CN111068696B - Supported acrolein catalyst and application thereof - Google Patents
Supported acrolein catalyst and application thereof Download PDFInfo
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- CN111068696B CN111068696B CN201811214018.6A CN201811214018A CN111068696B CN 111068696 B CN111068696 B CN 111068696B CN 201811214018 A CN201811214018 A CN 201811214018A CN 111068696 B CN111068696 B CN 111068696B
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- 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
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
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- 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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention relates to a supported acrolein catalyst and application thereof, and the technical scheme is as follows: the supported acrolein catalyst comprises a carrier and an active component supported on the carrier, wherein the general formula of the active component is as follows: biMo a Fe b Cu c X d J e Z f O g Wherein X is at least one selected from the group consisting of Al, ga, ge, in, sn, sb, TI, pb and Po, J is at least one selected from the group consisting of Sc, Y, ti, zr, hf, V, nb, ta, W, tc, re, ru, os, rh, ir, pd, pt, ag, au, cd, la and Nd, and Z is at least one selected from the group consisting of Li, na, K, rb, cs, fr, be, mg, ca, sr, ba and Ra.
Description
Technical Field
The invention relates to a supported acrolein catalyst, a preparation method thereof and application thereof in preparing acrolein by propylene oxidation.
Background
Acrolein is the simplest unsaturated aldehyde and is also an important chemical synthesis intermediate, the largest application field is to synthesize methionine, and the acrolein is widely used for synthesizing important chemical products such as picoline, pyridine, glutaraldehyde, acrylic acid and the like, and can also be used as an important raw material for synthesizing 1, 3-propanediol. The acrolein has active chemical property, complex synthesis process and few domestic manufacturers, and is mainly used as an intermediate product for producing acrylic acid.
Acrolein was produced at the earliest by the gas phase condensation of formaldehyde acetaldehyde and was industrialised in 1942, the catalyst at that time being silica gel impregnated with sodium silicate. This process route is used all the way after that until the propylene oxidation process is industrialized. At present, propylene is largely used for preparing acrolein in industry, and the acrolein accounts for more than 80 percent. Propylene can be used as a raw material for selective oxidation to prepare acrolein, or acrolein can be used as an intermediate product for continuous oxidation to generate acrylic acid. The acrolein is prepared by adopting a propylene selective oxidation production process, the catalyst is generally Mo-Bi multi-component composite oxide, the basic elements of the catalyst are Mo and Bi, and other elements for improving the performance of the catalyst, such as Nb, sn, cr, W, fe, co, ni, sb, cu, zn and the like, are added. Co element is added to Mo-Bi catalyst by Japanese catalyst chemical company, and the single pass yield of acrolein is improved. ZL201410096092.8 adopts Mo-Bi series catalyst, mn, fe and Co elements are introduced, pH value is regulated by adding ammonia water, and the catalyst is prepared by adopting a blending one-step combustion method, so that the catalyst activity is improved to a certain extent, but the mechanical strength of the catalyst needs to be increased. The catalyst carrier can make the catalyst have proper shape, size and mechanical strength, so that the catalyst active components are loaded on the carrier with large specific surface area, the mechanical strength of the catalyst can be increased, the loading amount of the active components is greatly increased, and the catalyst active components are exerted to a great extent through synergistic effect. The coated spherical catalyst is adopted by Japanese Kagaku Kogyo Co Ltd, and has good mechanical strength and good product selectivity. However, the catalytic activity, yield, etc. of the acrolein catalyst obtained in the prior art need to be further improved.
Disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problem of low acrolein yield of the existing catalyst, and provide a novel supported acrolein catalyst which has the characteristic of high acrolein yield.
The second technical problem to be solved by the invention is a preparation method of the catalyst.
The third technical problem to be solved by the present invention is the application of the catalyst as one of the above problems.
