CN117696058B - Catalyst carrier, catalyst, preparation method and application of catalyst - Google Patents

Abstract

The invention belongs to the technical field of catalytic materials, and particularly relates to a catalyst carrier, a catalyst, a preparation method and application thereof. The catalyst carrier provided by the invention, wherein silicon aluminum element and other element components form a composite inorganic oxide, the catalyst carrier can be regulated and controlled to have a specific structure by limiting the element proportion, particularly limiting the molar ratio of aluminum to silicon in the carrier (a/b is not less than 1.5 and not more than 3.3) and selecting IIA group elements, and the catalyst carrier is used in a catalyst, so that the connectivity between an active component and the carrier can be enhanced, the loading capacity is increased, the wear resistance is improved, the stability of the catalyst is improved, the pulverization degree of the catalyst is obviously reduced, the reaction can be carried out at a higher airspeed, the reaction capacity of the catalyst is improved, and meanwhile, the activity and the selectivity of the catalyst are also superior to those of the prior art. In addition, the catalyst carrier provided by the invention has good heat conduction performance, can rapidly transfer reaction heat to a heating medium, and finally ensures that the temperature of a hot spot of a bed layer is low.

Description

Catalyst carrier, catalyst, preparation method and application of catalyst

Technical Field

The invention belongs to the technical field of catalytic materials, and particularly relates to a catalyst carrier, a catalyst, a preparation method and application thereof.

Background

The solid catalyst is widely used in various heterogeneous catalytic reactions, and the carrier and the active component are two essential components of the solid catalyst. Wherein, the carrier plays roles of supporting, dispersing and diluting active components in the solid catalyst and improving the strength of the catalyst, and some carriers can play important roles of promoting catalysis, co-catalysis and the like. It can be seen that the quality of the support properties directly affects the solid catalyst properties.

The method for preparing unsaturated aldehyde and unsaturated carboxylic acid by using low-carbon olefin to make selective catalytic oxidation and its catalyst have been used in industry. The main and side reactions of the chemical reaction are strong exothermic reactions, hot spots are easy to form in the reactor, and when the exothermic reaction is serious, the catalyst is deactivated and the bed layer is sintered, so that the reaction can not be performed finally. Therefore, the catalyst prepared by direct extrusion molding using the active component has disadvantages in that: firstly, the active components are large in usage amount, concentrated in active sites and small in pore size, so that the reaction is severe, the reaction effect is not ideal, the hot spot temperature is high, and if the activity is controlled improperly, the temperature is easy to fly; secondly, the extrusion molding catalyst has poor strength, is easy to pulverize and has short service life; third, the high production cost is caused by the large amount of active components, and the production process of extrusion molding is more complex. Aiming at the problems, in order to fully utilize active components and prolong the service life of the catalyst, the structure of the solid catalyst needs to be adjusted to meet the actual industrial requirements. In this regard, researchers have developed supported catalysts. The supported catalyst has the advantages of high strength, high abrasion resistance, easy filling, avoiding the generation of local hot spots, improving the reaction performance and prolonging the service life of the catalyst.

At present, a method for preparing unsaturated aldehyde and/or unsaturated carboxylic acid by utilizing a supported catalyst to prepare low-carbon olefin through selective catalytic oxidation is proposed. For example, the prior patent literature discloses a surface-modified support, a composite metal oxide catalyst prepared from the surface-modified support, and its use in converting a low-carbon olefin into an unsaturated aldehyde and/or an unsaturated carboxylic acid. However, the pulverization degree of the catalyst is still higher, and the raw material conversion rate, the target product yield and the like are still required to be further improved.

Disclosure of Invention

Therefore, the technical problem to be solved by the invention is to overcome the defects of high pulverization degree, raw material conversion rate, target product yield and the like of the supported catalyst in the prior art, thereby providing a catalyst carrier, a catalyst, a preparation method and application thereof.

Therefore, the invention provides the following technical scheme:

the invention provides a catalyst carrier, which is a composite inorganic oxide, wherein the composition general formula of the composite inorganic oxide is as follows: al _aSi_bX¹ _cX² _dX³ _eO_x;

In the general formula:

X ¹ is at least one of zinc, cadmium, titanium, zirconium, vanadium, niobium, chromium, manganese and iron, cobalt and nickel of IIB group elements;

x ² is at least one of Na and K of IA group element;

x ³ is at least one of calcium and magnesium of IIA group element;

a, b, c, d, e and x are the atomic ratio of each element, wherein a is more than or equal to 1 and less than or equal to 10,0.3 and b is more than or equal to 5.2, and a/b is more than or equal to 1.5 and less than or equal to 3.3; c is more than or equal to 0.001 and less than or equal to 0.1,0.001, d is more than or equal to 2.7,0.01, e is more than or equal to 0.1, and x is a value determined by the oxidation degree of the metal element.

Optionally, the shape of the catalyst carrier is annular, spherical, cylindrical, hollow cylindrical or bar-shaped;

and/or, in a microscopic state, the surface of the catalyst support has a fluff structure, a fiber structure, a brush structure, a crack structure or a cluster structure composed of linear fibers.

The invention also provides a preparation method of the catalyst carrier, which comprises the following steps:

and mixing the raw material components containing the elements in the general formula with a binder, forming, and calcining to obtain the catalyst carrier.

Optionally, the mass ratio of the raw material components to the binder is 100: (0-10);

and/or the binder comprises at least one of water, silica sol, alumina sol, polyvinyl alcohol, graphite, or crystalline cellulose.

In the present invention, the raw material component of the catalyst carrier containing each element is not particularly limited as long as it is a compound capable of becoming the corresponding oxide upon calcination, and is water-soluble or poorly-soluble. As specific examples of the raw material compound, there may be mentioned halides, sulfates, nitrates, ammonium salts, oxides, carboxylates, ammonium salts of carboxylic acids, ammonium halides, acetylacetonates, alkoxides and the like of the respective elements in the general formula. Specific examples of the raw material compound for aluminum include aluminum sol, aluminum sulfate, aluminum hydroxide, and aluminum oxide. Specific examples of the silicon raw material compound include silica sol, fine silica powder, and granular silica. In addition, natural mineral raw materials containing these elements such as boehmite, quartz, bauxite, feldspar, fluorite, magnesite, anatase, clay, kaolin, mullite, talc and the like can also be used. The compounds containing the respective components alone may be used, or the raw material compounds containing 2 or more components may be used. When the raw material component is selected from these components capable of being used as a binder, such as an aluminum sol, a silica sol, etc., other binder components may not be additionally added.

Optionally, the calcining temperature is 900-1600 ℃ and the calcining time is 0.5-5h;

optionally, the calcination temperature is 1200-1450 ℃.

