stirring and heating. 500 g of water was added and stirred, and the temperature was raised to 60°C. 0.63 g of Ru(NO)(N03) 3、 0.26 g of RhCl3-3H20 and 0.62 g of La(N03)3-6H20 were dissolved in 500 g of water to form a homogeneous solution. The solution and 7.53 g of 20% ammonia water were added to the suspension of the carrier and water simultaneously over 20 min, and the mixture was stirred for 60 min. The mixture was filtered and washed until neutral. The filter cake was dried at 110°C for 5 h, then cooled to room temperature. The mixture was formed into small balls with a diameter of 3 mm using 100 g of citric acid and 200 g of water. The mixture was dried at 110°C for 6 h, then calcined at 500°C in a muffle furnace for 6 h, and cooled to room temperature. The prepared catalyst was labeled as A-4.

[0116] (2) Preparation of catalyst B: Weigh 0.2g Co(NO3)2·6H2O and 27.83g NaNO3 and add 280g water to prepare a homogeneous mixed solution. Then weigh 200g modified alumina G-Al2O3-4# and add it to the mixed solution. Stir evenly and impregnate at 50℃ for 4h. Then dry at 90℃ for 10h. Cool to room temperature and add it to a solution prepared with 400g water and 0.99g Ni(NO3)2·6H2O. Stir evenly and heat to 80℃. Then add a homogeneous solution prepared with 80g water and 3.96g Na2CO3. After the addition is complete, continue stirring for 60min. Filter and dry the filter cake at 120℃ for 5h. Then calcine in a muffle furnace at 500℃ for 4h. Then cool to room temperature and set aside for use. The obtained catalyst is designated as B-4.

[0117] (3) Preparation of core@shell bifunctional catalyst: Weigh 200g of catalyst B-4, add 20g of acetic acid and 250g of water, and stir into a uniform paste; separately weigh 200g of catalyst A-4, uniformly coat the surface of catalyst A-4 with the catalyst B-4 paste, dry at 110℃ for 10h, then calcine in a muffle furnace at 800℃ for 8h, and then cool to room temperature. The obtained catalyst is designated as C-4.

[0118] Catalyst Preparation Example 5

[0119] (1) Preparation of catalyst A: Weigh 200g of modified alumina G-Al2O3-1# into a glass container equipped with stirring and heating, add 500g of water, stir, and heat to 60℃; weigh 0.69g of (NH4)2RuCl6, 0.0032g of AgNO3 and 0.019g of Ba(NO3)2, add 400g of water to prepare a uniform mixed solution, and simultaneously add this solution and 3.57g of 20% ammonia water dropwise to the suspension system of the support and water over 5min. After the addition is complete, continue stirring for 60min, filter, wash until neutral, dry the filter cake at 110℃ for 5h, then cool to room temperature, add 5g of citric acid and 200g of water to form small balls with a diameter of 3mm, dry at 110℃ for 6h, then calcine at 800℃ in a muffle furnace for 6h, and then cool to room temperature for later use. The obtained catalyst is designated as A-5;

[0120] (2) Catalyst B preparation: 2 g of CoCl2-6H2O and 0.29 g of KNO3 were weighed and dissolved in 240 g of water to form a homogeneous solution. Then, 200 g of modified alumina G-Al2O3-1# was weighed and added to the solution, stirred uniformly, and then soaked at 50°C for 4 h. The mixture was dried at 90°C for 10 h, cooled to room temperature, and then added to an aqueous solution prepared by dissolving 400 g of water and 18.2 g of Zn(NO3)2-6H2O. The mixture was stirred uniformly and heated to 60°C. Then, a homogeneous solution prepared by dissolving 1800 g of water and 182.0 g of K2CO3 was added. After the addition was completed, the mixture was stirred for another 150 min. The filter cake was dried at 110°C for 7 h, and then calcined at 700°C for 6 h in a muffle furnace. The catalyst was cooled to room temperature and was ready for use. The prepared catalyst was labeled as B-5.

