Modified silicon oxide-containing material and preparation method and application thereof, hydrogenation catalyst and preparation method and application thereof

Abstract

The invention provides a modified silicon oxide-containing material and a preparation method and application thereof, and a hydrogenation catalyst and a preparation method and application thereof. The invention provides a modified silicon oxide-containing material, the modified silicon oxide-containing material comprises a silicon oxide-containing material and a modification auxiliary agent, the modification auxiliary agent comprises at least one of oxides of VIB group metal, VIIB group metal and VIII group metal, and the crystallinity of the auxiliary agent metal oxide in the modified silicon oxide-containing material is below 30%. The modified silicon oxide-containing material provided by the invention is uniform in pore size distribution and has a developed pore structure.

Description

Technical Field

[0001] The invention relates to the technical field of catalytic hydrogenation, and in particular to a modified silicon oxide-containing material, a preparation method and application thereof, a hydrogenation catalyst, a preparation method and application thereof. Background Art

[0002] Butanol is an important organic chemical raw material and solvent. It can be directly used as a raw material for synthetic plastics, coatings, and additives. Plasticizers prepared with butanol as raw material are widely used in various plastics and rubber products. For a long time, the main methods for industrial butanol production include fermentation, propylene carbonyl synthesis, Reppe method, and acetaldehyde alcohol condensation method. Due to various limitations, all production methods except carbonyl synthesis have been eliminated. Propylene carbonyl synthesis is also called hydroformylation synthesis. The process of propylene carbonyl synthesis to produce butanol includes propylene formylation to obtain n-butyraldehyde and isobutyraldehyde, followed by catalytic hydrogenation of butyraldehyde to obtain the product butanol. Among them, the formylation process is divided into high-pressure cobalt method, modified cobalt method, high-pressure rhodium method, and modified rhodium method. The modified rhodium method has the advantages of low temperature, low pressure, high rate, few side reactions, and long life of rhodium catalyst, and is widely used. Regardless of the method used to produce butanol by carbonyl synthesis, it is necessary to go through the step of catalytic hydrogenation of butyraldehyde. There are two main routes for hydrogenation of butyraldehyde: gas phase method and liquid phase method. At present, most of the industrial butanol production units use gas phase hydrogenation process with copper-based catalysts. Representative catalyst brands include NCH6-1 / NCH6-2 developed by Sinopec Nanhua Group Research Institute and VAH-1 / VAH-2 developed by Daqing Petrochemical Research Institute, all of which are copper-zinc-aluminum catalysts. The performance of copper-based catalysts for butanol hydrogenation plays a decisive role in the production efficiency of butanol units, so in-depth research and development of copper-based catalysts have continued to appear in papers and patents in recent years.

[0003] CN102350360A discloses a method for preparing a gas-phase aldehyde hydrogenation catalyst by the Nanjing Chemical Research Institute, which uses nitrates of components such as copper, zinc, and aluminum to coprecipitate with a precipitant, and simultaneously adds a small amount of an auxiliary agent. The obtained catalyst has good low-temperature activity and selectivity.

[0004] CN1695802A discloses a method for preparing a copper-zinc aldehyde hydrogenation to alcohol catalyst by a co-precipitation method using a two-step neutralization process and adding a metal auxiliary agent. The method co-precipitates a portion of zinc with the auxiliary aluminum, and the remaining zinc is co-precipitated with copper, and then the two precipitates are mixed to obtain a catalyst with a high specific surface area and a reasonable pore size distribution. The catalyst also has the characteristics of high hydrogenation activity and good thermal stability, and effectively improves the yield of the target product.

[0005] CN114054033A discloses a gas-phase aldehyde hydrogenation catalyst prepared by an acid-base two-step co-precipitation method. First, the precursor salt is complexed with citric acid, and then sodium carbonate is directly added to the mother liquor for precipitation. The obtained catalyst has a suitable specific surface area and pore volume, and exhibits good conversion rate and selectivity in the hydrogenation of butyraldehyde and octenal.

[0006] CN113042060A discloses a method for preparing an aldehyde hydrogenation catalyst, which comprises adding a certain amount of a pore-enlarging agent to a solution of a precursor salt and then performing a coprecipitation reaction. This method can effectively increase the pore size of the obtained catalyst, improve the internal diffusion performance of the material, reduce the catalyst bulk density, and reduce the use cost.

[0007] The catalyst for preparing butanol by hydrogenation of butyraldehyde published by Wanhua Chemical in CN108043411A, the components are copper oxide, zinc oxide and silicon oxide, and the synchronous precipitation method is adopted to precipitate the copper and zinc components at two different temperatures respectively, to obtain two different pore structures, and then the catalyst forms a double pore system. It can be seen from the content of the above patents that people have a deep understanding of the influence of the adjustment of the pore structure of the hydrogenation catalyst on the hydrogenation performance. However, including those mentioned in the above patents and other copper-zinc hydrogenation catalysts, most of them are prepared by coprecipitation method, the pores of the catalyst are mostly stacked pores between oxide particles, and the pore size distribution is uneven, which is not conducive to the mass transfer and heat transfer of the materials in the catalyst, and may cause excessive hydrogenation, esterification, etherification and other side reactions, so that the product selectivity decreases. In addition, the copper-based catalyst prepared by the coprecipitation method is generally in an irregular state, the copper oxide particle size distribution is wide and the dispersibility in the catalyst is poor, the utilization efficiency of the active component is low, and the preparation repeatability is also relatively general, so that the stability and activity of the catalyst in practical applications are still to be improved. Summary of the invention

[0008] The purpose of the present invention is to overcome the problems of uneven catalyst pore distribution, small specific surface area and pore volume, poor dispersion of active components, low utilization rate, poor stability, and unsatisfactory hydrogenation activity and selectivity in the prior art, and to provide a modified silicon oxide-containing material and a preparation method and application thereof, a hydrogenation catalyst and a preparation method and application thereof. The catalyst has a developed pore structure and a high specific surface area and pore volume, improves the diffusion efficiency of the substrate and reaction heat in the catalyst, and at the same time makes the active components have a good dispersion degree on the carrier surface and have a strong interaction with the auxiliary agent, thereby improving the utilization rate of the active components and having excellent hydrogenation activity, product selectivity and stability.

[0009] In order to achieve the above-mentioned object, the first aspect of the present invention provides a modified silicon oxide-containing material, the modified silicon oxide-containing material comprises a silicon oxide-containing material and a modification aid, the modification aid comprises at least one of oxides of Group VIB metals, Group VIIB metals and Group VIII metals, and the crystallinity of the metal oxide of the modification aid in the modified silicon oxide-containing material is less than 30%;

[0010] The second aspect of the present invention provides a method for preparing the modified silicon oxide-containing material of the present invention, the method comprising: dissolving a modification aid precursor, optionally an organic acid and a mesoporous silicon oxide-containing material, removing the solvent, first drying, and first calcining.

[0011] The third aspect of the present invention provides the use of the modified silicon oxide-containing material of the present invention as a carrier in the preparation of a supported catalyst.