The invention also provides a catalyst, which comprises a carrier and an active component carried on the surface of the carrier, wherein the carrier is the catalyst carrier or the catalyst carrier prepared by the preparation method.

Optionally, the active component is a composite metal oxide containing molybdenum, bismuth and iron, and the general formula composition is shown in the following formula (I):

Mo_aBi_bFe_cA¹ _dB² _eC³ _fSi_gO_x(I)

In the general formula:

A ¹ is selected from at least one of cobalt, nickel and manganese of VIII B group elements;

B ² is at least one of copper, hafnium, scandium, vanadium, tungsten and zirconium in group IB and IVB-VIB elements;

C ³ is selected from at least one of Na, K, rb and Cs of IA family element; si is silicon and O is oxygen;

a to f are the proportions of the respective elements, and when a=12, b=0.6 to 6, c=0.1 to 8, d=3 to 10, e=1 to 5, f=0.05 to 1, g=0 to 40; x is a number satisfying the oxidation state of other metal elements in the general formula.

8. The catalyst of claim 6, wherein the active component is a composite metal oxide containing molybdenum, vanadium, tellurium, copper, and having a general formula composition represented by the following formula (II):

Mo_aV_bCu_cTe_dM¹ _eM² _fM³ _gO_x(Ⅱ)

In the general formula:

m ¹ is selected from at least one element selected from tungsten and niobium;

m ² is at least one element selected from magnesium, calcium, strontium and barium;

m ³ is at least one element selected from the group consisting of antimony, tin, and phosphorus, bismuth, and titanium;

a to g are the proportions of the elements, and when a=12, b=1 to 8, c=0.1 to 4, d=0.05 to 1, e=0.5 to 3, and f=0.01 to 1; g=0.01 to 30; x is a number satisfying the oxidation state of other metal elements in the general formula.

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

S1, preparing an active component precursor;

s2, mixing the catalyst carrier with the active component precursor, granulating and roasting to obtain the catalyst.

Optionally, the mass ratio of the catalyst carrier to the active component precursor is 1: (0.2-0.6).

Typically, but not by way of limitation, some wetting agent (e.g., water) and reinforcing components (e.g., glass fibers) may be added during the pelletization process to facilitate the formation of the components while increasing the strength of the catalyst. The amounts added are conventional in the art and may, for example, be 5 to 10% of the mass of the active ingredient precursor, respectively.

In the present invention, the method for preparing the active ingredient precursor is conventional in the art, for example: the raw material components containing each element in the active component can be dissolved in water and/or concentrated nitric acid, spray-dried and pre-calcined to obtain an active component precursor; or coprecipitating part of raw material components containing elements in the active components to obtain solid powder, and then directly mixing the solid powder with oxides of elements in the rest active components to obtain an active component precursor.

The invention also provides application of the catalyst in converting low-carbon olefin into unsaturated aldehyde and/or unsaturated carboxylic acid.

In the preparation process of the catalyst, the precalcination temperature is 300-400 ℃ and the precalcination time is 1-5h. The roasting temperature is 380-510 ℃ and the roasting time is 4-8h.

In the present invention, the catalyst represented by the formula (I) is a first reaction catalyst for converting an olefin into an unsaturated aldehyde, and the catalyst represented by the formula (II) is a second reaction catalyst for converting an unsaturated aldehyde into an unsaturated acid.

Optionally, the low-carbon olefin is subjected to gas-phase catalytic oxidation reaction with oxygen molecules or oxygen-containing gas to generate unsaturated aldehyde and/or unsaturated carboxylic acid.

In the present invention, the lower olefin is a C3-C4 olefin, for example, propylene or isobutylene.

The technical scheme of the invention has the following advantages:

Compared with the prior art, the catalyst carrier provided by the invention adopts the conventional silicon oxide or aluminum oxide as the carrier and adopts other elements to modify, and the catalyst carrier has a specific structure through the limitation of element proportion, particularly the limitation of the molar ratio of aluminum to silicon (a/b is more than or equal to 1.5 and less than or equal to 3.3) in the carrier and the selection of IIA group elements, so that the connectivity between an active component and the carrier can be enhanced, the loading capacity is increased, the wear resistance is improved, the stability of the catalyst is improved, the pulverization degree of the catalyst is obviously reduced, the reaction can be carried out under higher airspeed, the reaction capability of the catalyst is improved, and meanwhile, the activity and the selectivity of the catalyst are better than those of the prior art. In addition, the catalyst carrier provided by the invention has good heat conduction performance, can rapidly transfer reaction heat to a heating medium, and finally ensures that the temperature of a hot spot of a bed layer is low.

The catalyst provided by the invention obviously improves the mechanical strength of the supported catalyst, improves the yield of target products, improves the conversion rate of reactants, reduces the reaction temperature, reduces the hot spot temperature generated by strong exothermic reaction, prolongs the service life of the catalyst, and enables the long-time stable and high-efficiency production of unsaturated aldehyde and unsaturated carboxylic acid to be possible by selecting the catalyst carrier with specific composition. Meanwhile, the adopted composite inorganic oxide carrier has obvious promotion effect on the catalytic action of the active components of the catalyst, so that the activity and the selectivity of the catalyst are improved.

The catalyst provided by the invention can be used for continuously, high-yield and stable conversion of unsaturated low-carbon olefin in a longer production period, can avoid runaway reaction caused by hot spot generation or peroxidation reaction, and can be used for stable operation for a long time, so that the composite metal oxide catalyst prepared by adopting the carrier disclosed by the invention can be actively applied to the production of unsaturated aldehyde and/or unsaturated carboxylic acid.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.

FIG. 1 is a scanning electron microscope picture of the catalyst support obtained in example 1 of the present invention;

FIG. 2 is a scanning electron microscope photograph of the catalyst carrier obtained in comparative example 1 of the present invention;

FIG. 3 is a scanning electron microscope photograph of the catalyst carrier obtained in example 6 of the present invention;

FIG. 4 is a scanning electron microscope photograph of the catalyst carrier obtained in comparative example 3 of the present invention.

Detailed Description

The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.

The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.

The following are test methods and definitions of catalyst performance parameters:

(one) drop impact Strength test

100G of the catalyst was dropped from the upper part of a vertically standing stainless steel pipe having a length of 3.8m and an inner diameter of 25mm, blocked with a stainless steel plate having a thickness of 2mm, and the crushed catalyst was sieved with a 20-mesh sample sieve, and the weight of the catalyst remaining on the sample sieve was measured.

The drop impact strength is defined as follows:

Drop impact strength (%) = (weight of catalyst remaining on the screen/weight of catalyst dropped) ×100.

