Carrier compositions, methods of making and using same

Abstract

The present application relates to the technical field of catalyst carrier preparation, and discloses a carrier composition, a preparation method and application thereof.The carrier composition comprises alumina, a molecular sieve with BEA structure and modified metal oxide, wherein the modified metal oxide is at least one of titanium oxide, zirconium oxide and cerium oxide;η of the modified metal oxide is less than 0.3, and θ is greater than or equal to 50;η is the weight percentage of the crystalline phase modified metal oxide in the carrier composition / the chemical composition weight percentage of the modified metal oxide in the carrier composition, and θ is the weight percentage of the modified metal oxide on the surface of the carrier composition / the chemical composition weight percentage of the modified metal oxide in the carrier composition; wherein, the ratio of B acid to L acid of the carrier composition is not less than 0.5.The carrier composition can be used for selective hydrogenation of butadiene and 1-butene isomerization reaction, and improves the reaction performance of butadiene hydrogenation.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalyst carrier preparation, and particularly relates to a carrier composition and a preparation method and application thereof. BACKGROUND

[0002] In petroleum chemical industry, naphtha steam cracking produces abundant C4 olefins, and C4 deep processing can produce a series of products such as alkylated gasoline, methyl tert-butyl ether, polymerization gasoline, oligomerization gasoline, tert-butyl alcohol, which can be used as clean blending products in gasoline. Low carbon, energy saving and environmental protection are the biggest features of C4 deep processing. In recent years, the refining and ethylene production capacity in China has been increasing, and the MTO process has also been significantly improved, which promotes the continuous growth of the total amount of C4, and with the continuous enrichment of the total amount of raw materials, the C4 deep processing industry is developing rapidly. However, a small amount of diene or alkyne is often contained in these C4 olefins; in the downstream olefin polymerization process, diene or alkyne is more likely to be adsorbed on the surface of the polymerization catalyst than mono-olefin, thereby causing the catalyst to be poisoned and inactivated, so the selective hydrogenation of diene to generate mono-olefin is often used to solve this problem.

[0003] In addition, in recent years, with the rapid development of the automobile industry, people's demand for fuel is increasing, and the isooctane process as a high-quality additive for gasoline has attracted widespread attention. At present, the raw materials for producing isooctane are mainly mixed C4 hydrocarbons from refineries, and concentrated sulfuric acid is used as a catalyst in this process. However, the butadiene in the raw material can react with concentrated sulfuric acid to form a soluble sulfuric ester, thereby affecting the catalytic effect of concentrated sulfuric acid.

[0004] 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 separating methanol and ether from the outlet material of the etherization device (carbon four after ether), 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 MTBE device 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.

[0005] In addition, the extraction distillation method is often used in industry to remove butadiene in C4 hydrocarbons, but it is difficult to reduce it to below 10 ppm, and research has found that selective hydrogenation of butadiene can effectively reduce the concentration of butadiene in C4 hydrocarbons, which is of great significance to the production of industrial alkylated oil, so it is urgent to develop a high-efficiency catalyst for selective hydrogenation of 1,3-butadiene.

[0006] The catalysts for selective hydrogenation of unsaturated hydrocarbons mainly include Au, Pd, Pt and other noble metal series. Although noble metals have high dissociation and activation capacity for hydrogen, they also have very high activity in the application of selective hydrogenation of unsaturated hydrocarbons. However, the limited natural resources and high price of noble metals restrict their long-term development in the field of catalysis. During the preparation and actual application of noble metal catalysts, the metal particles are prone to agglomeration, which reduces the contact area between the reactants and the metal active centers, and thus 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 to further study the performance of the catalyst as a selective hydrogenation catalyst for unsaturated hydrocarbons.

[0007] The preparation approaches of high-efficiency catalysts include: 1. adding other metals to the noble metal catalyst to modify the catalyst, so as to reduce the adsorption capacity of the active sites of the catalyst for mono-olefins, and thus to improve the hydrogenation selectivity of the catalyst for generating mono-olefins; and 2. modifying the carrier, so that the generated mono-olefins can easily and quickly leave the surface of the catalyst, and thus to avoid the further hydrogenation of the mono-olefins to generate alkanes.

[0008] Patent application CN1238239A provides a catalyst for selective hydrogenation of di-olefins in C4 alkylation raw materials and a preparation method thereof. The catalyst uses δ, θ and α mixed-phase alumina as a carrier, and prepares a supported Pd catalyst to improve the activity and selectivity of the catalyst. However, it does not show whether the catalyst has the 1-butene skeletal isomerization performance. Patent application CN1621396A provides a method for removing di-olefins in C4 alkylation raw materials. The method uses a Pd catalyst supported by a carrier with superparamagnetic property and a fluidized bed hydrogenation process. Although the method has the advantages of high butadiene hydrogenation activity and low butene loss rate, it does not show whether the catalyst has the 1-butene skeletal isomerization performance. Patent application CN101850250A uses the method of modifying the surface of the carrier with magnesium-aluminum spinel and introducing the additive Pb to improve the service life of the Pd catalyst. However, it does not mention whether the catalyst has the 1-butene skeletal isomerization performance. Patent application CN103418379A uses the method of modifying the carrier with calcium oxide and introducing WO3 as an additive to improve the mono-olefin yield and sulfur resistance of the Pd catalyst. However, it does not mention whether the catalyst has the 1-butene skeletal isomerization performance. Patent application CN1676214A introduces two additives X1 and X2 into the Pd catalyst supported by 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. The application also provides a pretreatment method for alkylation raw materials. The butadiene hydrogenation rate is more than 99%, and the 1-butene isomerization rate can reach 70%. However, it does not mention the reaction performance of the butadiene hydrogenation selectivity. SUMMARY

[0009] The present application aims to overcome the problem of poor butadiene selective hydrogenation performance and 1-butene isomerization rate in the prior art, and provides a carrier composition, a preparation method and application thereof, which can be used as a carrier of a butadiene selective hydrogenation and 1-butene isomerization catalyst, and can improve the hydrogenation and skeletal isomerization activity and selectivity of the catalyst.

