CN115475623A - Catalyst for preparing acrolein by selective oxidation of propylene and preparation method and application thereof - Google Patents

Catalyst for preparing acrolein by selective oxidation of propylene and preparation method and application thereof Download PDF

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CN115475623A
CN115475623A CN202110667448.9A CN202110667448A CN115475623A CN 115475623 A CN115475623 A CN 115475623A CN 202110667448 A CN202110667448 A CN 202110667448A CN 115475623 A CN115475623 A CN 115475623A
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catalyst
source
solution
gas
mixed
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王伟华
徐文杰
杨斌
宋卫林
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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
    • B01J23/76—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
    • 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
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8877—Vanadium, tantalum, niobium or polonium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a catalyst for preparing acrolein by selectively oxidizing propylene and a preparation method and application thereof. The catalyst comprises a carrier and an active component, wherein the general formula of the active component is as follows: bi 2 O 3 ·aMoO 3 ·bV 2 O 5 ·cCuO·dSb 2 O 3 ·eXO m ·fZO n Wherein X is selected from Sc, Y, ti, zr, hf, nb, ta, cr, ti, zr, hf, nb, ta, ti, zr, nb, ta, or Ta W, mn, tc, re, fe, ru, os, co, rh,Ir, ni, pd, pt, ag, au, zn, cd, lanthanoid and actinide, and Z is at least one element selected from Li, na, K, rb and Cs. The catalyst can be used in the industrial production of acrolein and has the characteristics of high selectivity of the acrolein and high mechanical strength.

Description

Catalyst for preparing acrolein by selective oxidation of propylene and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst for preparing acrolein by selectively oxidizing propylene, a preparation method thereof and application of the catalyst in preparing the acrolein by oxidizing the propylene.
Background
Acrolein is a very important synthetic intermediate in chemical industry, and is widely used in resin production and organic synthesis, especially in the production of acrylic acid as the most important intermediate. Propylene is a colorless combustible gas with active chemical properties, contains unsaturated carbon-carbon double bonds in molecules, is easy to generate addition reaction and can also generate addition polymerization reaction, and the acrylonitrile is produced. Propylene oxide, polypropylene, synthetic fibers, synthetic rubbers and plastics. The Beili petrochemical group company builds 5000 tons of acrolein production process, and becomes the largest acrolein production base in China.
At present, propylene is mainly used for preparing acrolein by oxidation in industry, namely, propylene is used as a raw material and can be selectively oxidized to prepare the acrolein. The catalyst for preparing acrolein by propylene oxidation is generally a Mo-Bi multicomponent composite oxide, the basic elements of which are Mo and Bi, and other enhancing elements can be added. CN 1210511A provides a preparation method of a composite oxide catalyst, which adopts coprecipitation, and adds Ni, co and Fe elements under the premise of a certain proportion of Mo and Bi, wherein the proportion of Ni and Co is higher, so that the stability of the Fe element can be improved, and the loss of Mo is reduced. Then, the active components of the catalyst prepared by the method are difficult to exert to a large extent, so that the activity of the catalyst is inhibited. Thus, the acrolein catalyst needs to be further developed and studied.
Disclosure of Invention
The invention aims to solve the technical problems that the existing catalyst is low in acrolein selectivity and mechanical strength, and provides a novel catalyst for preparing acrolein by selectively oxidizing propylene.
The second technical problem to be solved by the invention is the preparation method of the catalyst.
The third technical problem to be solved by the invention is the application of the catalyst.
In view of the above problems, an object of the present invention is to provide a catalyst for producing acrolein by selective oxidation of propylene, comprising a carrier and an active component, wherein the active component of the catalyst is represented by the general formula: bi 2 O 3 ·aMoO 3 ·bV 2 O 5 ·cCuO·dSb 2 O 3 ·eXO m ·fZO n ，
Wherein X is at least one element selected from Sc, Y, ti, zr, hf, nb, ta, cr, W, mn, tc, re, fe, ru, os, co, rh, ir, ni, pd, pt, ag, au, zn, cd, lanthanoid (La-Lu) and actinide (Ac-Lr), and Z is at least one element selected from Li, na, K, rb and Cs; a is MoO 3 And Bi 2 O 3 A is 2.0-15.0, preferably a is 3.0-10.0; b is V 2 O 5 And Bi 2 O 3 B is 0.1-2.0, preferably, b is 0.2-0.8; c is CuO and Bi 2 O 3 C is 0.1-2.0, preferably, c is 0.2-0.8; d is Sb 2 O 3 And Bi 2 O 3 D is 0.1-2.0, preferably, d is 0.2-0.8; e is XO m And Bi 2 O 3 E is 0.1-2.0, preferably, e is 0.2-0.8; f is ZO n And Bi 2 O 3 F is 0.1-2.0, preferably, f is 0.2-0.8; m and n are the number of moles of oxygen atoms required to satisfy the valences of the elements in the active component.
In the above technical solution, preferably, X is selected from one or more of Sc, Y, ti, zr, hf, nb, W, mn, fe, co, ni, ag, au, and Zn, and Z is selected from at least one or more of Li, na, and K.