[0012] A fourth aspect of the present invention provides a hydrogenation catalyst, which comprises the modified silicon oxide-containing material of the present invention and an active component supported on the modified silicon oxide-containing material, wherein the active component comprises copper oxide and optionally zinc oxide;

[0013] In the XRD spectrum of the hydrogenation catalyst, characteristic peaks exist at 2θ=20-30°, 35.4±1°, and 38.2±1°.

[0014] A fifth aspect of the present invention provides a method for preparing the hydrogenation catalyst of the present invention, the preparation method comprising:

[0015] (1) adding a carrier to a metal ammonia complex solution containing an active component, and then distilling ammonia to obtain a mixed solution;

[0016] (2) The mixed solution is subjected to hydrothermal treatment, cooling, secondary drying, secondary calcination, and molding;

[0017] Wherein, the carrier is the modified silicon oxide-containing material described in the first aspect of the present invention.

[0018] A sixth aspect of the present invention provides a use of the hydrogenation catalyst of the present invention in preparing alcohols by hydrogenating aldehydes.

[0019] Compared with the prior art, the present invention has the advantages of:

[0020] The modified silicon oxide-containing material provided by the invention has uniform pore size distribution and a developed pore structure.

[0021] The modified silicon oxide-containing material provided by the present invention is applied to the preparation of catalysts, so that the active components of the catalyst have high dispersibility and utilization rate, which is beneficial to the diffusion of raw materials and products in the catalyst and reduces mass transfer resistance; it also enables the heat of hydrogenation reaction to be transferred in time, promotes uniform temperature distribution in the catalyst, reduces the number of hot spots, avoids excessive side reactions, and makes the catalyst highly active, highly selective, and has good stability.

[0022] The preparation method of the hydrogenation catalyst provided by the present invention increases the contact probability between the catalyst and the auxiliary agent component through the ammonia evaporation-hydrothermal process, strengthens the interaction, improves the electronic state of the active component, promotes the effective adsorption of the reactants, and improves the activity and stability of the catalyst, thereby solving the problems of the catalyst prepared by the previous coprecipitation method being mainly stacked pores, uneven pore size distribution, poor mass transfer and heat transfer performance, poor dispersibility of the active component and low utilization rate.

[0023] The invention provides a hydrogenation catalyst which is suitable for preparing alcohol by hydrogenation of aldehyde, and is particularly suitable for preparing butanol by hydrogenation of butyraldehyde, and has excellent hydrogenation activity and selectivity of product butanol. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is a TEM image of the catalyst obtained in Example 1;

[0025] Figure 2 is the nitrogen adsorption-desorption curve of the catalyst obtained in Example 1;

[0026] Figure 3 is the pore size distribution diagram of the catalyst obtained in Example 1;

[0027] Figure 4 is the small angle XRD pattern of the catalyst obtained in Example 1;

[0028] Figure 5 is the XRD pattern of the catalyst prepared in Example 1;

[0029] Figure 6 This is the evaluation result of the stability of the butyraldehyde gas phase hydrogenation performance of the catalyst obtained in Example 1. DETAILED DESCRIPTION

[0030] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0031] The first aspect of the present invention provides a modified silicon oxide-containing material, which comprises a silicon oxide-containing material and a modification aid, wherein the modification aid comprises at least one of oxides of Group VIB metals, Group VIIB metals and Group VIII metals, and the crystallinity of the aid metal oxide in the modified silicon oxide-containing material is less than 30%.

[0032] The modified silicon oxide-containing material provided by the invention has uniform pore size distribution and a developed pore structure.

[0033] According to a particularly preferred embodiment of the present invention, the silicon oxide-containing material is selected from at least one of SBA-15, MCM-41 and KIT-6. By adopting the above-mentioned preferred embodiment, the pore size distribution of silicon dioxide can be further improved.

[0034] According to a particularly preferred embodiment of the present invention, the crystallinity of the auxiliary metal oxide in the modified silicon oxide-containing material is 5-30%. By adopting the above-mentioned preferred embodiment, the pore size distribution of silicon dioxide can be further improved.

[0035] In the present invention, as long as the purpose of the present invention can be achieved, there is no particular requirement for the mass content of the auxiliary metal oxide in the modified silicon oxide-containing material. According to a particularly preferred embodiment of the present invention, the mass content of the auxiliary metal oxide in the modified silicon oxide-containing material is 3-30%, preferably 6-25%. By adopting the above-mentioned preferred embodiment, the pore size distribution of silicon dioxide can be further improved.

[0036] The pore volume of the modified silicon oxide-containing material with pores having a pore diameter of 4-14 nm accounts for 65-98% of the total pore volume, preferably 75-95%.

[0037] According to a particularly preferred embodiment of the present invention, the specific surface area of ​​the modified silicon oxide-containing material is 350-750 m 2 g -1 , preferably 600-750m 2 g -1 .

[0038] According to a particularly preferred embodiment of the present invention, the total pore volume of the modified silicon oxide-containing material is 0.3-1.4 cm 2 g -1 , preferably 0.5-1.2cm 2 g -1 .

[0039] According to a particularly preferred embodiment of the present invention, the most probable pore size of the modified silicon oxide-containing material is 6-12 nm, preferably 5-10 nm, and more preferably 7-10 nm.

[0040] According to a particularly preferred embodiment of the present invention, the modification aid comprises oxides of Group VIB metals, Group VIIB metals and Group VIII metals. By adopting the above-mentioned preferred embodiment, the pore size distribution of silicon dioxide can be further improved.

[0041] According to a particularly preferred embodiment of the present invention, the molar ratio of Group VIB metal, Group VIIB metal and Group VIII metal in the modification agent as oxides is 0.5-2: 0.5-2: 1. By adopting the above preferred embodiment, the pore size distribution of silica can be further improved.

[0042] According to a particularly preferred embodiment of the present invention, the Group VIB metal is selected from at least one of molybdenum, tungsten and chromium, preferably molybdenum. By adopting the above-mentioned preferred embodiment, the pore size distribution of silicon dioxide can be further improved.

[0043] According to a particularly preferred embodiment of the present invention, the Group VIIB metal is selected from manganese and / or technetium, preferably manganese. By adopting the above-mentioned preferred embodiment, the pore size distribution of silicon dioxide can be further improved.

[0044] According to a particularly preferred embodiment of the present invention, the Group VIII metal is selected from at least one of iron, cobalt, nickel, ruthenium, rhodium and palladium, preferably at least one of iron, cobalt and nickel. By adopting the above preferred embodiment, the pore size distribution of silicon dioxide can be further improved.

[0045] The present invention provides a method for preparing the modified silicon oxide-containing material of the present invention, which comprises: dissolving a modification auxiliary agent precursor, optionally an organic acid and a mesoporous silicon oxide-containing material, removing the solvent, first drying and first calcining.

[0046] The modified silicon oxide-containing material having the above-mentioned characteristics can be obtained by the method of the present invention.

[0047] In the present invention, the first drying conditions can be conventionally selected in the art. According to a particularly preferred embodiment of the present invention, the first drying conditions include: a temperature of 80-120°C, preferably 90-110°C; and a time of 8-12h, preferably 10-12h.

[0048] In the present invention, the conditions for the first calcination can be conventionally selected in the art. According to a particularly preferred embodiment of the present invention, the conditions for the first calcination include: a temperature of 300-500°C, preferably 350-450°C; and a time of 4-8h, preferably 4-6h.

