阅读说明：本技术 丙烯酸的合成方法 (Method for synthesizing acrylic acid ) 是由 王伟华 宋卫林 徐文杰 杨斌 汪国军 于 2018-06-12 设计创作，主要内容包括：本发明涉及丙烯酸的合成方法,主要解决现有催化剂丙烯醛转化率低和丙烯酸收率低的问题,通过采用丙烯酸的合成方法,包括在催化剂存在下,丙烯醛与含氧气的氧化性气体反应得到丙烯酸；其中所述催化剂包括载体和负载于载体上的活性组分,所述活性组分通式表示为：VMo<Sub>a</Sub>Nb<Sub>b</Sub>W<Sub>c</Sub>X<Sub>d</Sub>Y<Sub>e</Sub>Z<Sub>f</Sub>O<Sub>g</Sub>,其中X为包括选自Sc、Ti、Y、Zr、Hf、Ta、Cr中的一种或多种,Y为包括选自Ga、Ge、In、Sn、TI、Pb、Cd、Mn、Tc、Re、Rh、Ir、Pd、Pt、Ag、Au、La中的至少一种,Z为选自碱金属或碱土金属中的一种或多种的技术方案,较好地解决了该技术问题,可用于丙烯酸的工业生产中。(The invention relates to a method for synthesizing acrylic acid, which mainly solves the problems of low conversion rate of acrolein and low yield of acrylic acid in the existing catalyst, and adopts the method for synthesizing acrylic acid, which comprises the steps of reacting acrolein with oxidizing gas containing oxygen in the presence of a catalyst to obtain acrylic acid; the catalyst comprises a carrier and an active component loaded on the carrier, wherein the active component is represented by the general formula: VMo a Nb b W c X d Y e Z f O g Wherein X is selected from one or more of Sc, Ti, Y, Zr, Hf, Ta and Cr, and Y is selected from Ga, Ge, In, Sn and TIAnd at least one of Pb, Cd, Mn, Tc, Re, Rh, Ir, Pd, Pt, Ag, Au and La, wherein Z is one or more selected from alkali metals or alkaline earth metals, so that the technical problem is well solved, and the method can be used in the industrial production of acrylic acid.)

1. A process for the synthesis of acrylic acid, comprising reacting acrolein with an oxygen-containing oxidizing gas in the presence of a catalyst to obtain acrylic acid; the catalyst comprises a carrier and an active component loaded on the carrier, wherein the active component is represented by the general formula: VMo_aNb_bW_cX_dY_eZ_fO_gWherein X is selected from one or more of Sc, Ti, Y, Zr, Hf, Ta and Cr, and Y is selected from Ga, Ge, In, Sn, TI, Pb, Cd, Mn, Tc, Re, Rh, Ir, Pd, Pt, Ag, Au and LaAt least one, Z is one or more selected from alkali metal or alkaline earth metal; a is the molar ratio of Mo to V, and the value of a is 2.0-8.0; b is the molar ratio of Nb to V, and the value of b is 0.2-0.8; c is the molar ratio of W to V, and the value of c is 0.2-1.0; d is the molar ratio of X to V, and the value of d is 0.2-1.0; e is the molar ratio of Y to V, and the value of e is 0.05-1.2; f is the molar ratio of Z to V, and the value of f is 0.05-1.2; g is the mole number of oxygen atoms needed to satisfy the valence of each element in the active component.

2. The method for synthesizing acrylic acid according to claim 1, wherein the reaction is carried out in the presence of a dilute gas phase material.

3. The method for synthesizing acrylic acid according to claim 1, wherein said oxidizing gas is selected from pure oxygen, oxygen-rich gas, and air.

4. The method for synthesizing acrylic acid according to claim 2, wherein said diluting gaseous material is steam.

5. The method for synthesizing acrylic acid according to claim 1, wherein the reaction temperature is 100 to 500 ℃.

6. The method for synthesizing acrylic acid according to claim 1, wherein the raw material gas for the reaction is a material consisting of acrolein, air and water vapor, and the ratio by volume of the acrolein: air: the steam is 1 (1-6) and 0.5-5.