In the above technical solution, preferably, the carrier is selected from at least one of lithium oxide, magnesium oxide, aluminum oxide, zirconium dioxide, silicon dioxide, titanium dioxide, vanadium dioxide, diatomaceous earth, kaolin, and pumice.
In the technical scheme, the carrier is in a powder state; the particle size of the carrier is 40 to 400 meshes, preferably 100 to 200 meshes.
In the above technical scheme, the content of the active component in the catalyst is preferably 10-80 w%, and more preferably 30-60 wt%.
In the above technical solution, the thermogravimetric analysis (TGA) curve of the catalyst comprises a stationary phase (first phase, <500 ℃) and a fast falling phase (second phase, > 500 ℃), wherein the temperature of the stationary phase is less than 500 ℃ and the temperature of the fast falling phase is greater than or equal to 500 ℃.
In the technical scheme, the mass loss rate of the catalyst is 0.1-0.25% in the range of 0-200 ℃ in the stationary stage (first stage); the mass loss rate of the catalyst is 0.02 to 0.06% in the range of 200 ℃ to less than 500 ℃ in the plateau stage (first stage).
In the above technical scheme, the mass loss rate of the catalyst is 1-1.5% in the range of 500 ℃ to 800 ℃ in the rapid decrease stage (second stage).
The mass loss rate is the percentage of the mass of catalyst reduction to the original catalyst mass over the temperature range.
In the above technical scheme, the ratio of the mass loss rate of the rapid decrease stage to the mass loss rate of the steady stage is (5-15): 1, preferably (5 to 10): 1.
the second object of the present invention is to provide a method for preparing the catalyst for preparing acrolein by selective oxidation of propylene, comprising the steps of:
(1) Respectively dissolving or dispersing each active component element source in water to prepare a solution of active component elements, and mixing to obtain a mixed solution;
(2) Mixing the mixed solution with a carrier;
(3) Drying and roasting.
In the technical scheme, each active component element is from a bismuth-containing compound, a molybdenum-containing compound, a vanadium-containing compound, a copper-containing compound, an antimony-containing compound, a transition metal-containing compound and an alkali metal-containing compound.
The active component element sources are a bismuth source, a molybdenum source, a vanadium source, a copper source, an antimony source, an X element source and a Z element source respectively.
In the technical scheme, the bismuth source is at least one of nitrate, carbonate and oxide of bismuth. Bismuth nitrate is preferred.
In the above technical solution, the molybdenum source is at least one of ammonium molybdate, ammonium paramolybdate and molybdenum oxide, and preferably ammonium molybdate.
In the above technical solution, the vanadium source is at least one of ammonium metavanadate, vanadyl sulfate, and vanadium oxide, preferably ammonium metavanadate.
In the above technical solution, the copper source is at least one of nitrate, carbonate, oxide and carbonate of copper, and is preferably copper nitrate.
In the above technical scheme, the antimony source is at least one of antimony oxide, antimony nitrate and antimony carbonate, and antimony trioxide is preferred.
In the above technical scheme, the source of the element X is at least one of nitrate, oxide and carbonate of the element X.
In the above technical scheme, the source of the Z element is at least one of nitrate, oxide and carbonate of the Z element.
In the above technical scheme, the dispersion medium in the active element liquid is or is mainly water.
In the technical scheme, each active component is dissolved respectively to obtain the active element liquid of each component.
In the above technical solution, the active element liquids of the components are preferably mixed in a specific order.
In the technical scheme, the vanadium source is mixed in the order of the copper source prior to the vanadium source.
In the technical scheme, the vanadium source is mixed in the sequence of the antimony source before the vanadium source.
In the above technical solution, it is further preferable that the copper source is mixed in order of the antimony source before the copper source.
In the above technical solution, the pH of the mixed solution after mixing the vanadium source, the copper source and the antimony source may be in a range common in the art, specifically 1, 2, 3, 4, 5, 6, 7, and preferably 2 to 5.
In the technical scheme, the vanadium source, the copper source and the antimony source are mixed, the pH value is adjusted, and then the mixture is magnetically stirred for 10-120 min. In the technical scheme, the pH value is adjusted by nitric acid, formic acid, citric acid or ammonia water. In the technical scheme, the active element mixed solution is a solution, a suspension, an emulsion or a mixture thereof.
In the above technical solution, the catalyst carrier is selected from at least one of lithium oxide, magnesium oxide, aluminum oxide, zirconium dioxide, silicon dioxide, titanium dioxide, vanadium dioxide, diatomaceous earth, kaolin, and pumice.
In the above technical scheme, the content of the active component in the catalyst is preferably 10-80 w%, preferably 30-60 wt% by weight.
In the above technical solution, the catalyst carrier is in a powder state, and has a particle size of 40 to 400 mesh, preferably 100 to 200 mesh.
In the above technical scheme, the drying and calcining steps are not particularly limited, and the required catalyst can be obtained by drying and calcining at a proper temperature and for a proper time.
The invention also aims to provide a catalyst for preparing the acrolein by selectively oxidizing the propylene, which is obtained by the preparation method.
The fourth purpose of the invention is to provide the application of the catalyst or the catalyst obtained by the preparation method in the preparation of acrolein through propylene oxidation.