In order to solve one of the technical problems, the technical scheme of the invention is as follows:
the supported acrolein catalyst comprises a carrier and an active component supported on the carrier, wherein the general formula of the active component is as follows: biMo a Fe b Cu c X d J e Z f O g Wherein X is at least one selected from the group consisting of Al, ga, ge, in, sn, sb, TI, pb and Po, J is at least one selected from the group consisting of Sc, Y, ti, zr, hf, V, nb, ta, W, tc, re, ru, os, rh, ir, pd, pt, ag, au, cd, la and Nd, and Z is at least one selected from the group consisting of Li, na, K, rb, cs, frAt least one of the group of elements consisting of Be, mg, ca, sr, ba and Ra; a is the mole ratio of Mo to Bi, and the value of a is 1.0-8.0; b is the mole ratio of Fe to Bi, and the value of b is 0.1-2.0; c is the molar ratio of Cu to Bi, and the value of c is 0.1-2.0; d is the molar ratio of X to Bi, and the value of d is 0.1-2.0; e is the molar ratio of J to Bi, and the value of e is 0.1-2.0; f is the mole ratio of Z to Bi, and the value of f is 0.1-2.0; g is the number of moles of oxygen atoms required to satisfy the valence of each element in the active component.
Among the above-mentioned embodiments, J preferably includes Nd and Ti at the same time, and Nd and Ti have a synergistic effect in improving the acrolein yield.
In the above-mentioned technical scheme, J preferably includes Nd and Zr at the same time as the second preferred technical scheme, and Nd and Zr have a synergistic effect in improving the acrolein yield.
In the above-mentioned embodiments, J is preferably composed of Nd and Hf at the same time, and Nd and Hf have a synergistic effect in improving the acrolein yield.
In the above technical scheme, as one of more preferable technical schemes, J preferably includes Nd, ti and Zr at the same time, and the three have ternary combination synergistic effect in improving acrolein yield.
In the above technical scheme, as a second more preferable technical scheme, J preferably includes Nd, ti and Hf at the same time, and the three have a ternary combination synergistic effect in improving the acrolein yield.
In the above-mentioned technical scheme, J is preferably a three-way combination of Nd, zr, and Hf, which are combined together, so that the three components have a three-way combination synergistic effect in terms of improvement of acrolein yield.
In the above-mentioned embodiments, the ratio of Nd to Ti is particularly limited, and may be, for example, but not limited to, 0.01 to 50 in terms of molar ratio, and within this data range, examples of non-limiting point values may be 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.1, 0.5, 1.0, 1.5, 2.0, 5.0, 10, 15, 20, 25, 30, 35, 40, 45, etc., more preferably 0.05 to 20.
In the above-mentioned embodiments, the ratio of Nd to Zr is particularly limited, and for example, the ratio may be, but not limited to, 0.01 to 50 in terms of mole ratio, and within this data range, examples of non-limiting point values may be 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.1, 0.5, 1.0, 1.5, 2.0, 5.0, 10, 15, 20, 25, 30, 35, 40, 45, etc., more preferably 0.05 to 20.
In the above-mentioned embodiments, the ratio of Nd to Hf is particularly limited, and may be, for example, but not limited to, 0.01 to 50 in terms of molar ratio, and within this data range, examples of non-limiting point values may be 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.1, 0.5, 1.0, 1.5, 2.0, 5.0, 10, 15, 20, 25, 30, 35, 40, 45, etc., more preferably 0.05 to 20.
In the above technical solution, more specific examples of the general formula of the active component may be, but are not limited to:
BiMo 1.0～8.0 Fe 0.1～2.0 Cu 0.1～2.0 Sn 0.1～2.0 Nd 0.05～1.0 Ti 0.05～1.0 Na 0.1～2.0 O g ；
BiMo 1.0～8.0 Fe 0.1～2.0 Cu 0.1～2.0 Sn 0.1～2.0 Nd 0.05～1.0 Zr 0.05～1.0 Na 0.1～2.0 O g ；
BiMo 1.0～8.0 Fe 0.1～2.0 Cu 0.1～2.0 Sn 0.1～2.0 Nd 0.05～1.0 Hf 0.05～1.0 Na 0.1～2.0 O g ；
BiMo 1.0～8.0 Fe 0.1～2.0 Cu 0.1～2.0 Sn 0.1～2.0 Nd 0.04～0.8 Ti 0.03～0.6 Zr 0.03～0.6 Na 0.1～2.0 O g ；
BiMo 1.0～8.0 Fe 0.1～2.0 Cu 0.1～2.0 Sn 0.1～2.0 Nd 0.04～0.8 Ti 0.03～0.6 Hf 0.03～0.6 Na 0.1～2.0 O g ；
BiMo 1.0～8.0 Fe 0.1～2.0 Cu 0.1～2.0 Sn 0.1～2.0 Nd 0.04～0.8 Zr 0.03～0.6 Hf 0.03～0.6 Na 0.1～2.0 O g ；
wherein g is the number of moles of oxygen atoms required to satisfy the valence of each element in the active component.