7. The method for synthesizing acrylic acid according to claim 6, wherein the volume space velocity of the raw material gas is 800 to 2000 hours^-1。

8. The method for synthesizing acrylic acid according to claim 1, wherein the content of the active component in the catalyst is 10 to 60 w% by weight.

9. The method for synthesizing acrylic acid according to claim 1, wherein the carrier is at least one selected from the group consisting of alumina, lithium oxide, magnesium oxide, zirconia, silica and titania.

10. The method for synthesizing acrylic acid according to claim 1, wherein the catalyst is prepared by a method comprising the steps of:

preparing mixed liquid of active component elements;

mixing the active component element mixed solution with a carrier;

and (4) roasting.

Technical Field

The present invention relates to a method for synthesizing acrylic acid.

Background

Acrolein is the simplest unsaturated aldehyde, is an important chemical synthesis intermediate, and is widely used for synthesis of important chemical products such as picoline, pyridine, glutaraldehyde, acrylic acid and the like. Acrylic acid is an important organic chemical raw material, is mainly used for manufacturing multifunctional high polymer materials such as acrylates, and is widely applied to the fields of papermaking, leather, coating, textile, plastics, rubber, oil additives, petroleum exploitation and the like. In recent years, the market demand for acrylic acid has increased worldwide, and the production of acrylic acid has been a focus of research.

The synthesis of acrylic acid by the acrolein oxidation process is currently used on a large industrial scale. The catalyst used for synthesizing acrylic acid by acrolein oxidation method is generally Mo-V series oxide, the basic elements of the catalyst are Mo and V, and other elements used for improving the performance of the catalyst, such as Nb, Sn, Cr, W, Fe, Co, Ni, Sb and the like, are added. US Pat7220698B2 describes the introduction of a trace amount of a catalyst poison into the catalyst preparation process to inhibit thermal degradation of the catalyst and provide stability to the catalyst. US Pat7456129B2 describes varying acid content, controlling acid strength, and improving catalyst performance during catalyst support preparation. CN 16997701 and CN1210511 propose a preparation method of a composite oxide catalyst, which is to Co-precipitate mixed liquor of various element components (containing Fe, Co, Mo, V, Bi, Ni, etc.), dry into powder, perform tabletting, extrusion molding, and finally bake to obtain the composite oxide catalyst. The acrylic acid catalyst can be successfully prepared by the methods and the performance of the catalyst is improved, but the catalyst has poor mechanical strength and low catalytic activity ratio, so that the practical application is limited.

The active components of the catalyst are loaded on the carrier with large specific surface area, so that the mechanical strength of the catalyst can be increased, the loading capacity of the active components is greatly increased, and the active components of the catalyst are exerted to a great extent through a synergistic effect. CN1130172 (preparation method of acrylic acid) describes a preparation method of a spherical catalyst, in which a carrier is added into an active component mixed solution, and is evaporated and dried, so that the active component is deposited on the surface of the carrier. However, the catalytic activity, selectivity and yield of the acrylic acid catalyst obtained in the prior art need to be further improved.

Disclosure of Invention

The invention aims to solve the technical problems of low acrolein conversion rate and low acrylic acid yield of the existing catalyst, and provides a novel acrylic acid synthesis method.

In order to solve the technical problems, the technical scheme of the invention is as follows:

a process for the synthesis of acrylic acid, comprising reacting acrolein with an oxygen-containing oxidizing gas in the presence of a catalyst to obtain acrylic acid; the catalyst comprises a carrier and an active component loaded on the carrier, wherein the active component is represented by the general formula: VMo_aNb_bW_cX_dY_eZ_fO_gWherein X is selected from one or more of Sc, Ti, Y, Zr, Hf, Ta and Cr, Y is selected from at least one of Ga, Ge, In, Sn, TI, Pb, Cd, Mn, Tc, Re, Rh, Ir, Pd, Pt, Ag, Au and La, and Z is selected from one or more of alkali metal or alkaline earth metal; a is the molar ratio of Mo to V, and the value of a is 2.0-8.0; b is the molar ratio of Nb to V, and the value of b is 0.2-0.8; c is the molar ratio of W to V, and the value of c is 0.2-1.0; d is the molar ratio of X to V, and the value of d is 0.2-1.0; e is the molar ratio of Y to V, and the value of e is 0.05-1.2; f is the molar ratio of Z to V, and the value of f is 0.05-1.2; g is the mole number of oxygen atoms needed to satisfy the valence of each element in the active component.

