CN111185186A - Single-phase composite metal oxide catalyst, preparation method and application thereof - Google Patents
Single-phase composite metal oxide catalyst, preparation method and application thereof Download PDFInfo
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- 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
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- 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
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Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a single-phase composite metal oxide catalyst, and a preparation method and application thereof. Compared with the existing heterogeneous composite metal oxide catalyst, the single-phase catalyst prepared by the invention can effectively reduce the barrier between active sites which must be overcome by component transfer, can accelerate the electron transfer rate, improve the redox capability of the catalyst, and reduce the surface acidity, thereby improving the conversion rate of isobutene and the yield of the target product methacrolein, and is expected to be industrially applied.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a single-phase composite metal oxide catalyst, and a preparation method and application thereof.
Background
Methyl Methacrylate (MMA) is an important organic chemical intermediate, is mainly used for producing organic glass, surface coatings, PVC modifiers and the like, and is widely applied to the fields of fine chemical industry, national defense, buildings and the like. Currently, the process for industrially producing MMA in China is mainly an acetone cyanohydrin method, but the method has the defects of serious pollution, low atom utilization rate and the like caused by using a highly toxic hydrocyanic acid raw material, so that the further development of the method is limited. In the process of producing MMA by oxidation of isobutene, due to the fact that the process is more and more concerned about the green and environment-friendly characteristics, a great deal of research work is conducted by various research units such as the team of Yangtze academy, Jilin university and the university of tobacco terrace in the process of the Chinese academy. In recent years, with the development of petrochemical industry, China has adopted a green chemical production route of producing MMA by using isobutene as a raw material and has realized industrialization, and selective oxidation of isobutene to prepare MAL is a key step in the production route. Isobutene or Tertiary Butanol (TBA) is taken as a raw material to directly participate in the reaction to generate methacrylic acid (MAA), and the MAA is an important monomer for forming acrylic resin, so that the reaction process of oxidizing isobutene or TBA into MAL is highly regarded by people, and meanwhile, the development of a high-efficiency catalyst is promoted, so that a target molecule is formed.
Many patents and literature describe catalysts for the selective oxidation of isobutylene to produce methacrolein, which have different final properties due to different promoters and preparation methods.
Document 1(CN1486787) discloses a novel composite oxide catalyst prepared by adding alkali metal elements and lanthanoid elements to Mo, Bi, Fe, B, and Co as main components, and the total selectivity of the catalyst can reach 87% by changing the dosage ratio of the main elements in an experiment, thereby obtaining a better effect.
Document 2(CN104437531) uses Mo, Bi, Fe, and Co as main components, and adds one or more of Cs, Pb, W, V, Ni, Sn, and Na, and selects SiO2Or Al2O3The catalyst prepared by the carrier can ensure that the conversion rate of isobutene reaches up to 98.5 percent and the selectivity of MAL reaches up to 89.1 percent.
Document 3(PERP Program, Methyl Methacrylate New Report Alert, Nexant ChemSystems,2006.) a CsFeCoBiMnMoOx catalyst was obtained by adding Cs and Mn elements mainly to Mo, Bi, Fe, Co, and evaluated at 350 ℃, with a conversion of isobutylene up to 98% and a selectivity of MAL of about 80%.
Document 4(Acta Phys. Chim. sin.2012,28(11),2690-2696) researches on the preparation of Mo-Bi-Fe-Co-Mn five-component catalyst by a coprecipitation method, and the amount of the MX phase of the catalyst reaches the maximum value. At this time, the conversion of isobutylene and the selectivity of methacrolein were 99.9% and 95.6%, respectively. Research shows that certain interaction exists among the components on the catalyst, and a specific phase MX in the catalyst is one of the key factors influencing the reaction activity.
Document 5(d.weber, p.weidler, b.krausshaar Czarnetzki1, Top cat, 60(17-18),1401-1407) synthesized a novel movnb (te) mixed oxide catalyst for the oxidation of isobutane and isobutylene to methacrolein and methacrylic acid. This novel crystalline MoVNb (Te) mixed oxide compound, designated herein as M3, is a high performance catalyst for the selective oxidation of isobutylene to MAL. The novel catalyst is distinguished by high activity and high stability.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a single-phase composite metal oxide catalyst, and a preparation method and application thereof.
