阅读说明：本技术 一种烯烃氧化催化剂及其制备方法和应用 (Olefin oxidation catalyst and preparation method and application thereof ) 是由 宋卫林 徐文杰 杨斌 王伟华 溪美珍 于 2019-09-29 设计创作，主要内容包括：本发明涉及氧化领域,具体提供一种烯烃氧化催化剂及其制备方法和应用,以催化剂重量百分比计,包括以下组分：(1)30～60％的含MoO-3、Bi-2O-3、Fe-2O-3和NiO的活性组分；(2)40～70％高空隙大孔载体。本发明中的催化剂用于丙烯选择氧化制备丙烯酸,在丙烯空气摩尔比为1:(6-8)、反应温度350-420℃、反应压力0-0.05MPa、原料气体积质量空速800-1100ml.g～(-1)h～(-1)条件下,其丙烯转化率大于97％、产物丙烯醛、丙烯酸总收率大于92％,且装置操作平稳、操作单行大、热点易控。(The invention relates to the field of oxidation, and particularly provides an olefin oxidation catalyst, a preparation method and an application thereof, wherein the olefin oxidation catalyst comprises the following components in percentage by weight: (1) 30-60% of MoO-containing 3 、Bi 2 O 3 、Fe 2 O 3 And NiO; (2) 40-70% of high-porosity macroporous carrier. The catalyst is used for preparing acrylic acid by selectively oxidizing propylene at the reaction temperature of 350-420 ℃ under the conditions that the molar ratio of propylene to air is 1 (6-8)The reaction pressure is 0-0.05MPa, and the volume mass space velocity of the raw material gas is 800- ‑1 h ‑1 Under the condition, the conversion rate of propylene is more than 97%, the total yield of acrolein and acrylic acid is more than 92%, the device is stable in operation, the single-row operation is large, and the hot spot is easy to control.)

1. An olefin oxidation catalyst is characterized by comprising the following components in percentage by weight:

(1) 30-60% of MoO-containing₃、Bi₂O₃、Fe₂O₃And NiO;

(2) 40-70% of high-porosity macroporous carrier;

the porosity of the high-porosity macroporous carrier is 40-70%, and the average pore diameter is 0.5-20 um.

2. The catalyst of claim 1,

the high-gap macroporous carrier is at least one of alumina, silica, titania and zirconia;

and/or

The high-porosity macroporous carrier has a porosity of 45-55% and an average pore diameter of 1-15 um.

3. The catalyst of claim 1, comprising MoO₃、Bi₂O₃、Fe₂O₃And NiO as an active component represented by the following general formula in terms of atomic ratio: MoBi_aFe_bNi_cX_dY_eZ_fQ_gO_χWherein X is at least one selected from Mg, Co, Ca, Cu, Zn and Mn; y is at least one selected from Nb, Sb and W; z is at least one selected from K, Rb, Na, Li, Ti and Cs; q is at least one of La, Ce, Sm and Th; the value range of a is 0.01-0.5; the value range of b is 0.01-0.7; the value range of c is 0.01-1; the value range of d is 0.02-0.8; the value range of e is 0.05-0.6; the value range of f is>0 is less than or equal to 0.05; the value range of g is 0.01-0.5; and chi is the total number of oxygen atoms required to satisfy the valences of the other elements.

4. The catalyst of claim 1, wherein the method of preparing the high-void, macroporous support comprises:

(1) mixing inorganic oxide, pore-forming agent and binder, kneading into clusters, and preparing into particles;

(2) drying the obtained granules at 20-180 deg.C;

(3) pre-sintering at 200-;

(4) roasting at 500-1600 deg.c in two steps: the first step, roasting at 1000-1600 ℃ oxygen-free atmosphere; second, baking at 500-1000 deg.C in oxygen-containing atmosphere.

5. The catalyst of claim 4,

the pore-forming agent is at least one of activated carbon, charcoal and graphite; and/or

The inorganic oxide is at least one of alumina, silica, titania and zirconia; and/or

The binder is one or more of cellulose, sugar and starch; and/or

The weight ratio of the inorganic oxide to the pore-forming agent to the binder is 10-20: 1-5: 1; and/or

The drying time is 1-10h, the presintering time is 5-15h, the first-step roasting time is 5-20h, and the second-step roasting time is 5-15 h.

6. A process for preparing the catalyst of any one of claims 1 to 5, which process comprises:

(1) adding a material containing an active component element Mo and optionally Y into water to prepare a mixture I; adding a material containing active component elements Bi, Fe, Ni, optionally X, optionally Z and optionally Q into water to prepare a mixture II;

(2) mixing the mixture I and the mixture II to prepare slurry;

(3) loading the slurry on a high-void macroporous carrier;

(4) and (4) roasting.

7. The preparation method according to claim 6, wherein a drying step is included after the step (3) and before the step (4), and the drying temperature is 80-150 ℃.

