CN111068711A - Acrylic acid catalyst and application thereof - Google Patents

Acrylic acid catalyst and application thereof Download PDF

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Publication number
CN111068711A
CN111068711A CN201811220148.0A CN201811220148A CN111068711A CN 111068711 A CN111068711 A CN 111068711A CN 201811220148 A CN201811220148 A CN 201811220148A CN 111068711 A CN111068711 A CN 111068711A
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catalyst
solution
mol
acrylic acid
molecular formula
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王伟华
宋卫林
徐文杰
杨斌
奚美珍
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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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    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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  • 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 an acrylic acid catalyst and application thereof, mainly solving the problems of low conversion rate of acrolein and low yield of acrylic acid in the existing catalyst, and adopting the acrylic acid catalyst, wherein the acrylic acid catalyst comprises a carrier and an active component loaded on the carrier, and the general formula of the active component is as follows: VMoaCubWcXdQeZfOgWherein X is selected from one or more of Al, Ga, Ge, In, Sn, Sb, TI, Pb, Bi and Po, Q is selected from at least one of Sc, Ti, Y, Zr, Hf, Ta, Tc, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Cd, La and Pr, and Z is selected from one or more of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba and RaSolves the technical problem well, and can be used in the industrial production of acrylic acid.

Description

Acrylic acid catalyst and application thereof
Technical Field
The invention relates to an acrylic acid catalyst, a preparation method thereof and application thereof in preparing acrylic acid by acrolein oxidation.
Background
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. Acrolein is the simplest unsaturated aldehyde and is also an important chemical synthesis intermediate, and is widely used for synthesizing important chemical products such as picoline, pyridine, glutaraldehyde, acrylic acid and the like, so that the production of acrylic acid by acrolein is in the trend. 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 catalyst carrier can enable the catalyst to have proper shape, size and mechanical strength, so that the mechanical strength of the catalyst can be increased by loading the active components of the catalyst on the carrier with large specific surface area, the loading amount of the active components is greatly increased, and the active components of the catalyst are exerted to a great extent through synergistic action. 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 catalyst which has the characteristics of high acrolein conversion rate and high acrylic acid yield.
The second technical problem to be solved by the invention is a preparation method of the catalyst.
The invention solves the technical problem of the prior art, and the other technical problem is the application of the catalyst.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows:
the acrylic acid catalyst comprises a carrier and an active component loaded on the carrier, wherein the active component is represented by the general formula: VMoaCubWcXdQeZfOgWherein X is selected from one or more of Al, Ga, Ge, In, Sn, Sb, TI, Pb, Bi and Po, Q is selected from at least one of Sc, Ti, Y, Zr, Hf, Ta, Tc, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Cd, La and Pr, and Z is selected from one or more of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba and Ra; 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 Cu to V, and the value of b is 0.1-1.0; c is the molar ratio of W to V, and the value of c is 0.1-1.0; d is the molar ratio of X to V, and the value of d is 0.1-1.0; e is the molar ratio of Q to V, and the value of e is 0.1-1.0; f is the molar ratio of Z to V, and the value of f is 0.1-1.0; g is the mole number of oxygen atoms needed to satisfy the valence of each element in the active component.
In the above-mentioned embodiments, as one of preferable embodiments, Q preferably includes Sc and Rh together, and Sc and Rh have a synergistic effect in improving the yield of acrylic acid.
In the above technical solution, as a second preferred technical solution, Q preferably includes Sc and Ir at the same time, and Sc and Ir have a synergistic effect in improving the yield of acrylic acid.
In the above technical solution, as a third preferred technical solution, Q preferably includes Sc and Pr at the same time, and Sc and Pr have a synergistic effect in improving the yield of acrylic acid.
In the above technical solutions, as one of more preferable technical solutions, Q preferably includes Sc, Rh, and Ir at the same time, and the three have a synergistic effect of ternary combination in improving the yield of acrylic acid.
In the above-mentioned technical solution, as a second more preferable technical solution, Q preferably includes Sc, Rh and Pr at the same time, and the three have a synergistic effect of ternary combination in the aspect of improving the yield of acrylic acid.
In the above technical solutions, as a third more preferable technical solution, Q preferably includes Sc, Ir and Pr at the same time, 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 scheme, the molar ratio of Cu 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 scheme, the molar ratio of Sn 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 Sc 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 Rh 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 Ir 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 Pr 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, more specific examples of the general formula of the active ingredient can be, but are not limited to:
VMo2.0～8.0Cu0.1～1.0W0.1～1.0Sn0.1～1.0Sc0.05～0.50Rh0.05～0.50Na0.1～1.0Og；
VMo2.0～8.0Cu0.1～1.0W0.1～1.0Sn0.1～1.0Sc0.05～0.50Ir0.05～0.50Na0.1～1.0Og；
VMo2.0～8.0Cu0.1～1.0W0.1～1.0Sn0.1～1.0Sc0.05～0.50Pr0.05～0.50Na0.1～1.0Og；
VMo2.0～8.0Cu0.1～1.0W0.1～1.0Sn0.1～1.0Sc0.04～0.40Rh0.03～0.30Ir0.03～0.30Na0.1～1.0Og；
VMo2.0～8.0Cu0.1～1.0W0.1～1.0Sn0.1～1.0Sc0.04～0.40Rh0.03～0.30Pr0.03～0.30Na0.1～1.0Og；
VMo2.0～8.0Cu0.1～1.0W0.1～1.0Sn0.1～1.0Sc0.04～0.40Ir0.03～0.30Pr0.03～0.30Na0.1～1.0Og；
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 10-80 w% by weight.
In the technical scheme, the content of the carrier in the catalyst is preferably 20-90 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.
To solve the second technical problem, the technical solution of the present invention is as follows:
the method for preparing a catalyst according to any of the preceding technical problems, comprising:
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 300-600 ℃ by way of example only.
In the above technical scheme, the roasting time is 1-15 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). But from the point of view of economy,the atmosphere for firing is preferably air. 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 10-80 w% of the content of the catalyst), and drying to obtain a catalyst precursor I. The drying temperature can be but is not limited to 50-120 ℃, and the drying time can be but is not limited to 1-15 hours.
3. Roasting
Calcining the catalyst precursor I to obtain the catalyst. The roasting temperature is, for example, but not limited to, 300-600 ℃, and the roasting time is, for example, but not limited to, 1-15 hours.
The catalyst prepared in this way is surprisingly good in terms of acrolein conversion and acrylic acid yield.
To solve the third technical problem, the technical scheme of the invention is as follows: use of a catalyst according to any of the preceding claims for the preparation of acrylic acid by oxidation of acrolein.
The technical key of the invention is the selection of the catalyst, which can be reasonably selected by the skilled person for the specific application method and process conditions without creative efforts, such as:
a process for producing acrylic acid by oxidizing acrolein, which comprises reacting acrolein with an oxygen-containing oxidizing gas in the presence of the catalyst according to any one of the above-mentioned technical problems.
In the above technical scheme, in order to make the reaction more stable and controllable, the reaction is preferably carried out in the presence of a dilute gas phase material.
In the above embodiment, the oxidizing gas may be pure oxygen or oxygen-rich, but air is preferred from the economical viewpoint.
In the above technical solution, the dilute gas phase material is preferably steam.