(II) pulverization degree test

100G of the catalyst was placed in a stainless steel cylinder 152mm long and 250mm in diameter at a rotation speed of 60 rpm for 5 minutes; the residual powder was removed by sieving with a 20 mesh sample sieve and weighed.

The expression of the chalking degree test result is as follows:

degree of pulverization (%) =100- (weight of catalyst-weight of catalyst remaining on the sieve)/weight of catalyst×100.

(III) the loading rate is defined as follows:

The loading (%) = [ (weight of the catalyst active component after calcination)/(weight of the carrier) ]×100.

The conversion, selectivity and yield of the reaction are defined as follows

Propylene/isobutylene conversion (mol%) = (moles of propylene/isobutylene involved in reaction)/(moles of propylene/isobutylene fed) ×100;

(meth) acrolein selectivity (mol%) = [ moles of (meth) acrolein formed)/(moles of propylene involved in the reaction) ×100;

Yield of (meth) acrolein (mol%) = [ number of moles of (meth) acrolein formed ]/(number of moles of propylene supplied) ×100.

Example 1

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ Carrier Al-Si-Ti-Fe-Mg ] preparation of Na-K-O oxide

6000G of boehmite powder (Walker, the same applies hereinafter), 4000g of fine silica powder, 10.65g of anatase (Walker, 99%, the same applies hereinafter), 106.46g of iron oxide, 8.3g of magnesium fluoride, 156g of sodium chloride and 99.4g of potassium chloride were mixed by a V-type mixer to obtain a solid mixture powder.

A proper amount of water (120 ml) was sprayed into the above solid powder as a binder to give the mixture a certain plasticity, and then the mixture was made into spherical particles with a size of 4.5mm by a multifunctional catalyst molding machine. The pellets were calcined at 1300 c for 3 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al _7.5Si₅Ti_0.01Fe_0.1Mg_0.01Na_0.2K_0.1O_x.

Fig. 1 is a scanning electron microscope picture of the obtained catalyst carrier, and it can be seen from the picture that the surface of the carrier can observe a high-pore special structure composed of a large number of villous or fibrous or branch-shaped structures in a microscopic state, and certain epitaxy is generated on the microscopic surface, so that the surface roughness of the carrier is enhanced, and meanwhile, a skeleton structure with microscopic scale is endowed to the surface active components of the carrier, so that the carrying capacity of the carrier is greatly enhanced.

[ Preparation of Supported composite Metal oxide catalyst ]

The basic preparation steps are as follows:

under the condition of heating and stirring, 420g of ammonium molybdate is dissolved in 2500ml of distilled water to obtain solution (A);

350g of cobalt nitrate, 75g of nickel nitrate, 80g of ferric nitrate and 30g of manganese nitrate are dissolved in 1000ml of distilled water to obtain a solution (B);

190g of bismuth nitrate was dissolved in 250ml of distilled water acidified with 25ml of concentrated nitric acid to obtain a solution (C);

then, mixing the solution (B) with the solution (C), adding the mixture into the solution (A), adding 3.0g of potassium nitrate and 200ml of 40% silica sol, drying the obtained solution by using a spray dryer at 200 ℃, and pre-calcining the dried solution at 300 ℃ for 3 hours to obtain an active component precursor; mo ₁₂Bi_2.0Fe_1.0Co_6.01Ni_1.3Mn_0.8K_0.15Si₂₀O_x.

The active component precursor is crushed and passes through a 60-mesh sample sieve to ensure that the particle size is smaller than 250 mu m.

500G of the carrier obtained above was fed into a rotary drum granulator, 300g of the active component precursor (the weight ratio of the active component precursor to the carrier is 0.6), 10wt% of glass fiber constituting the active component precursor and 5% of water were sprayed simultaneously into the rotary drum granulator, and the active component precursor and glass fiber mixture was carried on the carrier to obtain catalyst particles; finally, the particles were dried and calcined in air at 510 ℃ for 5 hours to obtain the composite metal oxide catalyst.

[ Test of Oxidation reaction ]

Test conditions: in a fixed bed reactor having an internal diameter of 25.4mm and a tube length of 4000mm, a catalyst loading height of 3500mm, propylene, oxygen (or air), nitrogen and water vapor were introduced thereinto, wherein propylene: oxygen (or air): nitrogen gas: steam=8:13.6 (65): 19.2:8, oxygen was used in this test. The total space velocity of the materials 2400h ^-1, the oxidation reaction is carried out under the conditions that the reaction temperature is 310-330 ℃ and the pressure is 1.0MPa, and the results are shown in Table 1.

Example 2

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ support Al-Si-Ti-Fe-Mg-Ca ] preparation of Na-K-O oxide

6600G of boehmite powder (Walker, GR), 300g of fine silica powder, 2781g of potassium feldspar powder (Xin mineral product, the same applies hereinafter), 78g of calcium fluoride (Hu test CP), 8g of anatase (Walker, 99%), 319.3g of ferric oxide, 4g of magnesium oxide and 5.85g of sodium chloride were mixed by a V-type mixer to obtain solid mixture powder.

Spraying a proper amount of water into the solid powder to be used as a binder, so that the mixture has certain plasticity, and then preparing spherical particles with the size of 4.5mm by adopting a multifunctional catalyst forming machine. The particles were calcined at 1250 ℃ for 1.5 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al _6.5Si_3.5Ti_0.01Fe_0.1Mg_0.01Ca_0.1Na_0.01K₁O_x.

Preparation of the supported composite oxide catalyst: the same procedure was followed for the preparation of the catalyst of example 1.

Test of oxidation reaction: the conditions were the same as in example 1. The results are shown in Table 1.

Example 3

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ Carrier Al-Si-Zn-Mn-Mg ] preparation of Na-K-O oxide

2178G of boehmite powder (Walker, GR), 6286.2g of quartz stone (bimodal), 126.3g of feldspar powder (Yifield mineral), 86.94g of manganese oxide, 136.3g of zinc chloride, 4.2g of sodium fluoride and 5.81g of potassium fluoride were mixed by a V-type mixer to obtain a solid mixture powder.

Spraying a proper amount of water into the solid powder to be used as a binder, so that the mixture has certain plasticity, and then preparing spherical particles with the size of 4.5mm by adopting a multifunctional catalyst forming machine. The particles were calcined at 1250 ℃ for 4 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al _8.5Si₅Zn_0.1Mn_0.1Mg_0.1Na_0.01K_0.01O_x.

Preparation of the supported composite oxide catalyst: the same procedure was followed for the preparation of the catalyst of example 1.

Test of oxidation reaction: the conditions were the same as in example 1. The results are shown in Table 1.