[0049] In the present invention, the optional range of the modification aid precursor is relatively wide. According to a particularly preferred embodiment of the present invention, the modification aid precursor is selected from soluble salts of Group VIB metals, Group VIIB metals and Group VIII metals, and preferably the soluble salt is selected from at least one of nitrates, acetates, ammonium salts and sulfates.

[0050] According to a particularly preferred embodiment of the present invention, the organic acid is selected from at least one of citric acid, ethylenediaminetetraacetic acid, and oxalic acid. By adopting the above preferred embodiment, the pore size distribution of silica can be further improved.

[0051] The present invention provides an application of the modified silicon oxide-containing material of the present invention as a carrier in the preparation of a supported catalyst, preferably in the preparation of a supported hydrogenation catalyst.

[0052] The modified silicon oxide-containing material provided by the present invention is applied to the preparation of catalysts, so that the active components of the catalyst have high dispersibility and utilization rate, which is beneficial to the diffusion of raw materials and products in the catalyst and reduces mass transfer resistance; it also enables the heat of hydrogenation reaction to be transferred in time, promotes uniform temperature distribution in the catalyst, reduces the number of hot spots, avoids excessive side reactions, and makes the catalyst highly active, highly selective, and has good stability.

[0053] A fourth aspect of the present invention provides a hydrogenation catalyst, which comprises the modified silicon oxide-containing material of the present invention and an active component supported on the modified silicon oxide-containing material, wherein the active component comprises copper oxide and optionally zinc oxide;

[0054] In the XRD spectrum of the hydrogenation catalyst, characteristic peaks exist at 2θ=20-30°, 35.4±1°, and 38.2±1°.

[0055] The catalyst of the invention has high activity, high selectivity and good stability.

[0056] In the present invention, as long as the purpose of the present invention can be achieved, there is no special requirement for the content of each component of the hydrogenation catalyst. According to a particularly preferred embodiment of the present invention, based on the total mass of the hydrogenation catalyst, the content of copper oxide is 20-50%; the content of zinc oxide is 0-30%; and the content of modified silicon oxide-containing material is 20-80%.

[0057] According to a particularly preferred embodiment of the present invention, based on the total mass of the hydrogenation catalyst, the content of copper oxide is 25-35%, the content of zinc oxide is 10-30%, and the content of modified silicon oxide-containing material is 40-65%. By adopting the above preferred embodiments, the activity, selectivity and stability of the catalyst can be further improved.

[0058] According to a particularly preferred embodiment of the present invention, the hydrogenation catalyst has a two-dimensional hexagonal mesoporous structure.

[0059] According to a particularly preferred embodiment of the present invention, the specific surface area of ​​the hydrogenation catalyst is 250-550m 2 g -1 , preferably 280-450m 2 g -1 .

[0060] According to a particularly preferred embodiment of the present invention, the pore volume of the hydrogenation catalyst is 0.4-1.2 cm 2 g -1 , preferably 0.5-1.0cm 2 g -1 .

[0061] According to a particularly preferred embodiment of the present invention, the most probable pore size of the hydrogenation catalyst is 5.0-10.0 nm, preferably 6.0-9.0 nm.

[0062] According to a particularly preferred embodiment of the present invention, the pore volume of pores with a pore diameter of 6-9 nm in the hydrogenation catalyst accounts for 70-95% of the total pore volume, preferably 75-90%.

[0063] According to a particularly preferred embodiment of the present invention, the average grain size of the copper oxide is 4-9 nm, preferably 6-8 nm.

[0064] A fifth aspect of the present invention provides a method for preparing the hydrogenation catalyst of the present invention, the preparation method comprising:

[0065] (1) adding a carrier to a metal ammonia complex solution containing an active component, and then distilling ammonia to obtain a mixed solution;

[0066] (3) The mixed solution is subjected to hydrothermal treatment, cooling, secondary drying, secondary calcination, and molding;

[0067] The carrier is the modified silicon oxide-containing material described in the present invention.

[0068] The catalyst having the above-mentioned characteristics of the present invention can be prepared by the method of the present invention.

[0069] According to a preferred embodiment of the present invention, the method for preparing the metal ammine complex solution comprises: dissolving an active component precursor and then adding ammonia water to form a metal ammine complex solution.

[0070] In the present invention, as long as the purpose of the present invention can be achieved, there is no particular requirement for the difference between the pH of the metal ammine complex solution and the pH of the mixed solution. According to a preferred embodiment of the present invention, the difference between the pH of the metal ammine complex solution and the pH of the second mixed solution is 4 to 6. By adopting the above preferred embodiment, the activity, selectivity and stability of the prepared catalyst can be further improved.

[0071] According to a particularly preferred embodiment of the present invention, the pH of the metal ammine complex solution is 11 to 12. By adopting the above preferred embodiment, the activity, selectivity and stability of the prepared catalyst can be further improved.

[0072] According to a particularly preferred embodiment of the present invention, the pH of the mixed solution is 6 to 7. By adopting the above preferred embodiment, the activity, selectivity and stability of the prepared catalyst can be further improved.

[0073] According to a particularly preferred embodiment of the present invention, the concentration of the ammonia water is 10-28 wt %.

[0074] According to a particularly preferred embodiment of the present invention, the mixing is carried out by stirring, preferably for at least 2 hours.

[0075] In the present invention, the evaporation conditions can be conventionally selected in the art. According to a particularly preferred embodiment of the present invention, the ammonia evaporation conditions include: a temperature of 70-90° C. During the evaporation process, solvent is appropriately added to prevent the solution from drying up.

[0076] In the present invention, the conditions for the hydrothermal treatment may be conventionally selected in the art. According to a particularly preferred embodiment of the present invention, the conditions for the hydrothermal treatment include: a temperature of 130-150°C, preferably 140-150°C.

[0077] According to a particularly preferred embodiment of the present invention, the hydrothermal treatment conditions include: temperature of 24-48h; preferably 36-48h. By adopting the above preferred scheme, the activity, selectivity and stability of the prepared catalyst can be further improved.

[0078] According to a particularly preferred embodiment of the present invention, the second drying conditions include: a temperature of 80-120°C, preferably 80-100°C.

[0079] According to a particularly preferred embodiment of the present invention, the second drying condition includes: a time of 6-12 hours, preferably 8-12 hours. By adopting the above preferred scheme, the activity, selectivity and stability of the prepared catalyst can be further improved.

[0080] In the present invention, the conditions for the second calcination can be selected according to conventional techniques in the art. According to a particularly preferred embodiment of the present invention, the conditions for the second calcination include: an oxygen-containing atmosphere at a temperature of 300-400°C, preferably 300-380°C.

[0081] According to a particularly preferred embodiment of the present invention, the second calcination conditions include: a time of 2-8 hours, preferably 4-8 hours. By adopting the above preferred scheme, the activity, selectivity and stability of the prepared catalyst can be further improved.

[0082] According to a particularly preferred embodiment of the present invention, the oxygen-containing atmosphere is an air atmosphere.