8. The production method according to claim 6, wherein the production method of the high-void macroporous carrier comprises:

(1) mixing inorganic oxide, pore-forming agent and binder, kneading into clusters, and preparing into particles;

(2) drying the obtained granules at 20-180 deg.C;

(3) pre-sintering at 200-;

(4) roasting at 500-1600 deg.c in two steps: the first step, roasting at 1000-1600 ℃ oxygen-free atmosphere; second, baking at 500-1000 deg.C in oxygen-containing atmosphere.

9. The method according to claim 6, wherein the temperature of the calcination is 350 to 600 ℃ and the time of the calcination is 1 to 4 hours.

10. Use of the catalyst according to any one of claims 1 to 5 and the catalyst prepared by the process according to any one of claims 6 to 9 in the preparation of acrolein and acrylic acid by oxidation of propylene.

Technical Field

The invention relates to a catalyst for the oxidation of olefins, a process for its preparation and its use.

Background

The selective oxidation of olefin to prepare alpha and beta unsaturated acid is an important chemical process. It is common in industry to first oxidize the olefin to give an unsaturated aldehyde and then oxidize the unsaturated aldehyde to give an unsaturated acid. The process is usually carried out in two stages using two reactors and two catalysts under different reaction conditions. The first stage reaction produces mainly acrolein and, in addition, about 20% acrylic acid. The active component of the catalyst is a complex Mo and Bi composite oxide system. The improvement of the catalyst is mainly carried out from the aspects of the activity and the stability of the catalyst, such as adding transition metal into an active component to improve the activity and increase the single yield of a product; adding rare earth elements to improve the redox capability; fe, Co, Ni and other elements are added to inhibit Mo sublimation, stabilize the active components of the catalyst, prolong the service life of the catalyst and the like. In addition, due to the violent exothermic phenomenon in the reaction, the control of the reaction temperature of the catalyst bed layer is very important, and the formation of hot spots not only deteriorates the reaction performance, but also shortens the service life of the catalyst and influences the stable operation of the device.

US Pat4224187, 4248803 proposes to improve the olefin conversion and the yield of the target product by improving the components of the catalyst and their dosage ratios and the catalyst preparation method. The method is used for selective oxidation of isobutene and has the problem of low reaction selectivity. Wherein, the conversion rate of isobutene reaches up to 99 percent, but the total yield of methacrolein and methacrylic acid is only 73.6 percent.

US Pat6268529 proposes a propylene oxidation catalyst with a propylene conversion of 98.1%, acrolein yield of 65.3%, acrylic acid yield of 20.8%, and total acrolein, acrolein yield of 86.1%.

CN1564709 improves catalyst performance by adding organic carboxylic acid to overcome catalyst nonuniformity caused by layering between metal salts in the process of catalyst preparation and coprecipitation. Is used for selective oxidation reaction of propylene. Wherein, the conversion rate of propylene is 98.12% at most, the selectivity of acrolein is 82.53% at most, and the total yield of acrolein and acrylic acid is 91.05%.

ZL97191983.6, ZL00122609.6 and ZL01111960.8 achieve the purposes of controlling reaction hot spots and prolonging the stability of the catalyst by arranging a plurality of catalyst layers with gradually increased reaction activity from a reaction gas inlet to an outlet along the axial direction of the reactor. The modulation of the reaction activity is realized by changing the proportion of active components of the catalyst to the inert carrier, changing the proportion of main components in the catalyst such as Bi, Fe and Mo, the calcination temperature of the catalyst, adjusting the type and the dosage of alkali metal and the like.

In order to control the formation of hot spots, the activity of the catalyst is usually modulated by changing the formula of the catalyst by a chemical method, which has the following disadvantages: 1. the composition of the finished catalyst deviates from the optimal value, the performance difference of each section of catalyst is large, the indexes of the catalyst such as conversion rate, selectivity and the like are easy to contradict with each other, and the adjustment margin is small; 2. the preparation process of the catalyst is complex, the quality management difficulty is increased, and the method is equivalent to the method for simultaneously producing various grades of catalysts.

Disclosure of Invention

The technical problem to be solved by the invention is to overcome the problems of low conversion rate of propylene and low yield of acrolein and acrylic acid of the existing catalyst, and provide a novel olefin oxidation catalyst, a preparation method and application thereof.

In order to achieve the above object, the present invention provides an olefin oxidation catalyst, comprising the following components by weight:

(1) 30-60% of MoO-containing₃、Bi₂O₃、Fe₂O₃And NiO;

(2) 40-70% of high-porosity macroporous carrier;

the porosity of the high-porosity macroporous carrier is 40-70%, and the average pore diameter is 0.5-20 um.

Preferably, the high-porosity macroporous carrier is at least one of alumina, silica, titania or zirconia; and/or the high-porosity macroporous carrier has a porosity of 45-55% and an average pore diameter of 1-15 um.