Example 4

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ carrier Al-Si-V-Co-Ni-Ca ] preparation of Na-K-O oxide

5000G of aluminum hydroxide, 2051.28g of fine silica powder, 64.81g of vanadium pentoxide, 5.34g of cobalt oxide, 20.71g of nickel nitrate hexahydrate, 27.8g of calcium fluoride, 3.56g of aluminum fluoride, 2.85g of sodium hydroxide and 5.22g of potassium chloride were mixed by using a V-type mixer to obtain a solid mixture powder.

Spraying a proper amount of water into the solid powder to be used as a binder, so that the mixture has certain plasticity, and then preparing spherical particles with the size of 4.5mm by adopting a multifunctional catalyst forming machine. The pellets were calcined at 1200 ℃ for 5 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al _9.5Si_4.8V_0.1Co_0.01Ni_0.01Ca_0.05Na_0.01K_0.01O_x.

Preparation of the supported composite oxide catalyst: the same procedure was followed for the preparation of the catalyst of example 1.

Test of oxidation reaction: the conditions were the same as in example 1. The results are shown in Table 1.

Comparative example 1

The comparative example provides a catalyst carrier and a catalyst comprising the carrier, and the specific composition and preparation method are as follows:

[ Carrier Al-Si-Ti-Fe-Mg ] preparation of Na-K-O oxide

6000G of boehmite powder (Walker, GR), 400g of fine silica powder, 10.65g of anatase (Walker, 99%), 106.46g of iron oxide, 8.3g of magnesium fluoride, 156g of sodium chloride and 99.4g of potassium chloride were mixed by a V-type mixer to obtain a solid mixture powder.

Spraying a proper amount of water into the solid powder to be used as a binder, so that the mixture has certain plasticity, and then preparing spherical particles with the size of 4.5mm by adopting a multifunctional catalyst forming machine. The pellets were calcined at 1300 c for 4 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al _7.5Si_0.5Ti_0.01Fe_0.1Mg_0.01Na_0.2K_0.1O_x. FIG. 2 is a SEM image of the comparative example conditional preparation of a support showing the morphology of the support surface. It can be seen that the surface is formed by stacking irregular small particles, and compared with the embodiment, the surface has compact overall structure, less pore structure and small pore size.

Preparation of the supported composite oxide catalyst: prepared in the same manner as the catalyst preparation of example 1 except that the carrier was replaced with the carrier described above.

Test of oxidation reaction: the procedure was carried out under the same conditions as in example 1. The results are shown in Table 1.

Comparative example 2

The comparative example provides a catalyst carrier and a catalyst comprising the carrier, and the specific composition and preparation method are as follows:

Preparation of supported composite oxide catalyst using 4.5mm alumina spheres as support: prepared in the same manner as the catalyst preparation of example 1 except that the support was replaced with alumina spheres.

Test of oxidation reaction: the procedure was carried out under the same conditions as in example 1. The results are shown in Table 1.

TABLE 1 Performance test results of the supported catalysts of examples 1 to 4 and comparative examples 1 and 2 (total space velocity 2400h ^-1)

Example 5

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ Carrier Al-Si-Ti-Fe-Mg ] preparation of Ca-O oxide ]

6600G of boehmite powder (Walker, GR), 3338.8g of fine silica powder, 10.3g of rutile (TCI, 99.9%), 313g of ferric nitrate, 80.6g of magnesium fluoride, 129.5g of calcium carbonate were mixed by using a V-type mixer to obtain a solid mixture powder.

Spraying a proper amount of water into the solid powder to be used as a binder, so that the mixture has certain plasticity, and then preparing spherical particles with the size of 4.5mm by adopting a multifunctional catalyst forming machine. The pellets were calcined at 1400 ℃ for 3 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al _8.5Si_4.3Ti_0.01Fe_0.1Mg_0.1Ca_0.1O_x.

[ Preparation of supported composite oxide catalyst ]:

500 ml of deionized water was added to the vessel, and 162.9 g of ammonium molybdate, 41.1 g of ammonium metavanadate and 24.8 g of ammonium paratungstate were sequentially added under vigorous stirring and heated to dissolve, and the mixed brine solution was A. In a second stainless steel vessel, 50 ml of deionized water was added, followed by 4.8 g of strontium nitrate and 35.4 g of copper nitrate with vigorous stirring, and heated to dissolve thoroughly, the mixed brine solution was B. The two solutions were mixed to form a coprecipitated slurry which was evaporated to dryness at 120 ℃ to a solid with continued heating and vigorous stirring, and then crushed to form powder C which passed through a 60 mesh screen. 53 g of powder C, 55 g of antimonous oxide and 300 meshes of 2.2 g of tellurium oxide are added into a mixer and are fully and uniformly mixed, so as to obtain active component precursor powder.

The active ingredient precursor powder is sieved through a 60 mesh sample sieve to have a particle size dimension of less than 250 μm.

And adding 500g of the obtained carrier into a rotary drum granulator, adding 140g of the active component precursor into the rotary drum granulator, and spraying aluminum sol accounting for 10wt% of the active component precursor powder as a wetting agent or a binding agent to enable the active component precursor powder to be carried on the carrier, so as to obtain the catalyst precursor. And drying the catalyst precursor, and performing decomposition and activation in a muffle furnace at 380 ℃ for 5 hours to form the final catalyst.

The catalyst active phase (without carrier) has the general formula: mo ₁₂V_4.5W_1.2Sr_0.3Cu_1.9Sb_11.2Te_0.2O_x.

[ Test conditions for Oxidation reaction ]

A catalyst finished product is filled in a stainless steel reaction tube with the length of 3500mm and the inner diameter of 26.6mm, the filling height is 3000mm, the total airspeed of 2600h ^-1 is adopted, mixed raw material gas consisting of 5% of acrolein, 5.5% of oxygen, 25% of water vapor and 64.5% of nitrogen is introduced, and the test result of the catalyst under the conditions that the reaction temperature is 255-275 ℃ and the pressure is 1.0MPa is shown in Table 2.

Example 6

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ support Al-Si-Ti-Fe-Mg-Ca ] preparation of Na-K-O oxide

6600G of boehmite powder (Walker, GR), 3771.4g of fine silica powder, 380.1g of ferric nitrate, 6.3g of titanium dioxide, 458.3g of magnesium hydroxide, 157.3g of calcium carbonate, 16.74g of sodium sulfate and 13.69g of potassium sulfate were mixed by a V-type mixer to obtain a solid mixture powder.

Spherical particles with a size of 4.5mm were produced using a disk granulator. The pellets were calcined at 1200 ℃ for 5 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al _1.4Si_0.8Ti_0.001Fe_0.02Mg_0.1Ca_0.02Na_0.003K_0.002O_x.