The method for preparing the acrolein by propylene oxidation comprises the step of reacting propylene with oxidizing gas containing oxygen in the presence of the catalyst for preparing the acrolein by propylene oxidation to obtain the acrolein.
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 propylene, air and steam, in terms of volume ratio, the ratio of propylene: air: steam =1: (1-12): (0.5-5).
In the technical scheme, the total space velocity of the raw material gas is preferably 800-1500 h -1 。
The catalyst of the invention is adopted, and the total space velocity of the raw material gas is 1250h -1 The selectivity of the acrolein can reach more than 88 percent at most, and the mechanical strength can reach more than 95N/m at most, thereby obtaining better technical effect and being used in the industrial production of the acrolein.
Drawings
FIG. 1 is a TGA graph of the catalyst prepared in comparative example 1.
Figure 2 is a TGA plot of the catalyst prepared in example 1.
Detailed Description
While the present invention will be described in conjunction with specific embodiments thereof, it is to be understood that the following embodiments are presented by way of illustration only and not by way of limitation, and that numerous insubstantial modifications and adaptations of the invention may be made by those skilled in the art in light of the teachings herein.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
The catalyst evaluation method of the present invention is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading amount: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -1 。
[ example 1 ]
1. Mixing the active element solutions of the components to obtain a mixed solution I;
dissolving the raw material components in water respectivelyAnd (4) hot water at 80 ℃ to obtain active element liquid of each component. Will contain 0.04 mole of V 2 O 5 Ammonium metavanadate (molecular formula: NH) 4 VO 3 ) The solution was added to a 500ml beaker and then 0.04 mol Bi was added during stirring 2 O 3 Bismuth nitrate (molecular formula: bi (NO)) 3 ) 3 ) Solution of 0.4 mol MoO 3 Ammonium molybdate (molecular formula is (NH) 4 ) 2 MoO 4 ) The solution was then added with copper nitrate containing 0.04 mol of CuO (formula: cu (NO) 3 ) 2 ) Solution of 0.04 mol Sb 2 O 3 Adjusting the pH value of the antimony trioxide solution to 3, and continuously adding the antimony trioxide solution containing 0.02 mol of WO 3 Ammonium tungstate (molecular formula (NH) 4 ) 10 W 12 O 41 ) Solution of sodium nitrate (molecular formula NaNO) containing 0.02 mol of Na 3 ) The solution was mixed well and evaporated under stirring at 80 ℃ until the concentration of the active ingredient in the mixed material solution was 0.5g/g (general formula of active ingredient: bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O) to obtain active component mixed liquor I.
2. Mixing the mixed solution I with a carrier;
200g of the active component mixed solution I is taken and uniformly mixed with 150g of alumina powder (100-200 meshes) to obtain a catalyst precursor I.
3. Drying, roasting and forming;
the catalyst precursor I was dried in an oven at 80 ℃ for 5 hours and then calcined in a muffle furnace at 450 ℃ for 4 hours to give a catalyst having the following composition:
40w％Bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O+60w％Al 2 O 3 。
4. catalyst evaluation
The evaluation method is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -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. Mixing the active element solutions of the components to obtain a mixed solution I;
dissolving the raw material components in hot water of 80 ℃ respectively to obtain active element liquid of each component. Will contain 0.04 mole of V 2 O 5 Ammonium metavanadate (molecular formula: NH) 4 VO 3 ) The solution was added to a 500ml beaker and then 0.04 mol of Bi was added during stirring 2 O 3 Bismuth nitrate (molecular formula: bi (NO)) 3 ) 3 ) Solution of 0.4 mol MoO 3 Ammonium molybdate (molecular formula is (NH) 4 ) 2 MoO 4 ) The solutions were then separately charged with copper nitrate containing 0.04 mol of CuO (formula: cu (NO) 3 ) 2 ) Solution of 0.04 mol Sb 2 O 3 Adjusting the pH value of the antimony trioxide solution to be 1, and continuously adding the antimony trioxide solution containing 0.02 mol of WO 3 Ammonium tungstate (molecular formula (NH) 4 ) 10 W 12 O 41 ) Solution of sodium nitrate (molecular formula NaNO) containing 0.02 mol of Na 3 ) The solution was mixed uniformly and evaporated at 80 ℃ with stirring until the concentration of the active ingredient in the mixed material solution was 0.5g/g (general formula of active ingredient: bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O) to obtain active component mixed liquor I.
2. Mixing the mixed solution I with a carrier;
200g of the active component mixed solution I is taken and uniformly mixed with 150g of alumina powder (100-200 meshes) to obtain a catalyst precursor I.
