Hydrogenation catalyst, process for its preparation and use

Abstract

The application relates to the technical field of catalysts, and discloses a hydrogenation catalyst and a preparation method and application thereof. The catalyst comprises Pd, a non-noble metal component and a carrier, wherein the carrier comprises alumina, a molecular sieve with a BEA structure and modified metal oxide, the modified metal oxide is at least one of titanium oxide, zirconium oxide and cerium oxide; wherein the modified metal oxide has a value of eta (eta) <0.3 and a value of theta (theta) >=50; and the non-noble metal component is selected from at least one of Cu, Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, W and Ca. The hydrogenation catalyst has excellent activity and butadiene hydrogenation selectivity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysts, in particular to a hydrogenation catalyst and a preparation method and application thereof. BACKGROUND

[0002] In petroleum chemical industry, naphtha steam cracking produces abundant low-chain C4 olefins, but a small amount of dienes or alkynes is often contained in these C4 olefins; in the downstream olefin polymerization process, dienes or alkynes are more likely to be adsorbed on the surface of the polymerization catalyst than mono-olefins, thus causing the catalyst to be poisoned and lose effectiveness, and therefore people often use the selective hydrogenation of dienes to generate mono-olefins to solve this problem.

[0003] Due to the high octane number, low vapor pressure and good solubility in gasoline hydrocarbons, the production of methyl tert-butyl ether (MTBE) has rapidly increased in recent years. After the separation of methanol and ether from the outlet material (carbon four after ether) of the etherization device for producing MTBE, the content of normal olefins can account for 40-100% by weight. At present, a large amount of normal butene resources after ether is mainly burned as liquefied gas, so it is urgent to find a new application approach. On the other hand, the continuous expansion of the production of MTBE devices makes the production of isobutene obtained from traditional petroleum catalytic cracking and thermal processing far from meeting the needs of production. Therefore, the skeleton isomerization of the material rich in normal butene after ether to produce isobutene can achieve the purpose of increasing the production of isobutene, which is an effective way to reuse normal butene.

[0004] The catalysts for selective hydrogenation of unsaturated hydrocarbons are mainly Au, Pd, etc. Although noble metals have very high dissociation and activation capacity for hydrogen, they also exhibit very high activity when applied to selective hydrogenation of unsaturated hydrocarbons, but the limited resources and high price of noble metals in nature restrict their long-term development in the field of catalysis. During the preparation and actual application of noble metal catalysts, metal particles are prone to agglomeration, which reduces the contact area between the reactants and the metal active centers, and reduces the utilization rate of the catalyst. Therefore, it is necessary to find a suitable carrier to prepare a catalyst in which noble metals are uniformly dispersed and are not prone to agglomeration, and then further study its performance as a selective hydrogenation catalyst for unsaturated hydrocarbons.

[0005] The preparation approaches of high-efficiency catalysts are: ① adding other metals to the noble metal catalyst to modify the catalyst, thereby reducing the adsorption capacity of the active sites of the catalyst for mono-olefins, and thus improving the hydrogenation selectivity of the catalyst for generating mono-olefins; ② modifying the carrier, so that the generated mono-olefins can easily and quickly leave the surface of the catalyst, avoiding further hydrogenation of mono-olefins to generate alkanes.

[0006] When copper catalyst is used for selective hydrogenation of acetylene, the catalyst has high selectivity, but because the reaction temperature is relatively high, diene and acetylene are easy to form polymer to deposit on the surface of the catalyst, causing the activity of the catalyst to decrease rapidly and the service time to be short. Palladium catalyst has excellent activity, and the reaction temperature is generally much lower than that of copper catalyst, so it has a relatively long service time, but the selectivity is poorer than that of copper catalyst, and palladium is easy to be combined with acetylene, causing the loss of palladium and the rapid deactivation of the catalyst. Generally, the method of adding an additive is used to improve the interaction between palladium and acetylene and prolong the service life of the catalyst.

[0007] U.S. Patent Application US3898298 discloses a noble metal Pd catalyst which uses Pd with a content of 0.05-0.2% as an active component and alumina as a carrier. The invention claims that the total conversion rate of vinyl acetylene in the C4 fraction reaches about 92%, but 1.28 kg of 1,3-butadiene is lost for every kg of vinyl acetylene converted, and the hydrogenation catalyst is only suitable for selective hydrogenation of C4 fraction with low acetylene content (below 1.0% wt).

[0008] Patent Application CN103418379A uses a carrier modified with calcium oxide and introduces WO3 as an additive to improve the monolefin yield and sulfur resistance of the Pd catalyst, and it does not mention whether the catalyst has 1-butene isomerization performance. Patent Application CN1676214A introduces two additives X1 and X2 on the basis of Pd catalyst supported on alumina, X1 is selected from one or more of B, P, and Si, and X2 is selected from one or more of K, Na, Li, Mg, and Sr, and provides a pretreatment method for alkylated raw materials, the butadiene hydrogenation rate is above 99%, and the 1-butene isomerization rate can reach 70%, but it does not mention the reaction performance of butadiene hydrogenation selectivity. The cost of the non-noble metal butadiene selective hydrogenation catalyst is relatively low, but the activity of the current non-noble metal butadiene selective hydrogenation catalyst is not high. Generally, the butadiene selective hydrogenation catalyst with noble metal as the active component has high activity and good selectivity, however, the price of the pure noble metal catalyst is high, and the activity of the butadiene selective hydrogenation catalyst prepared by replacing part of the noble metal with non-noble metal according to the existing method is not high. SUMMARY

[0009] The application aims to overcome the problems of poor activity of hydrogenation catalyst and poor performance of butadiene selective hydrogenation reaction in the prior art, and provides a hydrogenation catalyst, a preparation method and application thereof. The catalyst has good activity and butadiene hydrogenation selectivity, uses noble metal and non-noble metal as active components at the same time, the non-noble metal component can timely react with mercaptan sulfur-containing compounds, effectively inhibits the interaction between sulfur compounds and noble metal, reduces the influence of sulfur compounds on catalyst poisoning, and improves the activity and selectivity of the hydrogenation catalyst. The catalyst is especially suitable for raw materials with high 1,3-butadiene volume fraction.

[0010] In order to achieve the above-mentioned purpose, the first aspect of the application provides a hydrogenation catalyst, wherein the catalyst comprises Pd, a non-noble metal component and a carrier, wherein the carrier comprises alumina, a molecular sieve with BEA structure and modified metal oxide, the modified metal oxide is at least one of titanium oxide, zirconium oxide and cerium oxide; wherein η < 0.3 and θ ≥ 50, η = weight percentage content of crystalline modified metal oxide in the carrier / chemical composition weight percentage content of the modified metal oxide in the carrier, θ = weight percentage content of the modified metal oxide on the surface of the carrier / chemical composition weight percentage content of the modified metal oxide in the carrier, the titanium oxide is calculated based on TiO2, the cerium oxide is calculated based on CeO2, and the zirconium oxide is calculated based on ZrO2; wherein the non-noble metal is at least one selected from Cu, Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, W and Ca.

[0011] The second aspect of the application provides a preparation method of a hydrogenation catalyst, wherein the method comprises the following steps:

[0012] (1) contacting alumina, a molecular sieve with BEA structure, water and an acid solution to form a slurry; then sequentially performing molding, drying and calcination on the slurry to form a mixed matrix carrier;

[0013] (2) contacting the mixed matrix carrier obtained in step (1) with a gas-carrying modified metal oxide precursor gas stream to obtain a mixed matrix loaded with a modified metal oxide precursor;

[0014] (3) hydrolyzing and calcining the mixed matrix loaded with the modified metal oxide precursor to obtain a carrier;

[0015] (4) introducing a Pd precursor and a non-noble metal component precursor onto the carrier by an impregnation method, and then performing drying and calcination;

[0016] wherein the non-noble metal is at least one selected from Cu, Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, W and Ca;

[0017] The modified metal oxide is at least one of titanium oxide, zirconium oxide and cerium oxide.

[0018] The third aspect of the present application provides an application of the non-noble metal hydrogenation catalyst in the selective hydrogenation of butadiene and the isomerization of 1-butene.

[0019] The hydrogenation catalyst provided by the present application contains Pd noble metal and replaces part of the noble metal with non-noble metal, thereby reducing the amount of noble metal, and the active component is the noble metal and the non-noble metal, which has higher hydrogenation isomerization activity and / or selectivity than the existing noble metal catalyst. In addition, it also has the advantage of higher n-butene isomerization selectivity.

[0020] At the same time, the non-noble metal component in the catalyst can react with the thiol sulfur-containing compound in time, effectively inhibiting the interaction between the sulfur-containing compound and the noble metal, reducing the poisoning effect of the sulfur-containing compound on the catalyst, and improving the activity and selectivity of the hydrogenation catalyst. The catalyst is particularly suitable for treating raw materials with a high volume fraction of 1,3-butadiene.