[0083] In the present invention, the active component precursor has a wide range of options, and commonly used types can be used in the present invention. According to a particularly preferred embodiment of the present invention, the active component precursor is a copper soluble salt and an optional zinc soluble salt, and the copper soluble salt is at least one of copper nitrate, copper chloride, copper acetate and copper sulfate; the zinc soluble salt is at least one of zinc nitrate, zinc chloride, zinc acetate and zinc sulfate.

[0084] The sixth aspect of the present invention provides an application of the hydrogenation catalyst of the present invention in the preparation of alcohols by hydrogenation of aldehydes, preferably in the preparation of alcohols by hydrogenation of C2-C5 aldehydes, and more preferably in the preparation of alcohols by hydrogenation of butyraldehyde.

[0085] The invention provides a hydrogenation catalyst which is suitable for preparing alcohol by hydrogenation of aldehyde, and is particularly suitable for preparing butanol by hydrogenation of butyraldehyde, and has excellent hydrogenation activity and selectivity of product butanol.

[0086] A seventh aspect of the present invention provides a method for preparing alcohol by hydrogenating butyraldehyde, the method comprising: contacting a butyraldehyde raw material with hydrogen in the presence of a catalyst;

[0087] The catalyst is the hydrogenation catalyst of the present invention after reduction.

[0088] By using the method of the present invention, the conversion rate of butyraldehyde is high and the selectivity of butanol is high.

[0089] In the present invention, the conditions of the contact reaction can be conventionally selected in the art. According to a preferred embodiment of the present invention, according to a particularly preferred embodiment of the present invention, the conditions of the contact reaction include: a reaction pressure of 0.3-0.6 MPa; a reaction temperature of 100-160° C.; a H2 / aldehyde molar ratio of 10-30; and a butyraldehyde liquid feed space velocity of 0.4-1 h -1 .

[0090] According to a particularly preferred embodiment of the present invention, the contact reaction conditions include: the reaction pressure is selected to be 0.4-0.45MPa; the reaction temperature is 110-130°C; the H2 / aldehyde molar ratio is 15-30; the butyraldehyde liquid feed space velocity is 0.4-0.6h -1 By adopting the above preferred embodiment, the conversion rate of butyraldehyde and the selectivity of butanol can be further improved.

[0091] According to a particularly preferred embodiment of the present invention, the reduction conditions include: temperature 180-280° C., preferably 200-260° C.; time 8-12 h, preferably 8-10 h.

[0092] According to a particularly preferred embodiment of the present invention, physically adsorbed water is removed before the reduction activation, and the conditions include: heating to 120-150° C. and maintaining for 4-8 hours in an inert atmosphere, preferably a nitrogen atmosphere.

[0093] In order to make the present invention easier to understand, the present invention will be described in detail below in conjunction with examples. These examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. If no specific conditions are specified in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. The raw materials involved in the examples are all commercially available unless otherwise specified.

[0094] In the present invention, the TEM photo of the catalyst is taken by a JEM-1011 electron microscope, and the electron acceleration voltage is 200 kV. Take an appropriate amount of sample powder and ultrasonically disperse it in anhydrous ethanol. Take a drop of the dispersion and drop it on a 3mm 300-mesh copper mesh carbon film, dry it under an infrared lamp, and then observe it under an electron microscope.

[0095] In the present invention, the pore structure properties of the sample were tested using a Micromeritics ASAP-3020 physical adsorption instrument. The sample was degassed at 300°C for 3 hours before the test, and the test was performed at liquid nitrogen temperature (-196°C). The specific surface area of ​​the sample was calculated by the Brunauer-Emmett-Teller (BET) multilayer physical adsorption model, and the pore size distribution was obtained by the Barrett-Joyner-Halenda method.

[0096] In the present invention, XRD spectrum: Philip X'pert Pro diffractometer is used to collect XRD spectrum of the catalyst, the X-ray radiation source is Cu target Kα ray (λ=0.15408nm) filtered by Ni filter, the collection step is 0.06° / s, the X-ray tube operating voltage is 40kV, and the current is 40mA.

[0097] Example 1

[0098] Weigh 20.583g of 50wt% manganese nitrate solution and 13.246g of citric acid in a beaker, add 100g of deionized water and stir to dissolve, then add 20g of mesoporous silica SBA-15 into the solution, and continue stirring the mixture for 2h. Transfer the mixture to an 80℃ oil bath and heat to evaporate the water, place the solid in a 100℃ oven and dry for 12h, then place it in a tubular furnace (with nitrogen, the same below) and calcine at 450℃ for 4h to obtain a modified silica carrier with a specific surface area of ​​632m 2 g -1 , pore volume is 0.93m 3 g -1 The pore volume of pores with a size of 4-14 nm accounts for 84% of the total pore volume, the most probable pore diameter is 7.6 nm, and the crystallinity of the additive is 16%.

[0099] Weigh 35.368g of copper nitrate trihydrate and 23.274g of zinc nitrate hexahydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly add 25% ammonia water by mass to adjust the pH value of the solution to 11. Then weigh 25g of the modified silica carrier obtained in the previous step and put it into the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 6. The mixed liquid in the beaker was transferred to a 250 ml high-pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed liquid in the hydrothermal autoclave was filtered, and the filter cake was washed three times with deionized water. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, which was recorded as CZS-1.

[0100] Figure 1 This is a transmission electron microscopy image of the catalyst prepared in Example 1, from which it can be seen that the catalyst has an orderly arranged mesoporous structure.

[0101] Figure 2 The adsorption-desorption curve of the catalyst prepared in Example 1 shows that the catalyst has a relatively high pore volume and a regular pore structure.

[0102] Figure 3 The pore size distribution diagram of the catalyst prepared in Example 1 shows that the pore size distribution of the catalyst is narrow and the pore size is uniform. These properties are conducive to the high dispersion of the active component copper oxide on the catalyst surface;

[0103] Figure 4 The small-angle XRD spectrum of the catalyst prepared in Example 1 shows that the pores of the catalyst are a two-dimensional hexagonal arrangement structure;

[0104] Figure 5 This is the XRD spectrum of the catalyst in Example 1. It can be seen that in addition to the diffraction broad band of 20-30° belonging to amorphous silicon oxide, the sample also shows a weak diffraction peak of the auxiliary oxide, indicating that it is in a low crystallinity state with high dispersibility; at the same time, there are diffraction peaks at 35.4 and 38.2.

[0105] Example 2

[0106] Weigh 24.292g of ferric nitrate nonahydrate and 13.246g of citric acid in a beaker, add 100g of deionized water and stir to dissolve, then add 20g of mesoporous silica SBA-15 into the solution, and continue stirring the mixture for 2h. Transfer the mixture to an 80℃ oil bath to heat and evaporate the water, place the solid in a 100℃ oven to dry for 12h, and then place it in a muffle furnace and calcine at 450℃ for 4h to obtain the modified silica carrier. Its specific surface area is 662m 2 g -1 , pore volume is 0.96m 3 g -1 The pore volume of pores with a size of 4-14 nm accounts for 83% of the total pore volume, the most probable pore diameter is 7.9 nm, and the crystallinity of the additive is 18%.