Fig. 3 is a scanning electron microscope characterization of the resulting support, from which it can be seen that the support surface is built up from a plurality of linear fiber-made cluster structures, with pore structures between the cluster structures and between the linear fibers, which facilitate efficient attachment of the active component precursor powders in the subsequent catalyst preparation procedure. And compared with fig. 1, it can be seen that the adjustment of the size of the crack gap on the surface of the carrier can be realized by adjusting and controlling the proportion of raw materials, the roasting temperature and the time, thereby indirectly influencing the coating effect. The reason for the occurrence of cracks on the surface of the support is thermal expansibility at high temperature, and the volume of particles constituting the support expands to some extent due to the thermal expansibility, so that a large number of crack structures are formed on the surface, thereby increasing the roughness of the surface of the support and simultaneously enabling the supported catalyst precursor powder to be filled therein. And finally, the carrying capacity of the carrier is greatly enhanced.

Preparation of the supported composite oxide catalyst: the same procedure was followed for the preparation of the catalyst of example 5.

Test of oxidation reaction: the conditions were the same as in example 5. The test results are shown in Table 2.

Example 7

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ carrier Al-Si-V-Fe-Ni-Ca ] preparation of Na-K-O oxide

5000G of aluminum nitrate, 301.86g of fine silica powder, 0.62g of vanadium pentoxide, 2.63g of ferric nitrate, 1.19g of nickel nitrate hexahydrate, 5.31g of calcium fluoride, 154.6g of sodium silicate nonahydrate and 59.25g of potassium chloride were mixed by using a V-type mixer to obtain a solid mixture powder.

Spherical particles with a size of 4.5mm were produced using a disk granulator. The pellets were calcined at 1300 c for 4 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₉₈Si₄₅V₀₀₀₅Fe₀₀₀₈Ni₀₀₀₃Ca₀₀₅Na₀₈K₀₅O_x.

Preparation of the supported composite oxide catalyst: the same procedure was followed for the preparation of the catalyst of example 5.

Test of oxidation reaction: the conditions were the same as in example 5. The results are shown in Table 2.

Example 8

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ carrier Al-Si-Zn-Zr-Cr-Mg ] preparation of Na-K-O oxide

5000G of aluminum nitrate, 60g of fine silica powder, 4.0g of zinc chloride, 18.0g of zirconium dioxide, 2.2g of chromium oxide, 11.8g of magnesium oxide, 83.27g of sodium silicate nonahydrate and 10.92g of potassium chloride were mixed by a V-type mixer to obtain a solid mixture powder.

Spherical particles with a size of 4.5mm were produced using a disk granulator. The pellets were calcined at 1300 c for 3 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₈Si_5.2Zn_0.01Zr_0.05Cr_0.005Mg_0.1Na_0.1K_0.05O_x.

Preparation of the supported composite oxide catalyst: the same procedure was followed for the preparation of the catalyst of example 5.

Test of oxidation reaction: the conditions were the same as in example 5. The results are shown in Table 2.

Example 9

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ carrier Al-Si-Co-Cd-Nb ] preparation of Mg-K-O oxide ]

5000G of aluminum nitrate, 361.9g of fine silica powder, 0.53g of cobalt oxide, 2.06g of cadmium chloride, 0.56g of niobium pentoxide, 6.68g of magnesium chloride and 52.3g of potassium chloride were mixed by a V-type mixer to obtain a solid mixture powder.

Spherical particles with a size of 4.5mm were produced using a disk granulator. The pellets were calcined at 1300 c for 3 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al _9.5Si_4.3Co_0.005Cd_0.008Nb_0.003Mg_0.05K_0.5O_x.

Preparation of the supported composite oxide catalyst: the same procedure was followed for the preparation of the catalyst of example 5.

Test of oxidation reaction: the conditions were the same as in example 5. The results are shown in Table 2.

Comparative example 3

The comparative example provides a catalyst carrier and a catalyst comprising the carrier, and the specific composition and preparation method are as follows:

[ support Al-Si-Ti-Fe-Mg-Ca ] preparation of Na-K-O oxide

6600G of boehmite powder (Walker, GR), 9428.57 fine silica powder, 380.1g of ferric nitrate, 6.3g of titanium dioxide, 458.3g of magnesium hydroxide, 157.3g of calcium carbonate, 16.74g of sodium sulfate and 13.69g of potassium sulfate were mixed by a V-type mixer to obtain a solid mixture powder.

Spherical particles with a size of 4.5mm were produced using a disk granulator. The pellets were calcined at 1200 ℃ for 5 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al _1.4Si₂Ti_0.001Fe_0.02Mg_0.1Ca_0.02Na_0.003K_0.002O_x. FIG. 4 is a SEM image of the comparative example conditional preparation of a support showing the morphology of the support surface. The whole structure of the surface of the carrier is compact, the pores are less, and the carrier is formed by stacking irregular small particles almost entirely.

Preparation of the supported composite oxide catalyst: the catalyst preparation was the same as in example 5.

Test of oxidation reaction: the conditions were the same as in example 5. The results are shown in Table 2.

Comparative example 4

The comparative example provides a catalyst carrier and a catalyst comprising the carrier, and the specific composition and preparation method are as follows:

preparation of supported composite oxide catalyst with 4.5mm silica spheres as carrier: the catalyst preparation was the same as in example 5.

Test of oxidation reaction: the conditions were the same as in example 5. The results are shown in Table 2.

TABLE 2 Performance test results of the catalysts of examples 5 to 9 and comparative examples 3 and 4 (total space velocity 2600h ^-1)

Example 10

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-Zn-Ca-O oxide ]

3060G of aluminum sol (10 wt%) and 480g of silica sol (25 wt%) were mixed under intense stirring, and then 9.1g of zinc chloride and 7.4g of calcium chloride were added thereto, followed by stirring at 60℃for 30 minutes, to obtain a liquid mixture.

Drying the liquid mixture at 120 ℃ to obtain solid powder, adding a proper amount of water as a binder to enable the mixture to have certain plasticity, and then preparing spherical particles with the size of 4.2mm by adopting a multifunctional catalyst forming machine. The pellets were calcined at 1500 ℃ for 30 minutes and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₁Si_0.3Zn_0.01Ca_0.01O_x.

[ Preparation of Supported composite oxide catalyst ]

Under the condition of heating and stirring, 420g of ammonium molybdate is dissolved in 2500ml of distilled water to obtain solution (A);

350g of cobalt nitrate, 150g of nickel nitrate, 19.3g of cesium nitrate and 130g of ferric nitrate are dissolved in 1000ml of distilled water to obtain a solution (B);

180g of bismuth nitrate was dissolved in 250ml of distilled water acidified with 25ml of concentrated nitric acid to obtain a solution (C);

Then, mixing the solution (B) and the solution (C) together, adding the mixture into the solution (A), adding 3.0g of potassium nitrate and 31.8g of zirconia, drying the obtained solution by a spray dryer, and pre-calcining at 300-400 ℃ for 1-3 hours to obtain active component precursor powder;

the active ingredient precursor powder is sieved through a 60 mesh sample sieve to have a particle size dimension of less than 250 μm.