[0010] To achieve the above-mentioned object, the present application provides a carrier composition, which comprises alumina, a molecular sieve with BEA structure and a modified metal oxide, wherein 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 composition / chemical composition weight percentage content of the modified metal oxide in the carrier composition, θ = weight percentage content of the modified metal oxide on the surface of the carrier composition / chemical composition weight percentage content of the modified metal oxide in the carrier composition, 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 ratio of B acid to L acid of the carrier composition is not less than 0.5.

[0011] The present application provides a preparation method of the carrier composition, which comprises the following steps:

[0012] (1) contacting alumina, a molecular sieve with BEA structure, water and an acid solution to form a slurry; then forming, drying and calcining 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 the carrier composition;

[0015] wherein the modified metal oxide is at least one of titanium oxide, zirconium oxide and cerium oxide; wherein the amounts of the alumina, the molecular sieve with BEA structure and the modified metal oxide are such that, based on the total amount of the carrier composition, the content of the alumina is 50-90 wt%, the content of the molecular sieve with BEA structure is 2-40 wt%, and the content of the modified metal oxide is 1-40 wt%.

[0016] The present application provides the application of the carrier composition in the butadiene selective hydrogenation and 1-butene isomerization catalyst.

[0017] The carrier composition provided by the application contains the molecular sieve with BEA structure and modified metal oxide, has lower η value and higher θ value, and can be used as a catalyst for selective hydrogenation of butadiene and isomerization of 1-butene, preferably for solid acid alkylation of raw material olefins to remove butadiene, and can improve the hydrogenation activity, skeletal isomerization activity and / or selectivity of the catalyst.

[0018] The preparation method of the carrier composition provided by the application can obtain the carrier composition provided by the application, and the obtained carrier composition has lower η value and higher θ value, and the preparation method is easy to implement. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 is the XRD spectrum of the carrier composition containing alumina, beta molecular sieve and titanium oxide. In the figure, 1 is the XRD spectrum of the carrier composition of Example 1 of the application; in the figure, 2 is the XRD spectrum of the alumina supported titanium oxide carrier composition prepared by impregnation method of Comparative Example 4 of the application for introducing modified metal TiO2; in the figure, 3 is the XRD spectrum of the physical mixture of alumina and titanium dioxide of Comparative Example 3 of the application;

[0020] In the XRD curve, 2θ = 25.37°, 48.12°, 53.97° and 55.1° are the diffraction peaks of TiO2(anatase). DETAILED DESCRIPTION

[0021] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values should be interpreted as approximately including values near the reported values. For ranges including both endpoints, any intervening values between the endpoints should be interpreted as being included in the range. For ranges excluding either or both endpoints, any intervening values including the excluded endpoint, are interpreted to be included in the range. For values which are less than or greater than a certain value, values from the lower limit, to the value itself, to the upper limit, are interpreted as being included in the range. For values which are less than or greater than a certain value, values from the lower limit, to the value itself, to the upper limit, are interpreted as being included in the range. For values which are less than or greater than a certain value, values from the lower limit, to the value itself, to the upper limit, are interpreted as being included in the range.

[0022] The first aspect of the application provides a carrier composition, which 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 the η of the modified metal oxide is less than 0.3, and the θ is greater than or equal to 50, η = weight percentage content of crystalline modified metal oxide in the carrier composition / chemical composition weight percentage content of the modified metal oxide in the carrier composition, θ = weight percentage content of the modified metal oxide on the surface of the carrier composition / chemical composition weight percentage content of the modified metal oxide in the carrier composition, the titanium oxide being calculated as TiO2, the cerium oxide being calculated as CeO2, and the zirconium oxide being calculated as ZrO2; wherein the ratio of B acid to L acid of the carrier composition is not less than 0.5.

[0023] The carrier composition provided by the present application introduces a molecular sieve with BEA structure and a modified metal oxide, the modified metal oxide has a relatively low η value and a relatively high θ value, and can be used as a catalyst for selective hydrogenation of butadiene, isomerization of 1-butene, and especially as a catalyst for removing butadiene from raw material olefins by solid acid alkylation, thereby improving the hydrogenation activity and / or selectivity of the catalyst.

[0024] The carrier composition provided by the present application can be used for preparing a catalyst for selective hydrogenation of butadiene and isomerization of 1-butene, preferably as a carrier of a catalyst for selective hydrogenation of butadiene and isomerization of 1-butene, and can also be used as a carrier of other hydrogenation reaction catalysts or oxidation catalysts, such as an unsaturated hydrocarbon hydrogenation catalyst, an organic matter complete oxidation catalyst or a NO oxidation catalyst. Meanwhile, when the carrier composition of the present application is used for selective hydrogenation of butadiene and isomerization of 1-butene, the carrier composition can meet the requirement of a relatively high acid center strength and density for the isomerization of butene, inhibit the generation of by-products such as propylene, pentene and high carbon number olefins, improve the anti-coking and deactivation ability of the catalyst, and has better product selectivity, conversion activity and longer activity period in the isomerization reaction, thereby prolonging the regeneration cycle and being more conducive to the long-period and stable operation of the device.

[0025] In the present application, the B acid and the L acid are measured by an infrared spectrometer.

[0026] In the present application, the amount of each substance in the carrier composition is not specifically limited, as long as the required carrier composition can be obtained. Preferably, the content of the alumina is 50-90 wt%, the content of the molecular sieve with BEA structure is 2-40 wt%, and the content of the modified metal oxide is 1-40 wt%, based on the total amount of the carrier composition; further preferably, the content of the alumina is 60-80 wt%, the content of the molecular sieve with BEA structure is 10-30 wt%, and the content of the modified metal oxide is 2-15 wt%. The advantage of this preferred embodiment is that the specific surface area of the carrier composition is large and the acid amount is appropriate.

[0027] In a preferred embodiment, the modified metal oxide in the carrier composition is titanium oxide. Preferably, the content of the titanium oxide calculated based on TiO2 is 2-20 wt%, for example 5-15 wt% or 5-10 wt% or 2.5-17 wt% or 3-13 wt%, the content of the zirconium oxide calculated based on ZrO2 is 0-8 wt%, for example 0-6 wt% or 0-5 wt% or 0-3 wt% or 1-6 wt%, and the content of the cerium oxide calculated based on CeO2 is 2-30 wt%, for example 5-15 wt% or 5-10 wt% or 2.5-17 wt% or 15-25 wt%, based on the total amount of the carrier composition.