[0107] Weigh 35.368g of copper nitrate trihydrate and 23.274g of zinc nitrate hexahydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly drop 25% ammonia water, and adjust the pH value of the solution to 11. Then weigh 25g of the modified silica carrier obtained in the previous step and put it into the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 7. The mixed liquid in the beaker was transferred to a 250 ml high-pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed liquid in the hydrothermal autoclave was filtered, and the filter cake was washed three times with deionized water. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, which was recorded as CZS-2.

[0108] Transmission electron microscopy images of the prepared catalysts Figure 1 Similar; the adsorption-desorption curves of the prepared catalysts are Figure 2 Similar; the pore size distribution of the prepared catalyst is Figure 3 Similar; the small angle XRD spectrum of the prepared catalyst is Figure 4 Similar; the XRD spectrum of the prepared catalyst is Figure 5 similar.

[0109] Example 3

[0110] Weigh 18.060g of cobalt nitrate hexahydrate and 13.246g of citric acid in a beaker, add 100g of deionized water and stir to dissolve, then add 20g of mesoporous silica SBA-15 into the solution, and continue stirring the mixture for 2h. Transfer the mixture to an 80℃ oil bath to heat and evaporate the water, place the solid in a 100℃ oven to dry for 12h, and then place it in a muffle furnace and calcine at 450℃ for 4h to obtain the modified silica carrier. Its specific surface area is 612m 2 g -1 , pore volume is 0.88m 3 g -1 The pore volume of pores with a size of 4-14 nm accounts for 79% of the total pore volume, the most probable pore diameter is 8.1 nm, and the crystallinity of the additive is 13%.

[0111] Weigh 35.368g of copper nitrate trihydrate and 23.274g of zinc nitrate hexahydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly add 25% ammonia water by mass to adjust the pH value of the solution to 12. Then weigh 25g of the modified silica carrier obtained in the previous step and put it into the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 6. The mixed liquid in the beaker was transferred to a 250 ml high-pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed liquid in the hydrothermal autoclave was filtered, and the filter cake was washed three times with deionized water. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, recorded as CZS-3.

[0112] Transmission electron microscopy images of the prepared catalysts Figure 1 Similar; the adsorption-desorption curves of the prepared catalysts are Figure 2 Similar; the pore size distribution of the prepared catalyst is Figure 3 Similar; the small angle XRD spectrum of the prepared catalyst is Figure 4 Similar; the XRD spectrum of the prepared catalyst is Figure 5 similar.

[0113] Example 4

[0114] Weigh 21.460g of nickel nitrate hexahydrate and 13.246g of citric acid in a beaker, add 100g of deionized water and stir to dissolve, then add 20g of mesoporous silica SBA-15 into the solution, and continue stirring the mixture for 2h. Transfer the mixture to an 80℃ oil bath to heat and evaporate the water, place the solid in a 100℃ oven to dry for 12h, and then place it in a muffle furnace at 450℃ for 4h to obtain the modified silica carrier. Its specific surface area is 743m 2 g -1 , pore volume is 1.08m 3 g -1 The pore volume of pores with a size of 4-14 nm accounts for 71% of the total pore volume, the most probable pore diameter is 5.4 nm, and the crystallinity of the additive is 9%.

[0115] Weigh 35.368g of copper nitrate trihydrate and 23.274g of zinc nitrate hexahydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly add 25% ammonia water by mass to adjust the pH value of the solution to 12. Then weigh 25g of the modified silica carrier obtained in the previous step and put it into the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 7. The mixed liquid in the beaker was transferred to a 250 ml high-pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed liquid in the hydrothermal autoclave was filtered, and the filter cake was washed three times with deionized water. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, recorded as CZS-4.

[0116] Transmission electron microscopy images of the prepared catalysts Figure 1 Similar; the adsorption-desorption curves of the prepared catalysts are Figure 2 Similar; the pore size distribution of the prepared catalyst is Figure 3 Similar; the small angle XRD spectrum of the prepared catalyst is Figure 4 Similar; the XRD spectrum of the prepared catalyst is Figure 5 similar.

[0117] Example 5

[0118] Weigh 13.617g of ammonium molybdate and 13.246g of citric acid in a beaker, add 100g of deionized water and stir to dissolve, then add 20g of mesoporous silica SBA-15 into the solution, and continue stirring the mixture for 2h. Transfer the mixture to an 80℃ oil bath to heat and evaporate the water, place the solid in a 100℃ oven to dry for 12h, and then place it in a muffle furnace and calcine at 450℃ for 4h to obtain the modified silica carrier. Its specific surface area is 698m 2 g -1 , pore volume is 0.96m 3 g -1 The pore volume of pores with a size of 4-14 nm accounts for 87% of the total pore volume, the most probable pore diameter is 7.1 nm, and the crystallinity of the additive is 5%.

[0119] Weigh 35.368g of copper nitrate trihydrate and 23.274g of zinc nitrate hexahydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly add 25% ammonia water by mass to adjust the pH value of the solution to 11. Then weigh 25g of the modified silica carrier obtained in the previous step and put it into the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 6. The mixed liquid in the beaker was transferred to a 250 ml high-pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed liquid in the hydrothermal autoclave was filtered, and the filter cake was washed three times with deionized water. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, which was recorded as CZS-5.

[0120] Transmission electron microscopy images of the prepared catalysts Figure 1 Similar; the adsorption-desorption curves of the prepared catalysts are Figure 2 Similar; the pore size distribution of the prepared catalyst is Figure 3 Similar; the small angle XRD spectrum of the prepared catalyst is Figure 4 Similar; the XRD spectrum of the prepared catalyst is Figure 5 similar.

[0121] Example 6

[0122] Weigh 21.460g of nickel nitrate hexahydrate and 13.246g of citric acid in a beaker, add 100g of deionized water and stir to dissolve, then add 20g of mesoporous silica MCM-41 into the solution, and continue stirring the mixture for 2h. Transfer the mixture to an 80℃ oil bath to heat and evaporate the water, place the solid in a 100℃ oven to dry for 12h, and then place it in a muffle furnace and calcine at 450℃ for 4h to obtain the modified silica carrier. Its specific surface area is 743m 2 g -1 , pore volume is 1.08m 3 g -1 The pore volume of pores with a size of 4-14 nm accounts for 71% of the total pore volume, the most probable pore diameter is 5.4 nm, and the crystallinity of the additive is 9%.

[0123] Weigh 58.368g of copper nitrate trihydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly drop 25% ammonia water to adjust the pH value of the solution to 11. Then weigh 25g of the modified silica carrier obtained in the previous step and put it into the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 6. The mixed liquid in the beaker was transferred to a 250 ml high-pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed liquid in the hydrothermal autoclave was filtered, and the filter cake was washed three times with deionized water. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, which was recorded as CZS-6.

[0124] Transmission electron microscopy images of the prepared catalysts Figure 1 Similar; the adsorption-desorption curves of the prepared catalysts are Figure 2 Similar; the pore size distribution of the prepared catalyst is Figure 3 Similar; the small angle XRD spectrum of the prepared catalyst is Figure 4 Similar; the XRD spectrum of the prepared catalyst is Figure 5 similar.

