CN113213539A - Continuous production method of MoVO composite metal oxide - Google Patents

Continuous production method of MoVO composite metal oxide Download PDF

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Publication number
CN113213539A
CN113213539A CN202110408873.6A CN202110408873A CN113213539A CN 113213539 A CN113213539 A CN 113213539A CN 202110408873 A CN202110408873 A CN 202110408873A CN 113213539 A CN113213539 A CN 113213539A
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China
Prior art keywords
metal oxide
reactor
movo
production method
composite metal
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CN202110408873.6A
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Inventor
李双明
吴越矶
于三三
王宪忠
沈赟
笪延清
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Shenyang University of Chemical Technology
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Shenyang University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

A continuous production method of MoVO composite metal oxide relates to a production method of metal oxide, and the method comprises the following steps: dissolving a Mo source precursor and a V source precursor in deionized water according to a certain molar ratio to prepare a precursor solution with the total concentration of Mo and V of 0.002-0.05M, continuously passing the solution through a pressure-resistant tubular reactor by using a high-pressure pump, controlling the reaction temperature and the reaction pressure at 200-400 ℃ and 0.5-15 MPa respectively, keeping the retention time of the precursor solution in the reactor at 0.05-0.5 h, collecting the product solution flowing out of the reactor, centrifuging, washing and drying to obtain the compound metal oxide powder with the general formula of MoxVyOz. The preparation method has simple process and quick reaction, does not need subsequent calcination treatment, and can change the crystal phase composition of the product by adjusting the process parameters.

