CN109305905B - Method for synthesizing acrylic acid - Google Patents

Method for synthesizing acrylic acid Download PDF

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Publication number
CN109305905B
CN109305905B CN201710628216.6A CN201710628216A CN109305905B CN 109305905 B CN109305905 B CN 109305905B CN 201710628216 A CN201710628216 A CN 201710628216A CN 109305905 B CN109305905 B CN 109305905B
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acrylic acid
catalyst
solution
active component
molecular formula
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CN109305905A (en
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王伟华
宋卫林
徐文杰
杨斌
薛立新
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

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: VMoaNbbXcYdOeWherein X is selected from one or more of Sc, Ti, Cr and W, and Y is selected from at least one of Fe, Co, Ni, Ru, Os, Ag, Sn, Sb, Bi, La and Ce.

Description

Method for synthesizing acrylic acid
Technical Field
The present invention relates to a method for the synthesis of 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 conversion rate of acrolein and low yield of acrylic acid in the existing catalyst, and provides a novel acrylic acid synthesis method which has the characteristics of high conversion rate of acrolein and high yield of acrylic acid.
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: VMoaNbbXcYdOeWherein X isComprises one or more of Sc, Ti, Cr and W, and Y comprises at least one of Fe, Co, Ni, Ru, Os, Ag, Sn, Sb, Bi, La and Ce; 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 X to V, and the value of c is 0.2-1.0; d is the molar ratio of Y to V, and the value of d is 0.05-1.2; e is the mole number of oxygen atoms required 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 technical solution, as one of preferable technical solutions, Y preferably includes Os and Sn at the same time, and Os and Sn have a synergistic effect in improving the yield of acrylic acid.
In the above technical solution, as a second preferred technical solution, Y preferably includes Os and Ru at the same time, and Os and Ru have a synergistic effect in improving the yield of acrylic acid.
In the above technical solution, as a third preferred technical solution, Y preferably includes Os and La simultaneously, and Os 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 Os, Sn, and Ru, and the three have a synergistic effect of ternary combination in improving the yield of acrylic acid.
In the above technical solution, as a second more preferable technical solution, Y simultaneously includes Os, La and Ru, and the three have a synergistic effect of ternary combination in the aspect of improving the yield of acrylic acid.
In the above technical solution, as a third preferred technical solution, Y simultaneously includes Os, La and Sn, 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 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 Os 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 Sn 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 Ru to V can 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:
VMo2.0～8.0Nb0.2～0.8Cr0.2～1.0Os0.05～0.60Sn0.05～0.60Oe；
VMo2.0～8.0Nb0.2～0.8Cr0.2～1.0Os0.05～0.60Ru0.05～0.60Oe；
VMo2.0～8.0Nb0.2～0.8Cr0.2～1.0Os0.05～0.60La0.05～0.60Oe；
VMo2.0～8.0Nb0.2～0.8Cr0.2～1.0Os0.05～0.45Sn0.05～0.3Ru0.05～0.45Oe；
VMo2.0～8.0Nb0.2～0.8Cr0.2～1.0Os0.05～0.45La0.05～0.3Ru0.05～0.45Oe；
VMo2.0～8.0Nb0.2～0.8Cr0.2～1.0Os0.05～0.45La0.05～0.3Sn0.05～0.45Oe；
wherein e 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 carrier is preferably at least one of alumina, lithium oxide, magnesium oxide, 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 dispersion 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 compounds of all the active elements present in the dispersion can be calcined to the form of oxides, 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 technical scheme, the catalyst is prepared in the following way:
a1, preparation of active element solution
Dissolving a compound of the required active component element to obtain an aqueous solution of the active element; 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.
a2, active element loading
And c, mixing the carrier particles with the active element mixture obtained in the step a1 (wherein the dosage of the active element mixture is 5-50 w% of the required amount of the catalyst), and drying to obtain the 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.
a3 baking
Calcining the catalyst precursor II to obtain the catalyst. The catalyst precursor II 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 the above manner 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 method, the conversion rate of the acrolein can approach to 99 percent, the yield of the acrylic acid can reach more than 96 percent, and the method obtains better technical effect and can be used in the industrial production of the 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) Added thereto, and ammonium chromate (molecular formula: (NH)4)2CrO4) Osmium tetroxide containing 0.04 mol of Os (molecular formula: OsO4) 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 component4Nb0.4Cr0.4Os0.4OeHas a concentration of 0.4gThe solution II is obtained in mg.