[0028] In a particularly preferred embodiment, the modified metal oxide is titanium dioxide, and the content of titanium oxide, based on the total amount of the carrier composition, is 2 to 20% by weight, preferably 5 to 15% by weight, calculated as TiO2. The advantage of this preferred embodiment is that there is a strong interaction between TiO2and alumina, and there is electron transfer, which is advantageous for the stable dispersion of the metal supported on the carrier composition.

[0029] According to the present application, preferably, the modified metal oxide monolayer is dispersed on the mixed matrix of alumina and molecular sieve having BEA structure.

[0030] In the present application, the percentage content of the crystalline modified metal oxide is measured by X-ray diffraction and phase-filtered modified Rietveld model using a fitting method, unless otherwise specified. For phase filtering, see R. V. Siriwardane, J. A. Poston, G. Evans, Jr. Ind. Eng. Chem. Res. 33 (1994), 2810-2818, and for the modified Rietveld model, see RIQAS rietveld Analysis, Operation Manual, Material Data, Inc., Berkley, CA (1999). The chemical composition percentage content of the modified metal oxide is the total content of the modified metal oxide in the carrier composition, and the chemical composition percentage content of the modified metal oxide is measured by X-ray fluorescence method or chemical analysis method.

[0031] In the present application, the weight percentage content of the modified metal oxide on the surface of the carrier composition is measured by XPS method, and the surface layer thickness is measured in the range of 5 nm from the outer surface.

[0032] In the present application, the structure of the alumina is not particularly limited. Preferably, the carrier composition has the phase structure of at least one of γ-alumina, η-alumina, ρ-alumina and χ-alumina. The advantage of this preferred embodiment is that it has better activity stability.

[0033] According to the present application, preferably, the specific surface area of the carrier composition is 150 to 500 m 2 / g, and the pore volume is 0.3 to 2 mL / g; further preferably, the specific surface area of the carrier composition is 200 to 400 m 2The specific surface area of the carrier composition is preferably 300-600 m2 / g, and the pore volume is preferably 0.5-1.5 mL / g. Preferably, the specific surface area of the carrier composition is reduced by a ratio of ≤ 15% compared with the mixed matrix carrier of pure alumina and molecular sieve with BEA structure (alumina not modified by introduction of a modified metal element). The advantage of this preferred embodiment is that the carrier composition has a large specific surface area, which is beneficial to the dispersion of the active metal.

[0034] According to the present application, preferably, the η of the modified metal oxide is 0, and the θ is 50-95, and further preferably, the θ is 60-90. The advantage of this preferred embodiment is that the modified metal is dispersed on the surface of the alumina in a monolayer form, forming more modified sites.

[0035] According to the present application, preferably, the ratio of B acid to L acid of the carrier composition is 0.5-5. The advantage of this preferred embodiment is that the carrier composition has acid sites of suitable strength, and the selectivity of the butene isomerization reaction is higher.

[0036] The second aspect of the present application provides a method for preparing a carrier composition, wherein the method comprises the following steps:

[0037] (1) contacting alumina, molecular sieve with BEA structure, water and acid solution to form a slurry; and then sequentially subjecting the slurry to shaping, drying and calcination to form a mixed matrix carrier;

[0038] (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 the modified metal oxide precursor;

[0039] (3) hydrolyzing and calcining the mixed matrix loaded with the modified metal oxide precursor to obtain the carrier composition;

[0040] wherein the modified metal oxide is at least one of titanium oxide, zirconium oxide and cerium oxide; and the amounts of the alumina, the molecular sieve with BEA structure and the modified metal oxide are such that, in the carrier composition, 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 composition.

[0041] According to the method of the present application, preferably, the amounts of the alumina, the molecular sieve with BEA structure and the modified metal oxide are such that, in the carrier composition, 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, based on the total amount of the carrier composition.

[0042] The carrier composition preparation method provided by the application can obtain the carrier composition provided by the application, the obtained carrier composition has a relatively low η value and a relatively high θ value, the preparation method is easy to implement, and the carrier composition provided by the application is used in selective hydrogenation of butadiene and 1-butene isomerization, and butene selectivity is relatively high.

[0043] Compared with a traditional preparation process, the preparation method also simplifies the preparation process and reduces operation cost in the preparation process.

[0044] In the application, the type of the alumina in step (1) is not specifically limited, as long as it can meet actual requirements. 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.

[0045] According to the 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.

[0046] According to the application, preferably, the specific surface area of the alumina is 100-300 m 2 / g, and the pore volume is 0.3-2 mL / g; further preferably, the specific surface area of the alumina is preferably 120-350 m 2 / g, and the pore volume is preferably 0.8-1.8 mL / g, for example, 0.85-1.2 mL / g.

[0047] According to the application, preferably, the specific surface area of the obtained carrier composition is reduced by ≤15% compared with the specific surface area of the alumina. The advantage of using this preferred embodiment is that the specific surface area of the carrier composition is large, which is beneficial to dispersion of the active metal.

[0048] In a preferred embodiment, the molecular sieve with BEA structure in the carrier composition can be hydrogen-type beta zeolite molecular sieve, and can also be beta zeolite molecular sieve modified by metal elements and / or non-metal elements. 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 phosphorus and rare earth metal-containing beta zeolite molecular sieve, and is 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 is 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 phosphorus and rare earth metal-containing beta zeolite molecular sieve, 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 advantage of using this preferred embodiment is that the carrier composition prepared has a suitable amount of acid, which is beneficial to butene isomerization.

[0049] 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 is further preferably 0.83-1.25. The advantage of using this preferred embodiment is that the carrier composition has acid centers with suitable strength, and the selectivity of butene isomerization reaction is higher.

[0050] According to the present application, preferably, the molar ratio of silicon oxide to aluminum oxide of the molecular sieve with BEA structure is 15-40.