[0121] (3) Preparation of a core-shell type bifunctional catalyst: 200 g of catalyst B-5 was weighed and added to 10 g of acetic acid and 400 g of water to form a homogeneous paste. Then, 200 g of catalyst A-5 was weighed and the paste of catalyst B-5 was uniformly coated on the surface of catalyst A-5. The mixture was dried at 110°C for 10 h, and then calcined at 500°C for 8 h in a muffle furnace. The catalyst was cooled to room temperature and was ready for use. The prepared catalyst was labeled as C-5.

[0122] Catalyst preparation example 6

[0123] The same as catalyst preparation example 1, except that in step (3), catalyst B-1 was 40 g, acetic acid was 3 g, water was 60 g, and catalyst A-1 was 400 g. The prepared catalyst was labeled as C-6.

[0124] Catalyst preparation example 7

[0125] The same as catalyst preparation example 1, except that in step (3), catalyst B-1 was 400 g, acetic acid was 50 g, water was 500 g, and catalyst A-1 was 100 g. The prepared catalyst was labeled as C-7.

[0126] Catalyst preparation comparative example 1

[0127] The same as catalyst preparation example 1, except that in steps (1) and (2), unmodified γ-Al2O3 powder was used to prepare catalysts A and B. The final prepared catalyst was labeled as D-1.

[0128] Catalyst preparation comparative example 2

[0129] Weigh 20.00g of Co(NO3)2·6H2O and 4.57g of Mn(NO3)2·4H2O, add 240g of water to prepare a homogeneous mixed solution. Then weigh 200g of modified alumina G-Al2O3-2# and add it to the mixed solution. Stir well, impregnate at 50℃ for 4h, then dry at 90℃ for 10h. Cool to room temperature and add it to a mixture of 600g water and 14.47g of [unclear - possibly a specific chemical formula or solution]. The solution of Fe(NO3)3·9H2O was stirred until homogeneous and heated to 80℃. Then, a homogeneous solution of 400g water and 14.47g (NH4)2CO3 was added. After the addition was complete, the mixture was stirred for 60min. The mixture was filtered, and the filter cake was dried at 120℃ for 5h. Then, it was calcined in a muffle furnace at 500℃ for 4h. After cooling to room temperature, 20g citric acid and 400g water were added to form small balls with a diameter of 3mm. The balls were dried at 110℃ for 6h and then calcined in a muffle furnace at 600℃ for 8h. After cooling to room temperature, the catalyst was designated as D-2.

[0130] Catalyst preparation Comparative Example 3

[0131] Weigh 200g of modified alumina G-Al2O3-1# into a glass container equipped with stirring and heating, add 500g of water, stir, and heat to 60℃; weigh 4.10g RuCl3·3H2O, 5.12g RhCl3·3H2O, 3.10g Ce(NO3)3·6H2O, 20.00g Co(NO3)2·6H2O, 4.57g Mn(NO3)2·4H2O, and 14.47g... Fe(NO3)3·9H2O was prepared into a homogeneous solution with 200g of water. This solution, along with 180g of 20% ammonia solution, was simultaneously added dropwise to the suspension system of the support and water over 60 minutes. After the addition was complete, stirring was continued for another 120 minutes. The mixture was filtered, washed until neutral, and the filter cake was dried at 120℃ for 6 hours. Then, it was cooled to room temperature, and 20g of citric acid and 400g of water were added to form small spheres with a diameter of 3mm. These spheres were dried at 110℃ for 6 hours and then calcined in a muffle furnace at 600℃ for 8 hours. Finally, the mixture was cooled to room temperature and left to stand. The resulting catalyst was designated D-3.

