CN115430437B - Molybdenum salt heterogeneous carrier and preparation method and application thereof - Google Patents
Molybdenum salt heterogeneous carrier and preparation method and application thereof Download PDFInfo
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- CN115430437B CN115430437B CN202211138046.0A CN202211138046A CN115430437B CN 115430437 B CN115430437 B CN 115430437B CN 202211138046 A CN202211138046 A CN 202211138046A CN 115430437 B CN115430437 B CN 115430437B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
Abstract
The invention discloses a molybdenum salt heterogeneous carrier, a preparation method and application thereof, and belongs to the technical field of material preparation and catalysis. Firstly, complexing molybdenum salt with an organic ligand to obtain a molybdenum salt precursor, and calcining the molybdenum salt precursor to obtain the molybdenum salt heterogeneous carrier. The heterogeneous carrier based on the guidance of strong and weak carrier interaction theory is prepared creatively, has extremely strong inhibition effect on two sintering modes of Ostwald ripening and particle aggregation and migration, which are involved in the use process of the catalyst, can greatly improve the stability of the catalyst, and can prolong the service life of the catalyst, so that the use cost of the catalyst is reduced. Has very strong guiding significance for actual production and life.
Description
Technical Field
The invention belongs to the technical field of material preparation and catalysis, and particularly relates to a molybdenum salt heterogeneous carrier, and a preparation method and application thereof.
Background
In the catalytic field, especially in the field of thermocatalysis, the stability of the catalyst has been a difficult problem for researchers. The catalyst has two sintering modes in the thermocatalytic process: one is sintering in an ostwald ripening manner, and the other is sintering in a particle aggregation and migration manner. Both sintering modes can reduce or even lose the catalytic activity of the catalyst. In practice, the reduction or deactivation of the catalyst has a great influence on the industrial catalytic process.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a molybdenum salt heterogeneous carrier and a preparation method and application thereof, wherein the operation is simple, the raw materials are easy to obtain, the cost is low, the energy consumption is low, and the prepared molybdenum salt heterogeneous carrier has extremely strong sintering resistance.
The invention is realized by the following technical scheme:
the invention discloses a preparation method of a molybdenum salt heterogeneous carrier, which comprises the following steps: step 1: generating a molybdenum salt precursor by regulating molybdenum salt and an organic ligand with acid;
step 2: calcining the molybdenum salt precursor obtained in the step 1 to obtain the multi-component coexisting molybdenum salt heterogeneous carrier.
Preferably, in step 1, the molybdenum salt is one or more of sodium molybdate, ammonium molybdate, molybdenum trichloride, and molybdenum pentachloride.
Preferably, in step 1, the organic ligand is an organic amine or an organic alcohol.
Further preferably, the organic amine is methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, or octylamine; the organic alcohol is methanol, ethanol, propanol, butanol or pentanol.
Preferably, in step 1, the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid.
Preferably, in step 1, the concentration of the acid is 1.0 to 5.0mol/L.
Preferably, in the step 2, the calcination temperature is 200-2000 ℃ and the calcination time is 6-12 h.
Preferably, the multicomponent coexisting molybdenum salt heterogeneous carrier obtained in the step 2 comprises two or more of molybdenum carbide, molybdenum oxide, molybdenum nitride, molybdenum phosphide and molybdenum disulfide.
The invention also discloses a molybdenum salt heterogeneous carrier prepared by the preparation method.