[0051] In a preferred embodiment, 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 is further preferably the specific surface area is 500-700 m 2 / g, and the pore volume is 0.3-0.7 mL / g. The advantage of using this preferred embodiment is that the carrier composition prepared has a large specific surface area, which is beneficial to the dispersion of active metals, has a good pore volume, which is beneficial to the diffusion of raw material molecules, and increases the reactivity.

[0052] 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 at least one of inorganic acid and / or organic acid soluble in water, and is further preferably at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.

[0053] 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, further preferably 10-35% by weight.

[0054] 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 value of the slurry is 1-5, further preferably 1.5-4.

[0055] According to the present application, preferably, the solid content of the slurry in step (1) is 20-45% by weight.

[0056] 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, 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, further preferably 0.5-1.8 mL / g. Preferably, the specific surface area of the obtained support composition is reduced by ≤15% compared to the specific surface area of alumina.

[0057] In the present application, the forming method of the conventional support is suitable for the present application, such as spray drying, extrusion forming and rolling ball forming. Preferably, the forming process of the mixed matrix support in the present application can adopt 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℃, outlet temperature 100-250℃; further preferably, pressure 6-10 MPa, inlet temperature 450-600℃, outlet temperature 120-200℃.

[0058] In the present application, the drying conditions in step (1) are selected in a wide range. Preferably, the drying conditions are: temperature 50-250℃, time 0.5-5 h; further preferably, temperature 80-200℃, time 1-4 h.

[0059] In the present application, the calcination conditions in step (1) are selected in a wide range. Preferably, the calcination conditions are: temperature 400-700℃, time 1-12 h; further preferably, temperature 450-650℃, time 2-8 h.

[0060] According to the present application, the modified metal oxide precursor is a substance capable of gasifying to form a gaseous metal oxide precursor at room temperature-350℃.

[0061] In the present application, the type of modified metal oxide precursor in step (2) is not specifically 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 electron transfer between the supported active metal, thereby promoting the adsorption of butadiene on the surface of the active metal and hydrogenation selectivity.

[0062] In a preferred embodiment, 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.

[0063] In a preferred embodiment, 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.

[0064] In a preferred embodiment, 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.

[0065] In a preferred embodiment, the modified metal oxide is a titanium oxide, and the content of the titanium oxide, based on the total amount of the support composition, is 2-20 wt%, preferably 5-15 wt%, based on TiO2. The use of this preferred embodiment has the advantage that the titanium oxide is monolayer-dispersed on the surface of the support, without entering the Al2O3 crystal phase or agglomerating to form TiO2 grains.

[0066] In the present application, the gas-carrying modified metal oxide precursor stream is brought into contact with the mixed matrix support, and the 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 of 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.

[0067] In a preferred embodiment, 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, based on the metal oxide, i.e. TiO2 for titanium oxide, ZrO2 for zirconium oxide and CeO2 for cerium oxide.

[0068] According to the present application, preferably, in step (2), the temperature of the gas is from room temperature to 350°C, for example, from room temperature to 300°C or from 15 to 300°C; the room temperature is from 15 to 40°C; the contact temperature is from 15 to 350°C, and the contact pressure is from 0.1 to 10 atm, preferably from 0.1 to 5 atm. The advantage of using this preferred embodiment is that the modified metal oxide precursor is completely and uniformly hydrolyzed.

[0069] 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 from 10 to 50:1, preferably from 15 to 30:1; wherein the volume of the gas is measured at standard conditions, and the volume of the mixed matrix support is measured as the bulk volume.

[0070] In a preferred embodiment, in step (2), the mixed matrix support is contacted with the modified metal oxide precursor gas stream carried by the gas in a fluidized state, or the mixed matrix support is contacted with the modified metal oxide precursor gas stream in a fixed bed, or the mixed matrix support is contacted with the modified metal oxide precursor gas stream under stirring; the fluidized state is a bubbling bed, a turbulent bed, a fast bed or a transport bed.

[0071] In a preferred embodiment, in step (2), the alumina is contacted with the modified metal oxide precursor gas stream carried by the gas, and the gas stream and the mixed matrix support of alumina and molecular sieve with BEA structure are contacted in a fluidized bed at a volume space velocity of from 3 to 80:1 min -1 , preferably from 5 to 30:1 min -1 , for example from 10 to 25:1 min -1 , wherein the volume flow rate of the gas stream is measured at standard conditions, the volume of the mixed matrix support of alumina and molecular sieve with BEA structure is measured as the bulk volume, and the fluidized bed can be a dispersed fluidized bed, a bubbling bed or a turbulent bed.

[0072] In the present application, when the modified metal oxide precursor on the mixed matrix support of alumina and molecular sieve with BEA structure reaches the preset loading amount, the contact with the modified metal oxide precursor gas stream carried by the gas is stopped, and a mixed matrix loaded with the modified metal oxide precursor is obtained. The time for which the mixed matrix support of alumina and molecular sieve with BEA structure is contacted with the modified metal oxide precursor gas stream carried by the gas is referred to as the loading time.

[0073] 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 hydrolyze 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 10-50:1, preferably in the range of 15-30:1, and wherein the water vapor in the gas containing water vapor is in the range of 0.1-100 vol%, preferably in the range of 3-100 vol%, for example in the range of 10-70 vol%, and wherein the gas other than water vapor in the gas containing water vapor is at least one of an inert gas, nitrogen and air; and preferably, the hydrolysis time is in the range of 1-50 h, further preferably in the range of 2-30 h. The hydrolysis time is generally equal to or greater than the loading time.

[0074] 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 400-700°C, and the calcination time is in the range of 1-12 h, further preferably, the calcination temperature is in the range of 450-650°C, and the calcination time is in the range of 2-8 h.

[0075] According to the present application, preferably, the calcination atmosphere can be an atmosphere containing oxygen or an atmosphere not containing oxygen.

[0076] In a preferred embodiment, the atmosphere containing oxygen can have an oxygen content in the range of 3-100 vol%, for example an air atmosphere or an oxygen atmosphere.

[0077] The third aspect of the present application provides the use of the support composition according to the first aspect in a 1-butene isomerization catalyst.