Adding 500g of the obtained carrier into a rotary drum granulator, adding 340g of the active component precursor into the rotary drum granulator, spraying aluminum sol accounting for 10wt% of the active component precursor into the rotary drum granulator as a wetting agent or a binder, and loading active component precursor powder on the surface modified carrier to obtain the catalyst precursor. And drying the catalyst precursor, and performing decomposition and activation in a muffle furnace at 480 ℃ for 6 hours to form the final catalyst.

The catalyst active phase (without carrier) has the general formula: mo (Mo) ₁₂Bi_1.87Fe_1.62Co_6.07Ni_2.6Zr_1.3Cs_0.5K_0.15

[ Test conditions for oxidation reaction ]: the volume ratio of isobutene, nitrogen, water vapor and air in the raw material gas of the fixed bed single tube reactor is 1:10:1.6:10.5, total gas space velocity 1200h ^-1. The prepared catalyst was placed in a reaction tube, and the catalyst loading height was 3400mm and the loading amount was 1720ml. The reaction temperature is 320-330 ℃; the pressure was 75Kpa. The results of the test on the catalyst are shown in Table 3.

Example 11

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-Cd-Mg-O oxide ]

2040G of alumina, 18.3g of cadmium chloride and 19g of magnesium chloride were sequentially added to 4800g of 25wt% silica sol with stirring, and stirred at 60℃for 30 minutes to obtain a mixture slurry.

Drying the slurry at 120 ℃ to obtain solid powder, adding a proper amount of water as a binder to enable the mixture to have certain plasticity, and then preparing spherical particles with the size of 4.2mm by a multifunctional catalyst forming machine. The pellets were calcined at 1550 ℃ for 30 minutes and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₂Si₁Cd_0.01Mg_0.01O_x.

Preparation of the supported composite oxide catalyst: the catalyst preparation was the same as in example 10.

Test conditions for oxidation reaction: the same as in example l 0. The results are shown in Table 3.

Example 12

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-Ca-O oxide ]

1200G of silica powder, 3060g of alumina and 34g of calcium oxide were milled for 30 minutes at 400 rpm by a ball mill to obtain a solid mixture powder.

Spraying a proper amount of 25wt% silica sol into the solid powder as a binder to make the mixture have certain plasticity, and then preparing spherical particles with the size of 4.2mm by a multifunctional catalyst forming machine. The pellets were calcined at 1400 ℃ for 1 hour and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₃Si₁Ca_0.03O_x.

Preparation of the supported composite oxide catalyst: the catalyst preparation was the same as in example 10.

Test conditions for oxidation reaction: the same as in example l 0. The results are shown in Table 3.

Example 13

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-Ti-Zr-Mg-O oxide ]

1260G of silica micropowder, 3060g of alumina, 18.5g of zirconium dioxide, 59.9g of titanium dioxide and 48.4g of magnesium oxide were milled for 30 minutes at 400 rpm by means of a ball mill, to obtain a solid mixture powder.

Spraying a proper amount of 25wt% silica sol into the solid powder as a binder to make the mixture have certain plasticity, and then preparing spherical particles with the size of 4.2mm by a multifunctional catalyst forming machine. The pellets were calcined at 1300 c for 2 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₄Si_1.4Ti_0.05Zr_0.01Mg_0.08O_x.

Preparation of the supported composite oxide catalyst: the catalyst preparation was the same as in example 10.

Test conditions for oxidation reaction: the same as in example l 0. The results are shown in Table 3.

Example 14

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-V-Ca-O oxide ]

3060G of alumina, 1440g of silica gel (FCP 200-300 mesh), 87.36g of vanadium pentoxide and 33.6g of calcium oxide were milled for 30 minutes at 400 rpm by using a ball mill, to obtain a solid mixture powder.

Spraying proper amount of 10wt% aluminum sol as adhesive to the solid powder to make the mixture possess certain plasticity, and making the mixture into spherical particle of 4.2mm size with multifunctional catalyst forming machine. The pellets were calcined at 1350 deg.c for 2 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₅Si₂V_0.08Ca_0.05O_x.

Preparation of the supported composite oxide catalyst: the catalyst preparation was the same as in example 10.

Test conditions for oxidation reaction: the same as in example l 0. The results are shown in Table 3.

Example 15

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of Al-Si-Nb-Ca-O oxide as a support ]

3060G of alumina, 1440g of silica gel (FCP 200-300 mesh), 15.95g of niobium oxide and 33.6g of calcium oxide were milled for 30 minutes at 400 rpm by a ball mill to obtain a solid mixture powder.

Spraying proper amount of 10wt% aluminum sol as adhesive to the solid powder to make the mixture possess certain plasticity, and making the mixture into spherical particle of 4.2mm size with multifunctional catalyst forming machine. The pellets were calcined at 1350 deg.c for 2 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₅Si₂Nb_0.01Ca_0.05O_x.

Preparation of the supported composite oxide catalyst: prepared in the same manner as the catalyst prepared in example 10.

Test conditions for oxidation reaction: the same as in example l 0. The results are shown in Table 3.

Example 16

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-Cr-Mg-O oxide ]

3060G of alumina, 1500g of silica gel (FCP 200-300 mesh), 10g of chromium trioxide and 20.15g of magnesium oxide were milled for 30 minutes at 400 rpm using a ball mill to obtain a solid mixture powder.

Spraying proper amount of 10wt% aluminum sol as adhesive to the solid powder to make the mixture possess certain plasticity, and making the mixture into spherical particle of 4.2mm size with multifunctional catalyst forming machine. The pellets were calcined at 1400 ℃ for 1 hour and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₆Si_2.5Cr_0.01Mg_0.05O_x.

Preparation of the supported composite oxide catalyst: the catalyst preparation was the same as in example 10.

Test conditions for oxidation reaction: the same as in example l 0. The results are shown in Table 3.

Comparative example 5

The comparative example provides a catalyst carrier and a catalyst comprising the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-O oxide ]

1260G of silica micropowder and 3060g of alumina were mixed to obtain a solid mixture powder. Spherical particles with a size of 4.2mm were produced using a disk granulator. The pellets were calcined at 1300 c for 2 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₄Si_1.4O_x.

Preparation of the supported composite oxide catalyst: the catalyst preparation was the same as in example 10.

Test conditions for oxidation reaction: the same as in example l 0. The results are shown in Table 3.