In the technical scheme, the reaction temperature can be selected from 100-500 ℃.
In the above technical solution, in the raw material gas composed of acrolein, air and water vapor, in terms of volume ratio, it is preferable that acrolein: air: the steam is 1 (1-6) and 0.5-5.
In the technical scheme, the air speed of the raw material gas is preferably 800-2000 ml.h-1·g-1。
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;
space velocity of raw materials: 1400 ml. h-1·g-1。
The catalyst of the present invention has acrolein converting rate up to 99% and acrylic acid yield up to 92%, and may be used in 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) Tin dioxide containing 0.04 mol of Sn (formula:SnO2) Scandium nitrate containing 0.04 mol of Sc (molecular formula: sc (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Copper nitrate (molecular formula: Cu (NO): containing 0.04 mol of Cu was added3)2) 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 component4Cu0.4W0.4Sn0.4Sc0.4Na0.4OgWas 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
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Cu0.4W0.4Sn0.4Sc0.4Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The evaluation method 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;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of 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) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Rhodium nitrate containing 0.04 mol of Rh (formula: rh (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Copper nitrate (molecular formula: Cu (NO): containing 0.04 mol of Cu was added3)2) 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 component4Cu0.4W0.4Sn0.4Rh0.4Na0.4OgWas 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
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Cu0.4W0.4Sn0.4Rh0.4Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The evaluation method 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;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of 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) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Iridium oxide containing 0.04 mol of Ir (molecular formula: IrO2) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Copper nitrate (molecular formula: Cu (NO): containing 0.04 mol of Cu was added3)2) 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 component4Cu0.4W0.4Sn0.4Ir0.4Na0.4OgWas 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
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Cu0.4W0.4Sn0.4Ir0.4Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The evaluation method 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;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of 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) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Praseodymium nitrate containing 0.04 mole of Pr (molecular formula: pr (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Copper nitrate (molecular formula: Cu (NO): containing 0.04 mol of Cu was added3)2) 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 component4Cu0.4W0.4Sn0.4Pr0.4Na0.4OgWas 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
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Cu0.4W0.4Sn0.4Pr0.4Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The acrolein conversion and acrylic acid yield were examined. The elemental composition of the catalyst and the evaluation results of 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) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Scandium nitrate containing 0.02 mol of Sc (molecular formula: sc (NO)3)3) Rhodium nitrate containing 0.02 mol of Rh (formula: rh (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Copper nitrate (molecular formula: Cu (NO): containing 0.04 mol of Cu was added3)2) 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 component4Cu0.4W0.4Sn0.4Sc0.2Rh0.2Na0.4OgWas 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
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Cu0.4W0.4Sn0.4Sc0.2Rh0.2Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The evaluation method 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;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of 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) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Scandium nitrate containing 0.02 mol of Sc (molecular formula: sc (NO)3)3) Iridium oxide containing 0.02 mol of Ir (molecular formula: IrO2) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Copper nitrate (molecular formula: Cu (NO): containing 0.04 mol of Cu was added3)2) 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 component4Cu0.4W0.4Sn0.4Sc0.2Ir0.2Na0.4OgWas 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
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Cu0.4W0.4Sn0.4Sc0.2Ir0.2Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The evaluation method 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;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of 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) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Scandium nitrate containing 0.02 mol of Sc (molecular formula: sc (NO)3)3) Praseodymium nitrate containing 0.02 mol of Pr (molecular formula: pr (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Copper nitrate (molecular formula: Cu (NO): containing 0.04 mol of Cu was added3)2) Adding the aqueous solution into the above solutions respectively, mixing, and evaporating at 80 deg.CThe mixed material solution is equivalent to VMo containing active component4Cu0.4W0.4Sn0.4Sc0.2Pr0.2Na0.4OgWas 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
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Cu0.4W0.4Sn0.4Sc0.2Pr0.2Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The evaluation method 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;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of 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) Tin dioxide containing 0.04 mol of Sn (formula:SnO2) Scandium nitrate containing 0.015 mol of Sc (molecular formula: sc (NO)3)3) Rhodium nitrate containing 0.015 mol of Rh (formula: rh (NO)3)3) Iridium oxide containing 0.01 mol of Ir (molecular formula: IrO2) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Copper nitrate (molecular formula: Cu (NO): containing 0.04 mol of Cu was added3)2) 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 component4Cu0.4W0.4Sn0.4Sc0.15Rh0.15Ir0.1Na0.4OgWas 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
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Cu0.4W0.4Sn0.4Sc0.15Rh0.15Ir0.1Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The evaluation method 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;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of 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) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Scandium nitrate containing 0.015 mol of Sc (molecular formula: sc (NO)3)3) Rhodium nitrate containing 0.015 mol of Rh (formula: rh (NO)3)3) Praseodymium nitrate containing 0.01 mole of Pr (molecular formula: pr (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Copper nitrate (molecular formula: Cu (NO): containing 0.04 mol of Cu was added3)2) 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 component4Cu0.4W0.4Sn0.4Sc0.15Rh0.15Pr0.1Na0.4OgWas 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
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Cu0.4W0.4Sn0.4Sc0.15Rh0.15Pr0.1Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The evaluation method 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;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of 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) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Scandium nitrate containing 0.015 mol of Sc (molecular formula: sc (NO)3)3) Iridium oxide containing 0.015 mol of Ir (molecular formula: IrO2) Praseodymium nitrate containing 0.01 mole of Pr (molecular formula: pr (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Copper nitrate (molecular formula: Cu (NO): containing 0.04 mol of Cu was added3)2) 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 component4Cu0.4W0.4Sn0.4Sc0.15Ir0.15Pr0.1Na0.4OgWas 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
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Cu0.4W0.4Sn0.4Sc0.15Ir0.15Pr0.1Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The evaluation method 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;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of the catalyst are shown in Table 1 for convenience of comparison.
TABLE 1
Figure BDA0001833103880000151