[0021] The catalyst preparation method provided by the present application first prepares a carrier with a relatively low η value and a relatively high θ value, and then loads the active noble metal component and the non-noble metal component as the active component, so that the preparation method is easy to implement. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 is the XRD spectrum of the carrier containing alumina, beta molecular sieve and titanium oxide. Wherein, 1 is the XRD spectrum of the carrier prepared in preparation example 1 of the present application; wherein, 2 is the XRD spectrum of the alumina supported titanium oxide carrier prepared by the impregnation method of introducing the modified metal TiO2 in preparation comparative example 4 of the present application; wherein, 3 is the XRD spectrum of the physical mixture of alumina and titanium dioxide in preparation comparative example 3 of the present application;

[0023] In the XRD curve, 2θ=25.37°, 48.12°, 53.97° and 55.1° are the diffraction peaks of TiO2(anatase). DETAILED DESCRIPTION

[0024] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The ranges or values should be construed to be roughly about the ranges or values. For values comprising ranges, the endpoints between the ranges of values, between the endpoints and the individual values, and between individual values, can be combined with one or more of the included ranges or values to create new ranges or values. Such new ranges or values are to be considered as included within the scope of what is specifically disclosed.

[0025] The first aspect of the present application provides a hydrogenation catalyst, wherein the catalyst comprises Pd, a non-noble metal component and a carrier, wherein the carrier comprises alumina, a molecular sieve with BEA structure and a modified metal oxide, the modified metal oxide being at least one of titanium oxide, zirconium oxide and cerium oxide; wherein η < 0.3 and θ ≥ 50, η = weight percentage of crystalline phase modified metal oxide in the carrier / chemical composition weight percentage of the modified metal oxide in the carrier, θ = weight percentage of the modified metal oxide on the surface of the carrier / chemical composition weight percentage of the modified metal oxide in the carrier, the titanium oxide being calculated based on TiO2, the cerium oxide being calculated based on CeO2 and the zirconium oxide being calculated based on ZrO2; wherein the non-noble metal component is selected from at least one of Cu, Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, W and Ca.

[0026] The hydrogenation catalyst provided by the present application is used in selective hydrogenation of butadiene and 1-butene isomerization reaction, and has higher activity and higher 1-butene isomerization selectivity than existing hydrogenation catalysts.

[0027] In the present application, the content of each substance in the catalyst is not specifically limited. Preferably, in the catalyst, the content of the carrier is 80-99% by weight based on the total amount of the catalyst, the content of Pd in the form of the element is 0.01-1.0% by weight, and the content of the non-noble metal component in the form of the element is 1-20% by weight; further preferably, in the catalyst, the content of the carrier is 85-95% by weight based on the total amount of the catalyst, the content of Pd in the form of the element is 0.02-0.5% by weight, and the content of the non-noble metal component in the form of the element is 3-15% by weight. The advantage of this preferred embodiment is that, in a C4 fraction with high butadiene content, the active component Pd is easily complexed with butadiene in the C4 fraction, so that Pd is gradually dissolved in the reaction material, resulting in serious loss of the active component Pd, and the loss of the active component Pd is aggravated with the increase of the butadiene content in the reaction material, so that the catalyst loses activity very quickly after a period of operation, and the service life of the catalyst in a material with high butadiene content can only be measured in months or even weeks. The catalyst disclosed in the present application uses Pd as the active component, and by adding a non-noble metal element, the interaction between the active component Pd and the non-noble metal element and the carrier is greatly enhanced, thereby better solving the problem of loss of the active component Pd.

[0028] According to a preferred embodiment of the present application, the non-noble metal component is selected from at least one of Cu, Co and Ni.

[0029] According to a preferred embodiment of the present application, the non-noble metal component is Cu. The advantage of using Cu as the non-noble metal component is that Cu has high butadiene hydrogenation activity, solves the problem of Pd loss, has high desulfurization activity, has better resistance to impurities and poisons, and has better adaptability to sulfur-containing compounds, and can be used to treat sulfur-containing C4 raw materials.

[0030] According to a preferred embodiment of the present application, the weight ratio of Pd and non-noble metal Cu in the catalyst is 0.01:20-1.0:1.0, preferably 0.5:3-0.02:15. By controlling the content of Pd and non-noble metal Cu, the strong interaction between copper and the carrier is regulated to anchor the active metal Pd as a site, which significantly enhances the stability of the active Pd, and at the same time, Cu can timely react with mercaptan sulfur compounds, effectively inhibiting the interaction between sulfur compounds and noble metals, and reducing the influence of sulfur compounds in the C4 fraction on catalyst poisoning.

[0031] In the present application, the amount of each substance in the carrier is not specifically limited, as long as the desired carrier can be obtained. Preferably, the content of the alumina is 50-90% by weight, the content of the molecular sieve with BEA structure is 2-40% by weight, and the content of the modified metal oxide is 1-40% by weight, based on the total amount of the carrier; further preferably, the content of the alumina is 60-80% by weight, the content of the molecular sieve with BEA structure is 10-30% by weight, and the content of the modified metal oxide is 2-15% by weight. The advantage of using this preferred embodiment is that the specific surface area of the carrier is large and the acid amount is appropriate.

[0032] According to a preferred embodiment of the present application, in the carrier, the modified metal oxide is titanium oxide. Preferably, the content of the titanium oxide calculated as TiO2 is 2-20% by weight, for example 5-15% by weight or 5-10% by weight or 2.5-17% by weight or 3-13% by weight, the content of the zirconium oxide calculated as ZrO2 is 0-8% by weight, for example 0-6% by weight or 0-5% by weight or 0-3% by weight or 1-6% by weight, and the content of the cerium oxide calculated as CeO2 is 2-30% by weight, for example 5-15% by weight or 5-10% by weight or 2.5-17% by weight or 15-25% by weight, based on the total amount of the carrier.

[0033] According to a particularly preferred embodiment of the present application, the modified metal oxide is titanium dioxide, and the content of the titanium oxide calculated as TiO2 is 2-20% by weight, preferably 5-15% by weight, based on the total amount of the carrier. The advantage of using this preferred embodiment is that there is a strong interaction between TiO2 and alumina, and there is electron transfer, which is beneficial to the stable dispersion of the metal loaded on the carrier.

[0034] According to the present application, preferably, the modified metal oxide monolayer is dispersed on the mixed matrix of alumina and molecular sieve with BEA structure.

[0035] In the present application, the percentage content of the crystalline phase modified metal oxide is measured by X-ray diffraction and phase-filtered modified Rietveld model, and the percentage content of the crystalline phase modified metal oxide is calculated by fitting method, unless otherwise specified. The phase filtering is described in R.V. Siriwardane, J.A. Poston, G. Evans, Jr. Ind. Eng. Chem. Res. 33 (1994), 2810-2818, and the modified Rietveld model is described in RIQAS rietveld Analysis, Operation Manual, Material Data, Inc., Berkley, CA (1999). The percentage content of the chemical composition of the modified metal oxide is the total content of the modified metal oxide in the carrier, and the percentage content of the chemical composition of the modified metal oxide is measured by X-ray fluorescence method or chemical analysis method.

[0036] In the present application, the weight percentage content of the modified metal oxide on the surface of the carrier is measured by XPS method, and the surface layer thickness is 5 nm from the outer surface.

[0037] In the present application, the structure of the alumina is not specifically limited. Preferably, the catalyst has at least one of the phase structures of γ-alumina, η-alumina, ρ-alumina and χ-alumina. The advantage of using this preferred embodiment is that it has better activity stability.

[0038] According to the present application, preferably, η of the modified metal oxide is 0, and θ is 50-95, and further preferably, θ is 60-90. The advantage of using this preferred embodiment is that the modified metal is dispersed on the surface of the alumina in the form of monolayer, and more modified sites are formed.

[0039] According to the present application, preferably, the ratio of B acid to L acid of the carrier is not less than 0.5, and further preferably, the ratio of B acid to L acid of the carrier is 0.5-5, and still further preferably, the ratio of B acid to L acid of the carrier is 0.8-1.5. The advantage of using this preferred embodiment is that the carrier has acid centers with appropriate strength, and the selectivity of butene isomerization reaction is higher.

[0040] In the present application, B acid and L acid are measured by infrared spectrometer for characterizing the surface acidity of the catalyst.

[0041] According to the present application, preferably, the specific surface area of the catalyst is 150-450 m 2 / g, and the pore volume is 0.3-2 mL / g; further preferably, the specific surface area of the catalyst is 200-400 m 2 / g, and the pore volume is 0.5-1.2 mL / g. The advantage of using this preferred embodiment is that, in the prior art, when alumina is used as a catalyst carrier, due to its acidic characteristics exhibited during the reaction, the olefins and alkynes are polymerized at the surface acid centers, and the generated colloid covers the hydrogenation active centers and blocks the catalyst pores, which seriously affects the activity, stability and service life of the catalyst; in the present application, a modified element, such as titanium oxide, is introduced during the preparation of the carrier, the titanium oxide is mixed with the alumina, the acidity and alkalinity of the catalyst are effectively adjusted, the generation of colloid on the surface of the catalyst is reduced, and the activity, stability and service life of the catalyst are improved. The catalyst has a high specific surface area and pore volume, which is beneficial to the diffusion of reactants and products.

[0042] In the present application, the specific surface area and pore volume of the catalyst are measured by BET testing.