Preferably, it contains MoO₃、Bi₂O₃、Fe₂O₃And NiO as an active component represented by the following general formula in terms of atomic ratio: MoBi_aFe_bNi_cX_dY_eZ_fQ_gO_χWherein X is at least one selected from Mg, Co, Ca, Cu, Zn and Mn; y is at least one selected from Nb, Sb and W; z is at least one selected from K, Rb, Na, Li, Ti and Cs; q is at least one of La, Ce, Sm and Th; the value range of a is 0.01-0.5; the value range of b is 0.01-0.7; the value range of c is 0.01-1.0; the value range of d is 0.02-0.8; the value range of e is 0.05-0.6; the value range of f is>0 is less than or equal to 0.05; the value range of g is 0.01-0.5; and chi is the total number of oxygen atoms required to satisfy the valences of the other elements.

Preferably, the method for preparing the high-porosity macroporous carrier comprises the following steps: (1) mixing inorganic oxide, pore-forming agent and binder, kneading into clusters, and preparing into particles; (2) drying the obtained granules at 20-180 deg.C; (3) pre-sintering at 200-; (4) roasting at 500-1600 deg.c in two steps: the first step, roasting at 1000-1600 ℃ oxygen-free atmosphere; second, baking at 500-1000 deg.C in oxygen-containing atmosphere.

Preferably, the pore-forming agent is at least one of activated carbon, charcoal, and graphite.

Preferably, the inorganic oxide is at least one selected from the group consisting of alumina, silica, titania and zirconia.

The invention provides a preparation method of the olefin oxidation catalyst, which comprises the following steps:

(1) adding a material containing an active component element Mo and optionally Y into water to prepare a mixture I; adding a material containing active component elements Bi, Fe, Ni, optionally X, optionally Z and optionally Q into water to prepare a mixture II;

(2) mixing the mixture I and the mixture II to prepare slurry;

(3) loading the slurry on a high-void macroporous carrier;

(4) and (4) roasting.

Preferably, wherein after step (2) and before step (3), a drying step is included.

Preferably, the drying temperature is 80-150 ℃.

Preferably, the roasting temperature is 350-600 ℃, and the roasting time is 1-4 hours.

Preferably, the method for preparing the high-porosity macroporous carrier comprises the following steps:

(1) mixing inorganic oxide, pore-forming agent and binder, kneading into clusters, and preparing into particles;

(2) drying the obtained granules at 20-180 deg.C;

(3) pre-sintering at 200-;

(4) roasting at 500-1600 deg.c in two steps: the first step, roasting at 1000-1600 ℃ oxygen-free atmosphere; second, baking at 500-1000 deg.C in oxygen-containing atmosphere.

Preferably, the binder is one or more of cellulose, sugar and starch.

Preferably, the weight ratio of the inorganic oxide to the pore-forming agent to the binder is 10-20: 1-5: 1.

preferably, the drying time is 1-10h, the pre-sintering time is 5-15h, the first-step roasting time is 5-20h, and the second-step roasting time is 5-15 h.

The invention provides the catalyst and the application of the catalyst prepared by the method in the preparation of acrolein and acrylic acid by propylene oxidation.

The invention adopts the catalyst forming process parameter adjustment to adjust the catalyst activity, is simple and easy to implement, can effectively control the temperature of the catalyst bed layer, avoids the temperature from being excessively accumulated to form obvious hot spots, improves the catalyst performance, simplifies the catalyst preparation process and improves the production efficiency. The main principle for regulating the activity of the catalyst is as follows: for shaped catalysts used in the oxidation of olefins such as propylene, the reaction control step is a diffusion step of the reactants and products; by controlling the addition of the pore-forming agent in the preparation of the catalyst forming process and adopting a preferred removal method, the pores among the formed catalyst particles can be adjusted, the diffusion speed of reaction gas in the catalyst is influenced, and the activity and the reaction performance of the catalyst are further changed; increasing the compression ratio decreases the catalyst activity and also decreases the reaction exotherm.

The catalyst is used for preparing acrylic acid by propylene selective oxidation, and the molar ratio of propylene to air is 1 (6-8), the reaction temperature is 350-420 ℃, the reaction pressure is 0-0.05MPa, and the volume mass space velocity of the raw material gas is 800-1100ml.g^-1h^-1Under the condition, the conversion rate of propylene is more than 97%, the total yield of acrolein and acrylic acid is more than 92%, the device is stable in operation, the single-row operation is large, and the hot spot is easy to control.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides an olefin oxidation catalyst, which comprises the following components in percentage by weight:

(1) 30-60% of MoO-containing₃、Bi₂O₃、Fe₂O₃And NiO;

(2) 40-70% of high-porosity macroporous carrier;

the porosity of the high-porosity macroporous carrier is 40-70%, and the average pore diameter is 0.5-20 um.