The technical scheme for solving the technical problems is as follows: a preparation method of a single-phase composite metal oxide catalyst comprises the following steps:
(1) dissolving a compound containing molybdenum element in water to obtain a solution A;
(2) dissolving a compound containing cobalt and a compound containing bismuth in a nitric acid solution to obtain a solution B;
(3) dissolving one or more than two of compounds containing iron, chromium, manganese, nickel, copper or zinc elements in water to obtain a solution C;
(4) stirring the solution A at the temperature of 10-100 ℃, dripping the solution B and the solution C into the solution A, and continuously stirring for 10min-5h to obtain a mixed solution;
(5) putting the mixed solution obtained in the step (4) into a reaction kettle, stirring and aging, wherein the reaction temperature is 60-300 ℃, and the reaction time is 1-24 h;
(6) after aging, drying and roasting to obtain a single-phase composite metal oxide catalyst;
wherein the atomic molar ratio of molybdenum, bismuth, cobalt, iron, chromium, manganese, nickel, copper and zinc elements is 12:2:4 (0-5): (0-3): (0-3): (0-3): (0-3): (0-3), and the dosage of iron, chromium, manganese, nickel, copper and zinc is not 0 at the same time.
Further, the concentration of the nitric acid solution is 5-25 wt%.
Further, the compound containing molybdenum element is ammonium molybdate, molybdenum nitrate or molybdenum trioxide; the compound containing cobalt element is cobalt nitrate, cobalt sulfate, cobalt chloride or cobalt acetate; the compound containing bismuth element is bismuth nitrate or bismuth acetate.
Further, the compound containing iron, chromium, manganese, nickel, copper or zinc is nitrate of the corresponding element.
Further, in the step (4), the temperature is preferably 30 to 80 ℃.
Further, in the step (5), the tolerance pressure in the reaction kettle is 2-6MPa, the reaction temperature is preferably 100-200 ℃, and the reaction time is preferably 2-8 h.
Further, in the step (6), in the roasting process, the roasting temperature is 400-.
Furthermore, in the step (6), the roasting temperature is preferably 500-550 ℃ and the roasting time is preferably 4-10h in the roasting process.
The second object of the present invention is to provide a single-phase composite metal oxide catalyst obtained by the above-mentioned production method.
The third purpose of the invention is to provide the application of the single-phase composite metal oxide catalyst in the reaction for producing the methacrolein by selectively oxidizing isobutene.
In a stainless steel tubular reactor (inner diameter 15mm, length 300mm), 5g of a single-phase composite metal oxide catalyst (20-40 mesh) was used, and the catalyst performance was tested at 0.1 MPa. Taking isobutene O2:N2As reactants, 1:2:10 (molar ratio) and setting space velocity to900h-1The catalyst of the present invention is used for catalytic reaction, and the product absorbed by the cooling absorbent is subjected to chromatographic analysis.
The invention has the characteristics and beneficial effects that:
compared with the existing heterogeneous composite metal oxide catalyst, the single-phase catalyst prepared by the invention can effectively reduce the barrier between active sites which must be overcome by component transfer, can accelerate the electron transfer rate, improve the redox capability of the catalyst, and reduce the surface acidity, thereby improving the conversion rate of isobutene and the yield of the target product methacrolein, and is expected to be industrially applied.
Drawings
FIG. 1 is a comparison of XRD patterns of the catalyst and active phase obtained in example 2 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
A preparation method of a single-phase composite metal oxide catalyst comprises the following steps:
(1) dissolving 25g of ammonium molybdate in 160mL of deionized water to obtain a solution A;
(2) dissolving 13.78g of cobalt nitrate and 9.3g of bismuth nitrate in 20mL of nitric acid solution to obtain a solution B;
(3) dissolving 14.75g of ferric nitrate in 20mL of deionized water to obtain a solution C;
(4) stirring the solution A at 60 ℃, dropwise adding the solution B and the solution C into the solution A, and continuously stirring for 30min to obtain a mixed solution;
(5) carrying out hydrothermal reaction on the mixed solution in the step (4), putting the mixed solution into a reaction kettle, stirring and aging, wherein the hydrothermal temperature is 120 ℃, reacting for 6 hours, and carrying out suction filtration;
(6) and after aging, drying in an oven at 120 ℃, crushing, and roasting at 550 ℃ to obtain the single-phase composite metal oxide catalyst, wherein the molar ratio of Mo, Bi, Co and Fe in the obtained catalyst is 12:2:4: 3.