[0043] The second aspect of the present application provides a preparation method of a non-noble metal hydrogenation catalyst, wherein the method comprises the following steps:

[0044] (1) contacting alumina, a molecular sieve with a BEA structure, water and an acid solution to form a slurry; then sequentially performing molding, drying and calcination on the slurry to form a mixed matrix carrier;

[0045] (2) contacting the mixed matrix carrier obtained in step (1) with a gas-carrying modified metal oxide precursor gas stream to obtain a mixed matrix loaded with a modified metal oxide precursor;

[0046] (3) hydrolyzing and calcining the mixed matrix loaded with the modified metal oxide precursor to obtain a carrier;

[0047] (4) introducing a Pd precursor and a non-noble metal component precursor onto the carrier by an impregnation method, and then performing drying and calcination;

[0048] The non-noble metal component is selected from at least one of Cu, Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, W and Ca;

[0049] The modified metal oxide is at least one of titanium oxide, zirconium oxide and cerium oxide.

[0050] The method of the present application is easy to implement, and compared with the traditional catalyst preparation process, the preparation method also simplifies the preparation process and reduces the operation cost in the preparation process.

[0051] According to the method of the present application, preferably, the amounts of the alumina, the molecular sieve with BEA structure, the modified metal oxide, Pd and the non-noble metal component are such that, based on the total amount of the catalyst, the content of the support in the catalyst is 80-99 wt%, the content of Pd in the catalyst is 0.01-1.0 wt% based on the elementary substance, and the content of the non-noble metal component in the catalyst is 1-20 wt% based on the elementary substance; further preferably, the content of the support in the catalyst is 85-95 wt%, the content of Pd in the catalyst is 0.02-0.5 wt% based on the elementary substance, and the content of the non-noble metal component in the catalyst is 3-15 wt% based on the elementary substance.

[0052] According to a preferred embodiment of the present application, the non-noble metal component is selected from at least one of Cu, Co and Ni.

[0053] According to a preferred embodiment of the present application, the non-noble metal component is Cu.

[0054] According to a preferred embodiment of the present application, the weight ratio of Pd and non-noble metal Cu in the catalyst is 0.01:20-1.0:1.0, preferably 0.02:15-0.5:3. By controlling the contents of Pd and non-noble metal Cu, the strong interaction between copper and the support is regulated, which is used as a site to anchor active metal Pd, significantly enhancing the stability of active Pd, while Cu can timely react with mercaptan sulfur-containing compounds, effectively inhibiting the interaction between sulfur-containing compounds and noble metals, and reducing the influence of sulfur-containing compounds in the C4 fraction on the catalyst poisoning.

[0055] In the present application, the type of alumina in step (1) is not specifically limited, as long as it can meet the preparation requirements of the non-noble metal catalyst. Preferably, in step (1), the alumina is selected from at least one of γ-alumina, η-alumina, ρ-alumina, χ-alumina and hydrated alumina, and further preferably, the alumina is selected from at least one of γ-alumina, η-alumina, ρ-alumina and χ-alumina.

[0056] According to the present application, preferably, the hydrated alumina is one or more of boehmite, diaspore, pseudoboehmite, gibbsite, bayerite, nordstrandite and amorphous aluminum hydroxide. Preferably, the average particle size (diameter) of the alumina is 0.5-50 μm, for example, 0.5-30 μm.

[0057] According to the present application, preferably, the specific surface area of the alumina is 100-300 m 2 / g, and the pore volume is preferably 0.8-1.8 mL / g, for example 0.85-1.2 mL / g. 2 / g, and the pore volume is preferably 0.8-1.8 mL / g, for example 0.85-1.2 mL / g.

[0058] The alumina in the above preferred embodiments has the advantages of high specific surface area and large pore volume, high active metal dispersion, and more active sites.

[0059] In the present application, the type of the molecular sieve with BEA structure is not specifically limited. Preferably, the molecular sieve with BEA structure is selected from at least one of hydrogen type beta zeolite molecular sieve, phosphorus-containing beta zeolite molecular sieve, rare earth metal-containing beta zeolite molecular sieve, and beta zeolite molecular sieve containing phosphorus and rare earth metal, and further preferably hydrogen type beta zeolite molecular sieve and / or rare earth metal-containing beta zeolite molecular sieve. Preferably, in the rare earth metal-containing beta zeolite molecular sieve, the rare earth element can be at least one of lanthanum, cerium, praseodymium, and neodymium, and more preferably lanthanum and / or cerium. Preferably, in the phosphorus-containing beta zeolite molecular sieve, the content of phosphorus element is 1-15% by weight based on the total amount of beta zeolite molecular sieve; in the rare earth metal-containing beta zeolite molecular sieve, the content of rare earth metal is 1-10% by weight based on the total amount of beta zeolite molecular sieve; and in the beta zeolite molecular sieve containing phosphorus and rare earth metal, the content of phosphorus element is 3-10% by weight and the content of rare earth metal is 2-8% by weight based on the total amount of beta zeolite molecular sieve. The preferred embodiments have the advantage that the prepared carrier has a suitable amount of acid, which further makes the catalyst more conducive to butene isomerization.

[0060] According to the present application, preferably, the ratio of B acid to L acid of the molecular sieve with BEA structure is 0.8-3.0, and further preferably 0.83-1.25. The preferred embodiments have the advantage that the carrier has acid centers with suitable strength, and the selectivity of butene isomerization reaction is higher.

[0061] According to the present application, preferably, the molar ratio of silicon oxide to alumina of the molecular sieve with BEA structure is 15-40.

[0062] According to a preferred embodiment of the present application, the specific surface area of the molecular sieve with BEA structure is 300-750 m 2 / g, and the pore volume is 0.2-0.8 mL / g, and further preferably the specific surface area is 500-700 m 2 / g, and the pore volume is 0.3-0.7 mL / g. The preferred embodiments have the advantage that the prepared carrier has a large specific surface area, which is conducive to active metal dispersion, has a good pore volume, which is conducive to raw material molecular diffusion, and increases the reactivity.

[0063] In the present application, the type of acid solution in step (1) is selected from a wide range. Preferably, the acid solution is selected from inorganic and / or organic acids soluble in water, and further preferably at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.

[0064] In the present application, the concentration of the acid solution in step (1) is not specifically limited. Preferably, the concentration of the acid solution is 5-40% by weight, and further preferably 10-35% by weight.

[0065] In the present application, the amount of the acid solution in step (1) is not specifically limited. Preferably, the amount of the acid solution is such that the pH of the slurry is 1-5, and further preferably 1.5-4.

[0066] According to the present application, preferably, the solid content of the slurry in step (1) is 20-45% by weight.

[0067] According to the present application, preferably, the specific surface area of the mixed matrix support is not less than 150 m 2 / g, preferably 150-500 m 2 / g, and further preferably 200-400 m 2 / g; further preferably, the pore volume of the mixed matrix support is not less than 0.3 mL / g, preferably 0.3-2 mL / g, and further preferably 0.5-1.8 mL / g. Preferably, the ratio of the specific surface area of the support to the specific surface area of alumina is not less than 90%.

[0068] In the present application, the forming method of the support is suitable for the present application, such as spray drying, extrusion and rolling. Preferably, the forming process of the mixed matrix support in the present application can use the following method: the slurry is spray dried by a spray dryer, and then the obtained microspheres are dried and calcined. Preferably, the spray drying conditions include: pressure 5-12 MPa, inlet temperature 400-700°C, and outlet temperature 100-250°C; further preferably, the pressure is 6-10 MPa, the inlet temperature is 450-600°C, and the outlet temperature is 120-200°C.

[0069] In the present application, the drying conditions in step (1) are selected from a wide range. Preferably, the drying conditions are: temperature 50-250°C, and time 0.5-5 h; further preferably, the temperature is 80-200°C, and the time is 1-4 h.

[0070] In the present application, the calcination conditions in step (1) are selected from a wide range. Preferably, the calcination conditions are: temperature 400-700°C, and time 1-12 h; further preferably, the temperature is 450-650°C, and the time is 2-8 h.

[0071] According to the present application, the modified metal oxide precursor is a substance capable of being vaporized to form a gaseous metal oxide precursor at room temperature to 350°C.

[0072] In the present application, the type of the modified metal oxide precursor in step (2) is not particularly limited. Preferably, the modified metal oxide precursor is at least one of a titanium oxide precursor, a zirconium oxide precursor and a cerium oxide precursor, and further preferably, the modified metal oxide precursor is a titanium oxide precursor. The use of this preferred embodiment has the advantage that the interaction between the titanium oxide precursor and the alumina is strong, which promotes the dispersion of the active metal while facilitating the electron transfer between the supported active metal, thereby promoting the adsorption of butadiene on the surface of the active metal and the hydrogenation selectivity.

[0073] According to a preferred embodiment of the present application, the titanium oxide precursor is selected from at least one of titanium tetrachloride, ethyl titanate, tetrabutyl titanate, isopropyl titanate and titanium acetate, and further preferably, the titanium oxide precursor is titanium tetrachloride.

[0074] According to a preferred embodiment of the present application, the zirconium oxide precursor is selected from at least one of zirconium tetrachloride, zirconium ethoxide, zirconium methoxide, zirconium isopropoxide and tetrabutyl zirconate, and further preferably, the zirconium oxide precursor is zirconium tetrachloride and / or zirconium methoxide.

[0075] According to a preferred embodiment of the present application, the cerium oxide precursor is selected from at least one of cerium trichloride, cerium ethoxide and cerium isopropoxide, and further preferably, the cerium oxide precursor is cerium trichloride and / or cerium isopropoxide.