In the above technical scheme, the content of the active component in the catalyst is preferably 10-90 w% by weight.
In the above technical scheme, the content of the carrier in the catalyst is preferably 10-90 w% by weight.
In the above technical solution, the shape and size of the carrier are not particularly limited, and comparable technical effects can be obtained, and for this reason, those skilled in the art can reasonably select. For convenience of comparison, the carriers of the embodiment of the invention are all spherical.
In the above technical solution, the carrier is preferably at least one selected from alumina, lithium oxide, magnesium oxide, zirconium dioxide, silicon dioxide and titanium dioxide.
In order to solve the second technical problem, the technical scheme of the invention is as follows:
the preparation method of the catalyst according to any one of the technical solutions of the above technical problems includes:
preparing an active component element mixed solution;
mixing the active component element mixed solution with a carrier;
and (5) roasting and molding.
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-described technical scheme, the conditions for firing are not particularly limited as long as the conditions for firing the specific compound form of all the active elements present in the above-described mixed solution into the form of oxide can be selected appropriately by those skilled in the art and without the need for creative efforts.
In the above technical scheme, the roasting temperature is 250-600 ℃ by way of example only.
In the above technical scheme, the roasting time is 1-15 hours by way of example only.
In the above technical solution, only by way of exampleThe roasting atmosphere is inert atmosphere or contains O 2 Is a gas atmosphere of (a). However, from an economical point of view, the baking atmosphere 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 by the following modes, and the specific steps are as follows:
1. preparation of active component element mixed solution
Dissolving a compound of a required active component element to obtain a mixed solution of the active element; the dissolution step is not particularly limited, and the specific dissolution procedure and process conditions can be appropriately selected by those skilled in the art.
2. Mixing the active component element mixed solution with a carrier
And (2) mixing the carrier particles with the mixed solution of the active elements obtained in the step (1) (wherein the dosage of the mixed solution of the active elements is 10-90 w% of the catalyst content), and drying to obtain the catalyst precursor I. The temperature of drying may be, but is not limited to, 50 to 150 ℃, and the time of drying may be, for example, but is not limited to, 1 to 15 hours.
3. Roasting and forming
Roasting the catalyst precursor I to obtain the catalyst. The firing temperature is, for example but not limited to, 250 to 600 c and the firing time is, for example but not limited to, 1 to 15 hours.
The catalyst prepared in this way is surprisingly good in terms of acrolein yield.
In order to solve the third technical problem, the technical scheme of the invention is as follows: the use of the catalyst according to any one of the technical schemes in the preparation of acrolein by propylene oxidation.
The technical key of the invention is the choice of catalyst, which can be reasonably selected by the person skilled in the art for the specific application of the method and process conditions and without the need for creative efforts, for example:
a process for producing acrolein by oxidizing propylene, comprising reacting propylene with an oxidizing gas containing oxygen 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 dilutable gas phase material.
In the above-described embodiments, the oxidizing gas may be pure oxygen or oxygen-enriched, but air is preferred from the economical point of view.
In the above technical solution, the dilutable gas phase material is preferably steam.
In the technical scheme, the reaction temperature can be selected to be 100-600 ℃.
In the above technical solution, in the raw material gas composed of propylene, air and steam, propylene is preferable as follows by volume ratio: air: steam=1 (1-20): 0.5-10.
In the above technical scheme, the space velocity of the raw material gas is preferably 500-2000 ml.h -1 ·g -1 。
The catalyst evaluation method of the invention is as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 350 ℃;
reaction time: 4 hours;
the volume ratio of the raw materials is as follows: propylene: air: water vapor = 1:10:3, a step of;
space velocity of raw material: 1200 ml.h -1 ·g -1 。
The catalyst of the invention has the acrolein yield reaching more than 92%, and obtains better technical effect, and can be used in the industrial production of acrolein.