3. Drying, roasting and forming;
the catalyst precursor I is dried in an oven at 80 ℃ for 5 hours and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain the catalyst with the following composition:
40w％Bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O+60w％Al 2 O 3 。
4. catalyst evaluation
The evaluation method is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading amount: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -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 ] A method for producing a polycarbonate
1. Mixing the active element solutions of the components to obtain a mixed solution I;
dissolving the raw material components in hot water of 80 ℃ respectively to obtain active element liquid of each component. Will contain 0.04 mole of V 2 O 5 Ammonium metavanadate (molecular formula: NH) 4 VO 3 ) The solution was added to a 500ml beaker and then 0.04 mol of Bi was added during stirring 2 O 3 Bismuth nitrate (molecular formula: bi (NO)) 3 ) 3 ) Solution of 0.4 mol MoO 3 Ammonium molybdate (molecular formula is (NH) 4 ) 2 MoO 4 ) The solution was then added with copper nitrate containing 0.04 mol of CuO (formula: cu (NO) 3 ) 2 ) Solution of 0.04 mol Sb 2 O 3 Adjusting the pH value of the antimony trioxide solution to 5, and continuously adding the antimony trioxide solution containing 0.02 mol of WO 3 Ammonium tungstate (molecularly)Formula (II): (NH) 4 ) 10 W 12 O 41 ) Solution of sodium nitrate (molecular formula NaNO) containing 0.02 mol of Na 3 ) The solution was mixed well and evaporated under stirring at 80 ℃ until the concentration of the active ingredient in the mixed material solution was 0.5g/g (general formula of active ingredient: bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O) to obtain active component mixed liquor I.
2. Mixing the mixed solution I with a carrier;
200g of the active component mixed solution I is taken and uniformly mixed with 150g of alumina powder (100-200 meshes) to obtain a catalyst precursor I.
3. Drying, roasting and forming;
the catalyst precursor I is dried in an oven at 80 ℃ for 5 hours and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain the catalyst with the following composition:
40w％Bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O+60w％Al 2 O 3 。
4. catalyst evaluation
The evaluation method is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -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. Mixing the active element solutions of the components to obtain a mixed solution I;
mixing the raw material componentsRespectively dissolving in hot water of 80 ℃ to obtain active element liquid of each component. Will contain 0.04 mole of V 2 O 5 Ammonium metavanadate (molecular formula: NH) 4 VO 3 ) The solution was added to a 500ml beaker and then 0.04 mol of Bi was added during stirring 2 O 3 Bismuth nitrate (molecular formula: bi (NO)) 3 ) 3 ) Solution of 0.4 mol MoO 3 Ammonium molybdate (molecular formula is (NH) 4 ) 2 MoO 4 ) The solution was then added with copper nitrate containing 0.04 mol of CuO (formula: cu (NO) 3 ) 2 ) Solution of 0.04 mol Sb 2 O 3 Adjusting the pH value of the antimony trioxide solution to 7, and continuously adding the antimony trioxide solution containing 0.02 mol of WO 3 Ammonium tungstate (molecular formula: (NH) 4 ) 10 W 12 O 41 ) Solution of sodium nitrate (molecular formula NaNO) containing 0.02 mol of Na 3 ) The solution was mixed well and evaporated under stirring at 80 ℃ until the concentration of the active ingredient in the mixed material solution was 0.5g/g (general formula of active ingredient: bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O) to obtain active component mixed liquor I.
2. Mixing the mixed solution I with a carrier;
200g of the active component mixed solution I is taken and uniformly mixed with 150g of alumina powder (100-200 meshes) to obtain a catalyst precursor I.
3. Drying, roasting and forming;
the catalyst precursor I is dried in an oven at 80 ℃ for 5 hours and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain the catalyst with the following composition:
40w％Bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O+60w％Al 2 O 3 。
4. catalyst evaluation
The evaluation method is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -1 。
The elemental compositions of the catalysts and the evaluation results of the catalysts are shown in Table 1 for convenience of comparison.
[ example 5 ] A method for producing a polycarbonate
1. Mixing the active element solutions of the components to obtain a mixed solution I;
dissolving the raw material components in hot water of 80 ℃ respectively to obtain active element liquid of each component. Will contain 0.04 mole of Sb 2 O 3 The antimony trioxide solution is added into a 500ml beaker, and then 0.04 mol of Bi is respectively added in the stirring process 2 O 3 Bismuth nitrate (molecular formula: bi (NO)) 3 ) 3 ) Solution of 0.4 mol MoO 3 Ammonium molybdate (molecular formula is (NH) 4 ) 2 MoO 4 ) The solution was then added with copper nitrate containing 0.04 mol of CuO (formula: cu (NO) 3 ) 2 ) Solution of 0.04 mol V 2 O 5 Ammonium metavanadate (molecular formula: NH) 4 VO 3 ) The solution was adjusted to pH 3 and further added with a solution containing 0.02 mol of WO 3 Ammonium tungstate (molecular formula (NH) 4 ) 10 W 12 O 41 ) Solution of sodium nitrate (molecular formula NaNO) containing 0.02 mol of Na 3 ) The solution was mixed uniformly and evaporated at 80 ℃ with stirring until the concentration of the active ingredient in the mixed material solution was 0.5g/g (general formula of active ingredient: bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O) to obtain active component mixed liquor I.
2. Mixing the mixed solution I with a carrier;
200g of the active component mixed solution I is taken and uniformly mixed with 150g of alumina powder (100-200 meshes) to obtain a catalyst precursor I.