[0076] In a preferred embodiment, the modified metal oxide is titanium oxide, and the content of the titanium oxide, based on the total amount of the support, is 2-20 wt%, preferably 2-15 wt% in terms of TiO2. The use of this preferred embodiment has the advantage that the titanium oxide monolayer is dispersed on the surface of the support without entering the Al2O3 crystal phase or agglomerating to form TiO2 grains.

[0077] In the present application, the gaseous stream of the modified metal oxide precursor carried by the gas is brought into contact with the mixed matrix support, and the gaseous stream comprises a gas (also referred to as a carrier gas) and a gaseous modified metal oxide precursor. The gas is an inactive gas that does not react with the modified metal oxide precursor. Preferably, in step (2), the gas is anhydrous inactive gas, and the water content in the anhydrous inactive gas is not more than 10 ppm, for example, 3-10 ppm. Preferably, the inactive gas is one or more of nitrogen, helium, neon and argon.

[0078] According to a preferred embodiment of the present application, the content of the modified metal oxide precursor in the gas-carrying modified metal oxide precursor stream is 0.1-5 g / L, preferably 0.5-2 g / L, wherein the content of the modified metal oxide precursor is calculated based on the metal oxide, the titanium oxide is calculated based on TiO2, the zirconium oxide is calculated based on ZrO2, and the cerium oxide is calculated based on CeO2.

[0079] According to the present application, preferably, in step (2), the temperature of the gas is room temperature-350°C, for example, room temperature-300°C or 15-300°C; the room temperature is 15-40°C; the contact temperature is 15-350°C, and the contact pressure is 0.1-10 atm, preferably 0.1-5 atm. The use of this preferred embodiment has the advantage that the modified metal oxide precursor is completely and uniformly hydrolyzed.

[0080] According to the present application, preferably, in step (2), the ratio of the volume flow rate of the gas per minute to the volume of the mixed matrix support is 10-50:1, preferably 15-30:1; wherein the volume of the gas is calculated based on the volume under standard conditions, and the volume of the mixed matrix support is calculated based on the bulk volume.

[0081] According to a preferred embodiment of the present application, in step (2), the mixed matrix support is contacted with the gas-carrying modified metal oxide precursor stream (hereinafter also referred to as the gas stream) in a fluidized state, or the mixed matrix support is contacted with the gas stream in a fixed bed, or the mixed matrix support is contacted with the gas stream under stirring; the fluidized state is a bubbling bed, a turbulent bed, a fast bed, or a transport bed.

[0082] According to a preferred embodiment of the present application, in step (2), the alumina is contacted with the gas-carrying modified metal oxide precursor stream, and the stream and the mixed matrix support of the alumina and the molecular sieve with BEA structure are contacted in a fluidized bed at a volume space velocity of 3-80:1 min -1 , preferably 5-30:1 min -1 , for example 10-25:1 min -1 , wherein the volume flow rate of the stream is calculated based on the volume of the gas under standard conditions, and the volume of the mixed matrix support of the alumina and the molecular sieve with BEA structure is calculated based on the bulk volume; the fluidized bed can be a dispersed fluidized bed, a bubbling bed, or a turbulent bed.

[0083] In the present application, when the modified metal oxide precursor on the mixed matrix support of the alumina and the molecular sieve with BEA structure reaches a preset loading amount, the contact with the gas-carrying modified metal oxide precursor stream is stopped, and a mixed matrix loaded with the modified metal oxide precursor is obtained. The time for which the mixed matrix support of the alumina and the molecular sieve with BEA structure is contacted with the gas-carrying modified metal oxide precursor stream is referred to as the loading time.

[0084] In the present application, the hydrolysis of the mixed matrix generally comprises contacting the mixed matrix support loaded with the modified metal oxide precursor with a gas containing water vapor to contact the modified metal oxide precursor with water, and to hydrolytically convert the modified metal oxide precursor into a hydrolysis product. Preferably, in step (3), the hydrolysis of the mixed matrix loaded with the modified metal oxide precursor is carried out by contacting the mixed matrix loaded with the modified metal oxide precursor with a gas containing water vapor, wherein the ratio of the gas containing water vapor to the mixed matrix (ratio of the volume of the gas containing water vapor to the bulk volume of the mixed matrix under standard conditions) is in the range of 10 to 50:1, preferably in the range of 15 to 30:1, and wherein the water vapor content of the gas containing water vapor is in the range of 0.1 to 100 vol.%, preferably in the range of 3 to 100 vol.%, for example in the range of 10 to 70 vol.%, and wherein the gas other than water vapor is at least one of an inert gas, nitrogen and air; and preferably, the hydrolysis time is in the range of 1 to 50 h, further preferably in the range of 2 to 30 h. The hydrolysis time is generally equal to or greater than the loading time.

[0085] In the present application, the conditions for the calcination are not particularly limited. Preferably, in step (3), the calcination temperature is in the range of 400 to 700°C, and the calcination time is in the range of 1 to 12 h, further preferably, the calcination temperature is in the range of 450 to 650°C, and the calcination time is in the range of 2 to 8 h.

[0086] According to the present application, preferably, in step (3), the calcination atmosphere can be an atmosphere containing oxygen or an atmosphere not containing oxygen.

[0087] According to a preferred embodiment of the present application, the oxygen content of the atmosphere containing oxygen can be in the range of 3 to 100 vol.%, for example an air atmosphere or an oxygen atmosphere.

[0088] In the present application, the type of the Pd precursor in step (4) is not particularly limited, and the Pd precursor conventionally defined in the art is suitable for the present application. Preferably, the Pd precursor is selected from at least one of a metal nitrate, a metal acetate, a metal chloride, a metal carbonate, a metal aceto complex, a metal hydroxide, a metal oxalate complex, a high-valent metal acid, a high-valent metal acid salt and a metal complex, further preferably at least one of a metal nitrate, a high-valent metal acid salt, a high-valent metal acid, an acetate, and more preferably at least one of a nitrate, an acetate and a high-valent metal acid salt.

[0089] According to a preferred embodiment of the present application, the high-valent metal acid salt is selected from at least one of palladium chloride, palladium nitrate, palladium acetate and tetraammine palladium (II) acetate.

[0090] According to a preferred embodiment of the present application, the non-noble metal component precursor is selected from at least one of an alkali carbonate, an acetate, a metal sulfate complex salt and a metal acetate complex salt.

[0091] In the present application, the introduction of the Pd precursor and the non-noble metal component precursor in step (4) by impregnation generally comprises dissolving the Pd precursor and the non-noble metal component precursor in water, adjusting the pH value of the mixed solution with an alkali solution to form an impregnation solution, and then impregnating the support with the impregnation solution to obtain a support impregnated with the Pd precursor and the non-noble metal component precursor. Any impregnation method conventionally defined in the art is suitable for the present application, such as isovolume impregnation and / or excess impregnation. Preferably, when the catalyst contains two or more components of Pd and non-noble metal components, the Pd precursor and the non-noble metal component precursor can be introduced onto the support by co-impregnation or stepwise impregnation. For example, the Pd precursor and the non-noble metal component precursor can be co-impregnated by dissolving the Pd precursor and the non-noble metal component precursor in water to form an impregnation solution, adjusting the pH value of the mixed solution with an alkali solution, mixing the impregnation solution with the support, impregnating the Pd precursor and the non-noble metal component precursor onto the support, and then drying and calcining. The Pd precursor and the non-noble metal component precursor can also be stepwise impregnated by dissolving the Pd precursor and the non-noble metal component precursor in water to form an impregnation solution, adjusting the pH value of the mixed solution with an alkali solution, and then contacting the support with the impregnation solution, respectively, to impregnate the Pd precursor and the non-noble metal component precursor onto the support, respectively, and drying and calcining the support obtained after each impregnation. The order of introducing the precursors of different components is not specifically limited in the present application. For example, the Pd precursor and the non-noble metal component precursor can be dissolved in water to form a solution and then impregnated onto the support, or the Pd precursor and the non-noble metal component precursor can be dissolved in water to form a solution, respectively, and the pH value of the mixed solution is adjusted with an alkali solution, which is used to impregnate the support in sequence. The support obtained after each impregnation is dried and optionally calcined. In a preferred embodiment, the water is at least one of deionized water, distilled water and de-cationic water.

[0092] In a preferred embodiment, the pH value of the solution containing the Pd and optionally the promoter component precursor active component is 7-8.

[0093] In a preferred embodiment, the pH value is adjusted by introducing an alkali solution, preferably an ammonia solution, into the solution containing the Pd and optionally the promoter component precursor active component. Preferably, the concentration of the ammonia solution is 10-30 wt.%.

[0094] In the present application, the impregnation process in step (4) is vacuum impregnation, and an equal volume of active metal precursor solution is added to the carrier. Preferably, the vacuum pressure is 0.01-0.2 MPa, the impregnation temperature is 10-150°C, and the time is 0.5-12 h, and further preferably, the vacuum pressure is 0.05-0.1 MPa, the impregnation temperature is 30-100°C, and the time is 1-5 h. The advantage of using this preferred embodiment is that the content of active components and auxiliary species such as Pd in the molecular sieve channels is increased simultaneously by vacuum impregnation. By taking advantage of the size limitation of the channels, the aggregation of active components such as Pd can be reduced, and the service life of the catalyst can be extended.