Description

Continuous production method of MoVO composite metal oxide
Technical Field
The invention relates to a method for producing metal oxide, in particular to a continuous production method of MoVO composite metal oxide.
Background
The MoVO composite metal oxide is Mo,The ternary composite metal oxide formed by combining the two V elements is a heterogeneous catalyst which has the greatest development prospect and research value in a plurality of oxidation reactions such as the preparation of acrylic acid by propane oxidation, the preparation of acrylonitrile by ammoxidation, the preparation of acrylic acid by glycerol oxidative dehydration, the preparation of ethylene by ethane oxidation and the like. The MoVO composite metal oxide can form a series of different crystal phases according to different preparation methods and process parameters: (Mo)0.3V0.7)2O5、(V0.07Mo0.93)5O14、Mo0.67V0.33O2、Mo4V6O25、Mo6V4O5、Mo6V9O40、MoV2O7.5、MoV2O8、MoVO5、V0.95Mo0.97O5And so on. Up to now, MoVO composite metal oxides with different crystal phase compositions have been prepared by domestic and foreign scholars by hydrothermal methods (RSC Advances. 2018, 8(22): 11975-82; ChemCat Chem. 2013, 5(10): 2869-73; ChemCat Chem. 2016, 8(14): 2415-20; J Phys Chem C. 2015, 119(13): 7195-. Although the methods realize the chemical preparation of the MoVO composite metal oxide, the samples directly prepared by the hydrothermal method or the sol-gel method have low crystallization degree and cannot meet the requirements of subsequent application, and the required crystalline phase can be formed only by performing high-temperature (500-600 ℃) calcination treatment on the prepared samples in a certain inert atmosphere, so that the technological process and the complexity are increased. And the methods are all intermittent operation, and industrial scale-up production is difficult to realize.
In view of the above, it is highly desirable to develop a simple and feasible method for preparing a compound metal oxide of MoVO suitable for industrial scale-up.
Disclosure of Invention
The invention aims to provide a continuous production method of MoVO composite metal oxide, which takes a Mo source and a V source precursor as raw materials and adopts a continuous feeding method to prepare the MoVO composite metal oxide. The method has simple process and short reaction time, does not need high-temperature calcination treatment, can continuously discharge materials, and can change the crystal phase composition of the product by adjusting parameters.
The purpose of the invention is realized by the following technical scheme:
a continuous production method of MoVO composite metal oxide comprises the following preparation processes:
firstly, dissolving a Mo source precursor and a V source precursor in deionized water to prepare a precursor solution with the concentration of 0.002-0.05M, then continuously passing the precursor solution through a pressure-resistant tubular reactor by using a high-pressure pump, controlling the reaction temperature to be 200-400 ℃ and the reaction pressure to be 0.5-15 MPa, allowing the precursor solution to stay in the reactor for 0.05-0.5 h, collecting a product solution flowing out of the reactor, centrifuging, washing and drying to obtain the compound metal oxide powder with the general formula of MoxVyOz.
According to the continuous production method of the MoVO composite metal oxide, the Mo source precursor is ammonium molybdate, and the V source precursor is one or more of ammonium vanadate and vanadyl sulfate.
According to the continuous production method of the MoVO composite metal oxide, the concentration of the precursor solution is the total concentration of Mo and V elements.
According to the continuous production method of the MoVO composite metal oxide, the precursor solution stays in the reactor for 0.05-0.5 h, and specifically, the time required from the precursor solution entering the reactor to leaving the reactor is shortened.
In the continuous production method of the MoVO composite metal oxide, x, y and z in the general formula MoxVyOz are respectively the molar ratio of each element, specifically 1, 0.05-10 and 1-10.
The invention has the advantages and effects that:
according to the method, a Mo source and a V source precursor are used as raw materials, the rapid preparation of the MoVO composite metal oxide is carried out by adopting a subcritical fluid method (0.05-0.5 h), the method can realize continuous feeding and continuous discharging, the obtained product does not need high-temperature heat treatment, the whole process is simple, and the industrial production is facilitated.
Detailed Description
The present invention will be described in detail with reference to examples.
Dissolving a Mo source and a V source precursor serving as raw materials in deionized water to prepare a precursor solution with the total concentration of Mo and V of 0.002-0.05M, continuously pumping the precursor solution into a pressure-resistant tubular reactor by using a high-pressure pump, controlling the temperature of the reactor to be 200-400 ℃ and the reaction pressure to be 0.5-15 MPa, allowing the precursor solution to stay in the reactor for 0.05-0.5 h, collecting a product solution flowing out of the reactor, centrifuging, washing and drying to obtain the compound metal oxide powder with the general formula of MoxVyOz. Wherein, the Mo source precursor is ammonium molybdate, and the V source precursor is one or more than one of ammonium vanadate and vanadyl sulfate.
Example 1:
weighing 3.53 g of ammonium molybdate and 1.17 g of ammonium metavanadate, dissolving the ammonium molybdate and the ammonium metavanadate in 2000 mL of deionized water to prepare a precursor solution with the total concentration of Mo and V of 0.015M, pumping the solution into a tubular reactor preheated to 250 ℃ by using a high-pressure pump, controlling the system pressure by using a backpressure valve to be 5 MPa, enabling the precursor solution to stay in the reactor for 0.1 hour by controlling the flow rate, flowing out, cooling and collecting the precursor solution in normal-temperature water, continuously reacting for 5.0 hours, centrifuging and washing the collected product solution, and drying the product solution in vacuum at 60 ℃ to obtain a main crystal phase (V, V and V) of which0.07Mo0.93)5O14The black powder of (1).
Example 2:
adding ammonium molybdate (0.53 g) and ammonium metavanadate (0.35 g) into 1.0L of water, stirring and dissolving to prepare a precursor solution, wherein the total concentration of Mo and V is 0.006M, continuously pumping the solution into a reactor by using a high-pressure pump after the temperature of the tubular reactor is stabilized at 200 ℃, controlling the pressure of a reaction system to be 14 MPa, allowing the precursor solution of Mo and V to stay in the reactor for 0.2 h, then flowing out of the reactor, cooling and collecting, continuously reacting for 3.0 h, centrifuging and washing the collected product solution for three times, and drying in vacuum to obtain a main crystal phase of MoV2O8The product of (1).
Example 3:
4.89 g vanadyl sulfate and 1.77 g ammonium molybdate were weighed out and dissolved in 1000Preparing a precursor solution with the total concentration of Mo and V of 0.04M in mL deionized water, pumping the solution into a tubular reactor preheated to 300 ℃, keeping the precursor solution in the reactor for 0.5 h under the system pressure of 1.2 MPa, continuously reacting for 8.0 h, centrifuging, washing and drying the collected product solution to obtain a product with a main crystal phase of V0.95Mo0.97O5The product of (1).
Example 4:
adding ammonium molybdate (1.76 g), ammonium metavanadate (1.17 g) and vanadyl sulfate (1.63 g) into 1.0L of water, stirring and dissolving to prepare a precursor solution, wherein the total concentration of Mo and V is 0.03M, continuously pumping the solution into a reactor by using a high-pressure pump after the temperature of a tubular reactor is stabilized at 350 ℃, controlling the pressure of a reaction system to be 10 MPa, staying the Mo and V precursor solution in the reactor for 0.3 h, then flowing out of the reactor, cooling and collecting, continuously reacting for 6 h, centrifuging and washing the collected product solution for three times, and drying in vacuum to obtain the product containing (V)0.07Mo0.93)5O14And V0.95Mo0.97O5Mixed crystal phases of (2).