3. Drying, roasting and forming;
the catalyst precursor I was dried in an oven at 80 ℃ for 5 hours and then calcined in a muffle furnace at 450 ℃ for 4 hours to give a catalyst having the following composition:
40w％Bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O+60w％Al 2 O 3 。
4. catalyst evaluation
The evaluation method is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -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. Mixing the active element solutions of the components to obtain a mixed solution I;
dissolving the raw material components in hot water of 80 ℃ respectively to obtain active element liquid of each component. Will contain 0.04 mol of V 2 O 5 Ammonium metavanadate (molecular formula: NH) 4 VO 3 ) The solution was added to a 500ml beaker and then 0.04 mol of Bi was added during stirring 2 O 3 Bismuth nitrate (molecular formula: bi (NO)) 3 ) 3 ) Solution of 0.4 mol MoO 3 Ammonium molybdate (molecular formula is (NH) 4 ) 2 MoO 4 ) Adding the solution containing 0.04 mol Sb 2 O 3 The antimony trioxide solution contains 0.04 mol CuO of copper nitrate (molecular formula: cu (NO)) 3 ) 2 ) The solution was adjusted to pH 3 and further added with a solution containing 0.02 mol of WO 3 Tungstic acid ofAmmonium (molecular formula (NH) 4 ) 10 W 12 O 41 ) Solution of sodium nitrate (molecular formula NaNO) containing 0.02 mol of Na 3 ) The solution was mixed well and evaporated under stirring at 80 ℃ until the concentration of the active ingredient in the mixed material solution was 0.5g/g (general formula of active ingredient: bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O) to obtain active component mixed liquor I.
2. Mixing the mixed solution I with a carrier;
200g of the active component mixed solution I is taken and uniformly mixed with 150g of alumina powder (100-200 meshes) to obtain a catalyst precursor I.
3. Drying, roasting and forming;
the catalyst precursor I is dried in an oven at 80 ℃ for 5 hours and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain the catalyst with the following composition:
40w％Bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O+60w％Al 2 O 3 。
4. catalyst evaluation
The evaluation method is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading amount: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -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. Mixing the active element solutions of the components to obtain a mixed solution I;
all the raw materials are mixedThe material components are respectively dissolved in hot water of 80 ℃ to obtain active element liquid of each component. Copper nitrate (formula: cu (NO): containing 0.04 mol of CuO was added 3 ) 2 ) The solution was added to a 500ml beaker and then 0.04 mol Bi was added during stirring 2 O 3 Bismuth nitrate (molecular formula: bi (NO)) 3 ) 3 ) Solution of 0.4 mol MoO 3 Ammonium molybdate (molecular formula is (NH) 4 ) 2 MoO 4 ) Adding the solution containing 0.04 mol Sb 2 O 3 The antimony trioxide solution of (a) contains 0.04 mol V 2 O 5 Ammonium metavanadate (molecular formula: NH) 4 VO 3 ) The solution was adjusted to pH 3 and further added with a solution containing 0.02 mol of WO 3 Ammonium tungstate (molecular formula: (NH) 4 ) 10 W 12 O 41 ) Solution of sodium nitrate (molecular formula NaNO) containing 0.02 mol of Na 3 ) The solution was mixed well and evaporated under stirring at 80 ℃ until the concentration of the active ingredient in the mixed material solution was 0.5g/g (general formula of active ingredient: bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O) to obtain active component mixed liquor I.
2. Mixing the mixed solution I with a carrier;
200g of the active component mixed solution I is taken and uniformly mixed with 150g of alumina powder (100-200 meshes) to obtain a catalyst precursor I.
3. Drying, roasting and forming;
the catalyst precursor I is dried in an oven at 80 ℃ for 5 hours and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain the catalyst with the following composition:
40w％Bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O+60w％Al 2 O 3 。
4. catalyst evaluation
The evaluation method is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -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. Mixing the active element solutions of the components to obtain a mixed solution I;
dissolving the raw material components in hot water of 80 ℃ respectively to obtain active element liquid of each component. Copper nitrate (formula: cu (NO 3)) containing 0.04 mol of CuO 2 ) The solution was added to a 500ml beaker and then 0.04 mol of Bi was added during stirring 2 O 3 Bismuth nitrate (molecular formula: bi (NO)) 3 ) 3 ) Solution of 0.4 mol MoO 3 Ammonium molybdate (molecular formula is (NH) 4 ) 2 MoO 4 ) Adding the solution containing 0.04 mol V 2 O 5 Ammonium metavanadate (molecular formula: NH) 4 VO 3 ) Solution of 0.04 mol Sb 2 O 3 Adjusting the pH value of the antimony trioxide solution to 3, and continuously adding the antimony trioxide solution containing 0.02 mol of WO 3 Ammonium tungstate (molecular formula (NH) 4 ) 10 W 12 O 41 ) Solution of sodium nitrate (molecular formula NaNO) containing 0.02 mol of Na 3 ) The solution was mixed well and evaporated under stirring at 80 ℃ until the concentration of the active ingredient in the mixed material solution was 0.5g/g (general formula of active ingredient: bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O) to obtain active component mixed liquor I.
2. Mixing the mixed solution I with a carrier;
200g of the active component mixed solution I is taken and uniformly mixed with 150g of alumina powder (100-200 meshes) to obtain a catalyst precursor I.