[0078] In a preferred embodiment, the use of the support composition in combination with an active metal component to prepare a catalyst in a butadiene selective hydrogenation, 1-butene isomerization reaction.

[0079] In a preferred embodiment, the active metal component is an oxide of the active metal and / or an elemental form of the active metal.

[0080] In a preferred embodiment, the active metal is selected from at least one of a metal of subgroup 8, a metal of subgroup 7, a metal of subgroup 5, a metal of subgroup 6, a metal of subgroup 1, a rare earth element, an alkaline earth metal and a metal of the fourth main group; further preferably, at least one of Pd, Pt, Cu and Ni.

[0081] According to the present application, the preparation method of the catalysts commonly defined in the art is suitable for the present application, for example, the catalysts can be prepared by impregnating the support composition with a solution of the active component precursor, usually comprising dissolving the active component precursor in water to form an impregnation solution, and then impregnating the support composition with the impregnation solution to obtain the support composition impregnated with the active metal component precursor. The impregnation method can be the existing impregnation method, for example, it can be the method of equal volume impregnation or excess impregnation or unsaturated impregnation, which will not be described here in detail, and the person skilled in the art can select according to the conventional requirements.

[0082] The present application provides a support composition which can be used to prepare a 1-butene isomerization catalyst with high activity and high selectivity for butadiene selective hydrogenation.

[0083] According to the present application, the hydrogenation reaction comprises butadiene selective hydrogenation and 1-butene isomerization reaction in a hydrogen-containing gas stream, and the reaction is carried out in a fixed bed micro-reactor. Preferably, the raw gas is a hydrogen-containing stream, the volume fraction of hydrogen is 0.1-5%, the volume fraction of 1,3-butadiene is 1-50%, the volume fraction of 1-butene is 1-50%, and the other gas is a carrier gas (for example, nitrogen). Preferably, the reaction conditions are as follows: the reaction temperature is 50-200°C, the reaction pressure is 0.05-2.5 MPa, the raw gas weight hourly space velocity is 0.5-50 h -1 .

[0084] In a preferred embodiment, the catalyst can be reduced and passivated before use. The present application does not have special limitations on the conditions of the reduction. Preferably, the reducing atmosphere is hydrogen and optionally an inert atmosphere (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. The present application does not have special limitations on the conditions of the passivation. Preferably, the passivation atmosphere is oxygen and optionally an inert atmosphere (for example, at least one of nitrogen, helium, argon and neon, preferably nitrogen), the oxygen content is preferably 5-10% by volume, the passivation temperature is 20-50°C, and the time is 1-10h.

[0085] The present application will be described in detail by way of examples.

[0086] In the examples and comparative examples, the properties of the raw materials used are as follows:

[0087] SB powder: Germany Sasol Company, solid content 75% by weight.

[0088] P25 (titanium dioxide): Germany Degussa Company, solid content 98% by weight.

[0089] Metallic salts and metal salts were purchased from Beijing Chemical Reagent Co., Ltd. of China National Pharmaceutical Group.

[0090] 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 obtained by gas chromatographic analysis.

[0091] 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.

[0092] 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. The 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 Manual, Qutokumpo Research Oy, Pori, Finland (1999)).

[0093] 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 and 150 W power. 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 of modified metal oxide on the surface of the support composition was determined by measuring 10 sample particles and taking the average.

[0094] Determination of B acid and L acid: the surface acidity of the catalyst was characterized using a Nicolet 560 infrared spectrometer from the United States Nicolet Company, the wave number was 1400-1700 cm -1 . The B acid in the catalyst was characterized by a characteristic peak at 1540 cm -1 . The L acid in the catalyst was characterized by a characteristic peak at 1450 cm -1characteristic peaks of the B acid and the L acid, and the ratio of the B acid to the L acid refers to the ratio of the peak area of the characteristic peak of the B acid to the peak area of the characteristic peak of the L acid.

[0095] Example 1

[0096] 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 and Reβmolecular sieve (Re is lanthanum, content is 5.3wt%, specific surface area is 675.5m 2 / g, pore volume is 0.38mL / g, the ratio of the B acid to the L acid is 1.03, and the molar ratio of silicon to aluminum is 27) were contacted with water and an acid solution (30wt% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) to form a slurry (solid content is 28wt%), and the pH of the slurry was adjusted to 2.1. The slurry was shaped (the shaping method was spray drying, and the spray drying was performed using a Niro Bowen Nozzle Tower™ model spray dryer, the spray drying pressure was 9.5MPa, the inlet temperature was 500°C, and the outlet temperature was about 150°C). The microspheres obtained by 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 231.5m 2 / g and a pore volume of 1.05mL / g.

[0097] The above-mentioned 500g of the mixed matrix support was placed in a fluidized reactor (the diameter of the reactor was 10cm, and the height was 40cm). Titanium tetrachloride was placed in a 20°C constant temperature bath. Nitrogen (temperature is 25°C) passed through the titanium tetrachloride at a flow rate of 10L / min, and then entered the fluidized reactor from the bottom of the fluidized reactor. After fluidization for 1h, the nitrogen passing through the titanium tetrachloride bath was stopped. Nitrogen (temperature is 25°C) passed through deionized water placed in a 50°C constant temperature bath at a flow rate of 10L / min, and then entered the fluidized reactor from the bottom of the reactor. Hydrolysis was performed for 4h to obtain a hydrolyzed support. The hydrolyzed support was calcined in an air atmosphere at 550°C for 4h to obtain a support composition, which was named S-1. The amounts of the above-mentioned substances were such that the contents of the substances in the support composition and the properties of the support composition were as shown in Table 1, and the XRD pattern of the support composition is shown in Figure 1. Figure 1

[0098] Example 2

[0099] 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 and Reβmolecular sieve (Re is lanthanum, content is 5.3wt%, specific surface area is 675.5m 2 ​ / g, pore volume 1.01 mL / g. 2 / g, pore volume 1.01 mL / g.

[0100] 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 a support composition, which was named S-2. The amounts of the above-mentioned substances were such that the contents of the substances in the support composition and the properties of the support composition were as shown in Table 1.