In the above-mentioned technical solutions, the reaction is preferably carried out in the presence of a dilute gas phase feed.

In the above technical solution, the oxidizing gas is preferably pure oxygen, oxygen-enriched oxygen, or air.

In the above technical solution, the dilute gas phase material is preferably water vapor.

In the technical scheme, the reaction temperature is preferably 100-500 ℃.

In the above technical scheme, the material comprising acrolein, air and water vapor is used as the raw material gas for reaction, and the ratio by volume of acrolein: air: the steam is 1 (1-6) and 0.5-5.

In the technical scheme, the preferred volume space velocity of the feed gas is 800-2000 hours^-1。

In the above-mentioned embodiments, as one of preferable embodiments, Y preferably includes Tc and Re together, and Tc and Re have a synergistic effect in improving the yield of acrylic acid.

In the above-mentioned second preferred embodiment, Y preferably includes both Tc and Mn, and Tc and Mn have a synergistic effect in increasing the yield of acrylic acid.

In the above technical solution, as a third preferred technical solution, Y preferably includes Tc and La simultaneously, and Tc and La have a synergistic effect in improving the yield of acrylic acid.

In the above technical solutions, as one of the more preferable technical solutions, Y simultaneously includes Tc, Re and Mn, and the three have a synergistic effect of ternary combination in the aspect of improving the yield of acrylic acid.

In the above-mentioned second preferred embodiment, Y simultaneously includes Tc, Mn and La, and the three components have a synergistic effect of ternary combination in improving the yield of acrylic acid.

In the above-mentioned technical solutions, as a third preferred technical solution, Y simultaneously includes Tc, Re and La, and the three have a synergistic effect of ternary combination in the aspect of improving the yield of acrylic acid.

In the above technical scheme, the molar ratio of Mo to V may be, but not limited to, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 7.0, and the like.

In the above technical solution, the molar ratio of Nb to V may be, but not limited to, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.70, and the like.

In the above technical scheme, the molar ratio of W to V may be, but not limited to, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.70, and the like.

In the above technical solution, the molar ratio of Cr to V may be, but not limited to, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.70, and the like.

In the above technical scheme, the molar ratio of Na to V may be, but not limited to, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.70, and the like.

In the above technical scheme, the molar ratio of Tc to V may be, but not limited to, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, etc.

In the above technical scheme, the molar ratio of Re to V may be, but not limited to, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, etc.

In the above technical scheme, the molar ratio of Mn to V may be, but not limited to, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, and the like.

In the above technical scheme, the molar ratio of La to V may be, but not limited to, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, etc.

In the above technical scheme, more specific examples of the general formula of the active ingredient can be, but are not limited to:

VMo_2.0～8.0Nb_0.2～0.8W_0.2～1.0Cr_0.2～1.0Tc_0.05～0.60Re_0.05～0.60Na_0.05～1.2O_g；

VMo_2.0～8.0Nb_0.2～0.8W_0.2～1.0Cr_0.2～1.0Tc_0.05～0.60Mn_0.05～0.60Na_0.05～1.2O_g；

VMo_2.0～8.0Nb_0.2～0.8W_0.2～1.0Cr_0.2～1.0Tc_0.05～0.60La_0.05～0.60Na_0.05～1.2O_g；

VMo_2.0～8.0Nb_0.2～0.8W_0.2～1.0Cr_0.2～1.0Tc_0.05～0.45Re_0.05～0.3Mn_0.05～0.45Na_0.05～1.2O_g；

VMo_2.0～8.0Nb_0.2～0.8W_0.2～1.0Cr_0.2～1.0Tc_0.05～0.45Mn_0.05～0.3La_0.05～0.45Na_0.05～1.2O_g；

VMo_2.0～8.0Nb_0.2～0.8W_0.2～1.0Cr_0.2～1.0Tc_0.05～0.45Re_0.05～0.3La_0.05～0.45Na_0.05～1.2O_g；

wherein g is the mole number of oxygen atoms required to satisfy the valence of each element in the active component.