Detailed Description
[ example 1 ]
1. Catalyst preparation
Bismuth nitrate containing 0.1 mol of Bi (molecular formula: bi (NO) 3 ) 3 ) Dissolved in 200g of hot water at 80 ℃. Ammonium molybdate containing 0.4 mole of Mo (formula: NH) 4 ) 2 MoO 4 ) Copper nitrate containing 0.04 mol of Cu was added thereto (molecular formula: cu (NO) 3 ) 2 ) Tin dioxide (partial) containing 0.04 mol of SnThe sub-formula is: snO (SnO) 2 ) Titanium dioxide containing 0.04 mole of Ti (formula: tiO (titanium dioxide) 2 ) Sodium nitrate (molecular formula: naNO) containing 0.04 mol of Na 3 ) Stirring to dissolve the whole to obtain a solution I. Ferric nitrate containing 0.04 mol of Fe (formula: fe (NO) 3 ) 3 ) Adding the aqueous solution into the above solution, mixing, and evaporating at 80deg.C to obtain a mixed solution equivalent to BiMo containing active component 4 Fe 0.4 Cu 0.4 Sn 0.4 Ti 0.4 Na 0.4 O g The concentration of (C) was 0.4g/g, giving solution II.
200g of spherical silica carrier with a diameter of 5mm and 200g of solution II were uniformly mixed and dried at 100℃for 4 hours to obtain a catalyst precursor I. The catalyst precursor I was calcined in a muffle furnace at 400℃for 5 hours to give a catalyst having the following composition: 33w% BiMo 4 Fe 0.4 Cu 0.4 Sn 0.4 Ti 0.4 Na 0.4 O g +67w％SiO 2 。
2. Catalyst evaluation
The evaluation method is as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 350 ℃;
reaction time: 4 hours;
the volume ratio of the raw materials is as follows: propylene: air: water vapor = 1:10:3, a step of;
space velocity of raw material: 1200 ml.h -1 ·g -1 。
The results of the evaluation of the catalysts in the examples are shown in Table 1 for comparison.
[ example 2 ]
1. Catalyst preparation
Bismuth nitrate containing 0.1 mol of Bi (molecular formula: bi (NO) 3 ) 3 ) Dissolved in 200g of hot water at 80 ℃. Ammonium molybdate containing 0.4 mole of Mo (formula: NH) 4 ) 2 MoO 4 ) Copper nitrate containing 0.04 mol of Cu was added thereto (molecular formula: cu%NO 3 ) 2 ) Tin dioxide containing 0.04 mol of Sn (formula: snO (SnO) 2 ) Zirconium nitrate containing 0.04 mol Zr (formula: zr (NO) 3 ) 4 ) Sodium nitrate (molecular formula: naNO) containing 0.04 mol of Na 3 ) Stirring to dissolve the whole to obtain a solution I. Ferric nitrate containing 0.04 mol of Fe (formula: fe (NO) 3 ) 3 ) Adding the aqueous solution into the above solution, mixing, and evaporating at 80deg.C to obtain a mixed solution equivalent to BiMo containing active component 4 Fe 0.4 Cu 0.4 Sn 0.4 Zr 0.4 Na 0.4 O g The concentration of (C) was 0.4g/g, giving solution II.
200g of spherical silica carrier with a diameter of 5mm and 200g of solution II were uniformly mixed and dried at 100℃for 4 hours to obtain a catalyst precursor I. The catalyst precursor I was calcined in a muffle furnace at 400℃for 5 hours to give a catalyst having the following composition: 33w% BiMo 4 Fe 0.4 Cu 0.4 Sn 0.4 Zr 0.4 Na 0.4 O g +67w％SiO 2 。
2. Catalyst evaluation
The evaluation method is as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 350 ℃;
reaction time: 4 hours;
the volume ratio of the raw materials is as follows: propylene: air: water vapor = 1:10:3, a step of;
space velocity of raw material: 1200 ml.h -1 ·g -1 。
The results of the evaluation of the catalysts in the examples are shown in Table 1 for comparison.
[ example 3 ]
1. Catalyst preparation
Bismuth nitrate containing 0.1 mol of Bi (molecular formula: bi (NO) 3 ) 3 ) Dissolved in 200g of hot water at 80 ℃. Ammonium molybdate containing 0.4 mole of Mo (formula: NH) 4 ) 2 MoO 4 ) Copper nitrate containing 0.04 mol of Cu was added thereto (molecular formula: cu (NO) 3 ) 2 ) Tin dioxide containing 0.04 mol of Sn (formula: snO (SnO) 2 ) Hafnium oxide containing 0.04 mol of Hf (formula: hfO (HfO) 2 ) Sodium nitrate (molecular formula: naNO) containing 0.04 mol of Na 3 ) Stirring to dissolve the whole to obtain a solution I. Ferric nitrate containing 0.04 mol of Fe (formula: fe (NO) 3 ) 3 ) Adding the aqueous solution into the above solution, mixing, and evaporating at 80deg.C to obtain a mixed solution equivalent to BiMo containing active component 4 Fe 0.4 Cu 0.4 Sn 0.4 Hf 0.4 Na 0.4 O g The concentration of (C) was 0.4g/g, giving solution II.