The invention also discloses application of the molybdenum salt heterogeneous carrier as a heterogeneous catalyst carrier.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the preparation method of the molybdenum salt heterogeneous carrier, the heterogeneous carrier prepared under the guidance of the strong and weak carrier interaction theory is based, and the catalyst with strong carrier interaction can undergo Ostwald ripening in the catalyst process, so that the active structure of the catalyst is damaged, and the activity of the catalyst is greatly reduced; particle aggregation and migration can occur in the catalytic process due to weak carrier interaction, so that the active structure of the catalyst is destroyed, and the activity of the catalyst is greatly reduced. The catalyst with strong carrier interaction has good inhibition effect on particle aggregation and migration, while the catalyst with weak carrier interaction has inhibition effect on Ostwald ripening. Thus, the heterogeneous carrier prepared simultaneously has two interactions and has extremely strong inhibition effect on the two sintering modes of Ostwald ripening and particle aggregation and migration involved in the use process of the catalyst. The molybdenum salt precursor is prepared by the water bath of the molybdenum salt and the organic ligand, and then the molybdenum salt heterogeneous carrier obtained by directly calcining the molybdenum salt precursor in situ overcomes the defect of the traditional catalyst in terms of sintering resistance, improves the stability of the catalyst, prolongs the service life and reduces the use cost of the catalyst. Meanwhile, the method for preparing the heterogeneous carrier by in-situ calcination overcomes the defects of complicated preparation steps and larger energy consumption of the traditional catalyst, and has the advantages of low cost, simple operation process, easily available raw materials, rich reserves and the like.
Further, the molybdenum salt is sodium molybdate, ammonium molybdate, molybdenum trichloride and molybdenum pentachloride, and has the advantages of readily available raw materials, low cost, high active site and higher selectivity.
Further, organic ligands are organic amines or organic alcohols, which easily give out lone pair electrons.
Further, the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid and acetic acid, and can promote coordination of molybdenum salt and organic ligand.
Further, the concentration of the acid is 1.0 to 5.0mol/L, and the coordination of the molybdenum salt and the organic ligand can be promoted at a proper reaction rate.
Further, the calcination temperature is 200-2000 ℃, and the calcination time is 6-12 hours, so that the prepared heterogeneous carrier crystal form is more stable.
According to the molybdenum salt heterogeneous carrier prepared by the preparation method disclosed by the invention, the interaction of strong and weak carriers formed by the multi-component structure enables the sintering resistance of the heterogeneous carrier to be greatly improved, so that the service life and the catalytic performance of the catalyst are improved.
The application of the molybdenum salt heterogeneous carrier disclosed by the invention as a heterogeneous catalyst carrier is based on the molybdenum salt heterogeneous carrier in which two or more components of molybdenum carbide, molybdenum oxide, molybdenum nitride, molybdenum phosphide and molybdenum disulfide coexist, the unique structure of the molybdenum salt heterogeneous carrier enables the heterogeneous carrier to have a stronger catalytic effect, other metal particles are loaded for catalysis, the catalytic performance of the catalyst is improved, the service life of the catalyst is prolonged, the catalytic range of the catalyst is widened, and more possibilities are provided for multi-field catalysis.
Drawings
FIG. 1 is an X-ray powder diffractometer (XRD) pattern of a molybdenum salt heterogeneous supported catalyst prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope (SEM-EDS) elemental analysis chart of the product obtained in example 1;
FIG. 3 is an X-ray powder diffractometer (XRD) pattern of the product obtained in example 1 before and after catalysis.
Detailed Description
The invention will now be described in further detail with reference to the drawings and examples, which are given by way of illustration and not limitation.
Example 1
1.2g of sodium molybdate and 1.1mL of methylamine are added into 60mL of deionized water, 1.0mol/L of dilute hydrochloric acid is added into the reaction solution until a large amount of white floccules are generated, and the molybdenum salt precursor powder is obtained through filtration and drying. Calcining the obtained molybdenum salt precursor powder at 200 ℃ for 12 hours to obtain the molybdenum salt heterogeneous carrier in which molybdenum oxide, molybdenum carbide and molybdenum nitride coexist.
Example 2
2.4g of ammonium molybdate and 2.2mL of ethylamine are added into 60mL of deionized water, 1.2mol/L of dilute hydrochloric acid and dilute sulfuric acid are added into the reaction liquid until a large amount of white floccules are formed, and molybdenum salt precursor powder is obtained through filtering and drying. Calcining the obtained molybdenum salt precursor powder at 300 ℃ for 11 hours to obtain the molybdenum salt heterogeneous carrier in which the molybdenum oxide, the molybdenum carbide and the molybdenum nitride coexist.