[0095] According to a preferred embodiment of the present application, in step (4), the liquid / solid volume ratio of the impregnation solution to the carrier is 0.3-5.0, preferably 0.5-4.0.

[0096] In the present application, the carrier after impregnation is dried and then calcined. In the present application, the conditions for drying and calcining are not specifically limited. Preferably, in step (4), the drying temperature is 50-250°C, and the time is 1-24 h; and further preferably, the drying temperature is 80-200°C, and the time is 2-15 h.

[0097] According to a preferred embodiment of the present application, in step (4), the calcination temperature is 400-700°C, and the calcination time is 0.5-12 h, and further preferably, the calcination temperature is 500-650°C, and the calcination time is 2-8 h. The advantage of using this preferred embodiment is that the active metal is dispersed on the surface of the carrier in the form of an oxide, and is not excessively sintered.

[0098] The third aspect of the present application provides the use of the hydrogenation catalyst of the first aspect in the selective hydrogenation of butadiene and the isomerization of 1-butene.

[0099] According to a preferred embodiment of the present application, the reaction comprises contacting a butadiene-containing raw material with the hydrogenation catalyst of the first aspect to perform the hydrogenation reaction.

[0100] According to a preferred embodiment of the present application, the contact conditions include a reaction temperature of 50-400°C, a pressure of 0.05-3 MPa, and a weight hourly space velocity of 0.5-50 h -1 , and further preferably, a reaction temperature of 80-350°C, a pressure of 0.1-2.0 MPa, and a weight hourly space velocity of 5-30 h -1 . Using the catalyst provided by the present application, high selectivity of butadiene hydrogenation can be achieved at a high space velocity, and the isomerization activity of 1-butene is high, and the catalyst has good sulfur resistance.

[0101] According to a preferred embodiment of the present application, the butadiene-containing raw material is a refinery sulfur-containing FCC byproduct C4 or an ethylene cracking raffinate C4.

[0102] According to one embodiment of the present application, the reaction is carried out in a fixed-bed microreactor under hydrogenation conditions. Preferably, the butadiene-containing feedstock is a hydrogen-containing stream, the hydrogen-containing stream contains 1-10% by volume of hydrogen, 1-50% by volume of 1,3-butadiene, 0-50% by volume of 1-butene, 0-50% by volume of n-butane, and other gases are carrier gases (for example, nitrogen), and the mercaptan content is 10-100 ppm, based on the total volume of the hydrogen-containing stream.

[0103] In one preferred embodiment, the catalyst is subjected to a reduction treatment before use. The present application does not have a particular limitation on the conditions of the reduction. Preferably, the reducing atmosphere is hydrogen and optionally an inert gas (for example, at least one of nitrogen, helium, argon and neon, preferably nitrogen), the hydrogen content is preferably 1-10% by volume, the reduction temperature is 50-200°C, and the time is 2-8h.

[0104] The present application will be described in detail below by way of examples.

[0105] In the examples and comparative examples, the properties of the raw materials used are as follows:

[0106] SB powder: Sasol, Germany, solid content 75% by weight.

[0107] P25 (titanium dioxide): Degussa, Germany, solid content 98% by weight.

[0108] Metallic acid salts and metal salts were purchased from Beijing Chemical Reagent Co., Ltd.

[0109] In each of the examples and comparative examples, the composition of the supported butadiene selective hydrogenation and 1-butene isomerization catalyst was determined by X-ray fluorescence, the butadiene selective hydrogenation and 1-butene isomerization product was obtained by chromatographic analysis, and the hydrogen purity was analyzed by gas chromatography.

[0110] The butadiene selective hydrogenation and 1-butene isomerization experiments of the examples and comparative examples of the present application were carried out in a fixed-bed reactor.

[0111] All X-ray diffraction measurements were performed using a Philips XRG3100 generator equipped with a long fine focus copper X-ray source driven at 40 kV, 30 mA, a Philips 3020 digital goniometer, a Philips 3710 MPD control computer, and a Kevex PSI Peltier-cooled silicon detector. The Kevex detector was operated using a Kevex 4601 ion pump controller, a Kevex 4608 Peltier power supply, a Kevex 4621 detector bias, a Kevex 4561A pulse processor, and a Kevex 4911-A single channel analyzer. Diffraction patterns were obtained using Philips APD version 4.1C software. All Rietveld calculations were performed using Material Data, Inc. Riqas version 3.1C software (Qutokumpu HSC Chemistry for Windows; User's Manual, Qutokumpo Research Oy, Pori, Finland (1999)).

[0112] XPS experiments were performed on a Thermo Fisher ESCALab 250 X-ray photoelectron spectrometer. The excitation source was monochromatic Al Kα X-rays at 1486.6 eV with a power of 150 W. The pass energy used for narrow scans was 30 eV. The base vacuum during analysis was approximately 6.5 x 10 -10 mbar. Binding energies were calibrated using the C1s peak of contaminant carbon (284.8 eV). The weight percent loading of modified metal oxide on the support surface was determined by measuring 10 sample particles and taking the average.

[0113] Determination of B acid and L acid: The surface acidity of the catalyst was characterized by using a Nicolet 560 infrared spectrometer from the U.S. Nicolet Company, and the wave number was 1400-1700 cm -1 -1. The B acid in the catalyst was characterized by a characteristic peak at 1540 cm -1 -1. The L acid in the catalyst was characterized by a characteristic peak at 1450 cm -1 -1. The ratio of B acid to L acid was calculated by integrating the peak areas of the corresponding peaks, and the ratio of the peak area of the characteristic peak of B acid to the peak area of the characteristic peak of L acid.

[0114] Preparation of the support and preparation of the comparative example

[0115] Preparation Example 1

[0116] SB powder was calcined at 500°C for 4 h to obtain γ-Al2O3, and the γ-Al2O3 had a specific surface area of 182 m 2 / g and a pore volume of 1.12 mL / g. The γ-Al2O3 and β zeolite (specific surface area 685.5 m2 / g, pore volume 0.38 mL / g, ratio of B acid to L acid 1.03, molar ratio of silica to alumina 27), water and acid solution (30 wt% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant)) to form a slurry (solid content 28 wt%, pH of the slurry 2.1); then the slurry is shaped (shaping method is spray drying, spray drying is carried out by using a Niro Bowen Nozzle Tower™ model spray dryer, spray drying pressure 9.5 MPa, inlet temperature 500°C, outlet temperature about 150°C), the microspheres obtained by spray drying are first dried at 180°C for 1 h, then calcined at 635°C for 1 h to form a mixed matrix support, the specific surface area of the mixed matrix support is 231.5 m 2 / g, pore volume 1.05 mL / g.

[0117] The above mixed matrix support 500 g is placed in a fluidized reactor (the diameter of the reactor is 10 cm, the height is 40 cm), titanium tetrachloride is placed in a 20°C constant temperature bath, nitrogen (temperature is 25°C) passes through the titanium tetrachloride at a flow rate of 10 L / min and then enters the fluidized reactor from the bottom of the fluidized reactor, after fluidization for 1 h, the nitrogen passing through the titanium tetrachloride bath is stopped; nitrogen (temperature is 25°C) passes through deionized water placed in a 50°C constant temperature bath at a flow rate of 10 L / min and then enters the fluidized reactor from the bottom of the reactor, hydrolysis is carried out for 4 h to obtain a hydrolyzed support. The hydrolyzed support is calcined in an air atmosphere at 550°C for 4 h to obtain a support, which is named S-1. The amounts of the above-mentioned substances are such that the contents of the substances in the support and the properties of the support are as shown in Table 1, and the XRD pattern of the support is shown in Figure 1 .

[0118] Preparation Example 2

[0119] The SB powder is calcined at 500°C for 4 h to obtain γ-Al2O3, the specific surface area of the γ-Al2O3 is 182 m 2 / g, pore volume 1.12 mL / g, the γ-Al2O3 and Reβ molecular sieve (Re is lanthanum, content 5.3 wt%, specific surface area 675.5 m 2 / g, pore volume 1.01 mL / g. 2 / g, pore volume 1.01 mL / g.

[0120] The above mixed matrix support 500 g was placed in a fluidized reactor (the diameter of the reactor was 10 cm and the height was 40 cm), titanium tetrachloride was placed in a 20 °C constant temperature bath, nitrogen (temperature was 25 °C) passed through the titanium tetrachloride at a flow rate of 10 L / min and then entered the fluidized reactor from the bottom of the reactor, after fluidization for 3 h, the nitrogen passing through the titanium tetrachloride bath was stopped; nitrogen (temperature was 25 °C) passed through deionized water placed in a 50 °C constant temperature bath at a flow rate of 10 L / min and then entered the fluidized reactor from the bottom of the reactor, after fluidization, hydrolysis was carried out for 10 h to obtain the hydrolyzed support. The hydrolyzed support was calcined in an air atmosphere at 550 °C for 4 h to obtain the support, which was named S-2. The amounts of the above-mentioned substances were such that the contents of the substances in the support and the properties of the support were as shown in Table 1.