200g of spherical silica carrier with a diameter of 5mm and 200g of solution II were uniformly mixed and dried at 100℃for 4 hours to obtain a catalyst precursor I. The catalyst precursor I was calcined in a muffle furnace at 400℃for 5 hours to give a catalyst having the following composition: 33w% BiMo 4 Fe 0.4 Cu 0.4 Sn 0.4 Hf 0.4 Na 0.4 O g +67w％SiO 2 。
2. Catalyst evaluation
The evaluation method is as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 350 ℃;
reaction time: 4 hours;
the volume ratio of the raw materials is as follows: propylene: air: water vapor = 1:10:3, a step of;
space velocity of raw material: 1200 ml.h -1 ·g -1 。
The results of the evaluation of the catalysts in the examples are shown in Table 1 for comparison.
[ example 4 ]
1. Catalyst preparation
Bismuth nitrate containing 0.1 mol of Bi (molecular formula: bi (NO) 3 ) 3 ) Dissolved in 200g of hot water at 80 ℃. Molybdic acid containing 0.4 mole of MoAmmonium (molecular formula is (NH) 4 ) 2 MoO 4 ) Copper nitrate containing 0.04 mol of Cu was added thereto (molecular formula: cu (NO) 3 ) 2 ) Tin dioxide containing 0.04 mol of Sn (formula: snO (SnO) 2 ) Neodymium nitrate containing 0.04 mol Nd (formula: nd (NO) 3 ) 3 ) Sodium nitrate (molecular formula: naNO) containing 0.04 mol of Na 3 ) Stirring to dissolve the whole to obtain a solution I. Ferric nitrate containing 0.04 mol of Fe (formula: fe (NO) 3 ) 3 ) Adding the aqueous solution into the above solution, mixing, and evaporating at 80deg.C to obtain a mixed solution equivalent to BiMo containing active component 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.4 Na 0.4 O g The concentration of (C) was 0.4g/g, giving solution II.
200g of spherical silica carrier with a diameter of 5mm and 200g of solution II were uniformly mixed and dried at 100℃for 4 hours to obtain a catalyst precursor I. The catalyst precursor I was calcined in a muffle furnace at 400℃for 5 hours to give a catalyst having the following composition: 33w% BiMo 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.4 Na 0.4 O g +67w％SiO 2 。
2. Catalyst evaluation
The evaluation method is as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 350 ℃;
reaction time: 4 hours;
the volume ratio of the raw materials is as follows: propylene: air: water vapor = 1:10:3, a step of;
space velocity of raw material: 1200 ml.h -1 ·g -1 。
The results of the evaluation of the catalysts in the examples are shown in Table 1 for comparison.
[ example 5 ]
1. Catalyst preparation
Bismuth nitrate containing 0.1 mol of Bi (molecular formula: bi (NO) 3 ) 3 ) Dissolved in 200g of hot water at 80 ℃. Ammonium molybdate containing 0.4 mole of Mo (formula: NH) 4 ) 2 MoO 4 ) Copper nitrate containing 0.04 mol of Cu was added thereto (molecular formula: cu (NO) 3 ) 2 ) Tin dioxide containing 0.04 mol of Sn (formula: snO (SnO) 2 ) Neodymium nitrate containing 0.02 mol Nd (formula: nd (NO) 3 ) 3 ) Titanium dioxide containing 0.02 mole of Ti (formula: tiO (titanium dioxide) 2 ) Sodium nitrate (molecular formula: naNO) containing 0.04 mol of Na 3 ) Stirring to dissolve the whole to obtain a solution I. Ferric nitrate containing 0.04 mol of Fe (formula: fe (NO) 3 ) 3 ) Adding the aqueous solution into the above solution, mixing, and evaporating at 80deg.C to obtain a mixed solution equivalent to BiMo containing active component 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.2 Ti 0.2 Na 0.4 O g The concentration of (C) was 0.4g/g, giving solution II.