3. Drying, roasting and forming;
the catalyst precursor I is dried in an oven at 80 ℃ for 5 hours and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain the catalyst with the following composition:
40w％Bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O+60w％Al 2 O 3 。
4. catalyst evaluation
The evaluation method is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -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. Mixing the active element solutions of the components to obtain a mixed solution I;
dissolving the raw material components in hot water of 80 ℃ respectively to obtain active element liquid of each component. Will contain 0.04 mole of V 2 O 5 Ammonium metavanadate (molecular formula: NH) 4 VO 3 ) The solution was added to a 500ml beaker and then 0.04 mol of Bi was added during stirring 2 O 3 Bismuth nitrate (molecular formula: bi (NO)) 3 ) 3 ) Solution of 0.4 mol MoO 3 Ammonium molybdate (molecular formula is (NH) 4 ) 2 MoO 4 ) The solution was then added with copper nitrate containing 0.04 mol of CuO (formula: cu (NO) 3 ) 2 ) Solution of 0.04 mol Sb 2 O 3 The antimony trioxide solution was adjusted to pH 3, and cobalt nitrate (molecular formula: 0.02 mol CoO) was continuously added thereto：Co(NO 3 ) 2 ) Solution of sodium nitrate (molecular formula NaNO) containing 0.02 mol of Na 3 ) The solution was mixed uniformly and evaporated at 80 ℃ with stirring until the concentration of the active ingredient in the mixed material solution was 0.5g/g (general formula of active ingredient: bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5CoO·0.5Na 2 O) to obtain active component mixed liquor I.
2. Mixing the mixed solution I with a carrier;
200g of the active component mixed solution I is taken and uniformly mixed with 150g of alumina powder (100-200 meshes) to obtain a catalyst precursor I.
3. Drying, roasting and forming;
the catalyst precursor I was dried in an oven at 80 ℃ for 5 hours and then calcined in a muffle furnace at 450 ℃ for 4 hours to give a catalyst having the following composition:
40w％Bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5CoO·0.5Na 2 O+60w％Al 2 O 3 。
4. catalyst evaluation
The evaluation method is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -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. Mixing the active element solutions of the components to obtain a mixed solution I;
dissolving the raw material components in 80 deg.C hot water to obtain active componentsAnd (5) preparing a vegetable liquid. Will contain 0.04 mole of V 2 O 5 Ammonium metavanadate (molecular formula: NH) 4 VO 3 ) The solution was added to a 500ml beaker and then 0.04 mol of Bi was added during stirring 2 O 3 Bismuth nitrate (molecular formula: bi (NO)) 3 ) 3 ) Solution of 0.4 mol MoO 3 Ammonium molybdate (molecular formula is (NH) 4 ) 2 MoO 4 ) The solution was then added with copper nitrate containing 0.04 mol of CuO (formula: cu (NO) 3 ) 2 ) Solution of 0.04 mol Sb 2 O 3 Adjusting the pH value of the antimony trioxide solution to 3, and continuously adding the antimony trioxide solution containing 0.02 mol of WO 3 Ammonium tungstate (molecular formula (NH) 4 ) 10 W 12 O 41 ) Solution of potassium nitrate (molecular formula KNO) containing 0.02 mol K 3 ) The solution was mixed well and evaporated under stirring at 80 ℃ until the concentration of the active ingredient in the mixed material solution was 0.5g/g (general formula of active ingredient: bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5K 2 O) to obtain active component mixed liquor I.
2. Mixing the mixed solution I with a carrier;
200g of the active component mixed solution I is taken and uniformly mixed with 150g of alumina powder (100-200 meshes) to obtain a catalyst precursor I.
3. Drying, roasting and forming;
the catalyst precursor I is dried in an oven at 80 ℃ for 5 hours and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain the catalyst with the following composition:
40w％Bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5K 2 O+60w％Al 2 O 3 。
4. catalyst evaluation
The evaluation method is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -1 。
The elemental compositions of the catalysts and the evaluation results of the catalysts are shown in Table 1 for convenience of comparison.
[ example 11 ]
1. Mixing the active element solutions of the components to obtain a mixed solution I;
dissolving the raw material components in hot water of 80 ℃ respectively to obtain active element liquid of each component. Will contain 0.04 mol of V 2 O 5 Ammonium metavanadate (molecular formula: NH) 4 VO 3 ) The solution was added to a 500ml beaker and then 0.04 mol of Bi was added during stirring 2 O 3 Bismuth nitrate (molecular formula: bi (NO)) 3 ) 3 ) Solution of 0.4 mol MoO 3 Ammonium molybdate (molecular formula is (NH) 4 ) 2 MoO 4 ) The solution was then added with copper nitrate containing 0.04 mol of CuO (formula: cu (NO) 3 ) 2 ) Solution of 0.04 mol Sb 2 O 3 Adjusting the pH value of the antimony trioxide solution to 3, and continuously adding the solution containing 0.08 mol of WO 3 Ammonium tungstate (molecular formula (NH) 4 ) 10 W 12 O 41 ) Solution of sodium nitrate (molecular formula NaNO) containing 0.02 mol of Na 3 ) The solution was mixed uniformly and evaporated at 80 ℃ with stirring until the concentration of the active ingredient in the mixed material solution was 0.5g/g (general formula of active ingredient: bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·2WO 3 ·0.5Na 2 O) to obtain active component mixed liquor I.