In the technical scheme, the content of the active component in the catalyst is preferably 10-60 w% by weight.

In the technical scheme, the content of the carrier in the catalyst is preferably 40-90 w% by weight.

In the above technical solutions, the shape and size of the carrier are not particularly limited, and all the carriers can obtain comparable technical effects, for which the skilled person can reasonably select. For convenience of comparison, the carriers of the embodiments of the present invention are all spherical.

In the above technical solution, the support is preferably at least one of alumina, lithium oxide, magnesia, zirconia, silica and titania.

In the technical scheme, the catalyst is prepared by adopting a method comprising the following steps:

preparing mixed liquid of active component elements;

mixing the active component element mixed solution with a carrier;

and (4) roasting.

In the above technical solution, the mixed solution may be a solution, a suspension, or a mixture of a solution and a suspension.

In the above technical solution, the conditions for 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 above mixed solution can be calcined into oxide forms, and those skilled in the art can select the conditions for calcination appropriately without creative efforts.

In the above technical scheme, the roasting temperature is 300-550 ℃ by way of example only.

In the above technical scheme, the roasting time is 1-12 hours, which is only an example.

In the above technical scheme, the roasting atmosphere is an inert atmosphere or an atmosphere containing O by way of example only₂Of the atmosphere (c). However, the atmosphere for the calcination is preferably air from the economical viewpoint. The atmosphere for calcination in the present invention is air unless otherwise specified.

In the above technical scheme, the catalyst can be prepared in the following manner:

1. preparation of active element solution

Dissolving a compound of the required active component elements to obtain a mixed solution of the active elements; the dissolution step is not particularly limited, and the specific dissolution procedure and process conditions may be appropriately selected by those skilled in the art.

2. Active element loading

And (2) mixing the carrier particles with the mixed liquid of the active elements obtained in the step (1) (wherein the dosage of the mixed liquid of the active elements is 5-50 w% of the required amount of the catalyst), and drying to obtain a catalyst precursor I. The drying temperature can be, but is not limited to, 60-100 ℃, and the drying time can be, but is not limited to, 2-8 hours.

3. Roasting

Calcining the catalyst precursor I to obtain the catalyst. The catalyst precursor I may further comprise a drying step before calcination, wherein the drying temperature is, for example and without limitation, 60-100 ℃, and the drying time is, for example and without limitation, 2-12 hours. The roasting temperature is, for example, but not limited to, 300-550 ℃, and the roasting time is, for example, but not limited to, 1-12 hours.

The catalyst prepared in this way is surprisingly good in terms of acrolein conversion and acrylic acid yield.

The catalyst evaluation method of the present invention is as follows:

a reactor: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;

catalyst loading: 200 g;

reaction temperature: 280 ℃;

reaction time: 4 hours;

the volume ratio of raw materials is as follows: acrolein: air: water vapor 1: 3.5: 2;

total volume space velocity of raw materials: 1400 hours^-1。

Acrolein conversion and acrylic acid yield are defined as follows:

acrolein conversion ═ 100% (molar amount of acrolein reaction/molar amount of acrolein total added);

the yield of acrylic acid (molar amount of acrylic acid produced/total molar amount of acrolein added) × 100%.

By adopting the catalyst, the conversion rate of acrolein can be close to 99%, the yield of acrylic acid can be close to 96%, and the catalyst has good technical effect and can be used in the industrial production of acrylic acid.