[0121] Preparation Example 3

[0122] The SB powder was calcined at 500 °C for 4 h to obtain γ-Al2O3, the specific surface area of which was 182 m 2 / g, pore volume 1.12 mL / g, the γ-Al2O3 and Hβ molecular sieve (specific surface area 688.4 m 2 / g, pore volume 0.36 mL / g, the ratio of B acid to L acid was 1.25, and the molar ratio of silicon to aluminum was 18), water and an acid solution (15 wt% hydrochloric acid (chemical pure, produced by Beijing Chemical Plant)) to form a slurry (solid content was 28 wt%, and the pH of the slurry was 2.1); then the slurry was shaped (the shaping method was spray drying, and a Niro Bowen Nozzle Tower™ model spray dryer was used for spray drying, the spray drying pressure was 8.5 MPa, the inlet temperature was 500 °C, and the outlet temperature was about 150 °C), and the microspheres obtained by spray drying were first dried at 180 °C for 1 h and then calcined at 635 °C for 1 h to form a mixed matrix support, the specific surface area of the mixed matrix support was 336.8 m 2 / g, and the pore volume was 0.87 mL / g.

[0123] The mixed matrix support 500 g was placed in a fluidized reactor (the diameter of the reactor was 10 cm, and the height was 40 cm), titanium tetrachloride was placed in a 20 °C constant temperature bath, nitrogen (temperature was 25 °C) was passed through the titanium tetrachloride at a flow rate of 10 L / min, and then entered the fluidized reactor from the bottom of the fluidized reactor. After fluidization for 7 h, the nitrogen passing through the titanium tetrachloride bath was stopped. Nitrogen (temperature was 25 °C) was passed through deionized water placed in a 50 °C constant temperature bath at a flow rate of 10 L / min, and then entered the fluidized reactor from the bottom of the reactor. After fluidization, hydrolysis was carried out for 25 h to obtain a hydrolyzed support. The hydrolyzed support was calcined in an air atmosphere at 550 °C for 4 h to obtain a support, which was named S-3. The amounts of the above-mentioned substances were such that the contents of the substances in the support and the properties of the support were as shown in Table 1.

[0124] Preparation Example 4

[0125] The method of Preparation Example 3 was followed, except that titanium tetrachloride and zirconium tetrachloride were placed in 20 °C constant temperature baths, respectively. Nitrogen (temperature was 25 °C) was passed through the titanium tetrachloride and the zirconium tetrachloride at a flow rate of 10 L / min, and then entered the fluidized reactor from the bottom of the fluidized reactor. After fluidization for 6 h, the nitrogen passing through the titanium tetrachloride and the zirconium tetrachloride baths was stopped. Nitrogen (temperature was 25 °C) was passed through deionized water placed in a 50 °C constant temperature bath at a flow rate of 10 L / min, and then entered the fluidized reactor from the bottom of the reactor. After fluidization, hydrolysis was carried out for 30 h to obtain a hydrolyzed support. The hydrolyzed support was calcined in an air atmosphere at 550 °C for 4 h to obtain a support, which was named S-4. The amounts of the above-mentioned substances were such that the contents of the substances in the support and the properties of the support were as shown in Table 1.

[0126] Preparation Example 5

[0127] The method of Preparation Example 3 was followed, except that titanium tetrachloride and cerium trichloride were placed in 20 °C constant temperature baths, respectively. Nitrogen (temperature was 25 °C) was passed through the titanium tetrachloride and the cerium trichloride at a flow rate of 10 L / min, and then entered the fluidized reactor from the bottom of the fluidized reactor. After fluidization for 6 h, the nitrogen passing through the titanium tetrachloride and the zirconium tetrachloride baths was stopped. Nitrogen (temperature was 25 °C) was passed through deionized water placed in a 50 °C constant temperature bath at a flow rate of 10 L / min, and then entered the fluidized reactor from the bottom of the reactor. After fluidization, hydrolysis was carried out for 30 h to obtain a hydrolyzed support. The hydrolyzed support was calcined in an air atmosphere at 550 °C for 4 h to obtain a support, which was named S-5. The amounts of the above-mentioned substances were such that the contents of the substances in the support and the properties of the support were as shown in Table 1.

[0128] Preparation Comparative Example 1

[0129] The SB powder was calcined at 500°C for 4h to obtain γ-Al2O3, which had a specific surface area of 182m 2 / g and a pore volume of 1.12mL / g. The γ-Al2O3, water and an acid solution (30wt% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) were contacted to form a slurry (solid content of 28wt%), and the pH of the slurry was adjusted to 2.1. The slurry was then shaped (the shaping method was spray drying, and a Niro Bowen Nozzle Tower™ model spray dryer was used for the spray drying, the spray drying pressure was 8.5MPa, the inlet temperature was 480°C, and the outlet temperature was about 150°C). The microspheres obtained by the spray drying were first dried at 180°C for 1h, and then calcined at 635°C for 1h to form a mixed matrix support. The mixed matrix support had a specific surface area of 181.5m 2 / g and a pore volume of 1.12mL / g. The support was obtained and named as DS-1. The amounts of the above-mentioned substances were such that the contents of the substances in the support and the properties of the support were as shown in Table 1.

[0130] Preparation of Comparative Example 2

[0131] The SB powder was calcined at 500°C for 4h to obtain γ-Al2O3, which had a specific surface area of 182m 2 / g and a pore volume of 1.12mL / g. The γ-Al2O3, water and an acid solution (30wt% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) were contacted to form a slurry (solid content of 28wt%), and the pH of the slurry was adjusted to 2.1. The slurry was then shaped (the shaping method was spray drying, and a Niro Bowen Nozzle Tower™ model spray dryer was used for the spray drying, the spray drying pressure was 8.5MPa, the inlet temperature was 480°C, and the outlet temperature was about 150°C). The microspheres obtained by the spray drying were first dried at 180°C for 1h, and then calcined at 635°C for 1h to form a mixed matrix support. The mixed matrix support had a specific surface area of 181.5m 2 / g and a pore volume of 1.12mL / g. The γ-Al2O3, water and an acid solution (30wt% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) were contacted to form a slurry (solid content of 28wt%), and the pH of the slurry was adjusted to 2.1. The slurry was then shaped (the shaping method was spray drying, and a Niro Bowen Nozzle Tower™ model spray dryer was used for the spray drying, the spray drying pressure was 8.5MPa, the inlet temperature was 480°C, and the outlet temperature was about 150°C). The microspheres obtained by the spray drying were first dried at 180°C for 1h, and then calcined at 635°C for 1h to form a mixed matrix support. The mixed matrix support had a specific surface area of 181.5m 2 / g and a pore volume of 1.12mL / g. The support was obtained and named as DS-1. The amounts of the above-mentioned substances were such that the contents of the substances in the support and the properties of the support were as shown in Table 1.

[0132] Preparation of Comparative Example 3

[0133] The SB powder was calcined at 500°C for 4h to obtain γ-Al2O3, which had a specific surface area of 182m 2 / g, with a pore volume of 1.12mL / g, γ-Al₂O₃ and Hβ molecular sieve (specific surface area 688.4m²) were added. 2 The microspheres, with a pore volume of 0.36 mL / g, a Brønsted acid to Lewis acid ratio of 1.25, and a silica-alumina molar ratio of 18, are reacted with water and an acid solution (15% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant)) to form a slurry (solid content 28% by weight, pH = 2.1). The slurry is then shaped (by spray drying using a Niro Bowen Nozzle Tower™ spray dryer at a pressure of 7.8 MPa, an inlet temperature of 490°C, and an outlet temperature of approximately 150°C). The microspheres obtained from the spray drying are first dried at 180°C for 1 hour, then calcined at 635°C for 1 hour to form a mixed matrix carrier with a specific surface area of ​​336.8 m². 2 / g, with a pore volume of 0.87mL / g; physically mixed with TiO2 and calcined at 550℃ for 4h in air atmosphere to obtain the support, named DS-3. The amounts of the above substances resulted in the content of each substance in the support and the properties of the support are shown in Table 1. The XRD pattern of the support is shown in... Figure 1 As shown.

[0134] Preparation of Comparative Example 4

[0135] Following the method of Preparation Example 3, the difference lies in that tetrabutyl titanate was mixed and stirred with deionized water for 30 min, and then impregnated onto the mixed matrix support by an equal volume impregnation method. The mixture was then calcined in air at 550°C for 4 h to obtain the support, which was named DS-4. The amounts of the above-mentioned substances, resulting in the content of each substance in the support and the properties of the support, are shown in Table 1. The XRD pattern of the support is shown in... Figure 1 As shown.

[0136] Preparation of Comparative Example 5

[0137] SB powder was calcined at 500℃ for 4 hours to obtain γ-Al2O3, which has a specific surface area of ​​182 m². 2 The microspheres, with a pore volume of 1.12 mL / g, were prepared by contacting γ-Al₂O₃, water, and an acid solution (15% wt% nitric acid (chemically pure, produced by Beijing Chemical Plant)) to form a slurry (solid content 28% wt%, pH = 2.1). The slurry was then shaped (by spray drying using a Niro Bowen Nozzle Tower™ spray dryer at a pressure of 8.3 MPa, inlet temperature of 500°C, and outlet temperature of approximately 150°C). The microspheres obtained from the spray drying were first dried at 180°C for 1 hour, and then calcined at 635°C for 1 hour to form a mixed matrix carrier with a specific surface area of ​​181.5 m². 2 / g, and the pore volume was 1.12 mL / g.