200g of spherical silica carrier with a diameter of 5mm and 200g of solution II were uniformly mixed and dried at 100℃for 4 hours to obtain a catalyst precursor I. The catalyst precursor I was calcined in a muffle furnace at 400℃for 5 hours to give a catalyst having the following composition: 33w% BiMo 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.2 Ti 0.2 Na 0.4 O g +67w％SiO 2 。
2. Catalyst evaluation
The evaluation method is as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 350 ℃;
reaction time: 4 hours;
the volume ratio of the raw materials is as follows: propylene: air: water vapor = 1:10:3, a step of;
space velocity of raw material: 1200 ml.h -1 ·g -1 。
The results of the evaluation of the catalysts in the examples are shown in Table 1 for comparison.
[ example 6 ]
1. Catalyst preparation
Bismuth nitrate containing 0.1 mol of Bi (molecular formula: bi (NO) 3 ) 3 ) Dissolved in 200g of hot water at 80 ℃. Ammonium molybdate containing 0.4 mole of Mo (formula: NH) 4 ) 2 MoO 4 ) Copper nitrate containing 0.04 mol of Cu was added thereto (molecular formula: cu (NO) 3 ) 2 ) Tin dioxide containing 0.04 mol of Sn (formula: snO (SnO) 2 ) Neodymium nitrate containing 0.02 mol Nd (formula: nd (NO) 3 ) 3 ) Zirconium nitrate containing 0.02 mol Zr (formula: zr (NO) 3 ) 4 ) Sodium nitrate (molecular formula: naNO) containing 0.04 mol of Na 3 ) Stirring to dissolve the whole to obtain a solution I. Ferric nitrate containing 0.04 mol of Fe (formula: fe (NO) 3 ) 3 ) Adding the aqueous solution into the above solution, mixing, and evaporating at 80deg.C to obtain a mixed solution equivalent to BiMo containing active component 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.2 Zr 0.2 Na 0.4 O g The concentration of (C) was 0.4g/g, giving solution II.
200g of spherical silica carrier with a diameter of 5mm and 200g of solution II were uniformly mixed and dried at 100℃for 4 hours to obtain a catalyst precursor I. The catalyst precursor I was calcined in a muffle furnace at 400℃for 5 hours to give a catalyst having the following composition: 33w% BiMo 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.2 Zr 0.2 Na 0.4 O g +67w％SiO 2 。
2. Catalyst evaluation
The evaluation method is as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 350 ℃;
reaction time: 4 hours;
the volume ratio of the raw materials is as follows: propylene: air: water vapor = 1:10:3, a step of;
space velocity of raw material: 1200 ml.h -1 ·g -1 。
The results of the evaluation of the catalysts in the examples are shown in Table 1 for comparison.
[ example 7 ]
1. Catalyst preparation
Bismuth nitrate containing 0.1 mol of Bi (molecular formula: bi (NO) 3 ) 3 ) Dissolved in 200g of hot water at 80 ℃. Ammonium molybdate containing 0.4 mole of Mo (formula: NH) 4 ) 2 MoO 4 ) Copper nitrate containing 0.04 mol of Cu was added thereto (molecular formula: cu (NO) 3 ) 2 ) Tin dioxide containing 0.04 mol of Sn (formula: snO (SnO) 2 ) Neodymium nitrate containing 0.02 mol Nd (formula: nd (NO) 3 ) 3 ) Hafnium oxide containing 0.02 mol of Hf (formula: hfO (HfO) 2 ) Sodium nitrate (molecular formula: naNO) containing 0.04 mol of Na 3 ) Stirring to dissolve the whole to obtain a solution I. Ferric nitrate containing 0.04 mol of Fe (formula: fe (NO) 3 ) 3 ) Adding the aqueous solution into the above solution, mixing, and evaporating at 80deg.C to obtain a mixed solution equivalent to BiMo containing active component 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.2 Hf 0.2 Na 0.4 O g The concentration of (C) was 0.4g/g, giving solution II.
200g of spherical silica carrier with a diameter of 5mm and 200g of solution II were uniformly mixed and dried at 100℃for 4 hours to obtain a catalyst precursor I. The catalyst precursor I was calcined in a muffle furnace at 400℃for 5 hours to give a catalyst having the following composition: 33w% BiMo 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.2 Hf 0.2 Na 0.4 O g +67w％SiO 2 。
2. Catalyst evaluation
The evaluation method is as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 350 ℃;
reaction time: 4 hours;
the volume ratio of the raw materials is as follows: propylene: air: water vapor = 1:10:3, a step of;
space velocity of raw material: 1200 ml.h -1 ·g -1 。
The results of the evaluation of the catalysts in the examples are shown in Table 1 for comparison.