Detailed Description

[ example 1 ]

1. Preparation of active element solution

Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V₄VO₃) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo₄)₂MoO₄) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)₄)₁₀W₁₂O₄₁) Ammonium chromate containing 0.04 mol Cr (formula: (NH)₄)₂CrO₄) Technetium heptaoxide containing 0.04 mol Tc (formula: tc₂O₇) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na₃) And stirred to dissolve the whole solution to obtain a solution I. Niobium oxalate (molecular formula is (NH) containing 0.04 mol of Nb₄)₃NbO(C₂O₄)₃) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component₄Nb_0.4W_0.4Cr_0.4Tc_0.4Na_0.4O_gWas 0.4g/g, to obtain a solution II.

2. Active element loading

200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.

3. Roasting

The catalyst precursor I was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:

31w％VMo₄Nb_0.4W_0.4Cr_0.4Tc_0.4Na_0.4O_g+69w％Al₂O₃。

4. catalyst evaluation

The acrolein conversion and acrylic acid yield were examined.

The evaluation results of the supporting step in the catalyst and the catalyst are shown in Table 1 for convenience of comparison.

[ example 2 ]

1. Preparation of active element solution

Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V₄VO₃) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo₄)₂MoO₄) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)₄)₁₀W₁₂O₄₁) Ammonium chromate containing 0.04 mol Cr (formula: (NH)₄)₂CrO₄) Rhenium heptoxide (molecular formula: re₂O₇) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na₃) And stirred to dissolve the whole solution to obtain a solution I. Niobium oxalate (molecular formula is (NH) containing 0.04 mol of Nb₄)₃NbO(C₂O₄)₃) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component₄Nb_0.4W_0.4Cr_0.4Re_0.4Na_0.4O_gWas 0.4g/g, to obtain a solution II.

2. Active element loading

200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.

3. Roasting

The catalyst precursor I was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:

31w％VMo₄Nb_0.4W_0.4Cr_0.4Re_0.4Na_0.4O_g+69w％Al₂O₃

4. catalyst evaluation

The acrolein conversion and acrylic acid yield were examined.

The evaluation results of the supporting step in the catalyst and the catalyst are shown in Table 1 for convenience of comparison.

[ example 3 ]

1. Preparation of active element solution

Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V₄VO₃) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo₄)₂MoO₄) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)₄)₁₀W₁₂O₄₁) Ammonium chromate containing 0.04 mol Cr (formula: (NH)₄)₂CrO₄) Manganese nitrate containing 0.04 mol of Mn (molecular formula: mn (NO)₃)₂) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na₃) And stirred to dissolve the whole solution to obtain a solution I. Niobium oxalate (molecular formula is (NH) containing 0.04 mol of Nb₄)₃NbO(C₂O₄)₃) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component₄Nb_0.4W_0.4Cr_0.4Mn_0.4Na_0.4O_gWas 0.4g/g, to obtain a solution II.

2. Active element loading

200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.

3. Roasting

The catalyst precursor I was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:

31w％VMo₄Nb_0.4W_0.4Cr_0.4Mn_0.4Na_0.4O_g+69w％Al₂O₃

4. catalyst evaluation

The acrolein conversion and acrylic acid yield were examined.

The evaluation results of the supporting step in the catalyst and the catalyst are shown in Table 1 for convenience of comparison.

[ example 4 ]

1. Preparation of active element solution

Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V₄VO₃) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo₄)₂MoO₄) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)₄)₁₀W₁₂O₄₁) Ammonium chromate containing 0.04 mol Cr (formula: (NH)₄)₂CrO₄) Lanthanum oxide containing 0.04 mol of La (formula: la₂O₃) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na₃) And stirred to dissolve the whole solution to obtain a solution I. Niobium oxalate (molecular formula is (NH) containing 0.04 mol of Nb₄)₃NbO(C₂O₄)₃) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component₄Nb_0.4W_0.4Cr_0.4La_0.4Na_0.4O_gWas 0.4g/g, to obtain a solution II.

2. Active element loading

200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.

3. Roasting

The catalyst precursor I was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:

31w％VMo₄Nb_0.4W_0.4Cr_0.4La_0.4Na_0.4O_g+69w％Al₂O₃

4. catalyst evaluation

The acrolein conversion and acrylic acid yield were examined.