TABLE 3 Performance test results of the isobutene Oxidation of the catalysts of examples 10 to 16 and comparative example 5

Example 17

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-Mn-Ca-O oxide ]

3060G of alumina, 1697g of silica gel (FCP 200-300 mesh), 22.34g of manganese dioxide and 9.73g of calcium oxide were milled for 30 minutes at 400 rpm by a ball mill to obtain a solid mixture powder.

Spraying a proper amount of water into the solid powder to be used as a binder, so that the mixture has certain plasticity, and then preparing spherical particles with the size of 4.5mm by adopting a multifunctional catalyst forming machine. The pellets were calcined at 1400 ℃ for 3 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₇Si_3.3Mn_0.03Ca_0.02O_x.

[ Preparation of Supported composite oxide catalyst ]

In a stainless steel vessel, 500 ml of deionized water was added, and 162.9 g of ammonium molybdate, 38.4 g of ammonium metavanadate and 20.7 g of ammonium paratungstate were sequentially added under vigorous stirring and heated to dissolve, and the mixed brine solution was a. In a second stainless steel vessel, 50 ml of deionized water was added, followed by 4.8 g of strontium nitrate, 33.5 g of copper nitrate and 19.5g of phosphorous acid under vigorous stirring, and heated to dissolve thoroughly, the mixed brine solution was B. The two solutions were mixed to form a coprecipitated slurry which was evaporated to dryness under continuous heating and vigorous stirring to a solid, which was then crushed to form powder C which passed through a 60 mesh screen. 53 g of powder C, 55 g of antimonous oxide and 300 meshes of 2.2 g of tellurium oxide are added into a mixer and are fully and uniformly mixed, so as to obtain active component precursor powder.

The active ingredient precursor powder is sieved through a 60 mesh sample sieve to have a particle size dimension of less than 250 μm.

And adding 500g of the obtained carrier into a rotary drum granulator, adding 170g of the active component precursor into the rotary drum granulator, and spraying aluminum sol accounting for 10wt% of the active component precursor as a wetting agent or a binder to enable the active component precursor powder to be carried on the surface modified carrier, so as to obtain the catalyst precursor. And drying the catalyst precursor, and performing decomposition and activation in a muffle furnace at 390 ℃ for 4 hours to form the final catalyst.

The catalyst active phase (without carrier) has the general formula: mo (Mo) ₁₂V_4.2W_1.0Sr_0.3Cu_1.8P_1.2Sb_11.2Te_0.2O_x

The catalyst thus prepared was subjected to a test for oxidation of methacrolein, and the outlet product of the oxidation in example 10 was supplemented with oxygen (in terms of isobutylene) in a molar ratio of 0.5 as a reaction raw material. The catalyst loading height was 2900mm and the loading was 1610ml. The reaction temperature is 280-290 ℃; the inlet pressure was 75Kpa. The results are shown in Table 4.

Example 18

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-Fe-Mg-O oxide ]

3060G of alumina, 1710g of fine silica powder, 59.88g of iron oxide and 49.99g of magnesium chloride were ground for 30 minutes using a ball mill at 400 rpm to obtain a solid mixture powder.

Spraying proper amount of 10wt% aluminum sol as adhesive to the solid powder to make the mixture possess certain plasticity, and making the mixture into spherical particle of 4.5mm size with multifunctional catalyst forming machine. The pellets were calcined at 1400 ℃ for 3 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₈Si_3.8Fe _0.1Mg_0.07O_x.

Preparation of the supported composite oxide catalyst: the same catalyst preparation as in example 17 was used, wherein the support prepared in this example was used.

Test of oxidation reaction: the reaction was carried out under the same conditions as in example 17. The results are shown in Table 4.

Example 19

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-Co-Ca-O oxide ]

3060G of alumina, 1720g of silica powder, 19.96g of cobalt oxide and 37.38g of calcium oxide were ground for 30 minutes at 400 rpm by a ball mill to obtain a solid mixture powder.

Spraying a proper amount of water into the solid powder to be used as a binder, so that the mixture has certain plasticity, and then preparing spherical particles with the size of 4.5mm by adopting a multifunctional catalyst forming machine. The pellets were calcined at 1600 c for 30 minutes and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₉Si_4.3Co _0.08Ca_0.1O_x.

Preparation of the supported composite oxide catalyst: the same catalyst preparation as in example 17 was used, wherein the support prepared in this example was used.

Test of oxidation reaction: the reaction was carried out under the same conditions as in example 17. The results are shown in Table 4.

Example 20

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-Ni-Mg-O oxide ]

3060G of alumina, 1620g of silica powder, 17.49g of nickel nitrate and 57.13g of magnesium chloride were milled for 30 minutes at 400 rpm by using a ball mill, to obtain a solid mixture powder.

Spraying a proper amount of water into the solid powder to be used as a binder, so that the mixture has certain plasticity, and then preparing spherical particles with the size of 4.5mm by adopting a multifunctional catalyst forming machine. The pellets were calcined at 1450 c for 2 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₁₀Si_4.5Ni _0.01Mg_0.1O_x.

Preparation of the supported composite oxide catalyst: the same catalyst preparation as in example 17 was used, wherein the support prepared in this example was used.

Test of oxidation reaction: the reaction was carried out under the same conditions as in example 17. The results are shown in Table 4.

Example 21

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-Ti-Mg-Na-O oxide ]

5150G of aluminum sulfate, 631.68g of fine silica powder, 24g of titanium dioxide, 2886.87g of sodium sulfate and 28.64g of magnesium chloride were ground for 30 minutes by a ball mill at 400 rpm to obtain a solid mixture powder.

Spraying a proper amount of water into the solid powder to be used as a binder, so that the mixture has certain plasticity, and then preparing spherical particles with the size of 4.5mm by adopting a multifunctional catalyst forming machine. The pellets were calcined at 1000 ℃ for 4 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₁Si_0.35Ti_0.01Mg_0.01Na_1.35O_x.

Preparation of the supported composite oxide catalyst: the same catalyst preparation as in example 17 was used, wherein the support prepared in this example was used.

Test of oxidation reaction: the reaction was carried out under the same conditions as in example 17. The results are shown in Table 4.

Example 22

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-Fe-Ca-Na-O oxide ]

6000G of aluminum sulfate, 708.27g of fine silica powder, 27.98g of iron oxide, 6726.68g of sodium sulfate and 38.89g of calcium chloride were ground for 30 minutes at 400 rpm by a ball mill to obtain a solid mixture powder.

Spraying a proper amount of water into the solid powder to be used as a binder, so that the mixture has certain plasticity, and then preparing spherical particles with the size of 4.5mm by adopting a multifunctional catalyst forming machine. The pellets were calcined at 900 ℃ for 5 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₁Si_0.34Fe _0.01Ca_0.01Na_2.7O_x.