Example 2
A preparation method of a single-phase composite metal oxide catalyst comprises the following steps:
(1) dissolving 25g of ammonium molybdate in 160mL of deionized water to obtain a solution A;
(2) dissolving 13.78g of cobalt nitrate and 9.3g of bismuth nitrate in 20mL of nitric acid solution to obtain a solution B;
(3) dissolving 14.75g of ferric nitrate and 2.96g of manganese nitrate in 20mL of deionized water to obtain a solution C;
(4) stirring the solution A at 70 ℃, dropwise adding the solution B and the solution C into the solution A, and continuously stirring for 20min to obtain a mixed solution;
(5) carrying out hydrothermal reaction on the mixed solution in the step (4), putting the mixed solution into a reaction kettle, stirring and aging, wherein the hydrothermal temperature is 140 ℃, reacting for 4 hours, and carrying out suction filtration;
(6) after aging, drying in an oven at 120 ℃, crushing, and roasting at 520 ℃ to obtain the single-phase composite metal oxide catalyst, wherein the molar ratio of Mo, Bi, Co, Fe and Mn in the obtained catalyst is 12:2:4: 3: 1.
example 3
A preparation method of a single-phase composite metal oxide catalyst comprises the following steps:
(1) dissolving 25g of ammonium molybdate in 160mL of deionized water to obtain a solution A;
(2) dissolving 13.78g of cobalt nitrate and 9.3g of bismuth nitrate in 20mL of nitric acid solution to obtain a solution B;
(3) dissolving 14.75g of ferric nitrate and 2.86g of copper nitrate in 20mL of deionized water to obtain a solution C;
(4) stirring the solution A at 55 ℃, dropwise adding the solution B and the solution C into the solution A, and continuously stirring for 35min to obtain a mixed solution;
(5) carrying out hydrothermal reaction on the mixed solution in the step (4), putting the mixed solution into a reaction kettle, stirring and aging, wherein the hydrothermal temperature is 160 ℃, reacting for 3 hours, and carrying out suction filtration;
(6) after aging, drying in an oven at 140 ℃, crushing, and roasting at 540 ℃ to obtain the single-phase composite metal oxide catalyst, wherein the molar ratio of Mo, Bi, Co, Fe and Cu in the obtained catalyst is 12:2:4: 3: 1.
example 4
A preparation method of a single-phase composite metal oxide catalyst comprises the following steps:
(1) dissolving 25g of ammonium molybdate in 160mL of deionized water to obtain a solution A;
(2) dissolving 13.78g of cobalt nitrate and 9.3g of bismuth nitrate in 20mL of nitric acid solution to obtain a solution B;
(3) dissolving 14.75g of ferric nitrate, 2.96g of zinc nitrate and 3.24g of nickel nitrate in 20mL of deionized water to obtain a solution C;
(4) stirring the solution A at 65 ℃, dropwise adding the solution B and the solution C into the solution A, and continuously stirring for 35min to obtain a mixed solution;
(5) carrying out hydrothermal reaction on the mixed solution in the step (4), putting the mixed solution into a reaction kettle, stirring and aging, wherein the hydrothermal temperature is 150 ℃, reacting for 4 hours, and carrying out suction filtration;
(6) after aging, drying in a 135 ℃ oven, crushing, and roasting at 550 ℃ to obtain the single-phase composite metal oxide catalyst, wherein the molar ratio of Mo, Bi, Co, Fe, Zn and Ni in the obtained catalyst is 12:2:4: 3: 1: 1.
taking the catalyst (Cat2) prepared in example 2, see figure 1, and comparing the XRD chart, the crystal form of the catalyst prepared in example 2 is the same as that of the active phase, which shows that the catalyst of the invention can be regarded as single-crystal phase composite metal oxide.
The catalysts obtained in examples 1 to 4 were used to test the isobutene conversion, the methacrolein selectivity and the CO content in the selective oxidation of isobutene2Selectivity, see Table 1.