[0132] Catalyst preparation Comparative Example 4

[0133] (1) Take 200 g of modified alumina G-Al203-1# in a glass container with stirring and heating, add 500 g of water, stir, and heat to 60°C; take 4.10 g of RuCl3-3H2O and 5.12 g of RhCl3-3H2O and 3.10 g of Ce(NO3)3-6H2O, and prepare a uniform mixed solution by adding 50 g of water, and drop the solution and 49 g of 20% ammonia water into the suspension system of the carrier and water at the same time within 30 min, continue stirring for 120 min after dropping, filter, wash to neutral, dry the filter cake at 120°C for 6 h, then cool to room temperature, add 10 g of acetic acid and 400 g of water, and stir into a uniform paste; take another 200 g of D-2 catalyst prepared in Comparative Example 2, evenly coat the paste on the surface of the D-2 catalyst, dry at 110°C for 10 h, then place in a muffle furnace and calcine at 500°C for 8 h, then cool to room temperature, and wait for use, and the prepared catalyst is recorded as D-4.

[0134] Hydrogenation Example 1

[0135] Fill 30 g of catalyst C-1 in a fixed bed with an inner diameter of 24 mm and a length of 80 cm, fill inert porcelain balls on the upper and lower ends of the fixed bed, use nitrogen and hydrogen to displace the reaction device respectively, exhaust the air, then pass hydrogen to 8 MPa, and set the hydrogen flow rate to 260 NL / h for continuous hydrogenation, then heat the reactor to 350°C at a heating rate of 60°C / h and maintain for 4 h, and activate the catalyst. After activation, keep other conditions unchanged, cool the reactor to 120°C and maintain. Prepare MXPN solution by using 1,3-cyclohexanedimethylamine as a solvent, and the mass ratio of solvent to MXPN is 6:1, then use a high-pressure constant-flow pump to pass MXPN solution into the reactor at a rate of 0.5 g / min, and continuously carry out hydrogenation reaction under stable conditions, and after 200 h, sample at the outlet of the reactor, and use gas chromatography for quantitative analysis: MXPN conversion rate is 100.0%, MXDA molar yield is 34.0%, and 1,3-BAC molar yield is 65.4%.

[0136] Hydrogenation Example 2

[0137] The same as Hydrogenation Example 1, except that the catalyst is replaced by C-2, the solvent is replaced by tetrahydrofuran, the mass ratio of solvent to MXPN is 10:1, the MXPN solution feeding rate is 1 g / min, the reaction temperature is 160°C, the pressure is 5 MPa, the hydrogen flow rate is 200 NL / h, and after 200 h, sample at the outlet of the reactor, and use gas chromatography for quantitative analysis: MXPN conversion rate is 100.0%, MXDA molar yield is 11.2%, and 1,3-BAC molar yield is 88.5%.

[0138] Hydrogenation Example 3

[0139] The same as hydrogenation example 1, except that the catalyst is replaced by C-3, the solvent is replaced by m-xylene diamine, the mass ratio of solvent to MXPN is 2:1, the hydrogen flow rate is 200 NL / h, and the sample is taken at the reactor outlet after 200 h, and quantitative analysis is carried out by gas chromatography: the conversion rate of MXPN is 100.0%, the molar yield of MXDA is 90.2%, and the molar yield of 1,3-BAC is 9.5%.

[0140] Hydrogenation examples 4-7

[0141] The same as hydrogenation example 1, except that the catalyst is replaced by C-4, C-5, C-6 and C-7 in example 4, example 5, example 6 and example 7 respectively. Among them, the solvent is replaced by isopropyl alcohol in example 4.

[0142] Hydrogenation examples 4-7

[0143] Table 2 results of hydrogenation examples 1-7 and comparative examples 1-5

[0144]

[0145] Hydrogenation example 8

[0146] The same as hydrogenation example 1, respectively at the reactor outlet at 200 h, 1000 h, 1500 h, 2000 h, 3000 h, sample analysis. The reaction results are shown in Table 3:

[0147] Table 3 results of hydrogenation example 8

[0148]

[0149]

[0150] Hydrogenation example 9

[0151] The same as hydrogenation example 1, except that the raw material is replaced by PXPN, the solvent is replaced by 1,4-cyclohexanediamine, the reaction temperature is 80℃, the pressure is 12 MPa, the hydrogen flow rate is 50 NL / h, and the sample is taken at the reactor outlet after 200 h, and quantitative analysis is carried out by gas chromatography: the conversion rate of PXPN is 99.9%, the molar yield of PXDA is 11.2%, and the molar yield of 1,4-BAC is 88.5%.