The evaluation results of the supporting step in the catalyst and the catalyst are shown in Table 1 for convenience of comparison.

[ example 5 ]

1. Preparation of active element solution

Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V₄VO₃) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo₄)₂MoO₄) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)₄)₁₀W₁₂O₄₁) Ammonium chromate containing 0.04 mol Cr (formula: (NH)₄)₂CrO₄) Technetium heptaoxide containing 0.02 mol Tc (formula: tc₂O₇) Rhenium heptoxide (molecular formula: re₂O₇) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na₃) And stirred to dissolve the whole solution to obtain a solution I. Niobium oxalate (molecular formula is (NH) containing 0.04 mol of Nb₄)₃NbO(C₂O₄)₃) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component₄Nb_0.4W_0.4Cr_0.4Tc_0.2Re_0.2Na_0.4O_gWas 0.4g/g, to obtain a solution II.

2. Active element loading

200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.

3. Roasting

The catalyst precursor I was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:

31w％VMo₄Nb_0.4W_0.4Cr_0.4Tc_0.2Re_0.2Na_0.4O_g+69w％Al₂O₃。

4. catalyst evaluation

The acrolein conversion and acrylic acid yield were examined.

The evaluation results of the supporting step in the catalyst and the catalyst are shown in Table 1 for convenience of comparison.

[ example 6 ]

1. Preparation of active element solution

Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V₄VO₃) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo₄)₂MoO₄) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)₄)₁₀W₁₂O₄₁) Ammonium chromate containing 0.04 mol Cr (formula: (NH)₄)₂CrO₄) Technetium heptaoxide containing 0.02 mol Tc (formula: tc₂O₇) Manganese nitrate containing 0.02 mol of Mn (molecular formula: mn (NO)₃)₂) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na₃) And stirred to dissolve the whole solution to obtain a solution I. Niobium oxalate (molecular formula is (NH) containing 0.04 mol of Nb₄)₃NbO(C₂O₄)₃) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component₄Nb_0.4W_0.4Cr_0.4Tc_0.2Mn_0.2Na_0.4O_gWas 0.4g/g, to obtain a solution II.

2. Active element loading

200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.

3. Roasting

The catalyst precursor I was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:

31w％VMo₄Nb_0.4W_0.4Cr_0.4Tc_0.2Mn_0.2Na_0.4O_g+69w％Al₂O₃。

4. catalyst evaluation

The acrolein conversion and acrylic acid yield were examined.

The evaluation results of the supporting step in the catalyst and the catalyst are shown in Table 1 for convenience of comparison.

[ example 7 ]

1. Preparation of active element solution

Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V₄VO₃) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo₄)₂MoO₄) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)₄)₁₀W₁₂O₄₁) Ammonium chromate containing 0.04 mol Cr (formula: (NH)₄)₂CrO₄) Technetium heptaoxide containing 0.02 mol Tc (formula: tc₂O₇) Lanthanum oxide containing 0.02 mol of La (molecular formula: la₂O₃) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na₃) And stirred to dissolve the whole solution to obtain a solution I. Niobium oxalate (molecular formula is (NH) containing 0.04 mol of Nb₄)₃NbO(C₂O₄)₃) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component₄Nb_0.4W_0.4Cr_0.4Tc_0.2La_0.2Na_0.4O_gWas 0.4g/g, to obtain a solution II.

2. Active element loading

200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.

3. Roasting

The catalyst precursor I was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:

31w％VMo₄Nb_0.4W_0.4Cr_0.4Tc_0.2La_0.2Na_0.4O_g+69w％Al₂O₃。

4. catalyst evaluation

The acrolein conversion and acrylic acid yield were examined.

The evaluation results of the supporting step in the catalyst and the catalyst are shown in Table 1 for convenience of comparison.