TABLE 1
As can be seen from the data in Table 1, it was found that the catalyst of the present invention was able to act on isobutylene at 380 deg.CThe alkene is basically completely reacted, and the selectivity of the target product is kept above 87%. CO 22The selectivity of (a) is kept low, indicating that the catalyst system does not cause deep oxidation of the target product. Especially, in the catalyst of example 4, the conversion of isobutylene and the selectivity of methacrolein were maintained at high levels. From the aspect of characterization, the catalyst of the single active phase formed by the invention can improve the performance of the catalyst.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method of a single-phase composite metal oxide catalyst is characterized by comprising the following steps:
(1) dissolving a compound containing molybdenum element in water to obtain a solution A;
(2) dissolving a compound containing cobalt and a compound containing bismuth in a nitric acid solution to obtain a solution B;
(3) dissolving one or more than two of compounds containing iron, chromium, manganese, nickel, copper or zinc elements in water to obtain a solution C;
(4) stirring the solution A at the temperature of 10-100 ℃, dripping the solution B and the solution C into the solution A, and continuously stirring for 10min-5h to obtain a mixed solution;
(5) putting the mixed solution obtained in the step (4) into a reaction kettle, stirring and aging, wherein the reaction temperature is 60-300 ℃, and the reaction time is 1-24 h;
(6) after aging, drying and roasting to obtain a single-phase composite metal oxide catalyst;
wherein the atomic molar ratio of molybdenum, bismuth, cobalt, iron, chromium, manganese, nickel, copper and zinc elements is 12:2:4 (0-5): (0-3): (0-3): (0-3): (0-3): (0-3), and the dosage of iron, chromium, manganese, nickel, copper and zinc is not 0 at the same time.
2. The production method according to claim 1, wherein the compound containing a molybdenum element is ammonium molybdate, molybdenum nitrate or molybdenum trioxide; the compound containing cobalt element is cobalt nitrate, cobalt sulfate, cobalt chloride or cobalt acetate; the compound containing bismuth element is bismuth nitrate or bismuth acetate.
3. The method according to claim 1, wherein the compound containing iron, chromium, manganese, nickel, copper or zinc is a nitrate of the corresponding element.
4. The method according to claim 1, wherein in the step (4), the temperature is 30 to 80 ℃.
5. The preparation method as claimed in claim 1, wherein in the step (5), the withstand pressure in the reaction kettle is 2-6MPa, the reaction temperature is 100-200 ℃, and the reaction time is 2-8 h.
6. The preparation method as claimed in claim 1, wherein in the step (6), the calcination temperature is 400-600 ℃ and the calcination time is 1-24 h.
7. A single-phase composite metal oxide catalyst obtained by the production method according to any one of claims 1 to 6.
8. Use of the single-phase composite metal oxide catalyst of claim 7 in the selective oxidation of isobutylene to produce methacrolein.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113908876A (en) * | 2021-10-28 | 2022-01-11 | 惠生工程（中国）有限公司 | Carbon quantum dot induction-based multi-metal composite oxide catalyst and preparation method and application thereof |
| CN114405515A (en) * | 2022-02-08 | 2022-04-29 | 烟台大学 | Gradient pore composite metal oxide catalyst, preparation method and application thereof |
| CN118253340A (en) * | 2024-05-29 | 2024-06-28 | 利华益利津炼化有限公司 | Preparation and application of catalyst for synthesizing methacrolein and diisobutylene from isobutene |
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| JPH0597761A (en) * | 1991-02-27 | 1993-04-20 | Mitsui Toatsu Chem Inc | Production of methacrolein and catalyst used for producing methacrolein |
| CN101385978A (en) * | 2007-09-12 | 2009-03-18 | 上海华谊丙烯酸有限公司 | Catalyst for synthesizing methylacrolein and preparation method thereof |
| CN109070061A (en) * | 2016-03-14 | 2018-12-21 | 赢创德固赛有限公司 | The method of mixed oxide catalyst of the hydro-thermal preparation based on molybdenum bismuth ferro-cobalt |
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2020
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| US4418007A (en) * | 1980-10-10 | 1983-11-29 | Rhone-Poulenc Industries | Preparation of mixed oxide catalysts comprising the oxides of molybdenum and/or tungsten |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113908876A (en) * | 2021-10-28 | 2022-01-11 | 惠生工程（中国）有限公司 | Carbon quantum dot induction-based multi-metal composite oxide catalyst and preparation method and application thereof |
| CN114405515A (en) * | 2022-02-08 | 2022-04-29 | 烟台大学 | Gradient pore composite metal oxide catalyst, preparation method and application thereof |
| CN114405515B (en) * | 2022-02-08 | 2024-01-30 | 烟台大学 | Step hole composite metal oxide catalyst, preparation method and application thereof |
| CN118253340A (en) * | 2024-05-29 | 2024-06-28 | 利华益利津炼化有限公司 | Preparation and application of catalyst for synthesizing methacrolein and diisobutylene from isobutene |
| CN118253340B (en) * | 2024-05-29 | 2024-09-24 | 利华益利津炼化有限公司 | Preparation and application of catalyst for synthesizing methacrolein and diisobutylene from isobutene |
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