Claims

1. A catalyst for the XPN hydroco-production of XDA and BAC, characterized in that, The catalyst is a core-shell type catalyst formed by coating B on the surface of A; The catalyst A comprises a carrier, active component one and an auxiliary agent one, the active component one comprises M1 and Ru; the M1 is selected from one or more of metals Pt, Pd, Rh, Au, Ag, Fe, Ni, Co, Cu, Re, Ir and Sn; the auxiliary agent one is selected from one or more of La, Ce, Ti, Ba and Zr; The catalyst B comprises a carrier, active component two and an auxiliary agent two, the active component two comprises M2 and Co; the M2 is selected from one or more of metals Fe, Ni, Cu, Mo and Zn; the auxiliary agent two is selected from one or more of Li, Na, K, Zn and Mn.

2. The catalyst according to claim 1, characterized in that, The content of Ru in the catalyst A is 0.001% to 20% of the mass of the carrier; the content of M1 is 0.0005% to 10% of the mass of the carrier; the mass ratio of M1 to the noble metal Ru is 0.001:1 to 10:1; the content of the auxiliary agent one is 0.001% to 10% of the mass of the carrier.

3. The catalyst of claim 1, wherein The content of Ru in the catalyst A is 0.05% to 10% of the mass of the carrier; the content of M1 is 0.01% to 5% of the mass of the carrier; the mass ratio of M1 to the noble metal Ru is 0.05:1 to 1:1; the content of the auxiliary agent one is 0.01% to 5% of the mass of the carrier.

4. The catalyst of claim 1, wherein The content of Co in the catalyst B is 0.01% to 30% of the mass of the carrier; the content of M2 is 0.001% to 15% of the mass of the carrier; the mass ratio of M2 to metal Co is 0.001:1 to 100:1; the content of the auxiliary agent two is 0.001% to 10% of the mass of the carrier.

5. The catalyst of claim 1, wherein The content of Co in the catalyst B is 0.1% to 20% of the mass of the carrier; the content of M2 is 0.05% to 5% of the mass of the carrier; the mass ratio of M2 to metal Co is 0.05:1 to 10:1; the content of the auxiliary agent two is 0.01% to 5% of the mass of the carrier.

6. The catalyst of claim 1, wherein The carrier of the catalyst A and B is modified alumina; The unmodified alumina raw powder is selected from one or more of γ-Al2O3, η-Al2O3, δ-Al2O3, θ-Al2O3, k-Al2O3, and α-Al2O3, and has a specific surface area of 20-1000 m 2 / g; a pore volume of 0.05-5 cm 3 / g; and an average pore diameter of 2-200 nm.

7. The catalyst of claim 6, wherein The specific surface area of the unmodified alumina raw powder is 50-200 m 2 / g; the pore volume of the unmodified alumina raw powder is 0.1-1 cm 3 / g; and the average pore diameter of the unmodified alumina raw powder is 10-50 nm.

8. The catalyst of claim 6, wherein The preparation method of the modified alumina comprises the following steps: dissolving a certain mass of a modifier precursor in water to prepare a uniform solution, then adding a certain mass of alumina powder, stirring uniformly, immersing at room temperature for a period of time, drying at 80-120°C for 2-10 hours, then calcining at a certain temperature for 2-10 hours, and then cooling to room temperature.