[0101] Example 3

[0102] The SB powder was calcined at 500 °C for 4 h to obtain γ-Al2O3, which had a specific surface area of 182 m 2 / g, pore volume 1.12 mL / g, 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% of hydrochloric acid (chemical pure, produced by Beijing Chemical Plant) were contacted 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 spray drying was carried out using a Niro Bowen Nozzle Tower™ model spray dryer, the spray drying pressure was 8.5 MPa, the inlet temperature was 500 °C, and the outlet temperature was about 150 °C); 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, which had a specific surface area of 336.8 m2 / g, and a pore volume of 0.87 mL / g.

[0103] The mixed matrix support 500 g was placed in a fluidized reactor (10 cm in diameter and 40 cm in height). Titanium tetrachloride was placed in a 20 °C constant temperature bath. Nitrogen gas (25 °C) was passed through the titanium tetrachloride at a rate of 10 L / min and then into the fluidized reactor from the bottom of the reactor. After 7 h of fluidization, the nitrogen gas was stopped from passing through the titanium tetrachloride bath. Nitrogen gas (25 °C) was passed through deionized water placed in a 50 °C constant temperature bath at a rate of 10 L / min and then into the fluidized reactor from the bottom of the reactor. After fluidization, the hydrolysis was carried out for 25 h to obtain the hydrolyzed support. The hydrolyzed support was calcined in air at 550 °C for 4 h to obtain the support composition, which was designated S-3. The amounts of the above-mentioned substances were such that the contents of the substances in the support composition and the properties of the support composition were as shown in Table 1.

[0104] Example 4

[0105] The procedure of Example 3 was followed, except that titanium tetrachloride and zirconium tetrachloride were placed in 20 °C constant temperature baths, respectively. Nitrogen gas (25 °C) was passed through the titanium tetrachloride and the zirconium tetrachloride at a rate of 10 L / min and then into the fluidized reactor from the bottom of the reactor. After 6 h of fluidization, the nitrogen gas was stopped from passing through the baths of the titanium tetrachloride and the zirconium tetrachloride. Nitrogen gas (25 °C) was passed through deionized water placed in a 50 °C constant temperature bath at a rate of 10 L / min and then into the fluidized reactor from the bottom of the reactor. After fluidization, the hydrolysis was carried out for 30 h to obtain the hydrolyzed support. The hydrolyzed support was calcined in air at 550 °C for 4 h to obtain the support composition, which was designated S-4. The amounts of the above-mentioned substances were such that the contents of the substances in the support composition and the properties of the support composition were as shown in Table 1.

[0106] Example 5

[0107] The procedure of Example 3 was followed, except that titanium tetrachloride and cerium trichloride were placed in 20 °C constant temperature baths, respectively. Nitrogen gas (25 °C) was passed through the titanium tetrachloride and the cerium trichloride at a rate of 10 L / min and then into the fluidized reactor from the bottom of the reactor. After 6 h of fluidization, the nitrogen gas was stopped from passing through the baths of the titanium tetrachloride and the zirconium tetrachloride. Nitrogen gas (25 °C) was passed through deionized water placed in a 50 °C constant temperature bath at a rate of 10 L / min and then into the fluidized reactor from the bottom of the reactor. After fluidization, the hydrolysis was carried out for 30 h to obtain the hydrolyzed support. The hydrolyzed support was calcined in air at 550 °C for 4 h to obtain the support composition, which was designated S-5. The amounts of the above-mentioned substances were such that the contents of the substances in the support composition and the properties of the support composition were as shown in Table 1.

[0108] Comparative Example 1

[0109] 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 was 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 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 spray drying were first dried at 180°C for 1h, and then calcined at 635°C for 1h to form a mixed matrix support, which had a specific surface area of 181.5m 2 / g and a pore volume of 1.12mL / g; a support composition was obtained, and was named DS-1. The amounts of the above-mentioned substances were such that the contents of the substances in the support composition and the properties of the support composition were as shown in Table 1.

[0110] Comparative Example 2

[0111] 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 and Reβ molecular sieve (Re is cerium, the content was 5.5wt%, the specific surface area was 675.5m 2 / g and a pore volume of 1.12mL / g, the γ-Al2O3 and Reβ molecular sieve (Re is cerium, the content was 5.5wt%, the specific surface area was 675.5m 2 / g and a pore volume of 1.12mL / g; a support composition was obtained, and was named DS-1. The amounts of the above-mentioned substances were such that the contents of the substances in the support composition and the properties of the support composition were as shown in Table 1.

[0112] Comparative Example 3

[0113] 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 and Hβ molecular sieve (with a specific surface area of 688.4m 2 / g, a pore volume of 0.36mL / g, a ratio of B acid to L acid of 1.25, and a Si / Al molar ratio of 18), water and an acid solution (15wt% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) were contacted to form a slurry (with a 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 7.8MPa, the inlet temperature was 490°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 336.8m 2 / g, and a pore volume of 0.87mL / g. TiO2was physically mixed with the mixed matrix support, and the mixture was calcined at 550°C for 4h in an air atmosphere to obtain a support composition, which was named as DS-3. The amounts of the above-mentioned substances were such that the contents of the substances in the support composition and the properties of the support composition were as shown in Table 1, and the XRD pattern of the support composition was as shown in Figure 1 .

[0114] Comparative Example 4

[0115] The method of Example 3 was followed, except that the tetrabutyl titanate was mixed with deionized water and stirred for 30min, and the mixture was impregnated into the mixed matrix support in an equal volume impregnation manner. The mixture was calcined at 550°C for 4h in an air atmosphere to obtain a support composition, which was named as DS-4. The amounts of the above-mentioned substances were such that the contents of the substances in the support composition and the properties of the support composition were as shown in Table 1, and the XRD pattern of the support composition was as shown in Figure 1 .

[0116] Comparative Example 5

[0117] The SB powder was calcined at 500°C for 4h to obtain γ-Al2O3, which had a specific surface area of 182m 2 / g, pore volume 1.12 mL / g. The γ-Al2O3, water and acid solution (15 wt% nitric acid (chemically pure, produced by Beijing Chemical Plant) were contacted to form a slurry (solid content 28 wt%), and the pH of the slurry was adjusted to 2.1. The slurry was then shaped (shaping method: spray drying, using a Niro Bowen Nozzle Tower™ model spray dryer, spray drying pressure 8.3 MPa, inlet temperature 500°C, outlet temperature about 150°C). 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 181.5 m 2 / g, pore volume 1.12 mL / g.