2. Mixing the mixed solution I with a carrier;
200g of the active component mixed solution I is taken and uniformly mixed with 150g of alumina powder (100-200 meshes) to obtain a catalyst precursor I.
3. Drying, roasting and forming;
the catalyst precursor I is dried in an oven at 80 ℃ for 5 hours and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain the catalyst with the following composition:
40w％Bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·2WO 3 ·0.5Na 2 O+60w％Al 2 O 3 。
4. catalyst evaluation
The evaluation method is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -1 。
The elemental composition of the catalyst and the evaluation results of the catalyst are shown in Table 1 for convenience of comparison.
[ example 12 ]
1. Mixing the active element solutions of the components to obtain a mixed solution I;
dissolving the raw material components in hot water of 80 ℃ respectively to obtain active element liquid of each component. Will contain 0.04 mole of V 2 O 5 Ammonium metavanadate (molecular formula: NH) 4 VO 3 ) The solution was added to a 500ml beaker and then 0.04 mol of Bi was added during stirring 2 O 3 Bismuth nitrate (molecular formula: bi (NO)) 3 ) 3 ) Solution of 0.4 mol MoO 3 Ammonium molybdate (molecular formula is (NH) 4 ) 2 MoO 4 ) The solution was then added with copper nitrate containing 0.04 mol of CuO (formula: cu (NO) 3 ) 2 ) Solution of 0.04 mol Sb 2 O 3 Adjusting the pH value of the antimony trioxide solution to 3, and continuously adding the antimony trioxide solution containing 0.02 mol of WO 3 Ammonium tungstate (molecular formula: (NH) 4 ) 10 W 12 O 41 ) Solution of sodium nitrate (molecular formula NaNO) containing 0.08 mol of Na 3 ) The solution was mixed well and evaporated under stirring at 80 ℃ until the concentration of the active ingredient in the mixed material solution was 0.5g/g (general formula of active ingredient: bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·2Na 2 O) to obtain active component mixed liquor I.
2. Mixing the mixed solution I with a carrier;
200g of the active component mixed solution I is taken and uniformly mixed with 150g of alumina powder (100-200 meshes) to obtain a catalyst precursor I.
3. Drying, roasting and forming;
the catalyst precursor I is dried in an oven at 80 ℃ for 5 hours and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain the catalyst with the following composition:
40w％Bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·2Na 2 O+60w％Al 2 O 3 。
4. catalyst evaluation
The evaluation method is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -1 。
The elemental compositions of the catalysts and the evaluation results of the catalysts are shown in Table 1 for convenience of comparison.
[ COMPARATIVE EXAMPLE 1 ]
1. Mixing the active element solutions of the components to obtain a mixed solution I;
dissolving the raw material components in 80 deg.C hot water to obtain active componentsAnd (5) preparing a vegetable liquid. Will contain 0.04 mole of Sb 2 O 3 The antimony trioxide solution is added into a 500ml beaker, and then 0.04 mol of Bi is respectively added in the stirring process 2 O 3 Bismuth nitrate (molecular formula: bi (NO)) 3 ) 3 ) Solution of 0.4 mol MoO 3 Ammonium molybdate (molecular formula is (NH) 4 ) 2 MoO 4 ) Adding 0.04 mol V 2 O 5 Ammonium metavanadate (molecular formula: NH) 4 VO 3 ) Solution, 0.04 mol CuO of copper nitrate (formula: cu (NO 3) 2 ) Adjusting the pH of the solution to 5, and continuing to add the solution containing 0.02 mol of WO 3 Ammonium tungstate (molecular formula (NH) 4 ) 10 W 12 O 41 ) Solution of sodium nitrate (molecular formula NaNO) containing 0.02 mol of Na 3 ) The solution was mixed well and evaporated under stirring at 80 ℃ until the concentration of the active ingredient in the mixed material solution was 0.5g/g (general formula of active ingredient: bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O) to obtain active component mixed liquor I.
2. Mixing the mixed solution I with a carrier;
200g of the active component mixed solution I is taken and uniformly mixed with 150g of alumina powder (100-200 meshes) to obtain a catalyst precursor I.
3. Drying, roasting and forming;
the catalyst precursor I is dried in an oven at 80 ℃ for 5 hours and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain the catalyst with the following composition:
40w％Bi 2 O 3 ·10MoO 3 ·V 2 O 5 ·CuO·Sb 2 O 3 ·0.5WO 3 ·0.5Na 2 O+60w％Al 2 O 3 。
4. catalyst evaluation
The evaluation method is as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading: 2.0 g;
reaction temperature: 360 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: propylene: air: steam =1:8:2;
total space velocity of raw material gas: 1250h -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 evaluation results
Figure BDA0003117439310000211
Figure BDA0003117439310000221

Claims (14)

1. A catalyst for preparing acrolein by selective oxidation of propylene comprises a carrier and an active component, wherein the active component has a general formula: bi 2 O 3 ·aMoO 3 ·bV 2 O 5 ·cCuO·dSb 2 O 3 ·eXO m ·fZO n ，
Wherein X is at least one element selected from Sc, Y, ti, zr, hf, nb, ta, cr, W, mn, tc, re, fe, ru, os, co, rh, ir, ni, pd, pt, ag, au, zn, cd, lanthanoid and actinoid, and Z is at least one element selected from Li, na, K, rb and Cs; a takes a value of 2.0 to 15.0; b takes a value of 0.1 to 2.0; c takes a value of 0.1 to 2.0; d takes a value of 0.1 to 2.0; e takes a value of 0.1 to 2.0; f takes a value of 0.1 to 2.0; m and n are the mole numbers of oxygen atoms required by the valence of elements in the active component;
preferably, a is 3.0-10.0, b is 0.2-0.8, c is 0.2-0.8, d is 0.2-0.8, e is 0.2-0.8, and f is 0.2-0.8.