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 II was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:
29w％VMo4Nb0.4Cr0.4Os0.4Oe+71w％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) Added thereto, and ammonium chromate (molecular formula: (NH)4)2CrO4) Tin nitrate containing 0.04 mol of Sn (molecular formula: sn (NO)3)2) 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 component4Nb0.4Cr0.4Sn0.4OeWas 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 II was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:
29w％VMo4Nb0.4Cr0.4Sn0.4Oe+71w％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) Added thereto, and ammonium chromate (molecular formula: (NH)4)2CrO4) Ammonium chlororuthenate containing 0.04 mol Ru (molecular formula: (NH)4)2RuCl6) 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 component4Nb0.4Cr0.4Ru0.4OeWas 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 II was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:
29w％VMo4Nb0.4Cr0.4Ru0.4Oe+71w％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) Added thereto, and ammonium chromate (molecular formula: (NH)4)2CrO4) Lanthanum nitrate containing 0.04 mol of La (formula: la (NO)3)3) 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 component4Nb0.4Cr0.4La0.4OeWas 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 II was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:
29w％VMo4Nb0.4Cr0.4La0.4Oe+71w％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) Added thereto, and ammonium chromate (molecular formula: (NH)4)2CrO4) Osmium tetroxide containing 0.02 mol of Os (molecular formula: OsO4) Tin nitrate containing 0.02 mol of Sn (molecular formula: sn (NO)3)2) 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 component4Nb0.4Cr0.4Os0.2Sn0.2OeWas 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 II was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:
29w％VMo4Nb0.4Cr0.4Os0.2Sn0.2Oe+71w％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) Dissolving in hot water of 80 deg.C (200 g)In (1). Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo4)2MoO4) Added thereto, and ammonium chromate (molecular formula: (NH)4)2CrO4) Osmium tetroxide containing 0.02 mol of Os (molecular formula: OsO4) Ammonium chlororuthenate containing 0.02 mol of Ru (molecular formula: (NH)4)2RuCl6) 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 component4Nb0.4Cr0.4Os0.2Ru0.2OeWas 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 II was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:
29w％VMo4Nb0.4Cr0.4Os0.2Ru0.2Oe+71w％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) Added thereto, and ammonium chromate (molecular formula: (NH)4)2CrO4) Osmium tetroxide containing 0.02 mol of Os (molecular formula: OsO4) Lanthanum nitrate containing 0.02 mol of La (molecular formula: la (NO)3)3) 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 component4Nb0.4Cr0.4Os0.2La0.2OeWas 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 II was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:
29w％VMo4Nb0.4Cr0.4Os0.2La0.2Oe+71w％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) Added thereto, and ammonium chromate (molecular formula: (NH)4)2CrO4) Osmium tetroxide containing 0.015 mol of Os (molecular formula: OsO4) Tin nitrate containing 0.01 mol of Sn (molecular formula: sn (NO)3)2) Containing 0.015 mol Ru ammonium chlororuthenate (molecular formula is (NH)4)2RuCl6) 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 component4Nb0.4Cr0.4Os0.15Sn0.1Ru0.15OeWas 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 II was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:
29w％VMo4Nb0.4Cr0.4Os0.15Sn0.1Ru0.15Oe+71w％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) Added thereto, and ammonium chromate (molecular formula: (NH)4)2CrO4) Osmium tetroxide containing 0.015 mol of Os (molecular formula: OsO4) Lanthanum nitrate containing 0.01 mol of La (formula: la (NO)3)3) Ammonium chlororuthenate containing 0.015 mol Ru (molecular formula: (NH)4)2RuCl6) 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 component4Nb0.4Cr0.4Os0.15La0.1Ru0.15OeWas 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 II was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:
29w％VMo4Nb0.4Cr0.4Os0.15La0.1Ru0.15Oe+71w％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) Added thereto, and ammonium chromate (molecular formula: (NH)4)2CrO4) Osmium tetroxide containing 0.015 mol of Os (molecular formula: OsO4) Lanthanum nitrate containing 0.01 mol of La (formula: la (NO)3)3) Tin nitrate containing 0.015 mol of Sn (molecular formula: sn (NO)3)2) And stirring to dissolve the mixture completely to obtain a solution I. Will contain 0.04 molNiobium oxalate of Nb (molecular formula is (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 component4Nb0.4Cr0.4Os0.15La0.1Sn0.15OeWas 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.
3. Roasting
The catalyst precursor II was dried at 90 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to give a catalyst having the following composition:
29w％VMo4Nb0.4Cr0.4Os0.15La0.1Ru0.15Oe+71w％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
Figure BDA0001363285750000131