Claims (10)

1. The acrylic acid catalyst comprises a carrier and an active component loaded on the carrier, wherein the active component is represented by the general formula: VMoaCubWcQdYeZfOgWherein X is selected from one or more of Al, Ga, Ge, In, Sn, Sb, TI, Pb, Bi and Po, Q is selected from at least one of Sc, Ti, Y, Zr, Hf, Ta, Tc, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Cd, La and Pr, and Z is selected from one or more of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba and Ra; 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 Cu to V, and the value of b is 0.1-1.0; c is the molar ratio of W to V, and the value of c is 0.1-1.0; d is the molar ratio of X to V, and d is 0.1 to1.0; e is the molar ratio of Q to V, and the value of e is 0.1-1.0; f is the molar ratio of Z to V, and the value of f is 0.1-1.0; g is the mole number of oxygen atoms needed to satisfy the valence of each element in the active component.
2. The catalyst according to claim 1, wherein the active component content in the catalyst is 10 to 80 w% by weight.
3. The catalyst according to claim 1, wherein the carrier content in the catalyst is 20 to 90 w% by weight.
4. The catalyst according to claim 1, wherein the carrier is at least one selected from the group consisting of alumina, lithium oxide, magnesia, zirconia, silica and titania.
5. A method of preparing the catalyst of claim 1, comprising:
preparing mixed liquid of active component elements;
mixing the active component element mixed solution with a carrier;
and (4) roasting.
6. The method according to claim 5, wherein the mixture is a solution, a suspension or a mixture of a solution and a suspension.
7. The method according to claim 5, wherein the calcination temperature is 300 to 600 ℃.
8. The method according to claim 5, wherein the calcination time is 1 to 15 hours.
9. The method according to claim 5, wherein the atmosphere for calcination is an inert atmosphere or an atmosphere containing O2Of the atmosphere (c).
10. Use of the catalyst of claim 1 in the manufacture of acrylic acid by oxidation of acrolein.
CN201811220148.0A 2018-10-18 2018-10-18 Acrylic acid catalyst and application thereof Pending CN111068711A (en)

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