2. The catalyst of claim 1, wherein:
the carrier is selected from at least one of lithium oxide, magnesium oxide, aluminum oxide, zirconium dioxide, silicon dioxide, titanium dioxide, vanadium dioxide, diatomite, kaolin and pumice; and/or the presence of a gas in the atmosphere,
the particle size of the carrier is 40 to 400 meshes, preferably 100 to 200 meshes.
3. The catalyst of claim 1, wherein:
the content of active components in the catalyst is 10-80 wt%, preferably 30-60 wt%.
4. A catalyst according to any one of claims 1 to 3, characterized in that:
the thermogravimetric analysis curve of the catalyst comprises a stable stage and a rapid reduction stage, wherein the temperature of the stable stage is less than 500 ℃, and the temperature of the rapid reduction stage is more than or equal to 500 ℃.
5. The catalyst of claim 4, wherein:
in the range of 0 ℃ to 200 ℃ in the stationary stage, the mass loss rate of the catalyst is 0.1-0.25%;
in the range of 200 ℃ to less than 500 ℃ in the stationary stage, the mass loss rate of the catalyst is 0.02 to 0.06 percent;
the mass loss rate of the catalyst is 1-1.5% in the range of 500 ℃ to 800 ℃ in the rapid decline stage.
6. A process for preparing a catalyst according to any one of claims 1 to 5, comprising the steps of:
(1) Respectively dissolving or dispersing each active component element source in water to prepare a solution of the active component elements, and mixing to obtain a mixed solution;
(2) Mixing the mixed solution with a carrier;
(3) Drying and roasting.
7. The method of claim 6, wherein: the active component element sources are respectively a bismuth source, a molybdenum source, a vanadium source, a copper source, an antimony source, an X element source and a Z element source, wherein,
the bismuth source is at least one of nitrate, carbonate and oxide of bismuth; and/or the presence of a gas in the atmosphere,
the molybdenum source is at least one of ammonium molybdate, ammonium paramolybdate and molybdenum oxide; and/or the presence of a gas in the gas,
the vanadium source is at least one of ammonium metavanadate, vanadyl sulfate and vanadium oxide; and/or the presence of a gas in the gas,
the copper source is at least one of nitrate, carbonate, oxide and carbonate of copper; and/or the presence of a gas in the gas,
the antimony source is at least one of antimony oxide, nitrate and carbonate; and/or the presence of a gas in the gas,
the X element source is at least one of nitrate, oxide and carbonate of the X element; and/or the presence of a gas in the gas,
the Z element source is at least one of nitrate, oxide and carbonate of the Z element.
8. The method of claim 6, wherein: in the step (1), the step (c),
the vanadium source is mixed in order of preference to the copper source.
9. The method of claim 8, wherein:
the vanadium source is mixed in order before the antimony source.
10. The production method according to claim 8 or 9, characterized in that:
the copper source is mixed in the order of the antimony source before the copper source.
11. The method of manufacturing according to claim 10, wherein:
adjusting the pH value of the mixed solution of the vanadium source, the copper source and the antimony source to 2-5; preferably by nitric acid, formic acid, citric acid or ammonia.
12. The method for producing according to claim 11, characterized in that:
after the pH value is adjusted, magnetic stirring is carried out for 10-120 min.
13. The catalyst obtained by the production method according to any one of claims 6 to 12.
14. Use of a catalyst according to any one of claims 1 to 5 or obtained by a process according to any one of claims 6 to 12 in the oxidation of propylene to acrolein.
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CN103769131A (en) * 2012-10-23 2014-05-07 中国石油天然气股份有限公司 Propylene selective-oxidation catalyst and preparation method thereof
CN103772172A (en) * 2012-10-23 2014-05-07 中国石油天然气股份有限公司 Method for producing acrolein by propylene selective-oxidation
CN103769132A (en) * 2012-10-23 2014-05-07 中国石油天然气股份有限公司 Low-carbon olefin oxidation catalyst and preparation method thereof
CN104649873A (en) * 2013-11-19 2015-05-27 中国石油天然气股份有限公司 Method used for selective oxidization of low-carbon olefin
CN106423186A (en) * 2015-08-12 2017-02-22 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method thereof
CN111068711A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Acrylic acid catalyst and application thereof
CN111068699A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Catalyst suitable for producing acrolein and use thereof
CN111068698A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Catalyst for preparing acrolein by propylene oxidation and application thereof
CN112844400A (en) * 2019-11-27 2021-05-28 中国科学院大连化学物理研究所 Bi-based polyacid catalyst and application thereof in preparation of 2-methylacrolein by oxidation of 2-methyl propylene

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