[ example 8 ]
1. Catalyst preparation
Bismuth nitrate containing 0.1 mol of Bi (molecular formula: bi (NO) 3 ) 3 ) Dissolved in 200g of hot water at 80 ℃. Ammonium molybdate containing 0.4 mole of Mo (formula: NH) 4 ) 2 MoO 4 ) Copper nitrate containing 0.04 mol of Cu was added thereto (molecular formula: cu (NO) 3 ) 2 ) Tin dioxide containing 0.04 mol of Sn (formula: snO (SnO) 2 ) Neodymium nitrate containing 0.02 mol Nd (formula: nd (NO) 3 ) 3 ) Titanium dioxide containing 0.01 mole of Ti (formula: tiO (titanium dioxide) 2 ) Zirconium nitrate containing 0.01 mol Zr (formula: zr (NO) 3 ) 4 ) Sodium nitrate (molecular formula: naNO) containing 0.04 mol of Na 3 ) Stirring to dissolve the whole to obtain a solution I. Ferric nitrate containing 0.04 mol of Fe (formula: fe (NO) 3 ) 3 ) Adding the aqueous solution into the above solution, mixing, and evaporating at 80deg.C to obtain a mixed solution equivalent to BiMo containing active component 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.2 Ti 0.1 Zr 0.1 Na 0.4 O g The concentration of (C) was 0.4g/g, giving solution II.
200g of spherical silica carrier with a diameter of 5mm and 200g of solution II were uniformly mixed and dried at 100℃for 4 hours to obtain a catalyst precursor I. The catalyst precursor I was calcined in a muffle furnace at 400℃for 5 hours to give a catalyst having the following composition: 33w% BiMo 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.2 Ti 0.1 Zr 0.1 Na 0.4 O g +67w％SiO 2 。
2. Catalyst evaluation
The evaluation method is as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 350 ℃;
reaction time: 4 hours;
the volume ratio of the raw materials is as follows: propylene: air: water vapor = 1:10:3, a step of;
space velocity of raw material: 1200 ml.h -1 ·g -1 。
The results of the evaluation of the catalysts in the examples are shown in Table 1 for comparison.
[ example 9 ]
1. Catalyst preparation
Bismuth nitrate containing 0.1 mol of Bi (molecular formula: bi (NO) 3 ) 3 ) Dissolved in 200g of hot water at 80 ℃. Ammonium molybdate containing 0.4 mole of Mo (formula: NH) 4 ) 2 MoO 4 ) Copper nitrate containing 0.04 mol of Cu was added thereto (molecular formula: cu (NO) 3 ) 2 ) Tin dioxide containing 0.04 mol of Sn (formula: snO (SnO) 2 ) Neodymium nitrate containing 0.02 mol Nd (formula: nd (NO) 3 ) 3 ) Titanium dioxide containing 0.01 mole of Ti (formula: tiO (titanium dioxide) 2 ) Hafnium oxide containing 0.01 mol of Hf (formula: hfO (HfO) 2 ) Sodium nitrate (molecular formula: naNO) containing 0.04 mol of Na 3 ) Stirring to dissolve the whole to obtain a solution I. Ferric nitrate containing 0.04 mol of Fe (formula: fe (NO) 3 ) 3 ) Adding the aqueous solution into the above solution, mixing, and evaporating at 80deg.C to obtain a mixed solution equivalent to BiMo containing active component 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.2 Ti 0.1 Hf 0.1 Na 0. 4 O g The concentration of (C) was 0.4g/g, giving solution II.
200g of spherical silica carrier with a diameter of 5mm and 200g of solution II were uniformly mixed and dried at 100℃for 4 hours to obtain a catalyst precursor I. The catalyst precursor I was calcined in a muffle furnace at 400℃for 5 hours to give the following compositionIs a catalyst of (a): 33w% BiMo 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.2 Ti 0.1 Hf 0.1 Na 0.4 O g +67w％SiO 2 。
2. Catalyst evaluation
The evaluation method is as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 350 ℃;
reaction time: 4 hours;
the volume ratio of the raw materials is as follows: propylene: air: water vapor = 1:10:3, a step of;
space velocity of raw material: 1200 ml.h -1 ·g -1 。
The results of the evaluation of the catalysts in the examples are shown in Table 1 for comparison.