According to the present invention, the high-void macroporous carrier may be any carrier as long as it satisfies the above-mentioned porosity and pore size requirements, and there is no particular requirement for the kind thereof, and any carrier of the prior art may be used in the present invention.

According to a preferred embodiment of the present invention, the high-void macroporous support preferably has a porosity of 45 to 55% and an average pore diameter of 1um to 15 um.

According to the present invention, it is preferable that the pore-forming agent is at least one of activated carbon, charcoal and graphite.

According to the present invention, it is preferable that the inorganic oxide is at least one selected from the group consisting of alumina, silica, titania and zirconia.

According to a preferred embodiment of the invention, the MoO is contained₃、Bi₂O₃、Fe₂O₃And NiO can be represented by the following general formula in terms of atomic ratio: MoBi_aFe_bNi_cX_dY_eZ_fQ_gO_χWherein X is preferably at least one selected from Mg, Co, Ca, Cu, Zn or Mn; y is at least one preferably selected from Nb, Sb and W; z is at least one selected from K, Rb, Na, Li, Ti and Cs; q is at least one of La, Ce, Sm and Th.

According to a preferred embodiment of the present invention, a is in a range of 0.01 to 0.5; the value range of b is 0.01-0.7; the value range of c is 0.01-1.0; the value range of d is 0.02-0.8; the value range of e is 0.05-0.6; the value range of f is more than 0 and less than or equal to 0.05; the value range of g is 0.01-0.5; and chi is the total number of oxygen atoms required to satisfy the valences of the other elements.

According to a preferred embodiment of the invention, the MoO is contained₃、Bi₂O₃、Fe₂O₃And NiO as an active component represented by the following general formula in terms of atomic ratio: MoBi_aFe_bNi_cX_dY_eZ_fQ_gO_χWherein X is at least one selected from Mg, Co, Ca, Cu, Zn and Mn; y is selected fromAt least one of Nb, Sb, and W; z is at least one selected from K, Rb, Na, Li, Ti and Cs; q is at least one of La, Ce, Sm and Th; the value range of a is 0.01-0.5; the value range of b is 0.01-0.7; the value range of c is 0.01-1; the value range of d is 0.02-0.8; the value range of e is 0.05-0.6; the value range of f is>0 is less than or equal to 0.05; the value range of g is 0.01-0.5; and chi is the total number of oxygen atoms required to satisfy the valences of the other elements.

The catalyst having the aforementioned composition can achieve the object of the present invention, and the preparation method thereof is not particularly required, and for the present invention, it is preferable that the preparation step of the catalyst comprises:

(1) adding a material containing an active component element Mo and optionally Y into water to prepare a mixture I; adding a material containing active component elements Bi, Fe, Ni, optionally X, optionally Z and optionally Q into water to prepare a mixture II;

(2) mixing the mixture I and the mixture II to prepare slurry;

(3) loading the slurry on a high-porosity macroporous carrier;

(4) and (4) roasting.

According to the invention, a drying step is included after step (3) and before step (4).

According to the invention, the slurry I can be a solution, a suspension or a mixture of the solution and the suspension.

According to the present invention, the conditions for the calcination are not particularly limited as long as the conditions are such that the specific compound forms of all the active elements present in the dispersion can be calcined into the oxide form, and those skilled in the art can select the conditions for the calcination appropriately without any creative effort.

According to a preferred embodiment of the invention, the drying temperature is, by way of example only, between 80 and 150 ℃.

According to a preferred embodiment of the present invention, the calcination time is 1 to 12 hours.

According to a preferred embodiment of the invention, the firing temperature is, by way of example only, 350 to 600 ℃. The roasting atmosphere is inert atmosphere or containsO₂Of the atmosphere (c). However, the atmosphere for the calcination is preferably air from the economical viewpoint. If not specially noted, the roasting atmosphere is air, and the roasting time is 1-4 hours.

According to a preferred embodiment of the present invention, the method for preparing the high-void macroporous carrier preferably comprises:

(1) mixing inorganic oxide, pore-forming agent and binder, kneading into clusters, and preparing into particles;

(2) drying the obtained granules at 20-180 deg.C;

(3) pre-sintering at 200-;

(4) roasting at 500-1600 deg.c in two steps: the first step, roasting at 1000-1600 ℃ oxygen-free atmosphere; second, baking at 500-1000 deg.C in oxygen-containing atmosphere.

According to the present invention, preferably, the oxygen-free atmosphere is an inert atmosphere, such as a nitrogen atmosphere.

The invention is preferably carried out in an air atmosphere, unless otherwise indicated.

According to a preferred embodiment of the invention, the binder is one or more of cellulose, sugar and starch.