Claims (9)

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: VMoaNbbXcYdOeWherein X is Cr, Y is Os and any one or more selected from Sn, Ru and La; 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 X to V, and the value of c is 0.2-1.0; d is the mole of Y and VD is 0.05-1.2; e is the mole number of oxygen atoms required by the valence of each element in the active component;
the carrier is alumina.
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, or air.
4. The method for synthesizing acrylic acid according to claim 2, wherein said dilute gas phase 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 800-2000 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 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.
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Citations (9)

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Publication number Priority date Publication date Assignee Title
GB1488044A (en) * 1973-10-23 1977-10-05 Union Carbide Corp Catalyst with mo,v,nb and process for preparing unsaturated acids
GB1488889A (en) * 1973-10-23 1977-10-12 Union Carbide Corp Catalyst with mo,v,ti and process for preparing unsaturated acids
CN1408700A (en) * 2001-09-19 2003-04-09 株式会社日本触媒 process for producing propenoic acid
JP2003236383A (en) * 2002-02-13 2003-08-26 Mitsubishi Chemicals Corp Method for manufacturing multiple oxide catalyst
CN1668567A (en) * 2002-07-18 2005-09-14 巴斯福股份公司 Heterogeneously catalyzed gas-phase partial oxidation of at least one organic compound
CN1753726A (en) * 2004-05-21 2006-03-29 三菱化学株式会社 Method for producing composite oxide catalyst
CN1764631A (en) * 2003-03-25 2006-04-26 巴斯福股份公司 Heterogeneously catalyzed partial gas phase oxidation of acrolein to acrylic acid
CN1853786A (en) * 2005-04-18 2006-11-01 株式会社日本触媒 Support for gas-phase oxidation catalyst and process for its production, gas-phase oxidation catalyst,and process for producing acrylic acid
CN1874985A (en) * 2003-10-29 2006-12-06 巴斯福股份公司 Method for long term operation of a multiphase catalysed gas phase partial oxidation of acrolein in order to form acrylic acid

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1488044A (en) * 1973-10-23 1977-10-05 Union Carbide Corp Catalyst with mo,v,nb and process for preparing unsaturated acids
GB1488889A (en) * 1973-10-23 1977-10-12 Union Carbide Corp Catalyst with mo,v,ti and process for preparing unsaturated acids
CN1408700A (en) * 2001-09-19 2003-04-09 株式会社日本触媒 process for producing propenoic acid
JP2003236383A (en) * 2002-02-13 2003-08-26 Mitsubishi Chemicals Corp Method for manufacturing multiple oxide catalyst
CN1668567A (en) * 2002-07-18 2005-09-14 巴斯福股份公司 Heterogeneously catalyzed gas-phase partial oxidation of at least one organic compound
CN1764631A (en) * 2003-03-25 2006-04-26 巴斯福股份公司 Heterogeneously catalyzed partial gas phase oxidation of acrolein to acrylic acid
CN1874985A (en) * 2003-10-29 2006-12-06 巴斯福股份公司 Method for long term operation of a multiphase catalysed gas phase partial oxidation of acrolein in order to form acrylic acid
CN1753726A (en) * 2004-05-21 2006-03-29 三菱化学株式会社 Method for producing composite oxide catalyst
CN1853786A (en) * 2005-04-18 2006-11-01 株式会社日本触媒 Support for gas-phase oxidation catalyst and process for its production, gas-phase oxidation catalyst,and process for producing acrylic acid

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