[ example 10 ]
1. Catalyst preparation
Bismuth nitrate containing 0.1 mol of Bi (molecular formula: bi (NO) 3 ) 3 ) Dissolved in 200g of hot water at 80 ℃. Ammonium molybdate containing 0.4 mole of Mo (formula: NH) 4 ) 2 MoO 4 ) Copper nitrate containing 0.04 mol of Cu was added thereto (molecular formula: cu (NO) 3 ) 2 ) Tin dioxide containing 0.04 mol of Sn (formula: snO (SnO) 2 ) Neodymium nitrate containing 0.02 mol Nd (formula: nd (NO) 3 ) 3 ) Zirconium nitrate containing 0.01 mol Zr (formula: zr (NO) 3 ) 4 ) Hafnium oxide containing 0.01 mol of Hf (formula: hfO (HfO) 2 ) Sodium nitrate (molecular formula: naNO) containing 0.04 mol of Na 3 ) Stirring to dissolve the whole to obtain a solution I. Ferric nitrate containing 0.04 mol of Fe (formula: fe (NO) 3 ) 3 ) Adding the aqueous solution into the above solution, mixing, and evaporating at 80deg.C to obtain a mixed solution equivalent to BiMo containing active component 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.2 Zr 0.1 Hf 0.1 Na 0.4 O g The concentration of (C) was 0.4g/g, giving solution II.
200g of spherical silica carrier with a diameter of 5mm and 200g of solution II were uniformly mixed and dried at 100℃for 4 hours to obtain a catalyst precursor I. The catalyst precursor I was calcined in a muffle furnace at 400℃for 5 hours to give a catalyst having the following composition: 33w% BiMo 4 Fe 0.4 Cu 0.4 Sn 0.4 Nd 0.2 Zr 0.1 Hf 0.1 Na 0.4 O g +67w％SiO 2 。
2. Catalyst evaluation
The evaluation method is as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 350 ℃;
reaction time: 4 hours;
the volume ratio of the raw materials is as follows: propylene: air: water vapor = 1:10:3, a step of;
space velocity of raw material: 1200 ml.h -1 ·g -1 。
The results of the evaluation of the catalysts in the examples are shown in Table 1 for comparison.
TABLE 1
Claims (11)
1. The supported acrolein catalyst comprises a carrier and an active component supported on the carrier, wherein the general formula of the active component is as follows: biMo a Fe b Cu c X d J e Z f O g Wherein X is at least one selected from the group consisting of Al, ga, ge, in, sn, sb, TI, pb and Po, J is at least one selected from Nd and Ti, zr and Hf, and Z is at least one selected from the group consisting of Li, na, K, rb, cs, fr, be, mg, ca, sr, ba and Ra; a is the mole ratio of Mo to Bi, and the value of a is 1.0-8.0; b is Fe and BiThe molar ratio, b, takes a value of 0.1-2.0; c is the molar ratio of Cu to Bi, and the value of c is 0.1-2.0; d is the molar ratio of X to Bi, and the value of d is 0.1-2.0; e is the molar ratio of J to Bi, and the value of e is 0.1-2.0; f is the mole ratio of Z to Bi, and the value of f is 0.1-2.0; g is the number of moles of oxygen atoms required to satisfy the valence of each element in the active component.
2. The catalyst according to claim 1, wherein the active component content of the catalyst is 10 to 90w% by weight.
3. The catalyst according to claim 1, wherein the carrier content in the catalyst is 10 to 90w% by weight.
4. The catalyst according to claim 1, characterized in that the support is selected from at least one of alumina, lithium oxide, magnesium oxide, zirconium dioxide, silica and titanium dioxide.
5. A method of preparing the catalyst as claimed in claim 1, comprising:
preparing an active component element mixed solution;
mixing the active component element mixed solution with a carrier;
and (5) roasting and molding.
6. The method of claim 5, wherein the mixture is a solution, a suspension or a mixture of a solution and a suspension.
7. The process according to claim 5, wherein the firing temperature is 250 to 600 ℃.
8. The process according to claim 5, wherein the calcination time is 1 to 15 hours.
9. The process according to claim 5, wherein the calcination atmosphere is an inert atmosphere or an O-containing atmosphere 2 Is of (1)And (5) an atmosphere.
10. The method according to claim 5, wherein the baking atmosphere is an air atmosphere.
11. Use of the catalyst of claim 1 in the oxidation of propylene to acrolein.
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