According to a preferred embodiment of the present invention, the weight ratio of inorganic oxide, pore former and binder can be selected within a wide range, preferably within the range of 10 to 20: 1-5: 1.

according to a preferred embodiment of the invention, the drying time is of little influence on the invention, preferably the drying time is 1-10 h.

According to the preferred embodiment of the present invention, the burn-in time can be selected in a wide range, and the burn-in time is preferably 5-15 h.

According to the preferred embodiment of the present invention, the time for the first step calcination can be selected from a wide range, and the time for the first step calcination is preferably 5 to 20 hours.

According to the preferred embodiment of the present invention, the time for the second-step firing can be selected within a wide range, and preferably the time for the second-step firing is 5 to 15 hours.

The invention provides the application of the catalyst in the preparation of acrolein and acrylic acid by propylene oxidation.

The technical key of the invention is the selection of the catalyst, which can be reasonably selected by the skilled person for the specific application method and process conditions without creative efforts, such as:

the method for preparing acrolein and acrylic acid by propylene oxidation comprises the step of reacting propylene with oxidizing gas containing oxygen in the presence of the catalyst to obtain the acrolein and the acrylic acid.

According to the present invention, in order to make the reaction more stable and controllable, it is preferable to carry out the reaction in the presence of a dilute gas phase material.

According to the invention, the oxidizing gas may be pure oxygen, enriched with oxygen, but is preferably air from an economic point of view.

According to the invention, the dilute gas phase feed is preferably steam.

According to the invention, the reaction temperature can be selected from 100-500 ℃.

According to the present invention, in a raw material gas composed of propylene, air and steam, in terms of volume ratio, propylene: air: the steam is 1 (6-8) and (0.5-5).

According to the invention, the volume mass space velocity of the raw material gas is as follows: 800-^-1h^-1

According to the invention, the volume space velocity of the feed gas is 800-2000 h^-1。

The investigation and evaluation conditions of the catalyst obtained by the method of the invention are as follows:

a reactor: fixed bed single-pipe reactor with inner diameter of 26.0 mm and reactor length of 3500 mm

Catalyst: 900 g

Reaction temperature: 380 deg.C

Reaction pressure: 0.02MPa

Raw material molar ratio: propylene and air 1:7

Propylene steam 1:2

Volume mass space velocity of raw material gas: 1000ml.g^-1h^-1

The reaction product was absorbed with dilute acid at 0 ℃ and the product was analyzed by gas chromatography. And calculating the carbon balance, wherein the carbon balance is effective data when the carbon balance is (95-105)%.

Propylene conversion, product yield and selectivity are defined as:

the invention adopts the adjustment of the molding process parameters to adjust the activity of the catalyst, is simple and easy to implement, can effectively control the temperature of the catalyst bed layer, avoids the formation of obvious hot spots due to excessive temperature accumulation, improves the performance of the catalyst, simplifies the preparation process of the catalyst and improves the production efficiency. The main principle for regulating the activity of the catalyst is as follows: for the formed catalyst adopted by the oxidation reaction, the reaction control step is a diffusion step of reactants and products; the pores among the catalyst forming particles can be adjusted by controlling the compression ratio in the preparation process of the catalyst forming, so that the diffusion speed of reaction gas in the catalyst is influenced, and the activity and the reaction performance of the catalyst are further changed; increasing the compression ratio decreases the catalyst activity and also decreases the reaction exotherm.

The volumetric mass space velocity in the present invention means the volume of the gaseous material to be treated per unit mass of the catalyst per unit time.

The catalyst is used for preparing acrylic acid by propylene selective oxidation, the molar ratio of propylene to air is 1 (6-8), the reaction temperature is 350-420 ℃, the reaction pressure is 0-0.05MPa, and the volume mass space velocity of the raw material gas is 800-1100ml.g^-1h^-1Under the condition, the conversion rate of propylene is more than 97%, the total yield of acrolein and acrylic acid is more than 92%, the device is stable in operation, the single-row operation is large, and the hot spot is easy to control.

Example 1

350 g of alumina, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be prepared into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃, and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity macroporous alumina (the porosity is 60 percent, and the average pore diameter is 1200 nm).

Weighing Bi equivalent to 50 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to obtain a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. And mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry, mixing the slurry with 50 g of high-porosity and large-pore alumina (with the porosity of 60 percent and the average pore diameter of 1200nm), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Example 2

350 g of alumina, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be prepared into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃, and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity macroporous alumina (the porosity is 60 percent, and the average pore diameter is 1200 nm).

Weighing Bi equivalent to 50 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to obtain a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. And mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry 1, mixing the slurry 1 with 50 g of high-porosity macroporous silica (with the porosity of 60 percent and the average pore diameter of 1200nm), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Example 3

350 g of alumina, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be prepared into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃, and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity macroporous alumina (the porosity is 60 percent, and the average pore diameter is 1200 nm).