[0118] 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 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 reactor. After fluidization for 3 h, the nitrogen passing through the ethyl titanate bath was stopped. Nitrogen (temperature 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 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 composition, which was named DS-5. The amounts of the above substances were such that the contents of the substances in the support composition and the properties of the support composition were as shown in Table 1.

[0119] Table 1

[0120]

[0121]

[0122] Note: The composition of the support composition is the result of XRF measurement of the modified metal oxide after normalization of the 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 composition, wherein part of the Al2O3 content is derived from the BEA structure molecular sieve, and part is derived from the SB powder.

[0123] Catalyst Preparation Example 1

[0124] An impregnation solution was prepared by dissolving 0.27 g of palladium (II) acetate tetraammine in 20 mL of water and ammonia (15 wt% concentration) to give a pH of 7.5. The solution was then added slowly to 19.84 g of S-1 carrier while stirring to ensure uniform loading of the solution onto the carrier. The impregnation temperature was 25°C. The impregnated solid was dried under a nitrogen purge at 120°C for 3 hours and then calcined in air at 600°C for 4 hours. The catalyst was designated as CAT-1. The catalyst formulation is shown in Table 2, where the carrier is calculated on a dry basis (calcined at 800°C for 1 hour) and the noble metal is calculated on a pure metal dry basis.

[0125] Catalyst Preparation Example 2-5

[0126] Catalysts were prepared according to Catalyst Preparation Example 1 using the impregnation method, except that the carrier was replaced with S-2 to S-5. The catalyst formulations for Catalyst Preparation Examples 2-5 are shown in Table 2, where the carrier is calculated on a dry basis (calcined at 800°C for 1 hour) and the noble metal is calculated on a pure metal dry basis.

[0127] Catalyst Preparation Comparative Examples 1-5

[0128] Catalysts were prepared according to Catalyst Preparation Example 1 using the impregnation method, except that the carrier was replaced with DS-1 to DS-5. The catalyst formulations are shown in Table 2, where the carrier is calculated on a dry basis (calcined at 800°C for 1 hour) and the noble metal is calculated on a pure metal dry basis.

[0129] Table 2 Catalyst Formulations

[0130]

[0131]

[0132] Test Example

[0133] Catalyst Test Examples 1-5 and Catalyst Test Comparative Examples 1-5: The above catalysts were evaluated for selective hydrogenation of butadiene and isomerization of 1-butene in a fixed bed reactor. The evaluation was performed in a fixed bed microreactor under the following conditions: reaction temperature 180°C, reaction pressure (inlet pressure) 1.5 MPa, feed gas flow rate 200 mL / min (hydrogen volume fraction 5%, 1,3-butadiene volume fraction 20%, 1-butene volume fraction 20%, and the balance nitrogen), and catalyst loading 5 g. Prior to use, the catalysts were reduced at 180°C for 2 hours in a nitrogen atmosphere with a hydrogen volume fraction of 5% and then passivated at 30°C for 2 hours in a nitrogen atmosphere with an oxygen volume fraction of 8%. The evaluation results are shown in Table 3.

[0134] wherein,

[0135]

[0136]

[0137] Table 3

[0138]

[0139]

[0140] As can be seen from Table 3, the butadiene selective hydrogenation and 1-butene isomerization catalyst carrier composition provided by the present application for 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 art method, and has higher isobutene selectivity under the condition of the same active metal component.

[0141] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present 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 present application, and all fall within the protection scope of the present application.

Claims

1. A carrier composition, characterized in that, The carrier composition comprises alumina, a molecular sieve with BEA structure and modified metal oxide, the modified metal oxide being at least one of titanium oxide, zirconium oxide and cerium oxide; wherein η of the modified metal oxide is less than 0.3 and θ is greater than or equal to 50, η = weight percentage content of crystalline phase modified metal oxide in the carrier composition / chemical composition weight percentage content of modified metal oxide in the carrier composition, θ = weight percentage content of modified metal oxide on the surface of the carrier composition / chemical composition weight percentage content of modified metal oxide in the carrier composition, 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 ratio of B acid to L acid of the carrier composition is not less than 0.5; 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 composition.

2. The carrier composition of claim 1, wherein, 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, based on the total amount of the carrier composition.

3. The carrier composition of claim 1 or 2, wherein, The modified metal oxide is titanium oxide, and the content of the titanium oxide calculated based on TiO2 is 2-20% by weight, based on the total amount of the carrier composition.

4. The carrier composition of claim 3, wherein, The content of the titanium oxide calculated based on TiO2 is 5-15% by weight, based on the total amount of the carrier composition.

5. The carrier composition of claim 1 or 2, wherein, The carrier composition has the phase structure of at least one of γ-alumina, η-alumina, ρ-alumina and χ-alumina.

6. The carrier composition of claim 1 or 2, wherein, The molecular sieve with BEA structure in the carrier composition 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.

7. The carrier composition of claim 1 or 2, wherein, The specific surface area of the carrier composition is 150-500 m 2 / g, and the pore volume is 0.3-2 mL / g.

8. The carrier composition of claim 7, wherein, The specific surface area of the carrier composition is 200-400 m 2 / g, and the pore volume is 0.5-1.5 mL / g.

9. The carrier composition of claim 1 or 2, wherein, The η of the modified metal oxide is 0 and the θ is 50-95.

10. The carrier composition of claim 1 or 2, wherein, The ratio of B acid to L acid of the carrier composition is 0.5-5.

11. A method of preparing the carrier composition of claim 1, wherein, The method comprises the following steps: (1) contacting alumina, a molecular sieve with BEA structure, water and an acid solution to form a slurry; and then sequentially performing shaping, drying and calcination on the slurry to form a mixed matrix carrier; (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; (3) hydrolyzing and calcining the mixed matrix loaded with the modified metal oxide precursor to obtain a carrier composition; The modified metal oxide is at least one of titanium oxide, zirconium oxide and cerium oxide; and the alumina, the molecular sieve with BEA structure and the modified metal oxide are used in an amount such that, based on the total amount of the carrier composition, 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.