Preparation of the supported composite oxide catalyst: the same catalyst preparation as in example 17 was used, wherein the support prepared in this example was used.

Test of oxidation reaction: the reaction was carried out under the same conditions as in example 17. The results are shown in Table 4.

Example 23

The embodiment provides a catalyst carrier and a catalyst containing the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-Ti-Mg-K-O oxide ]

5150G of aluminum sulfate, 631.68g of fine silica powder, 24g of titanium dioxide, 5241.74g of potassium sulfate, 16.87g of calcium oxide and 28.64g of magnesium chloride were ground for 30 minutes by a ball mill at 400 rpm to obtain a solid mixture powder.

Spraying a proper amount of water into the solid powder to be used as a binder, so that the mixture has certain plasticity, and then preparing spherical particles with the size of 4.5mm by adopting a multifunctional catalyst forming machine. The pellets were calcined at 1100 ℃ for 3.5 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₁Si_0.35Ti _0.01Mg_0.01Ca_0.01K₂O_x.

Preparation of the supported composite oxide catalyst: the same catalyst preparation as in example 17 was used, wherein the support prepared in this example was used.

Test of oxidation reaction: the reaction was carried out under the same conditions as in example 17. The results are shown in Table 4.

Comparative example 6

The comparative example provides a catalyst carrier and a catalyst comprising the carrier, and the specific composition and preparation method are as follows:

[ preparation of support Al-Si-Ti-O oxide ]

5150G of aluminum sulfate, 360.96g of silicon micropowder and 4.8g of titanium dioxide were milled for 30 minutes by using a ball mill at 400 rpm to obtain a solid mixture powder.

Spraying a proper amount of water into the solid powder to be used as a binder, so that the mixture has certain plasticity, and then preparing spherical particles with the size of 4.5mm by adopting a multifunctional catalyst forming machine. The pellets were calcined at 1000 ℃ for 4 hours and then cooled to room temperature to obtain a composite oxide catalyst support represented by the general formula Al ₅Si₁Ti_0.01O_x.

Preparation of the supported composite oxide catalyst: the same catalyst preparation as in example 17 was used, wherein the support prepared in this example was used.

Test of oxidation reaction: the reaction was carried out under the same conditions as in example 17. The results are shown in Table 4.

Comparative example 7

The comparative example provides a catalyst carrier and a catalyst comprising the carrier, and the specific composition and preparation method are as follows:

As a carrier, 4.5mm alumina spheres (Cheng Xing) were used.

Preparation of the supported composite oxide catalyst: the same catalyst preparation as in example 17 was used, wherein the support prepared in this example was used.

Test of oxidation reaction: the reaction was carried out under the same conditions as in example 17. The results are shown in Table 4.

TABLE 4 Performance test results of the oxidation reactions of the catalysts of examples 17 to 23 and comparative examples 6 and 7

It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (9)

1. The catalyst carrier is characterized by being a composite inorganic oxide, and the composition general formula of the composite inorganic oxide is as follows: al _aSi_bX¹ _cX² _dX³ _eO_x;

In the general formula:

X ¹ is at least one of zinc, cadmium, titanium, zirconium, vanadium, niobium, chromium, manganese, iron, cobalt and nickel;

x ² is at least one of sodium and potassium;

X ³ is at least one of calcium and magnesium;

a, b, c, d, e and x are the atomic ratio of each element, wherein a is more than or equal to 1 and less than or equal to 10,0.3 and b is more than or equal to 5.2, and a/b is more than or equal to 1.5 and less than or equal to 3.3; c is more than or equal to 0.001 and less than or equal to 0.1,0.001, d is more than or equal to 2.7,0.01, e is more than or equal to 0.1, and x is a value determined by the oxidation degree of the metal element;

The shape of the catalyst carrier is annular, spherical, cylindrical or bar;

And, in a microscopic state, the surface of the catalyst support has a fluff structure, a fiber structure, a branch structure, a crack structure or a cluster structure composed of linear fibers.

2. A method for preparing the catalyst carrier according to claim 1, comprising the steps of:

and mixing the raw material components containing the elements in the general formula with a binder, forming, and calcining to obtain the catalyst carrier.

3. The method for preparing a catalyst carrier according to claim 2, wherein the mass ratio of the raw material components to the binder is 100: (0-10), the mass of the binder is not 0;

and/or the binder comprises at least one of water, silica sol, alumina sol, polyvinyl alcohol, graphite, or crystalline cellulose.

4. The method for preparing a catalyst carrier according to claim 2, wherein the calcination temperature is 1200 to 1450 ℃ and the calcination time is 0.5 to 5 hours.

5. A catalyst comprising a carrier and an active component carried on the surface of the carrier, wherein the carrier is the catalyst carrier according to claim 1 or the catalyst carrier prepared by the preparation method according to any one of claims 2 to 4.

6. The catalyst according to claim 5, wherein the active component is a composite metal oxide containing molybdenum, bismuth and iron, and the general formula composition is shown in the following formula (I):

Mo_aBi_bFe_cA¹ _dB² _eC³ _fSi_gO_x(I)

a ¹ is at least one of cobalt, nickel and manganese;

b ² is at least one selected from copper, hafnium, scandium, vanadium, tungsten, zirconium;

C ³ is at least one selected from sodium, potassium, rubidium, cesium;

Si is silicon and O is oxygen;

a to f are the proportions of the respective elements, and when a=12, b=0.6 to 6, c=0.1 to 8, d=3 to 10, e=1 to 5, f=0.05 to 1, g=0 to 40; x is a number satisfying the oxidation state of other metal elements in the general formula.

7. The catalyst according to claim 5, wherein the active component is a composite metal oxide containing molybdenum, vanadium, tellurium, copper, and having a general formula composition represented by the following formula (II):

Mo_aV_bCu_cTe_dM¹ _eM² _fM³ _gO_x(Ⅱ)

M ¹ is at least one element selected from tungsten and niobium;

m ² is at least one element selected from magnesium, calcium, strontium and barium;

M ³ is at least one element selected from antimony, tin, phosphorus, bismuth and titanium;

a to g are the proportions of the elements, and when a=12, b=1 to 8, c=0.1 to 4, d=0.05 to 1, e=0.5 to 3, and f=0.01 to 1; g=0.01 to 30; x is a number satisfying the oxidation state of other metal elements in the general formula.

8. A method for preparing the catalyst according to any one of claims 5 to 7, comprising the steps of:

S1, preparing an active component precursor;

s2, mixing the catalyst carrier with the active component precursor, granulating and roasting to obtain the catalyst.

9. Use of a catalyst according to any one of claims 5 to 7 for the conversion of light olefins to unsaturated aldehydes and/or unsaturated carboxylic acids.