Weighing Bi equivalent to 50 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, iron nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to give a mixture i; adding bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate and lanthanum nitrateThen the mixture II is obtained in 50ml of water. Mixing the mixture I and the mixture II to obtain slurry, and concentrating to obtain 80ml of slurry 1; mixing the slurry 1 with 50 g of high-porosity macroporous titanium oxide (porosity is 60%, average pore diameter is 1200nm), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Example 4

280 g of alumina, 70 g of silica, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be made into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃ and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity and large-pore alumina and silica composite carrier (the porosity is 60%, the average pore diameter is 1200nm, and the weight ratio of silica to alumina is 1: 4).

Weighing Bi equivalent to 50 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to obtain a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. Mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml slurry 1, mixing the slurry 1 with 50 g of high-porosity and large-pore alumina and silica composite carrier (the porosity is 60%, the average pore diameter is 1200nm, and the weight ratio of silica to alumina is 1: 4), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Example 5

210 g of alumina, 70 g of silica, 70 g of zirconia, 60 g of charcoal and 20 g of dextrin were mixed uniformly, 110 g of water was added, and the mixture was kneaded into pellets. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃ and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity and large-pore alumina, silica and zirconia composite carrier (the porosity is 60%, the average pore diameter is 1200nm, and the weight ratio of the silica to the alumina to the zirconia is 1: 3: 1).

Weighing Bi equivalent to 50 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to obtain a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. Mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry 1, mixing the slurry 1 with 50 g of high-porosity and large-pore alumina, silica and zirconia composite carrier (the porosity is 60%, the average pore diameter is 1200nm, and the weight ratio of the silica to the alumina to the zirconia is 1: 3: 1), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Example 6

350 g of alumina, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be prepared into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃, and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity macroporous alumina (the porosity is 60 percent, and the average pore diameter is 1200 nm).

Weighing Bi equivalent to 50 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to obtain a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. And mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry 1, loading the slurry 1 on 50 g of high-porosity macroporous alumina (with the porosity of 60 percent and the average pore diameter of 1200nm) by adopting a multi-time impregnation method (drying at 100 ℃ before each impregnation), drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Example 7

350 g of alumina, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be prepared into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃, and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity macroporous alumina (the porosity is 60 percent, and the average pore diameter is 1200 nm).

Weighing Bi equivalent to 50 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein Bi, Fe, Ni, K, Mg, La, SbAnd the atomic ratios of Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2), respectively, wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to obtain a mixture I; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. And mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry 1, spraying the slurry 1 on the surface of 50 g of high-porosity macroporous alumina (with the porosity of 60 percent and the average pore diameter of 1200nm) by adopting a spray drying method, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Example 8

350 g of alumina, 55 g of charcoal and 20 g of dextrin are mixed uniformly, 105 g of water is added, and the mixture is kneaded into a mass to be made into granules. Drying at 120 deg.C for 2 hr, heating to 250 deg.C in air atmosphere, holding the temperature for 8 hr, heating to 1100 deg.C in nitrogen atmosphere, holding the temperature for 15 hr, cooling to 900 deg.C, and holding the temperature in air atmosphere for 10 hr to obtain high-porosity macroporous alumina (porosity 55%, average pore diameter 1000 nm).

Weighing Bi equivalent to 50 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, iron nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to give a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. Mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml slurry 1, mixing the slurry 1 with 50 g of high-porosity macroporous alumina (porosity 55%, average pore diameter 1000nm), stirring, steaming at 80 deg.C until no visible liquid exists, drying at 120 deg.C for 12 hr, and calcining at 550 deg.C in air atmosphereThe catalyst was obtained in 2 hours. The catalyst evaluation results are shown in Table 1.

Example 9

350 g of alumina, 50 g of charcoal and 20 g of dextrin are mixed uniformly, 100 g of water is added, and the mixture is kneaded into a mass to be prepared into granules. Drying at 120 deg.C for 2 hr, heating to 250 deg.C in air atmosphere, holding the temperature for 8 hr, heating to 1100 deg.C in nitrogen atmosphere, holding the temperature for 15 hr, cooling to 900 deg.C, and holding the temperature in air atmosphere for 10 hr to obtain the high-porosity and large-pore alumina (porosity 50%, average pore diameter 1500 nm).

Weighing Bi equivalent to 50 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, iron nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to give a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. And mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry 1, mixing the slurry 1 with 50 g of high-porosity and large-pore alumina (with the porosity of 50 percent and the average pore diameter of 1500nm), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Example 10

350 g of alumina, 40 g of charcoal and 30 g of dextrin are mixed uniformly, 100 g of water is added, and the mixture is kneaded into a mass to be prepared into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃, and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity macroporous alumina (the porosity is 45 percent, and the average pore diameter is 600 nm).