[0138] The mixed matrix support 500 g was placed in a fluidized reactor (the diameter of the reactor was 10 cm, and the height was 40 cm), titanium tetrachloride was placed in a 20 °C constant temperature bath, nitrogen (temperature was 25 °C) passed through the titanium tetrachloride at a flow rate of 10 L / min and then entered the fluidized reactor from the bottom of the fluidized reactor, after fluidization for 3 h, the nitrogen passing through the ethyl titanate bath was stopped; nitrogen (temperature was 25 °C) passed through deionized water placed in a 50 °C constant temperature bath at a flow rate of 10 L / min and then entered the fluidized reactor from the bottom of the reactor, after fluidization, hydrolysis was carried out for 9 h to obtain a hydrolyzed support. The hydrolyzed support was calcined in an air atmosphere at 550 °C for 4 h to obtain a support, which was named DS-5. The amounts of the above-mentioned substances were such that the contents of the substances in the support and the properties of the support were as shown in Table 1.

[0139] Table 1

[0140]

[0141]

[0142] Note: The composition of the support is the result of the modified metal oxide measured by XRF and normalized to alumina. The contents of SiO2, Al2O3, TiO2, ZrO2, CeO2 and the molecular sieve with BEA structure in Table 1 are based on the total amount of the support, wherein the content of Al2O3 is partly derived from the BEA structure molecular sieve and partly derived from the SB powder.

[0143] Catalyst examples and comparative examples

[0144] Examples 1-6

[0145] The precursor of Pd was tetraammine palladium (II) acetate, the precursor of Cu was basic copper carbonate, the precursor of Co was cobalt acetate, the precursor of Ni was nickel acetate, and 20 mL of an impregnation solution was prepared by mixing water and ammonia water (concentration 15 wt%) so that the pH of the impregnation solution was 7.5. The concentration of the impregnation solution was selected according to the catalyst formula, 20 g of the support was taken, and the impregnation solution was slowly added to the support while stirring to allow the impregnation solution to be uniformly loaded on the support. The impregnation temperature was 25 °C, the impregnated support was dried under nitrogen blowing at 120 °C for 3 h, and then calcination was carried out in air, the calcination temperature was 600 °C, and the calcination time was 4 h. The catalyst formula and properties are shown in Table 2, wherein the support is calculated according to the dry basis (calcination at 800 °C for 1 hour), and the noble metal and the non-noble metal are both calculated according to the elemental dry basis.

[0146] Comparative examples 1-5

[0147] Take the precursor of Pd, copper carbonate, cobalt acetate, nickel acetate and water, and ammonia (concentration 15 wt%) to prepare 20 mL impregnation solution, so that the pH of the impregnation solution is 7.5, the concentration of the impregnation solution is selected according to the catalyst formula, take 20 g of the carrier prepared in Comparative Examples 1-5, slowly add the impregnation solution to the carrier, stir while adding, make the impregnation solution uniformly loaded on the carrier, the impregnation temperature is 25℃, the impregnated solid is dried at 120℃ under nitrogen blowing for 3h, and then calcined in air; the calcination temperature is 600℃, and the calcination time is 4h. The catalyst formula is shown in Table 2, wherein the carrier is calculated according to the dry basis (800℃ calcined for 1 hour), and the noble metal Pd and non-noble metal components are calculated according to the elemental dry basis.

[0148] Comparative Example 6

[0149] According to the method of Example 1, except that Pt is used instead of Pd element, the precursor of Pt is taken as platinum nitrate, and the catalyst formula and properties are shown in Table 2.

[0150] Comparative Example 7

[0151] According to the method of Example 1, except that Zn is used instead of Cu element, the precursor of Zn is taken as zinc nitrate, and the catalyst formula and properties are shown in Table 2.

[0152] Table 2 Catalyst formula and properties

[0153]

[0154]

[0155] Test Example

[0156] The catalysts in the above examples and comparative examples were evaluated for selective hydrogenation of butadiene and isomerization of 1-butene in a fixed bed reactor. The reaction was carried out in a fixed bed microreactor (referred to as fixed bed microreactor). The evaluation conditions were as follows: reaction temperature 125℃, reaction pressure (inlet pressure of the reactor) 1.5 MPa, feed gas flow rate 200 mL / min (hydrogen volume fraction 5%, 1,3-butadiene volume fraction 40%, 1-butene volume fraction 20%, mercaptan 35 ppm, and the rest nitrogen), and catalyst loading 5 g. Before use, the catalyst was reduced at 180℃ for 2 hours in a nitrogen atmosphere with a hydrogen volume concentration of 5%. The evaluation results are shown in Table 3.

[0157] wherein,

[0158]

[0159]

[0160] Table 3

[0161]

[0162]

[0163] As shown in Table 3, the butadiene selective hydrogenation and 1-butene isomerization catalyst carrier provided by the application is used for the butadiene selective hydrogenation and 1-butene isomerization catalyst, and the butadiene selective hydrogenation and 1-butene isomerization catalyst has higher conversion activity than the butadiene selective hydrogenation and 1-butene isomerization catalyst prepared by the prior method, has outstanding butadiene selective hydrogenation and 1-butene isomerization activity and selectivity at a lower reaction temperature under the condition of reducing the amount of noble metal, and has better resistance to impurities and poisons, especially has better adaptability to low-sulfur C4 fraction.

[0164] The preferred embodiments of the application are described in detail above, but the application is not limited thereto. Within the technical concept of the application, various simple modifications can be made to the technical solutions of the application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosed content of the application and belong to the protection scope of the application.

[0165] The preferred embodiments of the application are described in detail above, but the application is not limited thereto. Within the technical concept of the application, various simple modifications can be made to the technical solutions of the application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosed content of the application and belong to the protection scope of the application.

Claims

1. A hydrogenation catalyst, characterized in that, The catalyst comprises Pd, a non-noble metal component, and a support, wherein the support comprises alumina, a molecular sieve having a BEA structure, and a modified metal oxide, wherein the modified metal oxide is at least one selected from titanium oxide, zirconium oxide, and cerium oxide; wherein the modified metal oxide has… θ≥50, θ = weight percentage of modified metal oxide on the carrier surface / weight percentage of chemical composition of modified metal oxide in the carrier, where titanium oxide is calculated as TiO2, cerium oxide as CeO2, and zirconium oxide as ZrO2; the non-noble metal component is selected from at least one of Cu, Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, W, and Ca. In the catalyst, based on the total amount of catalyst, the content of the support is 80-99% by weight, the content of Pd (based on elemental content) is 0.01-1.0% by weight, and the content of the non-precious metal component (based on elemental content) is 1-20% by weight.

2. The catalyst according to claim 1, wherein, In the catalyst, based on the total amount of catalyst, the content of the support is 85-95% by weight, the content of Pd as elemental is 0.02-0.5% by weight, and the content of the non-precious metal component as elemental is 3-15% by weight.

3. The catalyst according to claim 1, wherein, The non-precious metal component is selected from at least one of Cu, Co and Ni.

4. The catalyst according to claim 3, wherein, The non-precious metal component is Cu.

5. The catalyst according to claim 4, wherein, In the catalyst, the weight ratio of Pd to non-noble metal Cu is 0.01:20-1.0:1.

0.

6. The catalyst according to claim 1 or 2, wherein, In the catalyst, based on the total amount of support, the content of alumina is 50-90% by weight, the content of molecular sieve with BEA structure is 2-40% by weight, and the content of modified metal oxide is 1-40% by weight.

7. The catalyst according to claim 6, wherein, In the catalyst, based on the total amount of support, the content of alumina is 60-80% by weight, the content of molecular sieve with BEA structure is 10-30% by weight, and the content of modified metal oxide is 2-15% by weight.

8. The catalyst according to claim 1, wherein, The modified metal oxide is at least one of titanium oxide, zirconium oxide, and cerium oxide. Based on the total amount of the carrier, the content of titanium oxide (calculated as TiO2) is 2-20% by weight, zirconium oxide (calculated as ZrO2) is 0-8% by weight, and cerium oxide (calculated as CeO2) is 0-8% by weight.

9. The catalyst according to claim 1, wherein, The catalyst has a phase structure of at least one of γ-alumina, η-alumina, p-alumina and χ-alumina.

10. The catalyst according to claim 1, wherein, The molecular sieve with the BEA structure is selected from at least one of hydrogen-type β-zeolite molecular sieves, phosphorus-containing β-zeolite molecular sieves, rare earth metal-containing β-zeolite molecular sieves, and β-zeolite molecular sieves containing both phosphorus and rare earth metals.

11. The catalyst according to claim 1, wherein, The modified metal oxide The value is 0, and θ is 50-95.

12. The catalyst according to claim 1, wherein, In the catalyst, the ratio of Brønsted acid to Lewis acid in the support is not less than 0.

5.

13. The catalyst according to claim 12, wherein, In the catalyst, the ratio of Brønsted acid to Lewis acid in the support is 0.5-5.

14. The catalyst according to claim 1, wherein, The catalyst has a specific surface area of ​​150-450 m². 2 / g, pore volume is 0.3-2mL / g.

15. The catalyst according to claim 14, wherein, The catalyst has a specific surface area of ​​200-400 m². 2 / g, pore volume is 0.5-1.2mL / g.