[ example 8 ]

1. Preparation of active element solution

Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V₄VO₃) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo₄)₂MoO₄) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)₄)₁₀W₁₂O₄₁) Ammonium chromate containing 0.04 mol Cr (formula: (NH)₄)₂CrO₄) Technetium heptaoxide containing 0.015 mol of Tc (molecular formula: tc₂O₇) Rhenium heptoxide (molecular formula: re₂O₇) Manganese nitrate containing 0.015 mol of Mn (molecular formula: mn (NO)₃)₂) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na₃) And stirred to dissolve the whole solution to obtain a solution I. Niobium oxalate (molecular formula is (NH) containing 0.04 mol of Nb₄)₃NbO(C₂O₄)₃) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component₄Nb_0.4W_0.4Cr_0.4Tc_0.15Re_0.1Mn_0.15Na_0.4O_gWas 0.4g/g, to obtain a solution II.

2. Active element loading

200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.

3. Roasting

The catalyst precursor I was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:

31w％VMo₄Nb_0.4W_0.4Cr_0.4Tc_0.15Re_0.1Mn_0.15Na_0.4O_g+69w％Al₂O₃

4. catalyst evaluation

The acrolein conversion and acrylic acid yield were examined.

The evaluation results of the supporting step in the catalyst and the catalyst are shown in Table 1 for convenience of comparison.

[ example 9 ]

1. Preparation of active element solution

Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V₄VO₃) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo₄)₂MoO₄) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)₄)₁₀W₁₂O₄₁) Ammonium chromate containing 0.04 mol Cr (formula: (NH)₄)₂CrO₄) Technetium heptaoxide containing 0.015 mol of Tc (molecular formula: tc₂O₇) Manganese nitrate containing 0.01 mol of Mn (molecular formula: mn (NO)₃)₂) Lanthanum oxide containing 0.015 mol of La (molecular formula: la₂O₃) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na₃) And stirred to dissolve the whole solution to obtain a solution I. Niobium oxalate (molecular formula is (NH) containing 0.04 mol of Nb₄)₃NbO(C₂O₄)₃) Adding the aqueous solution into the above solutions respectively, mixing, and evaporating at 80 deg.C to mixThe material solution is equivalent to VMo containing active component₄Nb_0.4W_0.4Cr_0.4Tc_0.15Mn_0.1La_0.15Na_0.4O_gWas 0.4g/g, to obtain a solution II.

2. Active element loading

200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.

3. Roasting

The catalyst precursor I was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:

31w％VMo₄Nb_0.4W_0.4Cr_0.4Tc_0.15Mn_0.1La_0.15Na_0.4O_g+69w％Al₂O₃

4. catalyst evaluation

The acrolein conversion and acrylic acid yield were examined.

The evaluation results of the supporting step in the catalyst and the catalyst are shown in Table 1 for convenience of comparison.

[ example 10 ]

1. Preparation of active element solution

Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V₄VO₃) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo₄)₂MoO₄) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)₄)₁₀W₁₂O₄₁) Ammonium chromate containing 0.04 mol Cr (formula: (NH)₄)₂CrO₄) Technetium heptaoxide containing 0.015 mol of Tc (molecular formula: tc₂O₇) Rhenium heptoxide (molecular formula: re₂O₇) Lanthanum oxide containing 0.015 mol of La (molecular formula: la₂O₃) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na₃) And stirred to dissolve the whole solution to obtain a solution I. Adding niobium oxalate (molecular formula) containing 0.04 mol of NbComprises the following steps: (NH)₄)₃NbO(C₂O₄)₃) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component₄Nb_0.4W_0.4Cr_0.4Tc_0.15Re_0.1La_0.15Na_0.4O_gWas 0.4g/g, to obtain a solution II.

2. Active element loading

200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.

3. Roasting

The catalyst precursor I was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:

31w％VMo₄Nb_0.4W_0.4Cr_0.4Tc_0.15Re_0.1La_0.15Na_0.4O_g+69w％Al₂O₃

4. catalyst evaluation

The acrolein conversion and acrylic acid yield were examined.

The evaluation results of the supporting step in the catalyst and the catalyst are shown in Table 1 for convenience of comparison.

TABLE 1