Claims (5)

1. A continuous production method of MoVO composite metal oxide is characterized by comprising the following preparation processes:
firstly, dissolving a Mo source precursor and a V source precursor in deionized water to prepare a precursor solution with the concentration of 0.002-0.05M, then continuously passing the precursor solution through a pressure-resistant tubular reactor by using a high-pressure pump, controlling the reaction temperature to be 200-400 ℃ and the reaction pressure to be 0.5-15 MPa, allowing the precursor solution to stay in the reactor for 0.05-0.5 h, collecting a product solution flowing out of the reactor, centrifuging, washing and drying to obtain the compound metal oxide powder with the general formula of MoxVyOz.
2. The continuous production method of MoVO composite metal oxide as claimed in claim 1, wherein the Mo source precursor is ammonium molybdate, and the V source precursor is one or more of ammonium vanadate and vanadyl sulfate.
3. The continuous production method of MoVO composite metal oxide as claimed in claim 1, wherein the concentration of the precursor solution is the total concentration of Mo and V.
4. The continuous production method of MoVO composite metal oxide as claimed in claim 1, wherein the precursor solution stays in the reactor for 0.05-0.5 h, specifically, the time required from the time the precursor solution enters the reactor to the time the precursor solution leaves the reactor.
5. The continuous production method of MoVO composite metal oxide as claimed in claim 1, wherein x, y and z in the general formula MoxVyOz are molar ratios of the elements, specifically 1, 0.05-10 and 1-10.
CN202110408873.6A 2021-04-16 2021-04-16 Continuous production method of MoVO composite metal oxide Pending CN113213539A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114308009A (en) * 2021-12-17 2022-04-12 中南民族大学 Micro-nano vanadium-molybdenum composite oxide and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000143244A (en) * 1998-07-24 2000-05-23 Mitsubishi Chemicals Corp Production of multiple metal oxide
CN104556198A (en) * 2015-01-08 2015-04-29 沈阳化工大学 Continuous production method and application of ultrafine cuprous oxide
CN109569577A (en) * 2019-01-15 2019-04-05 山东玉皇化工有限公司 O composite metallic oxide catalyst and its preparation method and application
CN109647446A (en) * 2019-01-10 2019-04-19 沈阳化工大学 A kind of fast preparation method of MoV base multi-element metal oxide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000143244A (en) * 1998-07-24 2000-05-23 Mitsubishi Chemicals Corp Production of multiple metal oxide
CN104556198A (en) * 2015-01-08 2015-04-29 沈阳化工大学 Continuous production method and application of ultrafine cuprous oxide
CN109647446A (en) * 2019-01-10 2019-04-19 沈阳化工大学 A kind of fast preparation method of MoV base multi-element metal oxide
CN109569577A (en) * 2019-01-15 2019-04-05 山东玉皇化工有限公司 O composite metallic oxide catalyst and its preparation method and application

Non-Patent Citations (1)

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Title
李娜等: "Mo-V-O复合金属氧化物的制备及其分子氧氧化苯甲醇反应的催化性能", 《精细石油化工》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114308009A (en) * 2021-12-17 2022-04-12 中南民族大学 Micro-nano vanadium-molybdenum composite oxide and preparation method and application thereof

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