Example 3
Adding 4.8g of molybdenum pentachloride and 4.4mL of propylamine into 60mL of deionized water, adding 1.8mol/L of dilute acetic acid, dilute nitric acid and dilute hydrochloric acid into the reaction solution until a large amount of white floccules are formed, filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder at 400 ℃ for 10 hours to obtain the molybdenum salt heterogeneous carrier in which the molybdenum oxide, the molybdenum carbide and the molybdenum nitride coexist.
Example 4
9.6g of molybdenum trichloride and 2.2mL of butylamine were added to 60mL of deionized water, and 2.0mol/L of dilute formic acid and dilute nitric acid were added to the reaction liquid until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder for 9 hours at the temperature of 500 ℃ to obtain the molybdenum salt heterogeneous carrier with the coexistence of the two components of molybdenum carbide and molybdenum nitride.
Example 5
9.6g of ammonium molybdate and 2.2mL of pentylamine were added to 60mL of deionized water, and 2.5mol/L of dilute phosphoric acid was added to the reaction solution until a large amount of white floc had formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder at 600 ℃ for 8 hours to obtain the molybdenum salt heterogeneous carrier with the coexistence of the three components of molybdenum carbide, molybdenum nitride and molybdenum phosphide.
Example 6
2.4g of molybdenum trichloride and 2.2mL of hexylamine were added to 60mL of deionized water, and 3.0mol/L of dilute nitric acid was added to the reaction solution until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. And calcining the obtained molybdenum salt precursor powder at 700 ℃ for 7 hours to obtain the molybdenum salt heterogeneous carrier in which two components of molybdenum carbide and molybdenum nitride coexist.
Example 7
To the reaction solution, 4.8g of molybdenum pentachloride and 2.2mL of heptylamine were added 60mL of deionized water, and 1.5mol/L of diluted hydrochloric acid and diluted formic acid were added until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder at 800 ℃ for 12 hours to obtain the molybdenum salt heterogeneous carrier with the two components of molybdenum carbide and molybdenum nitride coexisting.
Example 8
3.6g of sodium molybdate, 1.2g of molybdenum pentachloride and 2.2mL of octylamine were added to 60mL of deionized water, and 3.5mol/L of dilute hydrochloric acid was added to the reaction solution until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder at 900 ℃ for 11 hours to obtain the molybdenum salt heterogeneous carrier with the two components of molybdenum carbide and molybdenum nitride coexisting.
Example 9
9.6g of ammonium molybdate, 4.8g of molybdenum trichloride and 2.2mL of methanol were added to 60mL of deionized water, and 4.0mol/L of dilute hydrochloric acid and dilute formic acid were added to the reaction solution until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder at 1000 ℃ for 10 hours to obtain the molybdenum salt heterogeneous carrier in which molybdenum oxide, molybdenum carbide and molybdenum nitride coexist.
Example 10
9.6g of ammonium molybdate, 1.2g of molybdenum trichloride and 2.2mL of ethanol were added to 60mL of deionized water, and 4.5mol/L of dilute hydrochloric acid was added to the reaction solution until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder for 9 hours at 1100 ℃ to obtain the molybdenum salt heterogeneous carrier with the coexistence of the three components of molybdenum oxide, molybdenum carbide and molybdenum nitride.
Example 11
9.6g of ammonium molybdate, 1.2g of sodium molybdate, 2.4g of molybdenum trichloride and 2.2mL of propanol and 60mL of deionized water were added, and 5.0mol/L of dilute hydrochloric acid and dilute acetic acid were added to the reaction solution until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder at 1200 ℃ for 8 hours to obtain the molybdenum salt heterogeneous carrier with the coexistence of the three components of molybdenum oxide, molybdenum carbide and molybdenum nitride.