[0125] Example 7

[0126] Weigh 21.460g of nickel nitrate hexahydrate into a beaker, add 100g of deionized water and stir to dissolve, then add 20g of mesoporous silica KIT-6 into the solution, and continue stirring the mixture for 2h. Transfer the mixture to an 80℃ oil bath to heat and evaporate the water, place the solid in a 100℃ oven to dry for 12h, and then place it in a muffle furnace and calcine at 450℃ for 4h to obtain the modified silica carrier. Its specific surface area is 543m 2 g-1 , pore volume is 0.81m 3 g -1 The pore volume of pores with a size of 4-14 nm accounts for 95% of the total pore volume, the most probable pore diameter is 9.1 nm, and the crystallinity of the additive is 9%.

[0127] Weigh 35.368g of copper nitrate trihydrate and 23.274g of zinc nitrate hexahydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly add 25% ammonia water by mass to adjust the pH value of the solution to 11. Then weigh 25g of the modified silica carrier obtained in the previous step and put it into the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 6. The mixed liquid in the beaker was transferred to a 250 ml high-pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed liquid in the hydrothermal autoclave was filtered, and the filter cake was washed three times with deionized water. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, which was recorded as CZS-7.

[0128] Transmission electron microscopy images of the prepared catalysts Figure 1 Similar; the adsorption-desorption curves of the prepared catalysts are Figure 2 Similar; the pore size distribution of the prepared catalyst is Figure 3 Similar; the small angle XRD spectrum of the prepared catalyst is Figure 4 Similar; the XRD spectrum of the prepared catalyst is Figure 5 similar.

[0129] Example 8

[0130] Weigh 20.997g of chromium nitrate nonahydrate and 13.246g of citric acid in a beaker, add 100g of deionized water and stir to dissolve, then add 20g of mesoporous silica SBA-15 into the solution, and continue stirring the mixture for 2h. Transfer the mixture to an 80℃ oil bath to heat and evaporate the water, place the solid in a 100℃ oven to dry for 12h, then place it in a tubular furnace and calcine at 450℃ for 4h in a nitrogen atmosphere to obtain a modified silica carrier with a specific surface area of ​​582m 2 g -1 , pore volume is 0.69m 3 g -1 The pore volume of pores with a size of 4-14 nm accounts for 68% of the total pore volume, the most probable pore diameter is 7.1 nm, and the crystallinity of the additive is 21%.

[0131] Weigh 35.368g of copper nitrate trihydrate and 23.274g of zinc nitrate hexahydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly add 25% ammonia water by mass to adjust the pH value of the solution to 11. Then weigh 25g of the modified silica carrier obtained in the previous step and put it into the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 6. The mixed liquid in the beaker was transferred to a 250 ml high-pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed liquid in the hydrothermal autoclave was filtered, and the filter cake was washed three times with deionized water. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, which was recorded as CZS-8.

[0132] Transmission electron microscopy images of the prepared catalysts Figure 1 Similar; the adsorption-desorption curves of the prepared catalysts are Figure 2 Similar; the pore size distribution of the prepared catalyst is Figure 3 Similar; the small angle XRD spectrum of the prepared catalyst is Figure 4 Similar; the XRD spectrum of the prepared catalyst is Figure 5 similar.

[0133] Example 9

[0134] Weigh 6.681g of 50wt% manganese nitrate solution, 4.389g of ammonium molybdate, 10.097g of ferric nitrate and 13.246g of citric acid in a beaker, add 100g of deionized water and stir to dissolve, then add 20g of mesoporous silica SBA-15 to the solution, and continue stirring the mixture for 2h. Transfer the mixture to an 80℃ oil bath and heat to evaporate the water, place the solid in a 100℃ oven and dry for 12h, then place it in a tubular furnace and calcine at 450℃ for 4h in a nitrogen atmosphere to obtain a modified silica carrier with a specific surface area of ​​633m 2 g -1 , pore volume is 0.91m 3 g -1 The pore volume of pores with a size of 4-14 nm accounts for 91% of the total pore volume, the most probable pore diameter is 7.3 nm, and the crystallinity of the additive is 11%.

[0135] Weigh 35.368g of copper nitrate trihydrate and 23.274g of zinc nitrate hexahydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly add 25% ammonia water by mass to adjust the pH value of the solution to 11. Then weigh 25g of the modified silica carrier obtained in the previous step and put it into the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 6. The mixed liquid in the beaker was transferred to a 250 ml high-pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed liquid in the hydrothermal autoclave was filtered, and the filter cake was washed three times with deionized water. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, which was recorded as CZS-9.

[0136] Transmission electron microscopy images of the prepared catalysts Figure 1 Similar; the adsorption-desorption curves of the prepared catalysts are Figure 2 Similar; the pore size distribution of the prepared catalyst is Figure 3 Similar; the small angle XRD spectrum of the prepared catalyst is Figure 4 Similar; the XRD spectrum of the prepared catalyst is Figure 5 similar.

[0137] Example 10

[0138] Weigh 20.583g of 50wt% manganese nitrate solution and 13.246g of citric acid in a beaker, add 100g of deionized water and stir to dissolve, then add 50g of 40wt% silica sol into the solution, and continue stirring the mixture for 2h. Transfer the mixture to an 80℃ oil bath to heat and evaporate the water, place the solid in a 100℃ oven to dry for 12h, and then place it in a tubular furnace and calcine at 450℃ for 4h in a nitrogen atmosphere to obtain a modified silica carrier with a specific surface area of ​​343m 2 g -1 , pore volume is 0.51m 3 g -1 The pore volume of pores with a size of 4-14 nm accounts for 66% of the total pore volume, the most probable pore diameter is 12.1 nm, and the crystallinity of the additive is 25%.

[0139] Weigh 35.368g of copper nitrate trihydrate and 23.274g of zinc nitrate hexahydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly add 25% ammonia water by mass to adjust the pH value of the solution to 11. Then weigh 25g of the modified silica carrier obtained in the previous step and put it into the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 6. The mixed liquid in the beaker was transferred to a 250 ml high-pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed liquid in the hydrothermal autoclave was filtered, and the filter cake was washed three times with deionized water. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, recorded as CZS-10.

[0140] Transmission electron microscopy images of the prepared catalysts Figure 1 Similar; the adsorption-desorption curves of the prepared catalysts are Figure 2 Similar; the pore size distribution of the prepared catalyst is Figure 3 Similar; the small angle XRD spectrum of the prepared catalyst is Figure 4 Similar; the XRD spectrum of the prepared catalyst is Figure 5 similar.

[0141] Embodiment 11

[0142] Weigh 20.583g of 50wt% manganese nitrate solution and 13.246g of citric acid in a beaker, add 100g of deionized water and stir to dissolve, then add 20g of mesoporous silica SBA-15 into the solution, and continue stirring the mixture for 2h. Transfer the mixture to an 80℃ oil bath and heat to evaporate the water, place the solid in a 100℃ oven and dry for 12h, then place it in a tubular furnace and calcine at 450℃ for 4h in a nitrogen atmosphere to obtain a modified silica carrier with a specific surface area of ​​632m 2 g -1 , pore volume is 0.93m 3 g -1 The pore volume of pores with a size of 4-14 nm accounts for 84% of the total pore volume, the most probable pore diameter is 7.6 nm, and the crystallinity of the additive is 16%.