9. The catalyst of claim 8, wherein The modifier precursor is one or more of LiOH·H2O, LiNO3, Li2CO3, LiOOCH·H2O, LiOAc, NaOH, NaNO3, NaNO2, Na2CO3, NaHCO3, NaOOCH·H2O, NaOAc, Na3PO4, Na2HPO4, NaH2PO4, KOH, KNO3, KNO2, K2CO3, KHCO3, KOOCH·H2O, KOAc, K3PO4, K2HPO4, KH2PO4, NH4OH, NH4NO3, (NH4)2CO3, NH4HCO3, NH4OOCH·H2O, NH4OAc, (NH4)3PO4, (NH4)2HPO4, NH4H2PO4, H3PO4, La(NO3)3·6H2O, Ce(NO3)3·6H2O, ZrOCl2·2H2O, Ca(NO3)2, Ba(NO3)2, BaCl2, Mg(NO3)2·6H2O, and Sr(NO3)2.

10. The catalyst of claim 8, wherein The modifier precursor has a mass ratio of 0.0001:1 to 0.5:1 to the alumina in terms of cations.

11. The catalyst of claim 8, wherein The modifier precursor has a mass ratio of 0.001:1 to 0.1:1 to the alumina in terms of cations.

12. The catalyst of claim 1, wherein The preparation method of the catalyst comprises the following steps: (1) Catalyst A preparation: a certain amount of modified alumina is weighed, water is added, stirring is performed, and the temperature is raised to a certain temperature; a certain amount of ruthenium precursor, active component M1 precursor and additive one precursor are weighed, and a uniform mixed solution is prepared by adding water, the solution and a certain amount of ammonia water are added to the suspension system of the carrier and water at the same time within 10-300 min, after the addition is completed, stirring is continued for a period of time, filtration is performed, the filter cake is dried at 80-120°C for 3-20 h, then the temperature is lowered to room temperature, the filter cake is added to a certain amount of citric acid and water to form a granular material with a certain shape and size, the granular material is dried at 80-120°C for 2-10 h, then the granular material is calcined in a muffle furnace at 200-800°C for 2-20 h, then the temperature is lowered to room temperature, and the granular material is ready for use; (2) Catalyst B preparation: a certain amount of Co precursor and additive two precursor are weighed, a uniform mixed solution is prepared by adding water, then a certain amount of modified alumina is weighed and added to the mixed solution, stirring is performed, the temperature is raised to a certain temperature, and the temperature is maintained for a period of time, then the temperature is lowered to 80-120°C, the temperature is maintained for 1-20 h, then the temperature is lowered to room temperature, the temperature is raised to 50-90°C, a certain amount of base solution is added, stirring is continued for a period of time after the addition is completed, filtration is performed, the filter cake is dried at 80-120°C for 2-10 h, then the filter cake is calcined in a muffle furnace at 400-900°C for 2-10 h, then the temperature is lowered to room temperature, and the filter cake is ready for use; (3) Preparation of the core-shell type bifunctional catalyst: a certain amount of catalyst B prepared in step (2) is weighed, and a certain amount of organic acid and water are added, and stirred to form a uniform paste; another certain amount of catalyst A prepared in step (1) is weighed, and the paste of catalyst B is uniformly coated on the surface of catalyst A, dried at 80-120℃ for 4-20h, calcined at a certain temperature for 2-10h, and then cooled to room temperature for use.

13. A process for the co-production of XDA and BAC from XPN comprising the steps of: The catalyst according to any one of claims 1-12 is packed in a fixed bed reactor, XPN is used as the hydrogenation reaction substrate, the mass concentration of the substrate is 1-50%, the reaction temperature is 40-200°C, the reaction pressure is 2-16 MPa, the reaction space velocity is 0.005-1.0 h -1 -1, and the molar ratio of H2 / XPN is 5-500.

14. A process for the co-production of XDA and BAC from XPN comprising the steps of: The catalyst according to any one of claims 1-12 is packed in a fixed bed reactor, XPN is used as the hydrogenation reaction substrate, the mass concentration of the substrate is 5-20%, the reaction temperature is 80-160°C, the reaction pressure is 5-10 MPa, the reaction space velocity is 0.05-0.5 h -1 -1, and the molar ratio of H2 / XPN is 10-50.

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