Weighing Bi equivalent to 50 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, iron nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to give a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. And mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry 1, mixing the slurry 1 with 50 g of high-porosity and large-pore alumina (with the porosity of 45 percent and the average pore diameter of 600nm), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Comparative example 1

350 g of alumina, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be prepared into granules. Drying at 120 deg.C for 2 hr, heating to 250 deg.C in air atmosphere, holding the temperature for 8 hr, heating to 1100 deg.C, and holding the temperature for 15 hr to obtain macroporous alumina (porosity 20%, average pore diameter 1200 nm).

Weighing Bi equivalent to 50 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, iron nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to give a mixture i; bismuth nitrate, ferric nitrate, nickel nitratePotassium nitrate, magnesium nitrate and lanthanum nitrate were added to 50ml of water to obtain a mixture II. And mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry 1, mixing the slurry 1 with 50 g of macroporous alumina (with the porosity of 20 percent and the average pore diameter of 1200nm), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Comparative example 2

350 g of alumina and 70 g of dextrin are mixed evenly, 110 g of water is added, and the mixture is kneaded into balls to be made into particles. Drying at 120 deg.C for 2 hr, heating to 250 deg.C in air atmosphere, holding the temperature for 8 hr, heating to 750 deg.C, and holding the temperature for 15 hr to obtain high-porosity alumina.

Weighing Bi equivalent to 50 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, iron nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to give a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. And mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry 1, mixing the slurry 1 with 50 g of high-void alumina, steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 2 hours in an air atmosphere to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Comparative example 3

350 g of alumina and 70 g of dextrin are mixed evenly, 70 g of water is added, and the mixture is kneaded into balls to be made into particles. Drying at 120 deg.C for 2 hr, heating to 950 deg.C in air atmosphere, and holding at constant temperature for 15 hr to obtain the high-porosity and large-pore alumina.

Is weighed quiteAt 50 g of Bi₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, iron nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to give a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. And mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry 1, mixing the slurry 1 with 50 g of alumina (with the porosity of 20 percent and the average pore diameter of 100nm), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Example 11

350 g of alumina, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be prepared into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃, and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity macroporous alumina (the porosity is 60 percent, and the average pore diameter is 1200 nm).

Weighing Bi equivalent to 30 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, iron nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water,obtaining a mixture I; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. And mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry 1, mixing the slurry 1 with 70 g of high-porosity and large-pore alumina (with the porosity of 60 percent and the average pore diameter of 1200nm), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Example 12

350 g of alumina, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be prepared into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃, and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity macroporous alumina (the porosity is 60 percent, and the average pore diameter is 1200 nm).

Weighing Bi equivalent to 60 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, iron nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to give a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. And mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry 1, mixing the slurry 1 with 40 g of high-porosity and large-pore alumina (with the porosity of 60 percent and the average pore diameter of 1200nm), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Comparative example 4

350 g of alumina, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be prepared into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃, and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity macroporous alumina (the porosity is 60 percent, and the average pore diameter is 1200 nm).

Weighing Bi equivalent to 20 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, iron nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to give a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. And mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry 1, mixing the slurry 1 with 80 g of high-porosity and large-pore alumina (with the porosity of 60 percent and the average pore diameter of 1200nm), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Comparative example 5

350 g of alumina, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be prepared into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃, and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity and large-pore alumina.

Weighing Bi equivalent to 80 g₂O₃、Fe₂O₃、NiO、K₂O、MgO、La₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, iron nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate, ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Mg, La, Sb, Nb and W to Mo are 0.3, 0.5, 0.8, 0.03, 0.5, 0.2, 0.1 and 0.2, respectively), wherein ammonium heptamolybdate, antimony trioxide, niobium oxalate and ammonium metatungstate are dissolved in 50ml of water to give a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, magnesium nitrate, lanthanum nitrate were added to 50ml of water to obtain a mixture II. And mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml of slurry 1, mixing the slurry 1 with 20 g of high-porosity and large-pore alumina (with the porosity of 60 percent and the average pore diameter of 1200nm), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Example 13

280 g of alumina, 70 g of silica, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be made into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃ and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity and large-pore alumina and silica composite carrier (the porosity is 60%, the average pore diameter is 1200nm, and the weight ratio of silica to alumina is 1: 4).