[0143] Weigh 35.368g of copper nitrate trihydrate and 23.274g of zinc nitrate hexahydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly add 25% ammonia water by mass to adjust the pH value of the solution to 10. Then weigh 25g of the modified silica carrier obtained in the previous step and put it into the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 7. The mixed liquid in the beaker was transferred to a 250 ml high-pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed liquid in the hydrothermal autoclave was filtered, and the filter cake was washed three times with deionized water. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, which was recorded as CZS-11.

[0144] Transmission electron microscopy images of the prepared catalysts Figure 1 Similar; the adsorption-desorption curves of the prepared catalysts are Figure 2 Similar; the pore size distribution of the prepared catalyst is Figure 3 Similar; the small angle XRD spectrum of the prepared catalyst is Figure 4 Similar; the XRD spectrum of the prepared catalyst is Figure 5 similar.

[0145] Example 12

[0146] Weigh 20.583g of 50wt% manganese nitrate solution into a beaker, add 100g of deionized water and stir to dissolve, then add 20g of powdered SiO2 into the solution, and continue stirring the mixture for 2h. Transfer the mixture to an 80℃ oil bath to heat and evaporate the water, dry the solid in a 100℃ oven for 12h, and then calcine it in a tube furnace at 450℃ for 4h to obtain a modified silica carrier. Its specific surface area is 232m 2 g -1 , pore volume is 0.33m 3 g -1 The pore volume of pores with a size of 4-14 nm accounts for 57% of the total pore volume, the most probable pore diameter is 14.2 nm, and the crystallinity of the additive is 29%.

[0147] Weigh 35.368g of copper nitrate trihydrate and 23.274g of zinc nitrate hexahydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly add 25% ammonia water by mass to adjust the pH value of the solution to 11. Then weigh 25g of the modified silica carrier obtained in the previous step and put it into the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 6. The mixed liquid in the beaker was transferred to a 250 ml high-pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed liquid in the hydrothermal autoclave was filtered, and the filter cake was washed three times with deionized water. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, which was recorded as CZS-12.

[0148] Transmission electron microscopy images of the prepared catalysts Figure 1 Similar; the adsorption-desorption curves of the prepared catalysts are Figure 2 Similar; the pore size distribution of the prepared catalyst is Figure 3 Similar; the small angle XRD spectrum of the prepared catalyst is Figure 4 Similar; the XRD spectrum of the prepared catalyst is Figure 5 similar.

[0149] Comparative Example 1

[0150] Weigh 35.368g of copper nitrate trihydrate and 23.274g of zinc nitrate hexahydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly drop 25% ammonia water by mass to adjust the pH value of the solution to 11. Then weigh 25g of mesoporous silica SBA-15 and add it to the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 6. The mixed solution in the beaker was transferred to a 250 ml high pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed solution in the hydrothermal autoclave was filtered, and the filter cake was washed with deionized water for 3 times. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, which was recorded as DB-2.

[0151] Comparative Example 2

[0152] Weigh 4.886g of sodium nitrate and 13.246g of citric acid in a beaker, add 100g of deionized water and stir to dissolve, then add 20g of mesoporous silica SBA-15 into the solution, and continue stirring the mixture for 2h. Transfer the mixture to an 80℃ oil bath to heat and evaporate the water, place the solid in a 100℃ oven to dry for 12h, then place it in a tubular furnace and calcine at 450℃ for 4h in a nitrogen atmosphere to obtain a modified silica carrier with a specific surface area of ​​646m 2 g -1 , pore volume is 0.95m 3 g -1 The pore volume of pores with a size of 4-14 nm accounts for 87% of the total pore volume, the most probable pore diameter is 7.8 nm, and the crystallinity of the additive is 3%.

[0153] Weigh 35.368g of copper nitrate trihydrate and 23.274g of zinc nitrate hexahydrate into another beaker, add 200g of deionized water and stir to dissolve, then slowly add 25% ammonia water by mass to adjust the pH value of the solution to 11. Then weigh 25g of the modified silica carrier obtained in the previous step and put it into the above solution, stirring and mixing for 4h. Then heat the solution in an 80℃ oil bath to evaporate the ammonia in the solution, add 30g of deionized water 3 times during this period to ensure that the solution is not evaporated to dryness, and stop heating when the pH value of the solution reaches 6. The mixed solution in the beaker was transferred to a 250 ml high pressure hydrothermal autoclave, and placed in a 150°C oven for hydrothermal treatment for 24 hours. Finally, the hydrothermal autoclave was taken out and cooled to room temperature. The mixed solution in the hydrothermal autoclave was filtered, and the filter cake was washed with deionized water for 3 times. The filter cake was dried in an oven at 100°C for 8 hours, ground into powder, placed in a muffle furnace, and calcined in air at 350°C for 4 hours. The obtained sample was tableted, crushed, and sieved to obtain a granular catalyst with a particle size of 10-20 mesh, which was recorded as DB-3.

[0154] Example 13

[0155] 10 ml of the catalyst obtained in the above-mentioned examples and comparative examples was loaded into a solid bed reactor, first heated to 120°C in a nitrogen atmosphere for 4 hours to remove physically adsorbed water on the catalyst surface, and then cooled to room temperature. Subsequently, the atmosphere was switched to hydrogen, heated to 280°C and maintained for 6 hours to obtain a reduction-activated catalyst, which was used in situ for the evaluation of butyraldehyde hydrogenation performance. The experimental conditions were a bed temperature of 110°C, a reaction pressure of 0.6 MPa, and a butyraldehyde liquid space velocity of 0.3 h -1 , hydrogen-to-aldehyde ratio 30:1, the hydrogenation product was analyzed by gas chromatography, the chromatographic detector was FID, and the experimental results are shown in Table 1.

[0156] Embodiment 14

[0157] 10 ml of the catalyst obtained in Example 1 was loaded into a solid bed reactor, first heated to 120°C in a nitrogen atmosphere for 4 hours to remove physically adsorbed water on the catalyst surface, and then cooled to room temperature. The atmosphere was then switched to hydrogen, heated to 280°C and maintained for 6 hours to obtain a reduction-activated catalyst, which was used in situ for the evaluation of butyraldehyde hydrogenation stability. The experimental conditions were a bed temperature of 140°C, a reaction pressure of 0.6 MPa, and a butyraldehyde liquid space velocity of 0.3 h -1 , hydrogen-formaldehyde ratio 30:1, reaction time 400h. The hydrogenation product was analyzed by gas chromatography, the chromatographic detector was FID, the experimental results are shown in Figure 6 .

[0158] Table 1

[0159] sample Butyraldehyde conversion rate / % Butanol selectivity / % CZS-1 98.5 99.5 CZS-2 98.2 99.3 CZS-3 98.2 99.3 CZS-4 98.5 99.2 CZS-5 98.3 99.5 CZS-6 96.4 99.1 CZS-7 97.5 99.1 CZS-8 97.4 99.1 CZS-9 99.6 99.5 CZS-10 95.1 99.1 CZS-11 96.3 98.5 CZS-12 92.3 95.5 DB-1 70.6 84.2 DB-2 76.5 96.5

[0160] As can be seen from the results in Table 1, the catalysts prepared by the method provided by the present invention all have high specific surface area and pore volume, and the well-developed and uniform pore structure of the catalyst can realize the efficient transfer of reactants and products, and can make the reaction heat diffuse and transfer in time, avoid the generation of local hot spots, and reduce the occurrence of side reactions. Thus, the catalyst shows excellent hydrogenation efficiency and ideal butanol selectivity in the butyraldehyde gas phase hydrogenation reaction.