Example 12
9.6g of ammonium molybdate, 1.2g of molybdenum trichloride, 3.6g of molybdenum pentachloride and 2.2mL of butanol were added to 60mL of deionized water, and 1.5mol/L of dilute hydrochloric acid was added to the reaction solution until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder at 1300 ℃ for 7 hours to obtain the molybdenum salt heterogeneous carrier in which the molybdenum oxide, the molybdenum carbide and the molybdenum nitride coexist.
Example 13
9.6g of sodium molybdate, 2.4g of ammonium molybdate, 3.6g of molybdenum trichloride and 2.2mL of amyl alcohol were added to 60mL of deionized water, and 2.0mol/L of dilute hydrochloric acid was added to the reaction solution until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder at 1400 ℃ for 6 hours to obtain the molybdenum salt heterogeneous carrier with the coexistence of the three components of molybdenum oxide, molybdenum carbide and molybdenum nitride.
Example 14
9.6g of ammonium molybdate, 1.2g of molybdenum pentachloride, 3.6g of sodium molybdate and 2.2mL of amyl alcohol were added to 60mL of deionized water, and 2.5mol/L of dilute hydrochloric acid was added to the reaction solution until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder at 1500 ℃ for 7 hours to obtain the molybdenum salt heterogeneous carrier in which the molybdenum oxide, the molybdenum carbide and the molybdenum nitride coexist.
Example 15
3.6g of molybdenum trichloride, 2.4g of ammonium molybdate, 3.6g of molybdenum pentachloride and 2.2mL of butanol were added to 60mL of deionized water, and 2.5mol/L of dilute hydrochloric acid was added to the reaction solution until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder at 1600 ℃ for 8 hours to obtain the molybdenum salt heterogeneous carrier in which the molybdenum oxide, the molybdenum carbide and the molybdenum nitride coexist.
Example 16
2.4g of molybdenum trichloride, 3.6g of molybdenum pentachloride, 4.8g of sodium molybdate and 2.2mL of propanol were added to 60mL of deionized water, and 3.0mol/L of dilute hydrochloric acid was added to the reaction solution until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder for 9 hours at 1700 ℃ to obtain the molybdenum salt heterogeneous carrier with the coexistence of the three components of molybdenum oxide, molybdenum carbide and molybdenum nitride.
Example 17
To the reaction solution, 4.8g of molybdenum pentachloride, 4.8g of sodium molybdate, 9.6g of ammonium molybdate and 2.2mL of ethanol were added 60mL of deionized water, and 2.0mol/L of dilute hydrochloric acid was added until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder for 10 hours at 1800 ℃ to obtain the molybdenum salt heterogeneous carrier with the coexistence of molybdenum oxide, molybdenum carbide and molybdenum nitride.
Example 18
9.6g of molybdenum pentachloride, 1.2g of molybdenum trichloride, 2.4g of sodium molybdate and 2.2mL of methylamine were added to 60mL of deionized water, and 2.6mol/L of dilute hydrochloric acid was added to the reaction solution until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder at 1900 ℃ for 11 hours to obtain the molybdenum salt heterogeneous carrier in which the molybdenum oxide, the molybdenum carbide and the molybdenum nitride coexist.
Example 19
To 60mL of deionized water were added 4.8g of molybdenum pentachloride, 3.6g of molybdenum trichloride, 2.4g of ammonium molybdate, 1.2g of ammonium molybdate and 2.2mL of propylamine, and 3.0mol/L of dilute hydrochloric acid was added to the reaction solution until a large amount of white floc was formed. And filtering and drying to obtain molybdenum salt precursor powder. Calcining the obtained molybdenum salt precursor powder for 12 hours at 2000 ℃ to obtain the molybdenum salt heterogeneous carrier in which molybdenum oxide, molybdenum carbide and molybdenum nitride coexist.