Weighing Bi equivalent to 80 g₂O₃、Fe₂O₃、NiO、Rb₂O、MgO、ZnO、MnO、Ce₂O₃、MoO₃、Sb₂O₃、Nb₂O₃And WO₃Bismuth nitrate, ferric nitrate, nickel nitrate, rubidium nitrate, magnesium nitrate, zinc nitrate, manganese nitrate, cerium nitrate, ammonium heptamolybdate, and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, Rb, Mg, Zn, Mn, Ce, and W to Mo are 0.02, 0.7, 0.02, 0.01, 0.2, 0.1, 0.5, 0.01, and 0.1, respectively), wherein ammonium heptamolybdate and ammonium metatungstate are dissolved in 50ml of water to obtain a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, rubidium nitrate, magnesium nitrate, zinc nitrate, manganese nitrateCerium nitrate was added to 50ml of water to obtain a mixture II. Mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml slurry 1, mixing the slurry 1 with 50 g of high-porosity and large-pore alumina and silica composite carrier (the porosity is 60%, the average pore diameter is 1200nm, and the weight ratio of silica to alumina is 1: 4), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 450 ℃ in air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Example 14

280 g of alumina, 70 g of silica, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be made into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃ and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity and large-pore alumina and silica composite carrier (the porosity is 60%, the average pore diameter is 1200nm, and the weight ratio of silica to alumina is 1: 4).

Weighing Bi equivalent to 80 g₂O₃、Fe₂O₃、NiO、K₂O、Cs₂O、Tl₂O、Co₂O₃、CaO、CuO、La₂O₃、Ce₂O₃、Sm₂O₃、MoO₃、Sb₂O₃And WO₃Bismuth nitrate, iron nitrate, nickel nitrate, potassium nitrate, cesium nitrate, thallium nitrate, cobalt nitrate, calcium nitrate, copper nitrate, lanthanum nitrate, cerium nitrate, samarium nitrate, ammonium heptamolybdate, antimony trioxide, and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, K, Cs, Tl, Co, Ca, Cu, La, Ce, Sm, Sb, and W to Mo are 0.5, 0.01, 1.0, 0.02, 0.01, 0.2, 0.1, 0.2, and 0.4, respectively), wherein ammonium heptamolybdate, antimony trioxide, and ammonium metatungstate are dissolved in 50ml of water to give a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, potassium nitrate, cesium nitrate, thallium nitrate, cobalt nitrate, calcium nitrate, copper nitrate, lanthanum nitrate, cerium nitrate, and samarium nitrate were added to 50ml of water to obtain a mixture II. Mixing mixture I and mixture II to obtain slurry, and concentrating to obtainWhen the volume of the slurry 1 is 80ml, the slurry 1 is mixed with 50 g of high-porosity and large-pore alumina and silica composite carrier (the porosity is 60%, the average pore diameter is 1200nm, and the weight ratio of silica to alumina is 1: 4), the mixture is stirred and steamed at 80 ℃ until no visible liquid exists, the mixture is dried at 120 ℃ for 12 hours, and the mixture is roasted at 450 ℃ for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

Example 15

280 g of alumina, 70 g of silica, 60 g of charcoal and 20 g of dextrin are mixed uniformly, 110 g of water is added, and the mixture is kneaded into a mass to be made into granules. Drying at 120 ℃ for 2 hours, heating to 250 ℃ in air atmosphere, keeping the temperature constant for 8 hours, heating to 1100 ℃ in nitrogen atmosphere, keeping the temperature constant for 15 hours, cooling to 900 ℃, and keeping the temperature constant for 10 hours in air atmosphere to obtain the high-porosity and large-pore alumina and silica composite carrier.

Weighing Bi equivalent to 80 g₂O₃、Fe₂O₃、NiO、Na₂O、MgO、Co₂O₃、MnO、PbO、La₂O₃、ThO₂、MoO₃And WO₃Bismuth nitrate, iron nitrate, nickel nitrate, sodium nitrate, magnesium nitrate, cobalt nitrate, manganese nitrate, lead nitrate, lanthanum nitrate, thorium nitrate, ammonium heptamolybdate, and ammonium metatungstate (wherein the atomic ratios of Bi, Fe, Ni, Na, Mg, Co, Mn, Pb, La, Th, and W to Mo are 0.4, 0.6, 0.02, 0.2, 0.1, 0.2, 0.1, and 0.3, respectively), wherein ammonium heptamolybdate and ammonium metatungstate are dissolved in 50ml of water to obtain a mixture i; bismuth nitrate, ferric nitrate, nickel nitrate, sodium nitrate, magnesium nitrate, cobalt nitrate, manganese nitrate, lead nitrate, lanthanum nitrate, thorium nitrate were added to 50ml of water to obtain a mixture II. Mixing the mixture I and the mixture II to obtain slurry, concentrating to obtain 80ml slurry 1, mixing the slurry 1 with 50 g of high-porosity and large-pore alumina and silica composite carrier (the porosity is 60%, the average pore diameter is 1200nm, and the weight ratio of silica to alumina is 1: 4), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 450 ℃ in air atmosphere for 2 hours to obtain the catalyst. The catalyst evaluation results are shown in Table 1.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

As can be seen from the results in table 1, the carrier of the present invention can achieve a good catalytic activity when used in an oxidation reaction, and has a high yield of the target product and a high conversion rate of the reactant.

TABLE 1