[0161] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A modified silicon oxide-containing material, characterized in that: The modified silicon oxide-containing material comprises a silicon oxide-containing material and a modification aid, wherein the modification aid comprises at least one oxide of Group VIB metal, Group VIIB metal and Group VIII metal, and the crystallinity of the aid metal oxide in the modified silicon oxide-containing material is below 30%.

2. The modified silicon oxide-containing material according to claim 1, wherein The silicon oxide-containing material is selected from at least one of SBA-15, MCM-41 and KIT-6; and / or The crystallinity of the auxiliary metal oxide in the modified silicon oxide-containing material is 5-30%; and / or The mass content of the auxiliary metal oxide in the modified silicon oxide-containing material is 3-30%, preferably 6-25%; and / or The pore volume of the modified silicon oxide-containing material with pores having a pore diameter of 4-14 nm accounts for 65-98% of the total pore volume, preferably 75-95%.

3. The modified silicon oxide-containing material according to claim 1 or 2, wherein: The specific surface area of ​​the modified silicon oxide-containing material is 350-750 m 2 g -1 , preferably 600-750m 2 g -1 ; and / or The total pore volume of the modified silicon oxide-containing material is 0.3-1.4 cm 2 g -1 , preferably 0.5-1.2cm 2 g -1 ; and / or The most probable pore size of the modified silicon oxide-containing material is 5-12 nm, preferably 5-10 nm.

4. The modified silicon oxide-containing material according to any one of claims 1 to 3, wherein: The modification aid comprises oxides of Group VIB metals, Group VIIB metals and Group VIII metals, preferably the molar ratio of Group VIB metals, Group VIIB metals and Group VIII metals in terms of oxides is 0.5-2:0.5-2:1; and / or The Group VIB metal is selected from at least one of molybdenum, tungsten and chromium, preferably molybdenum; and / or The Group VIIB metal is selected from manganese and / or technetium, preferably manganese; and / or The Group VIII metal is selected from at least one of iron, cobalt, nickel, ruthenium, rhodium and palladium, preferably at least one of iron, cobalt and nickel.

5. The method for preparing the modified silicon oxide-containing material according to any one of claims 1 to 4, characterized in that: The method comprises: dissolving a modification auxiliary agent precursor, an organic acid and a mesoporous silicon oxide-containing material, removing the solvent, first drying and first calcining.

6. The preparation method according to claim 5, wherein: The first drying conditions include: a temperature of 80-120° C., preferably 90-110° C.; and / or a time of 8-12 hours, preferably 10-12 hours; and / or The conditions for the first calcination include: a temperature of 300-500° C., preferably 350-450° C.; and / or a time of 4-8 hours, preferably 4-6 hours.

7. The preparation method according to claim 5 or 6, wherein: The modification aid precursor is selected from soluble salts of Group VIB metals, Group VIIB metals and Group VIII metals, preferably the soluble salt is selected from at least one of nitrates, acetates, ammonium salts and sulfates; and / or The organic acid is selected from at least one of citric acid, ethylenediaminetetraacetic acid and oxalic acid.

8. Use of the modified silicon oxide-containing material according to any one of claims 1 to 4 as a carrier in the preparation of a supported catalyst, preferably in the preparation of a supported hydrogenation catalyst.

9. A hydrogenation catalyst, characterized in that The hydrogenation catalyst comprises the modified silicon oxide-containing material according to any one of claims 1 to 4 and an active component supported on the modified silicon oxide-containing material; The active components include copper oxide and optionally zinc oxide; In the XRD spectrum of the hydrogenation catalyst, characteristic peaks exist at 2θ=20-30°, 35.4±1°, and 38.2±1°.

10. The hydrogenation catalyst according to claim 9, wherein Based on the total mass of the hydrogenation catalyst, the content of copper oxide is 20-50%, preferably 25-35%; the content of zinc oxide is 0-30%, preferably 10-30%; and the content of modified silicon oxide-containing material is 20-80%, preferably 40-65%.

11. The hydrogenation catalyst according to claim 9 or 10, wherein The hydrogenation catalyst has a two-dimensional hexagonal mesoporous structure; and / or The specific surface area of ​​the hydrogenation catalyst is 250-550m 2 g -1 , preferably 280-450m 2 g -1 ; and / or The pore volume of the hydrogenation catalyst is 0.4-1.2 cm 2 g -1 , preferably 0.5-1.0cm 2 g -1 ; and / or The most probable pore size of the hydrogenation catalyst is 5.0-10.0 nm, preferably 6.0-9.0 nm; and / or The pore volume of pores with a pore diameter of 6-9 nm in the hydrogenation catalyst accounts for 70-95% of the total pore volume, preferably 75-90%.

12. The hydrogenation catalyst according to any one of claims 9 to 11, wherein The average grain size of the copper oxide is 4-9 nm, preferably 6-8 nm.

13. The method for preparing the hydrogenation catalyst according to any one of claims 9 to 12, characterized in that: The preparation method comprises: (1) adding a carrier to a metal ammonia complex solution containing an active component, and then distilling ammonia to obtain a mixed solution; (2) The mixed solution is subjected to hydrothermal treatment, cooling, secondary drying, secondary calcination, and molding; Wherein, the carrier is the modified silicon oxide-containing material as described in any one of claims 1-4.

14. The preparation method according to claim 13, wherein: The method for preparing the metal ammine complex solution comprises: dissolving an active component precursor and then adding ammonia water to form a metal ammine complex solution; and / or The difference between the pH of the metal ammine complex solution and the pH of the mixed solution is 4-6; and / or The pH of the metal ammine complex solution is 11-12; and / or The pH of the mixed solution is 6-7.

15. The preparation method according to claim 13 or 14, wherein: The conditions for distilling ammonia include: a temperature of 70-90° C.; and / or The conditions of the hydrothermal treatment include: a temperature of 130-150° C., preferably 140-150° C.; and / or a time of 24-48 hours, preferably 36-48 hours; and / or The second drying conditions include: a temperature of 80-120° C., preferably 80-100° C.; and / or a time of 6-12 hours, preferably 8-12 hours; and / or The conditions for the second calcination include: in an oxygen-containing atmosphere, a temperature of 300-400° C., preferably 300-380° C.; and / or a time of 2-8 hours, preferably 4-8 hours.

16. The preparation method according to claim 14, wherein: The active component precursor is a copper soluble salt and an optional zinc soluble salt, wherein the copper soluble salt is at least one of copper nitrate, copper chloride, copper acetate and copper sulfate; the zinc soluble salt is at least one of zinc nitrate, zinc chloride, zinc acetate and zinc sulfate.

17. Use of the hydrogenation catalyst according to any one of claims 9 to 12 in preparing alcohols by hydrogenation of aldehydes, preferably in preparing alcohols by hydrogenation of C2-C5 aldehydes, and more preferably in preparing alcohols by hydrogenation of butyraldehyde.

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