16. The method for preparing the hydrogenation catalyst according to claim 1, wherein, The method includes the following steps: (1) Alumina, molecular sieve with BEA structure, water and acid solution are brought into contact to form a slurry; the slurry is then successively shaped, dried and calcined to form a mixed matrix carrier; (2) The mixed matrix carrier obtained in step (1) is brought into contact with the gas-carried modified metal oxide precursor gas flow to obtain a mixed matrix loaded with modified metal oxide precursor. (3) Hydrolyze the mixed matrix of the loaded modified metal oxide precursor, calcine it, and obtain the support; (4) Pd precursor and non-precious metal component precursor are introduced onto the carrier by impregnation, followed by drying and calcination; The non-precious metal component is selected from at least one of Cu, Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, Ce, W and Ca; The modified metal oxide is at least one of titanium oxide, zirconium oxide and cerium oxide; The amounts of alumina, BEA-structured molecular sieve, modified metal oxide, Pd, and non-precious metal components used in the catalyst are such that, based on the total amount of catalyst, the content of the support is 80-99% by weight, the content of Pd (based on elemental composition) is 0.01-1.0% by weight, and the content of the non-precious metal components (based on elemental composition) is 1-20% by weight.

17. The preparation method according to claim 16, wherein, In the catalyst, based on the total amount of catalyst, the content of the support is 85-95% by weight, the content of Pd as elemental is 0.02-0.5% by weight, and the content of the non-precious metal component as elemental is 3-15% by weight.

18. The preparation method according to claim 16, wherein, The non-precious metal component is selected from at least one of Cu, Co and Ni.

19. The preparation method according to claim 18, wherein, The non-precious metal component is Cu.

20. The preparation method according to claim 19, wherein, In the catalyst, the weight ratio of Pd to non-noble metal Cu is 0.01:20-1.0:1.

0.

21. The preparation method according to claim 16, wherein, In step (1), the alumina is selected from at least one of γ-alumina, η-alumina, p-alumina, χ-alumina and hydrated alumina.

22. The preparation method according to claim 16, wherein, In step (1), the specific surface area of ​​the alumina is 100-300 m². 2 / g, with a pore volume of 0.3-2.0 mL / g.

23. The preparation method according to claim 22, wherein, In step (1), the specific surface area of ​​the alumina is 120-250 m². 2 / g, pore volume is 0.8-1.8mL / g.

24. The preparation method according to claim 16, wherein, In step (1), the molecular sieve with the BEA structure is selected from at least one of hydrogen-type β-zeolite molecular sieve, phosphorus-containing β-zeolite molecular sieve, rare earth metal-containing β-zeolite molecular sieve, and β-zeolite molecular sieve containing phosphorus and rare earth metal.

25. The preparation method according to claim 16, wherein, In step (1), the acid solution is selected from water-soluble inorganic acids and / or organic acids.

26. The preparation method according to claim 25, wherein, In step (1), the acid solution is selected from at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.

27. The preparation method according to claim 16, wherein, In step (1), the amount of acid solution used is such that the pH value of the slurry is 1-5.

28. The preparation method according to claim 27, wherein, In step (1), the amount of acid solution used is such that the pH value of the slurry is 1.5-4.

29. The preparation method according to claim 16, wherein, In step (1), the specific surface area of ​​the mixed matrix carrier is not less than 150 m². 2 / g.

30. The preparation method according to claim 29, wherein, In step (1), the specific surface area of ​​the mixed matrix carrier is 150-500 m². 2 / g.

31. The preparation method according to claim 30, wherein, In step (1), the specific surface area of ​​the mixed matrix carrier is 200-400 m². 2 / g.

32. The preparation method according to claim 16, wherein, In step (1), the pore volume of the mixed matrix carrier is not less than 0.3 mL / g.

33. The preparation method according to claim 32, wherein, In step (1), the pore volume of the mixed matrix carrier is 0.3-2 mL / g.

34. The preparation method according to claim 33, wherein, In step (1), the pore volume of the mixed matrix carrier is 0.5-1.5 mL / g.

35. The preparation method according to claim 16, wherein, In step (1), the drying conditions are: temperature of 50-250℃ and time of 0.5-5h; the calcination conditions are: temperature of 400-700℃ and time of 1-12h.

36. The preparation method according to claim 16, wherein, In step (2), the modified metal oxide precursor is at least one of titanium oxide precursor, zirconium oxide precursor and cerium oxide precursor.

37. The preparation method according to claim 36, wherein, The titanium oxide precursor is selected from at least one of titanium tetrachloride, ethyl titanate, tetrabutyl titanate, isopropyl titanate, and titanium acetate; the zirconium oxide precursor is selected from at least one of zirconium tetrachloride, zirconium ethanol, zirconium methoxide, zirconium isopropoxide, and tetrabutyl zirconate; the cerium oxide precursor is selected from at least one of cerium trichloride, cerium ethanol, and cerium isopropoxide.

38. The preparation method according to claim 16, wherein, In step (2), the modified metal oxide is titanium oxide, and the content of titanium oxide, calculated as TiO2, is 2-20% by weight, based on the total amount of the carrier.

39. The preparation method according to claim 38, wherein, In step (2), the content of titanium oxide, calculated as TiO2, is 5-15% by weight, based on the total amount of the carrier.

40. The preparation method according to claim 16, wherein, In step (2), the gas is an anhydrous inactive gas, and the water content in the anhydrous inactive gas does not exceed 10 ppm.

41. The preparation method according to claim 16, wherein, In step (2), the content of modified metal oxide precursor in the gas stream carrying the modified metal oxide precursor is 0.1-5 g / L, wherein the content of modified metal oxide precursor is calculated as metal oxide.

42. The preparation method according to claim 16, wherein, In step (2), the gas temperature is room temperature - 350°C, the contact temperature is 15-350°C, and the contact pressure is 0.1-10 atm.

43. The preparation method according to claim 16, wherein, In step (2), the ratio of the volumetric flow rate of the gas per minute to the volume of the mixed matrix carrier is 10-80:1; wherein the volume of the gas is measured in terms of volume under standard conditions, and the volume of the mixed matrix carrier is measured in terms of bulk volume; in step (2), the mixed matrix carrier is in contact with the gas flow of the modified metal oxide precursor carried by the gas in a fluidized state, or in contact with the gas flow under stirring; the fluidized state is a bubbling bed, a turbulent bed, a fast bed, or a conveying bed.

44. The preparation method according to claim 43, wherein, In step (2), the ratio of the gas volume flow rate per minute to the volume of the mixed matrix carrier is 20-60:1; wherein the gas volume is measured in terms of volume under standard conditions, and the mixed matrix carrier volume is measured in terms of bulk volume.

45. The preparation method according to claim 16, wherein, In step (3), the mixed matrix of the modified metal oxide precursor is prepared by hydrolysis as follows: the mixed matrix of the modified metal oxide precursor is contacted with a gas containing water vapor, wherein the ratio of the gas containing water vapor to the mixed matrix is ​​3-50:1, the ratio being the ratio of the volume of the gas containing water vapor to the volume of the mixed matrix under standard conditions, wherein the proportion of water vapor in the gas containing water vapor to the total volume of the gas is 0.1-100% by volume, and the other gases in the gas containing water vapor are at least one of inert gas, nitrogen and air.

46. ​​The preparation method according to claim 45, wherein, In step (3), the ratio of the water vapor-containing gas to the mixed matrix is ​​10-30:1, where the ratio is the ratio of the water vapor-containing gas to the mixed matrix volume under standard conditions, and the proportion of water vapor in the total gas volume is 3-100%.

47. The preparation method according to claim 16, wherein, In step (3), the hydrolysis time is 1-50h.

48. The preparation method according to claim 47, wherein, In step (3), the hydrolysis time is 2-30 hours.

49. The preparation method according to claim 16, wherein, In step (3), the roasting temperature is 400-700℃ and the roasting time is 1-12h.

50. The preparation method according to claim 16, wherein, In step (4), the pH of the solution of Pd and the non-precious metal component precursor is 7-8.

51. The preparation method according to claim 16, wherein, In step (4), the immersion temperature is 10-150℃ and the time is 1-24h.

52. The preparation method according to claim 16, wherein, In step (4), the drying temperature is 50-250℃ and the time is 1-24h.

53. The preparation method according to claim 16, wherein, In step (4), the roasting temperature is 400-700℃ and the roasting time is 0.5-12h.

54. The use of the hydrogenation catalyst according to any one of claims 1-15 in the selective hydrogenation of butadiene and the isomerization reaction of 1-butene.

55. The application according to claim 54, wherein, The reaction involves contacting a butadiene-containing feedstock with the hydrogenation catalyst described in any one of claims 1-15 to carry out a hydrogenation reaction.

56. The application according to claim 55, wherein, The contact conditions include: a reaction temperature of 50-400℃, a pressure of 0.05-3MPa, and a weight hourly space velocity of 0.5-50h⁻¹. -1 .

57. The application according to claim 55, wherein, The butadiene-containing feedstock is C4 by-product from sulfur-containing FCC in a refinery or C4 raffinate from ethylene cracking.

58. The application according to claim 55, wherein, The butadiene-containing feedstock is a hydrogen-containing stream, with the following volume fractions: hydrogen gas fraction 1-10%, 1,3-butadiene volume fraction 1-50%, 1-butene volume fraction 0-50%, n-butane volume fraction 0-50%, other gases serving as carrier gases, and thiol content 10-100 ppm.

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