12. The method of making according to claim 11, wherein, In step (1), the alumina is selected from at least one of γ-alumina, η-alumina, ρ-alumina, χ-alumina and hydrated alumina.

13. The method of making according to claim 11, wherein, In step (1), the alumina has a specific surface area of 100-300 m 2 / g and a pore volume of 0.3-2.0 mL / g.

14. The production method according to claim 13, wherein In step (1), the alumina has a specific surface area of 120-250 m 2 / g and a pore volume of 0.8-1.8 mL / g.

15. The method of making according to claim 11, wherein, In step (1), 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.

16. The method of making according to claim 11, wherein, In step (1), the acid solution is selected from inorganic acid and / or organic acid soluble in water.

17. The method of making according to claim 16, wherein, In step (1), the acid solution is at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.

18. The method of making according to claim 11, wherein, In step (1), the acid solution is used in an amount such that the pH value of the slurry is 1-5.

19. The method of making according to claim 18, wherein, In step (1), the acid solution is used in an amount such that the pH value of the slurry is 1.5-4.

20. The method of manufacturing according to claim 11, wherein, In step (1), the mixed matrix support has a specific surface area of not less than 150 m 2 / g.

21. The method of making according to claim 20, wherein, In step (1), the mixed matrix support has a specific surface area of 150-500 m 2 / g.

22. The method of making according to claim 21, wherein, In step (1), the mixed matrix support has a specific surface area of 200-400 m 2 / g.

23. The method of manufacturing according to claim 11, wherein, In step (1), the mixed matrix support has a pore volume of no less than 0.3 mL / g.

24. The method of manufacturing according to claim 23, wherein, In step (1), the mixed matrix support has a pore volume of 0.3-2 mL / g.

25. The method of manufacturing according to claim 24, wherein, In step (1), the mixed matrix support has a pore volume of 0.5-1.5 mL / g.

26. The method of manufacturing according to claim 11, wherein, In step (1), the drying condition is that the temperature is 50-250 ℃ and the time is 0.5-5 h.

27. The method of manufacturing according to claim 11, wherein, In step (1), the calcination condition is that the temperature is 400-700 ℃ and the time is 1-12 h.

28. The method of manufacturing according to claim 11, wherein, In step (2), the modified metal oxide precursor is at least one of titanium oxide precursor, zirconium oxide precursor and cerium oxide precursor.

29. The method of making according to claim 28, wherein, In step (2), the titanium oxide precursor is at least one of titanium tetrachloride, ethyl titanate, tetrabutyl titanate, isopropyl titanate and titanium acetate; the zirconium oxide precursor is at least one of zirconium tetrachloride, zirconium ethoxide, zirconium methoxide, zirconium isopropoxide and tetrabutyl zirconate; and the cerium oxide precursor is at least one of cerium trichloride, cerium ethoxide and cerium isopropoxide.

30. The method of manufacturing according to claim 11, wherein, In step (2), the modified metal oxide is titanium oxide, and the content of the titanium oxide, based on the total amount of the support composition, is 2-20% by weight in terms of TiO2.

31. The method of manufacturing according to claim 30, wherein, In step (2), the content of the titanium oxide, based on the total amount of the support composition, is 5-15% by weight in terms of TiO2.

32. The method of manufacturing according to claim 11, wherein, In step (2), the gas is anhydrous inactive gas, and the water content in the anhydrous inactive gas is no more than 10 ppm.

33. The method of manufacturing according to claim 11, wherein, In step (2), the content of the modified metal oxide precursor in the gas stream carrying the modified metal oxide precursor is 0.1-5 g / L, wherein the content of the modified metal oxide precursor is based on the metal oxide.

34. The method of manufacturing according to claim 11, wherein, In step (2), the temperature of the gas is room temperature-350 ℃, the contact temperature is 15-350 ℃, and the contact pressure is 0.1-10 atm.

35. The method of manufacturing according to claim 11, wherein, 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; wherein the volume of the gas is based on the volume under standard conditions, and the volume of the mixed matrix support is based on the bulk volume.

36. The method of manufacturing according to claim 35, wherein, In step (2), the ratio of the volume flow rate of the gas per minute to the volume of the mixed matrix support is 15-30:1; wherein the volume of the gas is based on the volume under standard conditions, and the volume of the mixed matrix support is based on the bulk volume.

37. The method of manufacturing according to claim 11, wherein, The mixed matrix support described in step (2) is contacted with a gas-carrying modified metal oxide precursor stream in a fluidized state, or under stirring; the fluidized state is a bubbling bed, a turbulent bed, a fast bed or a transport bed.

38. The method of manufacturing according to claim 11, wherein, In step (3), the hydrolysis of the mixed matrix support loaded with the modified metal oxide precursor is carried out by contacting the mixed matrix support loaded with the modified metal oxide precursor with a water vapor-containing gas, the ratio of the water vapor-containing gas to the mixed matrix support is 10-50:1, the ratio is the ratio of the water vapor-containing gas to the bulk volume of the mixed matrix support under standard state, the proportion of water vapor in the water vapor-containing gas is 0.1-100% by volume, and the other gas in the water vapor-containing gas is at least one of an inert gas, nitrogen and air.

39. The method of manufacturing according to claim 38, wherein, In step (3), the ratio of the water vapor-containing gas to the mixed matrix support is 15-30:1, the ratio is the ratio of the water vapor-containing gas to the bulk volume of the mixed matrix support under standard state, and the proportion of water vapor in the water vapor-containing gas is 3-100% by volume.

40. The method of manufacturing according to claim 39, wherein, In step (3), the hydrolysis time of the hydrolysis is 1-50 h.

41. The method of manufacturing according to claim 40, wherein, In step (3), the hydrolysis time of the hydrolysis is 2-30 h.

42. The method of manufacturing according to claim 11, wherein, In step (3), the calcination temperature is 400-700℃, and the calcination time is 1-12 h.

43. Use of the support composition described in any one of claims 1-10 in a 1-butene isomerization catalyst.

Images