FIG. 1 is an X-ray powder diffractometer (XRD) pattern of a molybdenum salt heterogeneous supported catalyst prepared in example 1, from which it can be seen that XRD diffraction peaks of the prepared product were compared with standard cards MoC (PDF # 15-0457), mo 2 N(PDF#25-1366)、Mo 2 O (PDF# 76-1807) match.
FIG. 2 is a scanning electron microscope (SEM-EDS) elemental analysis of the product of the present invention, and it can be seen from the figure that EDS elemental analysis of the prepared product is a composite of four elements Mo-C-N-O.
Combining fig. 1 and fig. 2, the product obtained in example 1 is a molybdenum salt heterogeneous carrier in which three components of molybdenum oxide-molybdenum carbide-molybdenum nitride coexist.
FIG. 3 shows the X-ray powder diffractometer (XRD) patterns of the product before and after catalysis, and the patterns show that the heterogeneous carrier has no obvious crystal form change before and after catalysis and has stable structure.
It is to be understood that the foregoing description is only a part of the embodiments of the present invention, and that the equivalent changes of the system described according to the present invention are included in the protection scope of the present invention. Those skilled in the art can substitute the described specific examples in a similar way without departing from the structure of the invention or exceeding the scope of the invention as defined by the claims, all falling within the scope of protection of the invention.
Claims (5)
1. The preparation method of the molybdenum salt heterogeneous carrier is characterized by comprising the following steps of:
step 1: generating a molybdenum salt precursor by regulating molybdenum salt and an organic ligand with acid; the organic ligand is organic amine or organic alcohol, and the organic amine is methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine or octylamine; the organic alcohol is methanol, ethanol, propanol, butanol or amyl alcohol; the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid and acetic acid;
step 2: calcining the molybdenum salt precursor obtained in the step 1 at the temperature of 200-1400 ℃ for 6-12 hours to obtain a molybdenum salt heterogeneous carrier; the molybdenum salt heterogeneous carrier comprises molybdenum carbide and other components, wherein the other components are one or more of molybdenum oxide, molybdenum nitride, molybdenum phosphide and molybdenum disulfide, and the molybdenum carbide is alpha-molybdenum carbide.
2. The method for preparing a heterogeneous carrier of molybdenum salt according to claim 1, wherein in the step 1, the molybdenum salt is one or more of sodium molybdate, ammonium molybdate, molybdenum trichloride and molybdenum pentachloride.
3. The method for preparing a molybdenum salt heterogeneous carrier according to claim 1, wherein in the step 1, the concentration of acid is 1.0-5.0 mol/L.
4. A molybdenum salt heterogeneous carrier prepared by the preparation method according to any one of claims 1 to 3.
5. The use of a molybdenum salt heterogeneous support according to claim 4 as heterogeneous catalyst support.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB655557A (en) * | 1946-09-04 | 1951-07-25 | Goodrich Co B F | Improvements in or relating to the production of aldehydes and to catalysts for use in oxidative processes |
| CN107597097A (en) * | 2017-09-04 | 2018-01-19 | 北京林业大学 | A kind of preparation method and applications of Supported molybdenum oxide catalyst |
| CN110201693A (en) * | 2019-06-14 | 2019-09-06 | 陕西科技大学 | A kind of molybdenum carbide catalyst and its preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB655557A (en) * | 1946-09-04 | 1951-07-25 | Goodrich Co B F | Improvements in or relating to the production of aldehydes and to catalysts for use in oxidative processes |
| CN107597097A (en) * | 2017-09-04 | 2018-01-19 | 北京林业大学 | A kind of preparation method and applications of Supported molybdenum oxide catalyst |
| CN110201693A (en) * | 2019-06-14 | 2019-09-06 | 陕西科技大学 | A kind of molybdenum carbide catalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| "In-situ synthesis of coupled molybdenum carbide and molybdenum nitride as electrocatalyst for hydrogen evolution reaction";Weiwen Wang et al.;《Journal of Alloys and Compounds》;第792卷;第230-239页 * |
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